Abstracts Book

3rd Mid-European Clay Conference – MECC 06 Abstracts Book

edited by Igor VLAHOVIĆ, Darko TIBLJAŠ, Goran DURN & Vanja BIŠEVAC Papers in this Abstract Book were reviewed in order to correct the text and to unify their ﬁnal layout.

We are grateful to the reviewers: Vladimir BERMANEC, Goran DURN, Biljana KOVAČEVIĆ ZELIĆ, Ladislav PALINKAŠ, Esad PROHIĆ, Mira RISTIĆ, Darko TIBLJAŠ & Neda VDOVIĆ Abstracts Book

CONTENTS

KEYNOTE ABSTRACTS

BAHRANOWSKI, K. & SERWICKA, M.: Layered minerals in catalysis...... 3 CUADROS, J.: Clay minerals in the making...... 4 DOHRMANN, R., RÜPING, K., KLEBER. M. & JAHN, R.: XRD texture measurements of oriented clay aggregates – a quantiﬁcation tool...... 5 MADEJOVÁ, J.: Near infrared spectroscopy: a powerful method to learn more on modiﬁed smectites...... 6 MURAD, E.: Mössbauer spectroscopy of geological materials...... 7 PETIT, S., JOUSSEIN, E. & GRAUBY, O.: New insight into halloysite physico-chemical properties...... 8 RAUCSIK, B., RAUCSIK-VARGA, A., SZAKMÁNY, Gy. & KOVÁCS-KISS, V.: Clay mineralogy, petrography and geochemistry of Late Palaeozoic siliciclastic rocks from the Mecsek–Villány area (SW Hungary): implications for source-area weathering, provenance and diagenesis...... 9 RUIZ-HITZKY, E.: Clay-based bionanocomposites...... 10 TIBLJAŠ, D. & ŠĆAVNIČAR, S.: Zeolite deposits in Croatia...... 11

ZNIDARČIĆ, D.: Engineering properties of clays...... 12 3r d Mid-European Clay Conference – MECC 06

ABSTRACTS

ABU-JDAYIL, B. & AL-MALAH, K.: Waterproof polymeric heat insulators based on clay ﬁllers: mechanical properties...... 15 ACTIŅŠ, A., SUPE, L. & SARCEVIČA, I.: Latvian smectite clay and bentonite interaction with tetraoctyl-ammonium bromide...... 16 ADAMCOVA, R., HAASOVA, Z. & MAAS, P.: Engineering geological research of highly compacted bentonites in Slovakia...... 17 AL-JUBOURY, A.: Clay mineralogy in northern Iraq during the Miocene: paleoenvironmental indicators...... 18 ANDREJKOVIČOVÁ, S., JANOTKA, I. & KOMADEL, P.: Phase composition and geotechnical evaluation of bentonite from Lieskovec, Slovakia...... 19

ARANDA, P., MANOVA, E., MARTÍN-LUENGO, M.A., LETAÏEF, S. & RUIZ-HITZKY, E.: TiO2/delaminated–clay nanocomposites...... 20 AUGUST, C.: Mineralogy of a Carboniferous bentonite from the Sudetes (SW Poland), northern margin of the Bo- hemian Massif – preliminary data...... 21 BALOGH, K., ÁRKAI, P., JUDIK, K., ITAYA, T., HYODO, H. & BALOGH, I.: Development of a simple method for Ar/Ar dating of micrometer-sized minerals: a progress report...... 22 BARUDŽIJA, U., TADEJ, N. & TADEJ, J.: Clay minerals assemblage in the Upper Albian carbonate succession (Tinjanska Draga, Istria, Croatia)...... 23 BAYHAN, E.: Upper Cretaceous–Lower Tertiary clay mineral successions of southern Haymana region (Ankara, Turkey)...... 24 BAYHAN, H., GÜLEÇ, F., BAYHAN, E., TEMEL, E. & HÜRYILMAZ, H.: Clay mineralogy of Tertiary sedimentary sequence from Gökçeada Island (northeast Aegean Sea, Turkey)...... 25 BIŠEVAC, V., BALEN, D., BALOGH, K. & TIBLJAŠ, D.: K–Ar dating of Cretaceous metamorphism recorded in the eastern part of Mt. Papuk, Slavonia, Croatia...... 26 BISHOP, J.L., BROWN, A.J., CLOUTIS, E., DYAR, M.D., HIROI, T., LANE, M.D., MILLIKEN, R.E., MURAD, E. & MUSTARD, J.F.: A multispectral study of clay minerals: Mössbauer, reflectance, transmittance, and emission spectroscopy...... 27 BLANCO GARCÍA, I., LUQUE, J., BARRENECHEA, J.F., AZCARATE, J.A., ELSEN, J., RODAS, M., SWENNEN, R., SÁNCHEZ, C.J. & DONDI, M.: Production of synthetic lightweight aggregates (LWA) from mining wastes...... 28 BLANCO GARCÍA, I., SWENNEN, R. & ELSEN, J.: Physical properties and behaviour during leaching of synthetic aggregates made with polluted dredged sediments from Flanders, Belgium...... 29 I Abstracts Book Abstracts II 3rd Mid-European Clay Conference – MECC 06 HONTY, M., ŠUCHA, V., KOMADEL, P., OSACK HARMADYOVM., GREGOR, G G GOREA, M., BENEA, M. & MARI inGOMES, Portugal C.S.F. &PERTEIRA SILVA, of J.B.: porcelain formulations Clay-based intopical used to be applications manufacture first the of year GOMES, C.S.F.: 1773: The GERARDI, J.: characteristicsBarrier of clay and claystone: the B GAUTIER, M., MULLER, F., ALB GALOVI F.,M PUDEL, G., FLECK, M the on alteration of physical influence The DRIEF,A.: BISHOP,DYAR,M.D.,& J.L. (Istria, hole”sequence “blue cover associated and bauxitesJurassic in minerals F.:Clay OTTNER, & G. DURN, DURN, G., MINDSZENTY, A. & GERMAN-HEINS, J.: Micromorphology of the pedo-sedimentary colluvial com DOU DOMINKOVI DOBNIKAR, M., DONDI, M., MIRTI P., GRECULA, SASV SACHSENHOFER,R., H.G., DILL, F.,DELLISANTI, V.MINGUZZI, VALDR& DAINYAK, L.G.: A new approach to the interpretation of Fe CZ CERJAN-STEFANOVI Č BUJD BRUS,J.,URBANOVA, KOLOUSEK,M., ANDERTOVA,D. & “geopolyofstability ofstudy J.:NMR Solid-state BOJAR, A.-V., OTTNER, F., GRIGORESCU, D. & CSIKI, Z.: Maastrichtian calcisols from the Hateg basin, South Car HRACHOV EKLOVSK Ó Ó Í RNIAK, K., BAHRANOWSKI, K., GAWE Car Flysch the Polish of from marls of illite/smectite transformation diagenetic and structure RNIAK, K.: The MEROV Š Á OV Experimental studyExperimental of iron–bentonite and pyrite–claystone interaction at low temperature household ceramic from Dev material from Lower Carboniferous black shales pathians (Arad county, Romania), a raw material for ceramic industry acids on NH of loess/paleosol section in milling of clay minerals of antigoritespectra and applications to alteration soil processes on Mars Croatia) plex in Sjenoko sorption on Fe-treated clays ate terrains Plio map some of metallogenic by firing (accompanied Europe Central of resources energy and 1:2.500,000) mineral of origin The M.: STRMI andthermal technological properties of commercial talc hedral charge montmorillonites complex exchange innatural zeolites rhodamine 6G mers” prepared from activated alkaline metakaoline...... pathians: and mineralogical stable isotopic investigations K, J., IYI, N. & CZ & N. J.,IYI, K, Ć Á , L., MILEUSNI , B., GRYGAR, T., MARTAUS, A., KOLOU Á Ý Á , J., CHOD , A. & BUJD trans , A., BUJD A., , Ć Ć ...... PALINKA ALAVANJA, S. & ORE ...... -vacant micaceous minerals ...... 4 -smectites: pollution prediction in waste landfill ...... š Ć ...... a (Istria, Croatia) ...... Á , Á ...... Á Ć Í – Š ,I OAE,P:Vlaie ubrfildwt oie montmorillonite modified K, I.&KOMADEL, with P.: Vulcanized filled rubber . K, J. & IYI, N.: Energy transfer between cations of laser dyes in dispersions of reduceddispersionsof in dyes laser cationsof between transfer Energy N.: IYI, J.& K, Ö ...... MEROV Š . . Quaternary claysQuaternary from NESlovenia K, J.: Spectroscopic study of interaction of porphyrin dyes with layered silicates , M., ...... , ZABUKOVEC-LOGAR, N., MARGETA, K., MARGETA, N., ZABUKOVEC-LOGAR, , ...... , S., PROCHASKA,S., , W., GARUTI, ZACCARINI,F.,G., D. ARBOUILLE, SCHULZ, & RL, L., RANGELOWA, J. & KR RANGELOWA,& L., J. RL, ...... Á ......

PEH, Z., DURN, G. & HALAMI ...... , K. & K. , ...... É ...... Ş Š ...... RIC, P., LE FORESTIER, L., B ...... , C.: Physico ...... Á arengrad, Srijem, Croatia ...... í ...... n Castle (Slovakia)n Castle , A.: Clay mineral template-controlledmineral Clayof assemblies A.: formation molecular of, ...... Č Č ...... Š ...... , B., ROKAVEC, D. & ZANELLI, C.: Mineralogical transformations during . . KOVI ...... AMBAL, R.: Mineralogical and petrographical analysis of Kalenderberg of analysis petrographical and Mineralogical R.: AMBAL, ...... È ...... Ł ...... nuneo otoldmcaia eomto nstructural, on deformation mechanical controlled of Inﬂuence G.: , Ć , A., RATAJCZAK, T. & SZYD ...... – ...... , J.: Application of IP method for discovering clay zones in carbon . chemical and mineralogical characterization of the H . . Ý ...... , M., MADEJOV ...... Š ...... EK, D., FUITOV ...... (Western Pomerania, N Poland) ...... Á ...... 2+ RI, T.,RI, PALINKAŠ,BOROJEVI L.A., ...... Ü ...... quadrupole doublets in M ...... GER, G.: Fluidised bed technology for drying and drying for technology bed Fluidised G.: GER, ...... Ć ...... É . ETTON ...... , J.: Mineralogical and geochemical characteristics ...... NY , J.-M. & BAILLIF, P.: Behaviour of carboxylic ...... Á ...... , J., VAL ...... Á ...... database ...... , L. & MACHOVI ...... Ú ...... Š ...... ILJEG, M. & VOJNOVI & M. ILJEG, ...... CHOV Ł ...... K . hra rpriso illitic of properties AK, T.: Thermal ...... Á ...... , J., BUJD ...... ö ...... ssbauer spectra of diocta ...... ö ...... ssbauer and reﬂectance and ssbauer ...... Č ...... , V.: Mechanism of As ...... Á ...... Ć ...... K, J. & UHL ...... Š ...... O ...... ă ...... Ć ...... Š ...... lmagiu clay ...... TARI ...... , B.: , ...... Metal Í ...... Ć ...... K, P.: ...... , S. , ...... ------. . . , . . .

56 55 54 53 52 51 50 49 48 47 46 45 44 43 42 41 40 39 38 37 36 35 34 33 32 31 30 Abstracts Book

HRUSKOVA, M., GRYGAR, T. & HRADIL, D.: Fast determination of CEC by Cu-trien method, its limitation and use...... 57 IONESCU, C., GHERGARI, L., HOECK, V., SIMON, V. & HORGA, M.: Thermal alteration of mineral phases in Bronze Age ceramics from Transylvania (Romania)...... 58 JANOTKA, I. & GALKO, I.: Cement suspensions for slurry cut-off walls with ultra fine ground Na-bentonite from Lieskovec and Jelšový potok deposits...... 59 JUDIK, K., RANTITSCH, G., RAINER, T.M., TIBLJAŠ, D. & ÁRKAI, P.: Correlation of organic and inorganic temperature indicators – a case study on low-temperature metamorphic rock series from Mt. Medvednica, Cro- atia...... 60 KAPUSTIN, A.E., KOZLOVSKIY, R.A. & BISH, D.L.: The structure and chemistry of natural takovite and synthetic analogue of takovite...... 61 KAUFHOLD, S. & DOHRMANN, R.: Detachment of colloids from bentonites in water...... 62 KELE, S., DE CRAEN, M., VAN GEET, M. & LIAN, W.: Geochemical studies on pore water from two different clay types in the frame of radioactive waste disposal researches...... 63 KHANKHASAEVA, S.Ts., BADMAEVA, S.V., DASHINAMZHILOVA, E.Ts. & DOBOLOVA, U.V.: The synthesis of iron-containing pillared clays from natural clays of Transbaikalia and research of their catalytic properties in wet oxidation of phenol by hydrogen peroxide...... 64

KŁAPYTA, Z.: Structural heterogeneity of alkylammonium-exchanged synthetic swelling fluoromicas...... 65 3r d Mid-European Clay Conference – MECC 06 KLIKA, Z., ČAPKOVÁ, P., HORÁKOVÁ, P., VALÁŠKOVÁ, M. & POSPÍŠIL, M.: Intercalated montmorillonites by different aggregates of methylene blue...... 66 KNIEWALD, G. & FIKET, Ž.: Sorption of arsenic on clay minerals – a theoretical approach...... 67 KOLOUŠEK, D., VOREL, J., DOUŠOVÁ, B., URBANOVÁ, M., BRUS, J., SLAVÍK, R., ANDERTOVÁ, J., MACHO- VIČ, V., BÍLEK, V. & HÁJEK, P.: Hydrothermal stability of geopolymers...... 68 KOMADEL, P. & STUCKI, J.W.: Iron phases occurring in Fe-rich bentonite from Lieskovec, Slovakia...... 69 KOVAČEVIĆ ZELIĆ, B., DOMITROVIĆ, D., MILEUSNIĆ, M. & TADEJ, N.: Chemical compatibility of GCL mineral component to site-specific liquid...... 70 KOVÁCS, J.: Geochemistry and weathering of the Late Cenozoic red clays in the Pannonian Basin...... 71 KOVANDA, F., ROJKA, T., MACHOVIČ, V. & BEZDIČKA, P.: Thermal behaviour of synthetic takovite-like anionic clays studied by high-temperature X-ray diffraction and Raman spectroscopy...... 72 KRUPSKAYA, V., VOEVODIN, L., PILOYAN, G. & NIKOLSKIJ, M.: Smectites from Ziryanovskoe deposit (Kurgan Region, Russia): Relation between composition, structure and technological properties...... 73 KUSHCHEVA, Y.V., GOLOVIN, D.I. & BUJAKAITE, M.I.: The possibility of the isotopic dating stages of postsedi- mentary transformations of clayey terrigenous deposits in the different geodynamical situations...... 74 LE FORESTIER, L., BAILLIF, P., PROUST, C. & MULLER, F.: Evolution of swelling and hydration properties of a compacted hectorite percolated by nickel solutions...... 75 LERF, A., WAGNER, F.E., POYATO, J., RAMÍREZ-VALLE, V. & PÉREZ-RODRÍGUEZ, J.L.: Fe3+ intercalation into vermiculite or deposition of iron oxyhydroxides? A Mössbauer spectroscopic investigation...... 76

LIEBER, D. & STANJEK, H.: Point of zero charge and surface acidity constants of Fe(OH)2...... 77 LUGOVIĆ, B., CRNJAKOVIĆ, M. & BIŠEVAC, V.: Mineralogical signatures of weathered Late Holocene ash layer from the island Mljet in Croatia...... 78 MAJDÁN, M., KRAUS, I. & GALKO, I.: Geological prospecting of kaolin and kaolinite clays deposits on territory of the Western Carpathians (Slovakia)...... 79 MAQUEDA, C., SANTAS ROMERO, A., MORILLO, E., PÉREZ-RODRÍGUEZ, J.L., LERF, A. & WAGNER, F.E.: Möss- bauer spectroscopy investigation of ground and acid treated vermicullite...... 80 MILDER, O.B., PIKULEV, A.I., SEMIONKIN, V.A. & NOVIKOV, E.G.: Particularities of Mössbauer spectroscopy for the archaeological potsherds dating...... 81 MOCKOVČIAKOVÁ, A. & ŠTYRIAKOVÁ, I.: Characterization of changes of low and high ordered kaolinite after bioleaching...... 82 MULLER, F., BÉNY, J.M. & GAUTIER, M.: Intercalation of aniline in Wyoming montmorillonite exchanged with different cations...... 83 III Abstracts Book Abstracts IV 3rd Mid-European Clay Conference – MECC 06 STUCKI, J.W., LEE, K., GOODMAN, B.A. & KOSTKA, of J.L.: Effects STR glauconiteSTARZEC, K. & of SKIBA, M.: Identification Ś SONDI, I.&VDOVI Š T.,ROJKA, KOVANDA, F., DOU RODR REATTO,BRUAND,A., F., MARTINS,MULLER, A., E.S., SILVA, GUIMAR E.M., RAUCSIK, B. & VARGA, A.: PRAUS, P., TURICOV POSP POPOVICI,VASILE,E., DVININOV, PODE,A., R., UseE.: REISZ, & E. of Romanian clays for wastewater textile POPOVICI, E., PODE, R., REISZ, E., COCHECI, L., PODE, V. & SEFTEL, E.M.: Sorption kinetics and equilibrium POP, D., T PODE, R., POPOVICI, E., COCHECI, L., REISZ, E. & SEFTEL, E.M.: Sorption equilibrium of phosphate anion on Carboniferous Basin Douro the of crystallochemistry F.:andROCHA, & mineralogy A. ClayJESUS, DE PINTO PERI PENTR History Austria:Lower northern of WIMMER-FREY, kilns & Brick PAPP, R. I.: ROETZEL, M., PERESSON, H., P F., OTTNER, SIEGHARDT, ERSTI M., N NAGY, N.M. & K MUTLU, H.,ALTUNEL, E.&UYSAL, I.T.: Dating of fault clays of North the Anatolian Fault Zone, Turkey M Š RODO EGVI TYRIAK, I. TYRIAK, Á É Ü LKOV METH, T. Cserh & SIPOS, P.: of Nature and alteration of (Luvisols) clay minerals in brown forest soil profiles LLER, R., VAL R., LLER, ÍČ Ć ÍŠ EK, I., UHL I., EK, Í , J., VUKOJEVI Ć DNA bound insmectite-bearing sediments tion inasub-surface soil compaction on orientation the of smectite particles NEWMOD tention insmectites ties Jurassic Leme hydroxides (M and clay in Spanish agricultural topsoils of LatosolsMineralogy along aregional toposequence across Plateau Central the (Brazil): First results...... sions of Mecsek the Mountains (Tisza Mega-unit, Hungary) with cationic surfactants talcite intercalated with pyrenetetrasulphonate acid, molecular simulations and experiment depollution of thiocyanate anion on Mg green clay,trine Rona limestone, Romania Mg (Early Stephanian C;NWPortugal) clinoptilolite: acomparison of batch and column methods and geology physico soils on the island Veliki Brijun, Croatia Mountains (North Hungary) ionic surfactants intercalated insynthetic clays GUEZ MART Á IL, M., VETE Ń , B., TO B., , Á K, M.&MADEJOV , J. & McCARTY, D.K.: Total surface area, surface charge density, cation exchange capacity and water re Ó x ...... IOSA . EWCA ..&KOI . nuneo h ytei odtoso the on conditions synthesis the of F.:Influence KOOLI, & SERWICKA,E.M. ZIMOWSKA,M., H., , Zn TH, E., WEISZBURG, T.G., S , 3-x Š ...... – TYRIAKOV Al-type hydrotalcitesAl-type chemical characteristics of porous clay heterostructures Š Ó EVSKI, A., EVSKI, . © ...... Ú Í ...... NYA, J.: Preparation of noble bentonites metal for catalytic purposes program K, P.,K, CHOV š Š Ć Ć Í III Á KA, M., deposits near Maovice (Dalmatia, Croatia): clay mineralogy and basic soil mechanic proper N, J.A., MORALES HERRAIZ, D. & GRAU CORBI, J.M.: Relationship between heavy metals ...... rpriso lymnrlsrae oie yitniepyia disintegration physical intensive by , N.:Properties of clay mineral surfacesmodified ...... MEDVIDOVI = Al, Cr, Fe, or Mn) during thermal treatment , M., Š ...... UCHA, V.,UCHA, ADAMCOV ...... Á Á ...... Climato- Š ...... , J.,J , C., CALBERG, , I. , Á Š TUDENTOV Č ...... TEVANI , J.: Acid treatment of clay minerals: aFTIRspectroscopic study ...... APKOV

, ...... Š Š . x OV PANOV ...... Zn ...... environmental controls on clay mineralogy of the Hettangian ...... Ć ...... Á 3-x Ć , N. & TRGO, M.: Theequilibriumisothermforleadremovalbynaturalzeolite ...... Ć , B. & KOLOU& B. , ...... Á ...... Al-type hydrotalcitesAl-type , T., MILEUSNI & ...... Ă D., BI D., ...... , P., BENE ...... S Á Á ...... Ă ...... , A. & A. , ...... , S. & KARTO ...... A,E TCLUNR . h O ae iiaeo h lacus the of silicate layer RAN, TOT E. & STICHLEUTNER, S.: The ...... Š ...... É ...... EVAC,LUGOVIV.& ...... R ...... RITTICH, B.: RITTICH, Á ...... Š . Ô ...... , L., MEL ...... , R., R., , ...... ME, R. & GRANDJEAN, J.:GRANDJEAN, & catdynamicsStructureandof R. ME, ...... Š . . – ...... EK, D.: Phase transformations of Co transformationsof Phase D.: EK, mcieitrtaicto sn optrsmltosin simulations computer using smectite interstratification ...... Č ...... Ć Š ...... APLOVI ...... OV , M.: Clay minerals and selected ecological aspects of aspects ecological selected and minerals Clay M.: , ...... Á ...... Á NOV ...... oicto ftemnmrloiesurface montmorillonite the of , G.: Modification ...... Bacterial destruction of smectite and bacterial bacterial and smectite of destruction Bacterial ...... Č ...... Á in situ ...... OV ...... , K. & Z ...... Ć ...... Á ...... , B.: Altered tephra layers in the Upper the in layers tephra Altered B.: , ...... biostimulation on iron mineral specia ...... &GLO . ffc fbentonite of Effect GALKO,I.: & M. , ...... Í ...... MA, V.: Structure analysis of hydro ...... Ã ...... ES, E.M. & BROSSARD,& E.M. M.: ES, ...... – ...... M ...... – ...... III ...... Bajocian succes ...... layered doublelayered ...... á – .. . ------. t . . . .

110 109 108 107 106 105 104 10 102 101 100 99 98 97 96 95 94 9 92 91 90 8 8 8 8 8 8 3 3 9 8 7 6 5 4 Abstracts Book

ŠTYRIAKOVÁ, I. & ŠTYRIAK, I.: Bacterial removal of Fe(III) impurities from clay: A potential new technology... 111 SZELIGA, W.: Clay minerals (I/S, kaolinite) in contact metamorphism related to Tertiary basalts intrusions in Lower Silesia (Poland)...... 112 TIBLJAŠ, D., AVANIĆ, R. & HANŽEL, D.: Glauconitic materials from Lower Miocene Macelj Formation (NW Croatia) – new data...... 113 TIBLJAŠ, D., BALEN, D., MAHEČIĆ, S., KOVAČIĆ, M., JOZIĆ, D., ŠPANIĆ, D., JUDIK, K. & ÁRKAI, P.: Clay minerals as indicators of thermal history of Palaeozoic rocks from Marija Gorica Hills, NW Croatia...... 114 TOMBÁCZ, E. & SZEKERES, M.: Comparing surface charge heterogeneity of 1:1 with 2:1 type clay particles in aqueous suspension...... 115 TÓTH, E. & WEISZBURG, T.G.: Two in one: two diﬀerent glauconite series from the same rock, Sümeg Marl Forma- tion, Lower Cretaceous, Bakony Mountains, Hungary...... 116 UHLÍK, P., ČIHÁK, J., TUČEK, Ľ., MALACHOVSKÝ, P. & DERCO, J.: Mineralogy of glauconite-rich sand deposits in the Southern Slovakia...... 117 VÁGVÖLGYI, V., KRISTÓF, J., HORVÁTH, E. & FROST, R.L.: Surface reactivity investigation of mechanochemically activated kaolinite...... 118 VAN CROMPHAUT, C., DE RESENDE, V.G., DE GRAVE, E., KLINGELHÖFER, G., VAN ALBOOM, A. & VAN- DENBERGHE, R.E.: Iron oxides on Mars: their characterization from MER Mössbauer spectra...... 119

VAVROVÁ, J., BIROŇ, A., GALKO, I. & MAJDÁN, M.: Mantienneite from Pinciná alginite deposit (Slovakia)...... 120 3r d Mid-European Clay Conference – MECC 06 VICZIÁN, I., DEZSŐ, J. & RAUCSIK, B.: Mineralogy of fine-grained sediments related to karst phenomena in Vil- lány Mts., SE Transdanubia, Hungary...... 121 WEISZBURG, T.G., TÓTH, E. & POP, D.: Continuous crystal chemical space for the dioctahedral iron-rich micas and related phases (celadonite, glauconite, Fe-illite)...... 122 WYSZOMIRSKI, P.: Triassic red clays in Poland and their importance for ceramic industry...... 123 ZAGÓRSKI, Z. & GRELA, S.: Preliminary mineralogical characteristics of soils developed from Lower Triassic clay deposits (Buntsandstein) in the Holy Cross Mts. (S Poland)...... 124 ZAITSEVA, T.S., GOROKHOV, I.M., IVANOVSKAYA, T.A., MELNIKOV, N.N. & YAKOVLEVA, O.V.: Mineral- ogy, Mössbauer characteristics and isotope age of Middle Riphean glauconites (the Olenek Uplift, Northern Siberia)...... 125 ZIMOWSKA, M., PLONA, J., MICHALIK-ZYM, A. & SERWICKA, E.M.: Influence of the synthesis condition on Cu–Mn layered double hydroxides...... 126 ZVIAGINA, B.B.: Crystal-chemical factors affecting the distribution of octahedral cations over cis- and trans-sites in dioctahedral smectites...... 127

V Abstracts Book Abstracts VI 3rd Mid-European Clay Conference – MECC 06 Abstracts Book 3r Keynote Abstracts d Mid-European Clay Conference – MECC 06

1 Abstracts Book Abstracts 2 3rd Mid-European Clay Conference – MECC 06 Abstracts Book

Layered minerals in catalysis

Krzysztof BAHRANOWSKI1 and Ewa M. SERWICKA2

Among the layered minerals, which have attracted most of ach was adopted in the synthesis of mesoporous materials the attention concerning the development of novel cata- from a layered sodium silicate named kanemite. The pro- lytic materials, clays, silicates and double hydroxides play posed formation mechanism was based on the idea of sili- the dominant role. Historically documented use of laye- cate sheet folding around the intercalated surfactant, hence red minerals as catalysts dates back to 1783, when Joseph the family of solids prepared in this way was called FSM Priestley described the reaction of ethanol dehydration to (folded-sheet mesoporous materials). Another approach, ethylene, prompted by the presence of clay. The advent of which merged the concept of clay pillaring and the prin- industrial application of clay catalysts was associated with ciple of surfactant-inorganic precursor self-assembly, led the introduction, shortly before the Second World War, of in 1995 to the preparation of smectite-derived materials a new technology of crude oil refining, known as catalytic known as porous clay heterostructures (PCHs). Ordered cracking, which used acid activated bentonite as a catalyst. porous structures of the FSM and PCH types opened new The use of clay catalysts dropped significantly in the sixti- opportunities for the design of catalytic materials and the es, when they were replaced with zeolites in the cracking number of papers on their application as catalysts or cata- process. The oil crisis in the early seventies stimulated the lyst supports is rapidly growing. investigation into the design of novel, large pore catalytic Layered double hydroxides (LDHs), also known as hy- 3r materials, and renewed the interest in clay minerals. As a drotalcite-like compounds or anionic clays, are considered d Mid-European Clay Conference – MECC 06 result a new class of porous materials, known as pillared in- the most promising precursors of mixed oxide catalytic terlayer clays (PILCs), was developed, whose concept was a materials. Their industrial application started with hydro- classical example of a nanotechnological approach to mate- genation processes developed in the seventies. The advan- rials synthesis. Although successful application of PILCs in tage of using LDH-type precursors consists primarily in crude oil refining failed due to their relatively low hydrot- their structural flexibility, allowing for accommodation of hermal stability, their investigation has been continued and a number of various elements within the layer and/or as the nineties saw a boom in synthesis, characterization and interlayer compensating anions, thus providing a homo- catalytic work on these materials. Currently most research geneous mixing of components at an atomic level, unat- into catalysis by PILCs is directed at tuning the catalytic tainable with other preparative techniques. Depending on properties to the requirements of a particular reaction by the adopted composition the LDH-derived catalysts are appropriate modification of the PILC structure, acid-base targeted at base or redox catalytic processes. and/or redox functions. The talk is illustrated by authors’ own works focused on An important stimulus for engineering new catalytic environmental catalysis. The discussed fields of application materials based on clays and layered silicates appeared in include the end-of-pipe processes and green chemistry re- the early nineties, when it was discovered that the use of actions. appropriate surfactant molecules as structure directing templates interacting with inorganic precursors allows for Acknowledgement: This work was supported by the Polish Com- preparation of ordered mesoporous molecular sieves with mittee for Scientific Research within the research project 2 P04D uniformly sized channels of tunable diameter. This appro- 050 26 (2003–2007).

1 Faculty of Geology, Geophysics and Environmental Protection, AGH – University of Science and Technology, al. Mickiewicza 30, 30-059 Kraków, Poland ([email protected]) 2 Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek 8, 30-239 Kraków, Poland 3 Abstracts Book Abstracts 4 3rd Mid-European Clay Conference – MECC 06 discussed in the talk, among which are the following. In following. the are which among talk, the in discussed be will examples Some systems.natural in also present be well very may features However, these pattern. formation the reaction proceeds, which may cause as changes in the chemistry clay water the in change a to subjected is actors re batch in synthesis example, For experiments. these of involved intrinsicfeaturesotherfromscale and time short the from derive may systems synthetic in observed xities complecomplex, the ofintermediate Some clayminerals. of formation the in or patternformation mineral clay the of evolution unexpected an in result that processes plex com indicate that results provided have systems natural in transformation or formation mineral clay of and hesis synt mineral clay of Studies conditions. formation their of understanding our match quite not do that semblages formation and transformation is frequently mineral challenged by mineral as clay about knowledge common Our Department ofMineralogy,Department Museum,London Natural History SW75BD, ([email protected]) United Kingdom Clay minerals inthemaking Javier CUADROS - - - - - rcmlxca iea sebae htw n nna ture. in find we that assemblages mineral clay complex or irregular the of some explain may they environmentsand as to quantitative the sess relevance ofsuchnaturalprocesses in us prompt examples these from results generate. The that the prevailing chemical and physical conditions would those from organismsmay produce clay minerals different living by promotedAlterationtalc–kerolite–smectite. kaolinite–halloysite–smectite and sequences the in example for blurred, be may minerals “established” between ries bounda the that so compositionchemical and perfection crystalline of range a in formed are minerals Claynature. di-tri-octahedral mixed a of and type mixed-layer the of mation of clay minerals resulting in complex intermediates clay of mineral formation dominated by case kinetic control. Transfor A rock? the or mation)controlled by fluids the for mineral clay (and alteration rock is conditions which - - - - - Abstracts Book

XRD texture measurements of oriented clay aggregates – a quantiﬁcation tool

Reiner DOHRMANN1, Katherina RÜPING1,2, Markus KLEBER3 and Reinhold JAHN2

Clay mineral quantification, although usually supple- and Cu Kα radiation. The samples were rotated in ϕ=90° mented by information from other analytical techniques, increments, while χ was varied in 5° increments (70° maxi- strongly relies on XRD. XRD analysis of oriented clay ag- mum). gregates generally involves empiric assumptions about the Na+ exchanged illite (<2 µm) and Ca2+ exchanged kaoli- preferred orientation (texture) which controls the XRD in- nite (<2 µm) were used as standard materials. The σ* values tensity of clay minerals. Texture is expressed by the param- of the illite (σ*=14°–15°) and kaolinite (σ*=18°–19°) on eter σ* and denotes the standard deviation of the tilt angles ceramic and glass slide at different ultrasonic treatments of 00l planes of the crystallites about their mean position are approximately the same. This indicates that the ultra- once parallel to the surface of sample (REYNOLDS, 1989). sonic treatments had no significant influence on the pre- The degree of preferred orientation depends on both type ferred orientation of these two pure clay minerals. These and morphology of the respective clay mineral. In order to pure minerals were mixed (80% illite, 20% kaolinite) and increase the XRD detection limit the preparation of XRD prepared on glass and ceramic slides. Results indicate that texture slides produced by sedimentation on glass or ce- again there is no dependency of the σ* values for kaoli- ramic slides (oriented clay aggregates) is frequently used. 3r nite and illite for the type of slide used. However, there d Mid-European Clay Conference – MECC 06 Ideally, oriented aggregates should exhibit perfect orien- is a pronounced difference between the σ* value of pure tation of the clay mineral flakes parallel to the refracting kaolinite (σ*=19°) and of kaolinite in the mixture (σ*=11°). plane. In this case, the standard deviation of the tilt angles The presence of illite influences the preferred orientation of the crystallites about the mean crystallite orientation of kaolinite in such a way that kaolinite is forced to have a (‘preferred orientation’), σ* would be close to zero. Em- better orientation as observed by SEM. The trend was con- pirical considerations have led to propose a default value firmed for mixtures with illite, kaolinite, and smectite. It of σ*=12° (REYNOLDS, 1986) for such instances where can be concluded that there are no universal mineral in- recorded diffraction intensities suggest preferred orienta- tensity factors for clay minerals in oriented clay aggregates tion to be typical for oriented aggregates. Peak intensity is which limits their use for the quantitative analysis. proportional to (1/σ*)2, so the estimated limiting values for the reported σ*-range from 4° to 30° will produce a 56-fold References difference in basal or 00l intensities (MOORE & REYN- KAHLE, M., KLEBER, M. & JAHN, R. (2002): Review of XRD-based OLDS, 1997). LIPPMANN (1970), ZEVIN & VIAENE quantitative analyses of clay minerals in soils: the suitability of min- (1990), and TAYLOR & NORRISH (1966) reported on pre- eral intensity factors.– Geoderma, 109, 191–205. ferred orientation of kaolinite varying between 8° and 20° LIPPMANN, F. (1970): Functions describing preferred orientation in flat for oriented aggregates and between 18° and 44° for pow- aggregates of flake-likely clay minerals and in other axially symmet- der samples. No σ* results for smectites have been reported ric fabrics.– Contr. Mineral. Petrol., 25, 77–94. in the literature. The changes in preferred orientation cause MOORE, D.M. & REYNOLDS, R.C. (1997): X-Ray Diffraction and the very large differences in intensities. Therefore the use of Identification and Analysis of Clay Minerals.– Oxford University Press, New York, 378 p. “Mineral Intensity Factors” as discussed in KAHLE et al. REYNOLDS, R.C. (1986): The Lorentz factor and preferred orientation in (2002) is confirmed to be insufficient for the quantification oriented clay aggregates.– Clays and Clay Minerals, 34, 359–367. of clay minerals in oriented aggregates. REYNOLDS, R.C. (1989): Principles and techniques of quantitative anal- 68 mg of clay sample was dispersed in 1.5 ml of deion- ysis of clay minerals by X-ray powder diffraction.– In: PEVEAR, D.R. ised water by ultrasonic treatment for 3 minutes at ultra- & MUMPTON, F.A. (eds.): Quantitative Mineral Analysis of Clays. CMS Workshop Lectures, Vol. 1, 4–36. sonic power of 32, 47, and 82 J s-1. The clay suspensions TAYLOR, R.M. & NORRISH, K. (1966): The measurement of orienta- were deposited on glass slides with a diameter of 2.4 cm tion distribution and its application to quantitative x-ray diffraction and equally sized ceramic slides applying vacuum filtra- analysis.– Clay Minerals, 6, 127–142. tion. XRD measurements were performed using a Seifert ZEVIN, L. & VIAENE, W. (1990): Impact of clay particle orientation on 3003 TT diffractometer with an open Eulerian cradle, a 0.2 quantitative clay diffractometry.– Clay Minerals, 25, 401–418. mm primary hole slit, a position sensitive detector (PSD)

1 Technical Mineralogy, Sedimentology, LBEG/BGR, Stilleweg 2, D-30655 Hannover, Germany ([email protected]) 2 MLU Halle–Wittenberg, Weidenplan 14, D-06099 Halle/Saale, Germany 3 LBNL, One Cyclotron Road, 94720 Berkeley, USA 5 Abstracts Book Abstracts 6 3rd Mid-European Clay Conference – MECC 06 in sample heated at 300 at heated sample in even found were positions octahedral the in presence its Li as radius ionic lar Ni Though heating. upon fixation position after final their both the size and the charge of interlayer cation affect that confirmed spectra NIR ferenttemperatures. The dif at hours 24 for heating bymontmorillonite saturated heat upon Li from prepared were fixation materials of series ing, their on cations exchangeable of effect ation in the previously vacant Tooctahedra. investigate the creation domains of trioctahedral as provedlocal a result of Li fix vibration, stretching Al–Mg–Li–OH the of tone cm 7070 at observed. A band near 7170 cm band overtone OH the intotwocomponents (nearcm 7170 of splitting and shift heat-treatedmontmorillonites.upwardof An spectra NIR beidellite for found and was nontronite, while pronounced changes occurred in heating the upon effect No samples. unheated and heated (200 for nontronite and beidellite iron-rich montmorillonites, were obtainedfor Li-saturated werespectra analyzed.NIR smectitesreduced-charge of series reduction,charge layer tempera smectites, of ture of heating and the oftype the interlayer cations composition on the chemical of effect the study to and layers mineral the into cationsexchangeable small of migration Tofollow smectites. of treatments ous vari upon occurring changes structural observe to copy the in clay mineral structure. variations the by affected sensitively are vibrations combination and overtones OH the to related bands the since minerals clay aboutinformation useful provide also can spectroscopy NIR Consequently, vibrations. C–H or to overtones and combinations of fundamental O–H, N–H range the cm 12000–4000 covering between region, NIR The importance. great of ration and the non-destructive nature of the techniques are spectroscopy, the speed, the simplicity of the sample prepa NIR enerandgy information. by Among the advantages NIR offered of transfer and delivery allowing of optical fibres tation and in data analysis as well as from the introduction spectroscopy has arisen from improvements in instrumen In the last years the growing interest in near infrared (NIR) Institute ofInorganic Chemistry, Slovak Academy ofSciences, SK-84536 Bratislava, Slovakia ([email protected]) hspprdmntae h oeta fNRspectros NIR of potential the demonstrates paper This Near infrared spectroscopy: methodto apowerful learnmore + no spectral features demonstrating features spectral no ° C. Ni(II) is supposed to be fixed be to supposed is Ni(II) C. -1 ° , contains bands corresponding bands contains , C for 24 hr to evoke Li-fixation) -1 sindt h rtover , assigned to the first -1 and cm 7100 nmdfidsmectites on modified + 2+ - and Ni and - has simi Jana MADEJOVÁ -1 ) were) 2+ -1 ------

hreo tutrlmdfiain fvrosdioctahedral various of chargemodifications on structural effect The phase. silica tion of layered structure to a protonatedpartly amorphous the of Si–OH overtone band near 7315 cm intensity increasing The dissolution. acid of course the in groups Si–OH of creation on information new fers tone band (~7070 cm overOH the of decrease gradual bycations octahedral of ever, is also well suited for monitoring the reducing content howspectroscopy, NIR progressed. dissolution of extent decompositionbands bendingrevealed layersof the the as tensity of the OH (950–800 cm stretching cm (~1030 band Si–O the of shift upward An region. IR middle menttraditionally has been studied by spectroscopy the in montmorillonites. of sheets tetrahedral the of cavities ditrigonal the in deep edges. particle the from mainly place took and slower was tion dissolu the interlayers,non-swelling to due low was tons surfaces and edges. If the accessibility of the layers for pro interlayer both at occurs structure smectite the of acid attack that confirm results The reduced. was attack acid the stricted the access of protons to the layers and the extent of re substantiallyinterlayers non-swelling of Development cm 1300–400 the process.monitorto this used traditionallyregion, spectral in observed were differences no case when the in even smectites of attack acid of extent the of cm 7314 near overtone Si–OH the hand other smectites was higher than that of NIR spectroscopy. On the unheated fromatoms octahedral the of spectroscopy leaching follow to MIR the of sensitivity The amorphous silica. protonated of formation progressive and structure the of degradation substantial Li- and a revealed Ni-montmorillonitesunheated of spectra The HCl. in dissolution their velopment of non-swelling interlayers substantially affected de a with connected decrease charge layer a that showed montmorillonites reduced-charge acid-treated of region overtone OH decreased. attack acid against morillonites mont of resistance the content Mg octahedral increasing with that proved spectra NIR investigated. was smectites h leaino h mciesrcueuo cdtreat acid upon structure smectite the of alteration The -1 ) along with gradual decrease in the in the in decrease gradual with along ) -1 ) intensity. Moreover, this region of of chemical composition chemical of -1 ) and Al–O–Si (~525 cm -1 indicates transforma -1 reflected and layer and

-1 -1 ------)

Abstracts Book

Mössbauer spectroscopy of geological materials

Enver MURAD

Many branches of the basic and applied sciences make use weathering reactions, and it has recently been used as an of physical techniques such as X-ray diffraction and various in-situ probe on Mars. Metastable phases can be studied by spectroscopic techniques. One of the most powerful of the taking spectra under protective environments or by cool- latter is Mössbauer spectroscopy, the technique of recoil-free ing samples to temperatures at which their transformation resonant emission and absorption of gamma rays. would essentially come to a standstill. Samples of complex Mössbauer spectroscopy has the advantage of being mineralogy may require pretreatments such as particle size oblivious to all elements except that under survey. In the fractionation or selective iron oxide removal prior to mea- case of materials formed on the Earth’s surface (i.e. in the surement, and/or more sophisticated techniques such as the weathering environment), the only propitious element is application of external magnetic fields. iron. Iron is the fourth most abundant element in the Earth’s In my lecture I will give enough introductory informa- crust, it is essential for life, and almost all environmental tion on the theory to provide a background for understand- materials contain iron in varying concentrations. It is thus ing the principles behind the measurements. I will then fortuitous that 57Fe is one of the most convenient nuclides present a description of the properties of selected materi- 57 for Mössbauer spectroscopy. Fe Mössbauer spectroscopy als formed on the Earth’s surface, their synthetic analogs allows a quantitative determination of the oxidation state(s) where applicable, and the products of their modification in 3r d Mid-European Clay Conference – MECC 06 of iron and the identification of magnetically ordered phases the course of natural processes or in processing as reflected (generally iron oxides and oxyhydroxides in samples formed in their Mössbauer spectra. This will be complemented by in the weathering environment), i.e. the characterization of remarks on the current status of lunar and planetary studies iron speciation – and thereby of environmental conditions using Mössbauer spectroscopy. – over a wide range of concentrations, and is consequently an effective environmental probe (MURAD & CASHION, Reference 2004). Thusö M ssbauer spectroscopy can be used to char- MURAD, E. & CASHION, J. (2004): Mössbauer Spectroscopy of Environ- acterize the iron-bearing constituents of clays, soils and mental Materials and their Industrial Utilization.– Springer Verlag, sediments, it has been successfully applied to the study of Boston/Norwell, 418 p.

Bayerisches Landesamt für Umwelt, Dienststelle Marktredwitz, D-95603 Marktredwitz, Germany ([email protected]) 7 Abstracts Book Abstracts 8 3rd Mid-European Clay Conference – MECC 06 1 RH onlyresultinapartialrehydration. at0% dehydration hydration experiments at 95% RH after re the Moreover, halloysites. of behavior dehydration the controls water, “hole” the waterand “associated” the molecule, of types different of presence the that show results 8.6–7 a of presence the with phase dehydrated a gives halloysite hydrated fully initially water molecules. On the other hand, the dehydration of an “hole” of presence the to due phase separate a as reacting state hydration intermediate one with proceeds hydration are not the same for all samples. For some of them, the de gardless of the size fraction, but the dehydration processes re behavior dehydration similar induce temperature in each halloysite sample, the decrease in RH and For the increase RH. 0.2% and 40 at analyses thermal by studied also were They temperature. various and (RH) humidity ative rel various under (XRD) were studied by X-ray diffraction halloysites reference some spherical), (tubular, halloysite vacuum. and flux saturated water under cell environmental an using (TEM) induced dehydration by transmission electron microscopy spherical (halloysite-10 hydrated halloysite of morphology will actual we the work, you this show In status. hydration its in alteration halloysite-(10 study to difficult extremely is it However, applications. environmental or hydration behavior of halloysites for a variety of industrial thus very important to fully understand the hydration–de is It 2005). al., et (JOUSSEIN species organic with contact mineral, its exchange properties, and its reactivity when in this of properties physical the in role important an play to as halloysite-(7 known polymorph dehydrated the producing irreversibly, halloysite-(10 or heating, air, vacuum, dry in standing the halloysite sample is left when labile highly is water interlayer the Because drate. hy natural a as found mineral kaolin only the is loysite weathered rocksandsoilsdevelopedonvolcanicash. both in widely occurs that mineral clay 1:1 a is Halloysite 2 CRMCN, Campus de Luminy, 13288Marseillecedex 9,France ([email protected]) CNRS UMR6532HydrASA. Faculté desSciences. 40,avenue Pineau, duRecteur 86022Poitiers cedex, France To study the dehydration behavior of several types of types several of behavior dehydration the study To New insight into halloysite physico-chemical properties Å .Teitrae ae fhlost seems ofhalloysite water interlayer ). The Å Å Sabine PETIT ) is very susceptible to dehydrate to susceptible very is ) ) and its change under vacuum under change its and ) Å Å mixed-layer at 7.9 at mixed-layer ) without inducing some inducing without ) 1 , EmmanuelJOUSSEIN Å . The . Hal ------E srnl dces atrdhdaino ape The ofsample. high- the than K for selective more is Puke Te low-charge dehydration after decrease strongly CEC at100 samples heating after and before measured were CEC and selectivity K samples, ofin all For TEM–EDX. by determined were particles dividual compositions chemical The spectroscopies. bauer ( MAS–NMR FTIR, by XRD, by studied were samples The Ca-saturation. and washing K-saturation, (ii) and K-saturation, (i) to submitted were hal (<0.1 sample loysitic SN2 clay fine “high-charge” a and Bay, Matauri and “low-charge” two select were samples re halloysite some topic, In this to halloysite. gard in evidenced been never have cations interlayer of presence the as well as charge the of origin NH as such cations, hydrated poorly for selectivity possible its (ii) and soils) halloysitic cmol (20–50 high relatively be can which (CEC), capacity exchange cationic possible its (i) to due countries JOUSSEIN, E., PETIT, S., CHURCHMAN, J., THENG, B., RIGHI, D. & D. RIGHI, B., THENG, J., CHURCHMAN, PETIT,S., E., JOUSSEIN, tion willbeproposed. dehydra of physico-chemical properties of halloysite after samples dehydrated the from measured CEC the for responsible be can which some that reveal data be evidenced by M to due charge No results reveal the Ca-saturation and is thus non exchangeable by Ca SN2 halloysites particles. A part of K is still remaining after and Puke Te in K of amount large relatively revealed copy micros electron analytical by particles single of analyses charge SN2; Matauri Bay being far less selective. Chemical Halloysite is also of interest for soil fertility in tropical in fertility soil for interest of also is Halloysite erals, 40,383–426. erals, DELVAUX, B. (2005): Halloysite clay minerals – a review.– Clay Min 1 andOlivierGRAUBY rsneo -pcfi ie nhalloysites. in sites presence of K-specific ö VI eeec hlosts nml T Puke Te namely halloysites, reference ssbauer spectroscopy. However, NMR . A hypothesis concerning the change the concerning hypothesis A . Al/Fe

µ IV m) from a Cameroon soil. Samples soil. Cameroon a from m)

Reference Al occur in the studied halloysites studied the in occur Al 2+ or Si/Fe or ° C/8hr. K selectivity as well as well as selectivity K C/8hr. 4 + , K , 27 l and Al 2 + and Cs and 3+ substitutions could substitutions 29 i, n M and Si), + . However, the However, . 2+ c kg . These -1 ö ed: in ss ------Abstracts Book

Clay mineralogy, petrography and geochemistry of Late Palaeozoic siliciclastic rocks from the Mecsek–Villány area (SW Hungary): implications for source-area weathering, provenance and diagenesis

Béla RAUCSIK1, Andrea RAUCSIK-VARGA2, György SZAKMÁNY2 and Viktória KOVÁCS-KISS3

Sandstone geochemistry is widely considered to be a and volcanic-arc provenance. Low-grade to medium-grade powerful tool for determining the sediment source areas metamorphic source components might be derived from and tectonic settings of ancient terrigenous deposits. local sources in the Baksa Subunit. The inferred sources Whole-rock chemistry can also detect variations in of fine-grained plutonic rocks are microgranite dikes of elements that are not picked up in modal analysis, for the Mórágy Complex (Kunság Unit). The high median of example rare earths elements (REE), Th, Zr, Sc, and Cr. In SiO2 and low Na2O, CaO, Sr, high field strength elements addition, variations in clay-mineral assemblages also may (HFSE), and REE contents in this formation reflect that be useful for detecting changes in the source areas and for source rocks were more mature than those which supplied recognizing the diagenetic conditions of sandstone units. detritus to the Permian strata. Our data also indicate a On the other hand, relatively few papers deal specifically more intense weathering in the source region. Additionally, 3r with clast composition of coexisting conglomerates in the high medians of K2O and Rb, together with the presence of d Mid-European Clay Conference – MECC 06 same locality; however, the clast types can provide a wealth abundant illite/sericite suggests a potassium metasomatism of information concerning the provenance and geological in the Téseny clastics. Characteristics of the Lower Permian evolution of the sediment source areas. Therefore, inte- Korpád Formation vary spatially, and are interpreted as grated examination of siliciclastic rocks, including clay local variations in composition of the source areas and mineralogy, whole-rock geochemistry, and clast petrogra- diagenetic conditions. Relatively immobile trace element phy and geochemistry, is particularly fruitful in provenance relations, however, clearly show that this formation was analysis and paleogeographic reconstruction. mainly derived from mature upper continental crust. Kor- In this work, results of clay mineralogical, petrographic pád-A group represents combined acidic–intermediate and geochemical studies of the Late Paleozoic siliciclastic volcanic and basement-uplift provenances. A possible successions from southern Transdanubia (Mecsek–Villány source for this group is the Carboniferous granitoid base- area, Tisza Mega-unit, SW Hungary) are presented. ment in the western Mecsek Mountains. On the other hand, the provenance of the Korpád-B group represents The Paleozoic formations studied in this paper are sources exclusively from the uplifted Baksa-type meta- the Téseny, Korpád, and Cserdi formations. The Téseny morphic rocks. The petrographic, clay-mineralogical Formation (Upper Carboniferous), which is interpreted and geochemical features of the Upper Permian Cserdi as fluvial system deposits, unconformably overlies the Formation, especially the presence of abundant acidic crystalline basement and has a maximum thickness of volcanic fragments and chlorite, together with the high ~1500 m. This formation is found partly in the western TiO , Th, U, Y, and Cr contents, and evolved HREE pattern flank of the Villány Mountains and also in the Drava Basin. 2 relative to the underlying formations, may reflect relatively It is composed of conglomerate, sandstone, and siltstone; proximal derivation from a felsic volcanic source. It may in addition, shale and coal seams also occur. The alluvial be possible to link huge amounts of felsic detritus in Cserdi Korpád Formation (Lower Permian) ranges up to 700 m in sediments to the Gyűrűfű Rhyolite Formation. These thickness and consists of polymictic basal conglomerate, upward variations to less mature deposits might be related breccia, sandstone, siltstone, and claystone. However, to such factors as increasing aridity and favoring conditions extreme variation in thickness has been documented. The of weathering-limited erosion in the source regions, and Cserdi Formation (Upper Permian) consists of up to 1000 the increase of tectonic activity including intense acidic m of polymictic conglomerate, sandstone, and siltstone volcanism during the Early Permian rifting in the southern beds representing debris flow-dominated alluvial fan margin of the European plate. deposits. The Upper Carboniferous/Pennsylvanian Téseny For- Acknowledgement: This study was financially supported by the mation consists of relatively metamorphic lithic-rich sand- Hungarian Scientific Research Found (OTKA) projects T 022938 stones with a combined recycled-orogen, basement-uplift, and T 034924 to György Szakmány.

1 Department of Earth and Environmental Sciences, Pannon University, Egyetem utca 10, H-8200 Veszprém, Hungary ([email protected]) 2 Department of Petrology and Geochemistry, Eötvös L. University, Pázmány P. sétány 1/C, H-1117 Budapest, Hungary 3 Research Institute for Technical Physics and Materials Science, Hungarian Academy of Sciences, Konkoly Thege M. út 29–33, H-1121 Budapest, Hungary 9 Abstracts Book Abstracts 10 3rd Mid-European Clay Conference – MECC 06 Fig. 1 Chitosan–montmorillonite bionanocomposite in a bilayer a in bionanocomposite Chitosan–montmorillonite 1 Fig. composite preparations (DARDER 2). etal., 2006) (Fig. nano biopolymer–clay for moieties inorganic suitable as other handthe clay minerals,such sepiolite,as appear also af is found derivatives ter combination of this LDH solid with anionic biopolymers. On the for behavior opposite The bionanocomposite.resulting the in exchangeabilityanion an in smectites starting the of ability exchange cation the the amount of intercalated chitosan it is possible to reverse controllingBy 2005b). al., onanocompositeset (DARDER correspondingbi the intercalate LDHsgivingcan geenan anionicway, polysaccharides such alginate as pectin, and carra similar a In 1). (Fig. 2005a) 2003, al., smectites et (DARDER with compounds intercalation polyelectro to charged leading positively lyte a as act medium acidic es as biomimetic materials. development of bionanocomposites, regarded in some cas the of examples are LDHs in macromolecules related and (enzymes) to smectites, as well as the intercalation of DNA behaviours proteinsfunctional providedofcorporationof in doublehydroxidessepiolite.The with (LDHs)also and layered involved in smectites, the assembling with diﬀerent zymes and nucleic acids are examples of these biopolymers (RUIZ- (biopolymers) origin Polysaccharides,2006). proteins,2005, al., en et HITZKY natural of are polymers polymer–clay nanocomposite family in which the involved the to belonginggroup emerging onanocomposites an are tural struc their of These view in studied largely level. been have materials nanometer the at interacting minerals clay to assembled are polymers synthetic which nanostructured in materials to refer nanocomposites Polymer–clay Instituto deCienciaMateriales deMadrid, CSIC,Cantoblanco, 28049 Madrid, Spain([email protected]) formation ainc iplmr sc a cioa i a slightly a in chitosan as such biopolymers Cationic

or functional properties (RUIZ-HITZKY, 2004). Bi (RUIZ-HITZKY,2004). properties functional or . Clay-based bionanocomposites Eduardo RUIZ-HITZKY con ------Fig. 2 SEMimageofasepiolite–chitosan bionanocomposite. DARDER, M., LOPEZ-BLANCO,ARANDA,DARDER,P.,M., M., AZNAR,A.J.,BRA & F. LEROUX, P., ARANDA, M., LOPEZ-BLANCO, M., DARDER, Chitosan– (2005a): RUIZ-HITZKY,E. & M. COLILLA, M., DARDER, RUIZ-HITZKY,& (2003): M. E. COLILLA, M., DARDER, and ionizable the biopolymers. ated to the ion-exchange properties determined by the clay associ properties functional with together components, provedmechanical behaviours compared toindividual the both to im showing polymers, natural and inherentclays components,i.e. properties ecological the exhibit they composites RUIZ-HITZKY, E., DARDER, M. & ARANDA, P. (2006): Polymer and Polymer P.(2006): ARANDA, & M. DARDER, RUIZ-HITZKY,E., Functional (2005): P. ARANDA, & M. DARDER, E., RUIZ-HITZKY, Inter From Materials: Organic–Inorganic (2004): E. RUIZ-HITZKY OJ UZHTK,E(06:McobosChitosan–Sepiolite Microfibrous RUIZ-HITZKY,E.(2006): & J. VO double hydroxides.– of Materials, Chemistry 17,1969–1977. layered on based Bio-nanocomposites (2005b): E. RUIZ-HITZKY, plied Clay 28,199–208. Science, Ap sensors.– electrochemical as application nanocomposites: clay nite.– of Materials Chemistry 15,3774–3780. clay nanocomposites on based chitosan intercalated in montmorillo as classified be can hybrids resulting The raie im.Aeia cetfi ulses(npress). (in Publishers Organized Films. American Scientific and Self-Assemblies, Supramolecules,Nanofabrication: Bottom-Up (ed.): K. ARIGA, In systems.– hybrid two-dimensional in sembling as organic–inorganic nanocomposites: solid biopolymer-layered 3650–3662. 15, Chemistry Materials of Journal nanocomposites.– biopolymer Wiley–VCH Materials. Verlag, & Weinheim. Hybrid P. Functional GÓMEZ-ROMERO, (eds.): In: C. 2. SÁNCHEZ, Chapter Devices.– to calations Nanocomposites.– of Materials, Chemistry 18,1602–1610. within the so-called ecomaterials group because References green nano green Biopolymer– ------Abstracts Book

Zeolite deposits in Croatia

Darko TIBLJAŠ and Stjepan ŠĆAVNIČAR

In spite of the fact that zeolites have been found at sev- cal composition of primary material and its granulometric eral locations in Croatia, so far only two regions with eco- characteristics. Huge reserves of volcaniclastic rocks make nomically interesting concentrations are known. Both are them economically interesting, nevertheless it will be nec- situated in northern part of the country i.e. in the part that essary to take care about raw material properties i.e. zeolite belongs to the Pannonian Basin. content and its chemical composition, when planning its The first one is located in the Macelj area in north-west- particular application. ern part of Hrvatsko Zagorje (NW Croatia) in which Low- The other deposit is located in Slavonian Mountains, er Miocene (Egerian–Ottnangian) volcaniclastic rocks, up on the southern slopes of Mt. Papuk in the vicinity of vil- to 100 meters in thickness, have been described on several lage Poljanska in Požega Valley (ŠĆAVNIČAR et al., 1983). localities. They occur in several horizons interbedded with In the deposit four horizons that are results of changes in shallow-sea clastic sediments within the elongated syncline climate and related variations in sedimentary basin char- which gradually sinks towards the east (ŠIMUNIĆ et al., acteristics can be differentiated; two with analcime-bear- 1995). They have variable primary composition, and con- ing rocks (used in cement industry) which are underlain tain various alteration products of volcanic glass. The alter- by sandy calcareous shales and separated by marly horizon. ation products comprise zeolites, clay minerals (smectite, The analcime-bearing rocks are of hybrid composition. 3r They contain, in layered or laminar alternation or mixed d Mid-European Clay Conference – MECC 06 authigenic mica), SiO2 phases and authigenic feldspars. Cl- inoptilolite is the most abundant zeolite, however analcime together, in various proportions, authigenic dolomite, volcaniclastic and pyroclastic particles from neighbouring an- and mordenite are also present. The type of exchangeable cient volcanoes as well as terrigenous psamitic and pelitic cations in clinoptilolite is variable; therefore clinoptilolites material. The analcime, that is present as dispersed grains were divided into three subgroups: Ca-rich, Ca–K, and or in monomineral laminae and thin layers, was formed Na-rich. Clinoptilolite content in the volcaniclastic rocks by alteration of pyroclastic material within closed hydro- discovered in Macelj area vary significantly, in some rocks logical system i.e. shallow saline alkaline lake which existed it is the dominant component, in others it is present only during early Miocene (Ottnangian) time due to arid and in traces. In Donje Jesenje quarry, in which due to exploi- semiarid climates. The conditions in such lake were also tation the best outcrops of these rocks can be found, the favourable for formation of dolomicrites. On the contrary variations, although present, are not so conspicuous, and calcareous footwall and marly interhorizon were depos- the average content of clinoptilolite is approximately 50 wt. ited during more humid climates in a lake characterized %. Alteration of volcanic glass is the result of burial diagen- by fresh water. esis. Different alteration products are most probably due to different temperatures to which sediments were exposed, References with increasing depth of burial clinoptilolite transformed ŠĆAVNIČAR, S., KRKALO, E., ŠĆAVNIČAR, B., HALLE, R. & TIBLJAŠ, to mordenite and analcime, while opal-CT changed to D. (1983): Analcime bearing deposits in Poljanska (Slavonia, north- opal-C and recrystallized to quartz. However different im- ern Croatia) (in Croatian with English abstract).– Rad JAZU, 404, mobile element content of rocks containing different alte- 137–169. ration products indicates that alteration was probably also ŠIMUNIĆ, An., AVANIĆ, R., ŠIMUNIĆ, Al. & HEĆIMOVIĆ, I. (1995) Lithostratigraphic classification of Early Miocene clastic rocks from dependent on chemical composition of the rocks. Some Hrvatsko Zagorje (in Croatian).– First Croatian Geological Con- types of alteration product were also dependent on chemi- gress, Opatija, Proceedings, 581–584, Zagreb.

Institute of Mineralogy and Petrology, Department of Geology, Faculty of Science, University of Zagreb, Horvatovac bb, HR-10000 Zagreb, Croatia ([email protected]) 11 Abstracts Book Abstracts 12 3rd Mid-European Clay Conference – MECC 06 n ms b dtrie wt a esnbe ee o cer of level reasonable a with determined be must properties and essential the are characteristics strength and conductivity hydraulic Deformation, conditions. loading various to response its quantify to and material the of ior behav the predict to order in known be should clays of properties engineering the instances these all In materials. ramic industry and in all other activities that involve earth ce the in operations, dredging and mining in layers, clay occurring innaturally found are engineering projects. They many in encountered routinely are arethey and minerals ubiquitous clay containing materials other and Clays University ofColoradoUniversity ofCivil, at Boulder, Environmental &Architectural Department Engineering, Boulder, USA ([email protected]) Engineering properties ofclaysEngineering properties Dobroslav ZNIDARČIĆ - - - tion oftheengineeringpropertiesclays. determina the was behavior reliable prediction of the ﬁeld a for element critical the instances all In industry. ceramic the in process manufacturing the and anchors foundation behavior include mine waste disposal, dredging theengi operations, deep ﬁeld sea the which predict to in used are properties neering ofprojects examples The projects. ous vari in encountered values of range the investigates and characteristics these determine to used methods testing discusses paper cannotbe The material. and a for invariable considered clay consistency the on depend tainty. They - - - Abstracts Book 3r Abstracts d Mid-European Clay Conference – MECC 06

13 Abstracts Book Abstracts 14 3rd Mid-European Clay Conference – MECC 06 Abstracts Book

Waterproof polymeric heat insulators based on clay ﬁllers: mechanical properties

Basim ABU-JDAYIL and Kamal AL-MALAH

Introduction properties of the composites depended on the filler type, There is an ongoing search for finding the proper alterna- filler content and, to a lesser degree, on polyester content. tives to preserve energy and minimize energy losses. Our The prepared samples resisted relatively high bending and country, like other countries, highly appreciates all forms compressive forces. The bentonite fillers with the highest content of Al O possessed the greatest bending and com- of energy saving, taking into account that Jordan faces a 2 3 shortage in renewable energy resources. Subsequently, heat pressive forces. In most cases, the mechanical strength insulators, part of building materials and some industrial of the composites increased with filler content to reach hardware, are steadily getting their importance as a means a maximum value, and then it decreased again. It seems of saving energy. Heat insulating materials available in the that the mechanical strength increase with increasing clay local market are relatively expensive and until now are content was a result of the catalytic effect of clay constitu- scarcely used by local contractors and small-size entrepre- ents. It should be recalled that the bentonite is a type of neurs. In this research, focus is made on the formulation clay mainly composed of montmorillonite that is a 2:1 type aluminosilicate. It has a crystalline structure with an octa- of polyester–clay composite as an insulating material that 3r gives the best in terms of thermal and mechanical proper- hedral layer of aluminium hydroxide between two tetrahe- d Mid-European Clay Conference – MECC 06 ties. Different types of local fillers were used in the formu- dral layers of silica (ALLAOUI et al, 2002). The increase in lations. In this paper, the effect of filler type and content on bentonite content in the composite increased the amount mechanical properties of the composite is presented. of the aluminosilicate which has a catalytic effect on the co-polymerization rate of the unsaturated polyester/sty- Experimental methods rene mixture in which a large number of cross-linking occured which resulted in an increase in the mechanical The type of polyester used is HM190 with a styrene con- strength (ISMAIL et al., 1999). Also, increasing bentonite tent of 33–35%, an acid content of 21–23% and a viscosity content has increased the amounts of MgO and CaO that of 300–400 mPa.s. Clay samples obtained from different reacted with the acidic groups of the unsaturated polyester areas in Jordan were used in this study as fillers. Different resin to form a dense network structure in the presence filler contents (25–60 wt%) at a constant styrene/polyester of styrene. For a composite with more than 40 wt% ben- ratio (18 wt%) and different styrene contents (5–12 wt%) tonite the specimens showed a decrease in its mechanical with constant filler content of 50 wt% composites were strength due to the relatively high viscosity of composite, prepared. The composites were prepared at room temperature using a high viscosity mixer. The different mechani- which decreased the impregnation process of bentonite cal tests were performed according the ASTM standards into the polyester. for composites and ceramics. The tensile strength of all composites was lower than the compressive strength, but it was one order of magni- Results and discussion tude greater than that of the commonly used insulating materials. However, one of the bentonite composites and From the experimental work performed in this project, we concluded that the natural clay (bentonite and feldspar) feldspar composites were somewhat distinguished with can be utilized to manufacture stable and compatible com- their tensile strengths, which are due to their high content of Al O and SiO . posite materials. An interesting point obtained from the 2 3 2 results, important from a technological and commercial References point of view, was that for all filler types the addition of the clay filler to the polyester composites improved the ALLAOUI, A., BAIA, S., CHENG, H.M., & BAIA, J.B. (2002): Mechanical and electrical properties of a MWNT/epoxy composite.– Composites mechanical properties of the polyester composite and Science and Technology, 62, 1993–1998 lowered its cost. Only if the filler content was higher than ISMAIL, M. R., ALI, M. A. M., EL-MILLIGY, A. A. & AFIFI, M. S. (1999): 60% wt the product formulation was found to be inconsis- Studies on Sand/Clay Unsaturated Polyester Composite Materials.– tent and non-reproducible. In most cases, the mechanical Journal of Applied Polymer Science, 72, 1031–1038.

Department of Chemical Engineering, University of Bahrain, P.O. Box 32038, Isa Town, Bahrain ([email protected]) 15 Abstracts Book Abstracts 16 3rd Mid-European Clay Conference – MECC 06 Fig. 1Theoreticalpositionsoftetraoctyl-ammoniumcationsbetween layers. TOA cation. of tails hydrophobic between hydrocarbons and alcohols for space free no is there reached, is organoclay in cations TOA of packing maximal the When impossible. is cations inorganic all of exchange wherewith cation, inorganic of not swell ininteractionwithalcoholsandhydrocarbons. do practically they – properties sorption poor have clays their but montmorillonite, Na is using tion exceeds clay 0. and TOABr of proportion when saturation shown is – diﬀerent is cation TOA 1993). LAGALY, & (CEC) – for bentonite CEC is 0.8–1.0 mgeq/g (JASMUND capacity exchange cation by limited is surfactant of tion clay (as of 0.05 mmol TOABr per 1 g clay). Normally sorp and TOABr of proportions small by already noticeable is it. proves organoclay in spacing basal of act with tetraoctyl-ammonium bromide (TOABr) – change (LAGALY &MERMUT,2001). space basal organoclay’s in positions take cations factant sur organic how established, been not has it still but lot, a studied and used been have clays of properties Sorption The ChairofPhysical Chemistry, Faculty ofChemistry, Kr. ofLatvia, University Valdemāra Street 48,LV-1013, ([email protected]) Latvia Riga, 5 mlg Ltin mcie ly atrhydroclassiﬁca (after clay smectite Latvian mmol/g. O cto i fre, t dmnin oesz area oversize dimensions its forked, is cation TOA bentonite TOA and clay smectite TOA Latvian Both Latvian smectite clay and bentonite (Kazakhstan) inter

aedﬀrn aiu aa spacing. basal maximum have diﬀerent

tetrasodium pyrophosphate) just like bentonite like just pyrophosphate) tetrasodium Latvian smectite clay smectite Latvian andbentonite interaction with Adris ACTIN¸ SARCEVI Š,LindaSUPEandInese tetraoctyl-ammonium bromidetetraoctyl-ammonium

orsodn organo corresponding

Swelling of clay of Swelling - - - - - shown in Fig. 1 (b) – hydrophobic chains interlace dense interlace chains hydrophobic – (b) 1 Fig. in shown is cations TOA of position probable Most clay). (Latvian 23.4 is spacing basal maximal 26 is (c)) 1 Fig. (see spacing basal maximal Calculated calculated. be can spacing basal and cation TOA of size theoretical formulas geometrical Using them. of examples some shows 1 Fig. - positions. canin spacing crease upto40 basal way structural This shown. is transformation specific too; salt as TOABr but cations, TOA most dense packing are with minority; they can adsorb not phases only Active packing. various with phases appear sequentially organoclay of formation the reason during – neous the is that – heteroge is clay smectite Latvian spacing. basal various of charge layer different have clay vian LAGALY G. & MERMUT A. (2001): R. Baseline Studies of the Clay Min JASMUND, K. & LAGALY, G. (1993): Tonminerale und Tone.– Steinkopf squeeze to allowing other moleculesin. not though space, out filling together hoeial O aincnb iutdinseveral besituated can cation TOA Theoretically It is experimentally established that bentonite and Lat Minerals, 49/5,393–397. Layers. Containing2:1 Minerals those of acteristics Char and Determination Layer-Charge Clays: Source Society erals Verlag, Darmstadt, 490p. Å . References Č A

Å Å . Experimentally acquired Experimentally . bnoie ad 27 and (bentonite) –

Clays and Clay and Clays Å - - - - - Abstracts Book

Engineering geological research of highly compacted bentonites in Slovakia

Renata ADAMCOVA, Zuzana HAASOVA and Peter MAAS

Article summarizes the experience from the research on tions (<0.250 mm) yielded always the highest dry densi- physical parameters of bentonites for their use as buffer ties. The effective porosity is higher there, which allowed material in the barrier system of the planned deep geologi- the air to escape from the pores during pressing. The air cal repository for the radioactive waste. Bentonites from 5 remaining in the very small pores in the finer fractions different deposits in Slovakia have been tested. However, behaves as an elastic material requiring higher pressures due to the research contract, we are not allowed to give for pressing bentonite to similar densities. In the finest information about the deposits, neither the exact mineral- fractions (<0.015 mm), the necessary pressure (up to 200 ogy, nor the chemistry of the bentonites. Natural bentonite MPa) was so high, that the sorbed water was pressed out was industrially dried, crushed and 3 different fractions from the sample. This caused sticking of the wet bentonite (<0.250 mm, <0.045 mm and <0.015 mm) were separated surface to the mould and increased the friction leading to using cyclone. One of the bentonites was also natrified by the shear stress and occurrence of shear failures (cracks) adding 4% of sodium-hydroxide. in these samples. Unfortunately, the best bentonites (with the highest content of smectite) sorb the highest amount

First of all, the Atterberg’s consistency limits have been 3r tested, as they can tell much about the sorption and swell- of the atmospheric water vapour. Therefore, we have defi- d Mid-European Clay Conference – MECC 06 ing capacity of the clay. Because a high swelling pressure nitely left the finest fractions (<0.015 mm) and preferred is needed, causing the closing of any cracks and failures in the coarser ones, where the risk of cracking is reduced. the barrier (so-called “self-healing” effect), the sample with Preferably coarser fractions have been used also for the highest liquid limit would be the most promising one. pressing standard-shaped samples for mechanical tests We applied two methods: the Cassagrande apparatus and (cylinders, cubes). We tested the uniaxial pressure strength the cone penetrometer method (BS 1377, 1990). However, that yielded values similar to rocks or weak rocks eventually the liquid limit of the natrified bentonite was already too (from 1 to 10 MPa). Here, the sorbed water vapour seems high (>600%!), higher than reported for MX-80 (STUDER to contribute to the cohesion. Therefore, certain water con- et al., 1984). The natural bentonite with the highest content is necessary for higher strength. Samples pressed from tent on exchangeable sodium yielded 160 to 190% and the an oven-dried bentonite behaved as cohesionless soils and best Ca-bentonite 100 to 158%, according to the grain size, lost their form by a simple manual manipulation. There- which is similar to the Montigel bentonite tested in Swit- fore, segments pressed from bentonites with higher smec- zerland (STUDER et al., 1984). Finer samples show higher tite content (i. e. higher equilibrium moisture) seem to be liquid limits. Presented values are results from the Cas- more suitable. There are still not enough results about the sagrande apparatus. Cone penetrometer test gave always deformation moduli there, but this research goes on. The lower numbers. shear strength has not been tested yet. Bentonite will be probably applied in the form of pre- Finally, swelling pressure was tested in consolidom- fabricated high-density segments. Dry densities of 1.8 to eters. One of the bentonites shows results very similar to -3 2.0 g.cm are required. Therefore, the compactibility of the the FEBEX bentonite (www.grimsel.com/febex), when an bentonite powder was the second most important ques- exponential trendline was drawn into the chart of the relation. Because the Proctor Standard compaction method tion between the dry density and the swelling pressure. A (i.e. compaction of wet soil in a mould with a rammer) free-swelling test followed. The hydraulic conductivity was never yielded such high values of the maximum dry densi- calculated next from the consolidation curve. Already at ty, specially designed moulds and a high-capacity hydrau- relatively low densities of about 1.3 g.cm-3, the hydraulic lic jack were applied for pressing high-density bentonite conductivity of the most perspective bentonite did not ex- cylinders, 50 mm in diameter and ca. 50 mm in the height. ceed 6.2·10-12 m.s-1. Curves of the necessary uniaxial pressure versus reached dry density have been constructed, that allowed a quan- References titative comparison. However, the quality of the pressed BS 1377 (1990): British Standard Methods of tests. Part 2: Soils for civil cylinders had to be considered, as well. We saw that the engineering. London. quality decreased and the pressure increased with the in- STUDER, J., AMMANN, W., MEIER, P., MÜLLER, CH. & GLAUSER, E. creasing content of both, the fine fraction and the sorbed (1984): Verfüllen und Versiegeln von Stollen, Schächten und Bohrlö- atmospheric water vapour in the sample. The coarse frac- chern. Technischer Bericht 84-33. NAGRA, Baden, 220 p.

Comenius University in Bratislava, Faculty of Natural Sciences, Department of Engineering Geology, Mlynska dolina, 842 15 Bratislava 4, Slovak Republic ([email protected]) 17 Abstracts Book Abstracts 18 3rd Mid-European Clay Conference – MECC 06 Fig. 1 SEM images showing the morphology of the observed kaolinite, sediments. these of evolution the for indication paleoenvironmental important an constitutes Iraq northern from taken sions JUBOURY, 1994). Clay mineralogy of the Miocene succes (AL- environment claystones and deposited in fluvial-tidal and siltstones sandstones, coarse to medium of sequence aclastic is formation rine conditions in northern Iraq. This foreland the in basin of Iraq in the Upper Miocene marked the end of ma Formation Injana fluviatile of influvial- deposition tobedeposited dominated deltaic system (AL-JUBOURY et al., 2001). The interpreted were clastics These coloration. red by characterized and formation the of unit cupying the upper oc two-thirds of the sequence of the upper claystones silty and sandstones fine by represented are and dominate clastics the basin Fat’ha of parts marginal the In 1997). NUMAN, – Formation Fat’ha Fars, (Lower theshallowing- to upward cyclic deposition of evaporates in middle Miocene rise gave These water. marine normal many small seas and lagoons sporadically replenished with rine conditions became progressively more restricted, with Ma basins. marginal in lagoons and seas epicontinental shallow within formations Jeribe and Dhiban Euphrates, Serikagni, of evaporates and carbonates Miocene early of deposition by started was Iraq is character and nature marine the by ized ofnorthern sedimentation Miocene The Research Center& Water forDams Resources, MosulUniversity, Iraq ([email protected]) and Q=Quartz. illite and palygorskite. Legend: K=Kaolinite, I=Illite, P=Palygorskite Clay Iraq mineralogy duringtheMiocene: innorthern Introduction paleoenvironmental indicators Ali AL-JUBOURY - - - - - ohxgnl lts f h suid alnt especially kaolinite studied the of plates do-hexagonal continental sediments. such in origin detrital its for indicators are images SEM in habit its as well as Miocene) (upper Formation clastic Injana the in kaolinites Common conditions. evaporitic ably formed in detrital system and were preserved in those prob most been had illite) and (kaolinite minerals Other environments evaporitic the within suitable conditions chemical in neoformation by authigenically formed was mineral this that indicated study (SEM) Microscope tron Elec Scanning Miocene. middle the to belonging mation For Fat’ha the of part detrital upper the and formation Euphrates of sediments Miocene lower the in especially il kaolinite, include; palygorskite and present lite minerals clay principal The NUMAN, N.M.S. (1997 N.M.S. NUMAN, Berlin Springer-Verlag, Sedimentology.– Clay (1989): H. CHAMLEY, (2001): AL-JUBOURY, A.M.S. & S.Q. AL-NAQIB, AL-JUBOURY, A.I., AL-JUBOURY & C 1A, (Figure origin D). authigenic their indicating fibers small and long as palygorskite show photomicrographs SEM Formation. Euphrates the of beds marl the of goons la and back-reef restricted in mineral clay neoformed as palygorskite of formation the for suitable are conditions climate and strong evaporation”. It seems that evaporative contrasted humidity, and warm exchange, water limited transgression, marine to subject basins restricted in tions condi “alkaline as formation palygorskite for conditions cal precipitation in evaporative basins. He summarized the chemi from derives palygorskite that shown has (1989) minerals. Mg-rich other associated and dolomite commonly with is and mineral clay fibrous a is skite Palygor Iraq. northern from olderTertiary successions Cretaceous and the in existed mineral This samples. studied the in mineral common cemented a is Illite 1B). (Figure sandstones carbonate in flakes white as appears Illite 1A). (Figure samples continental Injana the from taken those cnigeeto mgsso h eldfie pseu defined well the show images electron Scanning succession inIraq.– Iraqi Journal, Geological 30 Heidelberg, 623 p. Iraq, Dirasat.– Pure and Applied 28,80–107. Sciences, Mosul, of South Miocene), (Middle Formation Fatha the units, clastic of environment depositional and mineralogy Sedimentology, versitatis Comenianae, Bratislava 50,45–53. Uni Geologica Acta Iraq.– Northern Miocene), (UpperFormation , A.I. (1994): Petrology and provenance of the UpperFarsprovenance the andPetrology of (1994): A.I. Results &Discussion ): A plate tectonic scenario for the Phanerozoic the for scenario tectonic plate A . ayosie s cmo mineral common a is Palygorskite References , 85–110. CHAMLEY ------.

Abstracts Book

Phase composition and geotechnical evaluation of bentonite from Lieskovec, Slovakia

Slávka ANDREJKOVIČOVÁ1, Ivan JANOTKA2 and Peter KOMADEL1

Powder XRD and IR spectroscopy were used to identify 16.2%, respectively. Free swell tests of 3–6% are typical for mineralogical composition of the bentonite samples from Ca–bentonites. All ten bentonite samples are characterized the Lieskovec deposit (Central Slovakia), developed from by low water sorption capacities (wP, wL, Es and free swell andesitic pyroclastics. The main mineral is a montmorillo- test). Permeability coefficients of L1, L15 and L22 are of the nite, the admixtures present in all samples include kaoli- order of 10-11 m.s–1, what is the primary requirement for nite, quartz, cristobalite and plagioclase, while muscovite/ using of bentonite for sealing purpose. k20–values of these illite and orthoclase appear in most samples. This bentonite samples differ only slightly, and are primarily dependent deposit is relatively homogeneous. Detailed analysis of the on the smectite content. Based on these results, bentonite infrared spectra shows that the dominant mineral in the from Lieskovec deposit is a promising material to be used samples is a Fe–montmorillonite with rather low isomor- after natrification as a sealing material in a function of geo- phous substitution in the octahedral (MgII for AlIII) and synthetic clay liner. tetrahedral (AlIII for SiIV) sheets (ANDREJKOVIČOVÁ et Reference

al., 2006). 3r

Basic geotechnical properties of ten bentonite samples ANDREJKOVIČOVÁ, S., MADEJOVÁ, J., CZÍMEROVÁ, A., GALKO, I., d Mid-European Clay Conference – MECC 06 DOHRMANN, R. & KOMADEL, P. (2006): Mineralogy and chem- are reported in Table 1. Diﬀerences between the lowest and istry of Fe–rich bentonite from Lieskovec deposit, Central Slovakia.– highest values of plasticity and liquid limits are 26.2% and Geologica Carpathica, in press.

Table 1 Geotechnical properties of bentonite samples from the Lieskovec deposit.

Property L1 L4 L5 L8 L11

Plasticity limit wP (%) 47.4 34.6 33.2 44.3 47.8

Liquid limit wL (%) 73.2 80.4 64.2 72.1 80.1

Plasticity index IP (%) 25.8 45.8 31.0 27.8 32.3 Water adsorption Enslin Es 24 h (%) 236.2 123.2 126.5 363.2 605.9 Free swell test (%) 4 4 5 5 6

–1 –11 Coefﬁcient of permeability k20 (m.s ) 2.4×10 – – – –

Property L12 L15 L20 L22 L26

Plasticity limit wP (%) 59.5 44.2 42.5 42.6 42.2

Liquid limit wL (%) 76.2 75.5 72.3 67.2 66.3

Plasticity index IP (%) 16.7 31.3 29.8 24.6 24.1 Water adsorption Enslin Es 24 h (%) 312.4 259.0 163.1 166.3 316.5 Free swell test (%) 5 5 3 4 4

–1 –11 –11 Coefﬁcient of permeability k20 (m.s ) – 2.1×10 – 2.7×10 –

1 Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK–84536 Bratislava, Slovakia ([email protected]) 2 Institute of Construction and Architecture, Slovak Academy of Sciences, Dúbravská cesta 9, SK–84503 Bratislava, Slovakia 19 Abstracts Book Abstracts 20 3rd Mid-European Clay Conference – MECC 06 1 procedure the following media isopropanol in intended with treatment was delamination and bromide cetyltrimethylammonium by prepared were clays modified ganically TiO dispersed of incorporation and Benahavis from (M vermiculite and (Tunisia), Gafsa smectite from iron-rich an USA), (Wyoming, Creek County tion of photodegradation of 2,4-dichlorophenol as atest. resultingpropertiesof the nanocomposites reacusing the photocatalytic the of some as well as route this by pared pre materials titania–silica/clay and titania/ of terization charac and preparation the concerning results introduce will communication ofview their catalytic properties. This in useful be to expected are which agglomerated, not but area surface specific large relatively of provided particles TiO nanosized incorporating materials obtain to is objective The instead.precursors alkoxyde titanium ing us but systems silica–clay of synthesis the for approach the following nanocomposites inorganic–inorganic new developed have we 2005), al., et ZHU 2003; al., et METH N 2002; al., et (LI problemssuch for solution a provide to appear materials titania–silica or titania–clay that and organicpollutants (ANPO, FUJISHIMA2000; 1999) al., et of decomposition for photocatalyst phase, is a very efficient TiO that Considering 2006). al., (LETA properties ion-exchange and textural esting inter show that materials giving hydrolyzed further and incorporated rivativessilane whichthe precursorin isfirst prepared bycolloidala route that implies of use the organo–clay de are nanocomposites inorganic–inorganic These (LETAgroup our by ported rerecently been hydrolysishas alkoxysilanes,of the from accomplished by incorporation of a silica matrix generated is silicatelayered the delaminationof which in clays other and smectites on based materials nanocomposite of type new A 2000). (PINNAVAIABEALL, studied & most the probably arenanocomposites polymer–clay them Among characteristics structural both and functional applications. the of smectite family silicates are materials of layered increasing interest on based on based solids Nanostructured 3 2 Department ofChemistry, K1N6N5,Canada Ontario ofOttawa, University Department Institute ofCatalysis, Bulgaria Bulgarian Academy ofSciences, “Acad. Str., G.Bonchev” bl. 11,1113Sofia, Instituto deCiencia deMateriales deMadrid, CSIC,Cantoblanco, 28049Madrid, Spain([email protected]) á tnad ymn mnmrloie Sy1 from (SWy–1) montmorillonite Wyoming Standard aa San wr te ly coe fr delamination for chosen clays the were Spain) laga, Pilar ARANDA TiO Ï EF & RUIZ-HITZKY,2003). & EF 2 /delaminated–clay nanocomposites 2 Sadok LETA , specially in the anatase the in specially , 1 2 aoatce. Or nanoparticles. , ElinaMANOVA Ï EF 2 anatase 1,3 Ï EF et EF andEduardo RUIZ-HITZKY É ------1,2 , M P25 anatase, having two-fold activities per unit mass for mass unit per activities two-fold having anatase, P25 commercial of that to comparable processes composition de the of kinetics and activitiessolution showaqueous in decomposition 2,4-dichlorophenol of test Photocatalytic catalysts. as systems these of interest potential the cating TiO and (clays counterparts individual positesshow areas surface higher and porosities than their nanocom inorganic–inorganic These clays. in delaminated consisting nanocomposites TiO of anatase formation the confirm andSEM–EDX TEM, determinations, porosity and area surface analyses, specific chemical and (TG–DTA) thermal FTIR, XRD, of means TiO giving 500 at Heating gels. mixtures slowly hydrolyzed till formation of homogeneous isopropoxide or titanium isopropoxide/tetramethoxysilane previously described (LETA ZHU, H.Y., LI, J.-Y. ZHAO, J.C. & CHURCHMAN, G.J. (2005): Photo (2005): G.J. CHURCHMAN, J.-Y.& ZHAO,J.C.H.Y.,LI, ZHU, PINNAVAIA, T.J. & BEALL, G.W. (eds.) (2000): Polymer–Clay Nanocom N LI, J., CHEN, C., ZHAO, J., ZHU, H. & ORTHMAN, J. (2002): Photodeg LETA LETA FUJISHIMA, A., HASHIMOTO, K. & WATANABE, T. (1999): TiO TiO of Utilization (2000): M. ANPO, nanocompositesthe here developed. É ª EH J, D J., METH, 79–88. 28, Science, Clay Appliedwater.– in pollutants organic of radation deg forhydrate titanium and clays layered from prepared catalysts posites.– Wiley, 370p. 3769. of 3762– 19, properties Langmuir, nanocomposites.– oxide–montmorillonite structural tin and Preparation (2003): J.H. FENDLER, 331–339. UV–VISunder irradiation.– radation of dye pollutants on TiO 401–409. 16, Materials, Functional Advanced nanocomposites.– porous–clay novelsolids: layered delaminationrouteoffor colloidal A (2006): E. Communications,Chemical 2996–2997. tocatalysis Fundamentals and Applications.– BKC, Tokyo. try.– Pure and Applied Chemistry, 72,1265–1270. Angeles MART Ï Ï EF, S., MARTIN-LUENGO, M.A., ARANDA, P. & RUIZ-HIZTKY, nanocomposites.– Silica–clay (2003): RUIZ-HITZKY,E. & EF,S. 2 ca drvtvs ht ee hrceie by characterized were that derivatives –clay 2 aoatce hmgnosy ipre in dispersed homogeneously nanoparticles É K Á Y I, S I., NY, ° i ar eoe h ognc matter organic the remove air in C Í 29 N-LUENGO References iNRtcnqe.Teestudies These techniques. NMR Si Ü 1 EH K, AE, . V T., MAREK, K., VEGH,

AppliedEnvironmental,B.Catalysis 37 Ï EF et al., 2006), using titanium 2 2 nanoparticles in silicate dispersed htctlss n re chemis green in photocatalysts 1 ,

2 separately) indi separately) É TS A & A. RTES, 2 Pho ------Abstracts Book

Mineralogy of a Carboniferous bentonite from the Sudetes (SW Poland), northern margin of the Bohemian Massif – preliminary data

Czeslaw AUGUST

It is well recognised that bentonites are good markers of positions. The first one is represented by lens-like small- ag the explosively erupted volcanic ash and can be used as gregates or thin veins (0.4 cm thick) composed of fibrous stratigraphic markers on both local and regional scales. crystals. The second one is represented by small crystals This presentation demonstrates an application of clay min- dispersed in the rock groundmass. erals in bentonites as indicators of diagenetic regime, par- The measurements of %S (20–30%, R1–R3) in the I/S ticularly the paleotemperature, of pyroclastic deposits. packets in the Lower Carboniferous bentonites from the The mineral composition of the bentonites was ana- Bardo Mts. testify that the maximum diagenetic paleo- lysed using X-ray diffraction and thermal analysis. The %S temperatures in these rocks attained ca. 120–135°C. The in the I/S packets was measured using ŚRODOŃ’s (1984) heavy mineral fraction of the bentonites contains idiomor- technique. Paleotemperatures were calculated based on phic zircon crystals, which clearly show their pyroclastic ŠUCHA et al. (1993) diagram. Zircon in heavy mineral origin. The mineral composition (clay minerals, calcite) of fraction was studied by optical microscopy. 3r

the bentonites from the Bardo Mts. point to an interme- d Mid-European Clay Conference – MECC 06 The studied bentonite beds have been identified in the diate composition of the pyroclastic material and its par- Bardo Mts. – a structural unit within the Sudetes, at the ent magma. Their volcanic source was possibly located in northern margin of the Bohemian Massif. The structural Intra-Sudetic depression, a neighbouring structural unit, complex of the Bardo Mts. consists of sedimentary rocks of where the presence of Lower Carboniferous andesites and the Late Ordovician to the earliest Late Carboniferous age. rhyodacites was documented (AWDANKIEWICZ, 1999). The bentonite layers occur within the Upper Viséan series composed of mudstone and claystone shales, greywackes References and carbonate rocks. The bentonite beds paleontologi- AUGUST, C., HAYDUKIEWICZ, J. & MUSZER, J. (2003): Bentonites cally are “dump” (HAYDUKIEWICZ & MUSZER, 2002). of Lower Carboniferous from Bardo Mts. unit (Western Sudetes).– Six bentonitic layers occur in the lower part of a section Spec. Pap. Miner. Soc. Pol., 22, 15–18. represented dominantly by mudstone and claystone shales. AWDANKIEWICZ, M. (1999): Volcanism in a late Variscan intramon- They are from 2–10 cm thick and generally light yellow to tane trough: the petrology and geochemistry of the Carboniferous and Permian volcanic rocks of the Intra-Sudetic Basin, SW Poland.– grey–brown in colour on fresh surfaces (AUGUST et al., Geologia Sudetica, 32, 83–111. 2003). HAYDUKIEWICZ, J. & MUSZER, J. (2002): Offshore to onshore tran- Examination of the bentonites shows that the major sition in the Upper Viséan paleontological record from the Papro- clay minerals are kaolinite and I/S mixed-layer packets. tnia section (Bardo Mts., Western Sudetes).– Geologia Sudetica, 34, 17–38. Both minerals occur in similar proportion. Chlorite, smec- ŚRODOŃ, J. (1984): X-ray powder diffraction identification of illitic matite and illite have been also detected in two bentonite beds. terials.– Clays Clay Minerals, 32, 337–349. All the analysed samples contain small amounts of FeOOH ŠUCHA, V., KRAUS, I., GERTHOFFEROVA, H., PETES, J. & SEREKO- substance. No relics of primary minerals were observed. VA M. (1993): Smectite to illite conversion in bentonites and shales Secondary calcite (up to 10% by volume) occurs in two of the East Slovak Basin.– Clay Minerals, 28, 243–253.

Institute of Geological Sciences, Wroclaw University, Poland ([email protected]) 21 Abstracts Book Abstracts 22 3rd Mid-European Clay Conference – MECC 06 2 1 for Ar/Ar dating of micrometer-sized minerals. tion of a simple, routinely applicable experimental method ing illite and I/Sare only exploited. partly its of dat spite of geochronological importance, the potential benefits in difficulties, these to Due complicated. very to need work experimental the the made vacuo in ampoule and the break quartz of point melting high tionline. The extrac the brokenin ampoulemusthavebeen the quartz, degassingmineral,regarding the melting high point the of which the from ampoule quartz a in irradiation before mineral the has been published by sealed ONSTOTT et al. (1997). They method sophisticated very but reliable A minerals. these of importance chronological the by stimulated been have es cape of partial The 1974). CADOGAN, & (TURNER formed 0.08 of layer depleted a and mineral the leave part of energetic 0 the in energies with recoiled the in reactor, nuclear the in irradiation micrometer- Namely,during minerals. dating sized for unsuitability its is serious most measurement.fora the drawbacks needed Amongfew the is e.g. mineral of amount smaller advantages: and accurate more are ages numerous has method This method. Ar) advanced more the by laboratories for used be dating (ore-)mineralization processes. dated is shear-zones from ( illite when confined be can ity ( silicates “crystallinity”phylomeasurementofwith connected is it when efficient, is method ofmetamorphism. time This the from low- and very low-grade metamorphic rocks will give illite–muscovite of age The dated.(ii) be candiagenesis by geological processes. (i)insinking basins E.g. illite formed of and rock-types of set a of studies geochronological in importance unique a have (I/S) and illite/smectite interstratified illite all of first minerals, micrometer-sizedof Dating 4 3 Kossuth Univ. Debrecen, Egyetem t. Res. Okayama Inst.Nat. Sci., Univ. Okayama 1–1Ridai-cho, 700–0005,Japan Sci., Inst. forGeochem.Res., HAS, Pf. 132 Inst. ofNucl. Res., HAS,Bemt18/c Á RKAI et al., 2000, 2002). (iv) Fine-grained minerals canminerals Fine-grained (iv) 2002). 2000, al., RKAIet ffrst ov h ako rA aigo lieadI/S and illite of dating Ar/Ar of task the solve to Efforts Recently conventional K/Ar dating is replaced in many h ups ftepeetwr a enteelabora the been has work present the of purpose The 39 Ar will resultAr will inerroneously old ages. Á 39 RKAI et al., 1996). al., et RKAI Ar leaving the mineral could not escape. Before Development ofasimplemethodfor Ar/Ar dating of 39 39 K(n,p) Ar atoms formed near to the surface may Kadosa BALOGHKadosa micrometer-sized minerals: aprogress report 39 Ar reaction the the reaction Ar , 4026Debrecen , 4032Debrecen , 1502Budapest (iii) – 400 keV energy range. A range. energy keV 400 Time of tectonic activ tectonic of Time Hironobu HYODO 40 Ar/ , Hungary (balogh@namafia.atomki.hu) , Hungary 1 39 , Hungary , P , Hungary Ar (shortly: Ar/ (shortly: Ar 39 é r uli are nuclei Ar ter µ m will be be will m Á RKAI 2 ------3 , Katalin JUDIK , Katalin and lts-ue hshsbe elzdb nigteproper for the used finding nippers the by quality of of Al and the suitable profile realized been the has This test-tube. off Al pinching vacuum-tight is process The the of system. essence vacuum the off pinched and evacuated tube, plastic with system vacuum purity,a to99.99% connected of test-tubes Al in placed were Minerals solution. the be vacuo. in sample irradiated the storing requires procedure this Ar,thereforeatmospheric and water absorbed water-glass from duringtime irradiationever the the togasextraction reactions when the mineral was dried in chemical water-glass, in vacuo. How the to promisingmore been hasIt mineral. due and salt the between unsuccesful, was idea This recoiled that expected vacuo. Itin been together has them fuse andpoint salt ing UNR .&CDGN ..(94:Psil ffc of P.H. CADOGAN, & G. Possible (1974): TURNER, effect ONSTOTT,P.J.VROLIK, (1997): T.C.,C., D.R. PEVEAR, MUELLER, & Á Á Á test-tube. the pinching off RKAI, P., MERRIMAN, R.J., ROBERTS, B., PEACOR, D.R. & T P.,RKAI, M DEM K., BALOGH, P., RKAI, Istv Closing the mineral in Al before irradiation proved toproved irradiation before Al in mineral the Closing melt low a with mineral the mixing was idea first Our nso h it ua cec ofrne,1601–1615. Conference), Science Lunar ings of Fifth the 40 Acta,Cosmochim. 61,3851–3861. Laser epizonal pelites.– Eur. J. Mineral., 8,1119–1137. vite and chlorite: comparison of XRD and TEM data for diagenetic to (1996): Crystallinity, size crystallite and lattice strain of illite–musco Alps,tral Switzerland. Schweiz.– Mineral. Petrol. Mitt., 82,272–290. Cen Helveticdomain,Kanderstegarea, the fromstudy case a cates: phyllosili on strain tectonic of FREY,& I. Possible(2002): M. effects 43/4, 351–378. Hung.,Hungary.–Geol. formation,southernClaystone ActaAlbitic Boda the site: repository waste radioactive possible a of alterations M Ar– Á TH á 39 40 n BALOGH Ar dating.– Geochim. Cosmochim. Acta, Suppl. 5 (Proceed 5 Suppl. Acta, Cosmochim. Geochim. dating.– Ar É Ar/ Z (00: opsto, igntc n post-diagenetic and diagenetic Composition, (2000): Z. , Ä 39 HLMANN, R.F.,HLMANN, SUCHY, V., SYKOROVK., BALOGH, rmcorb nlsso n-rie lie–Geochim. illite.– Ar microprobe analyses of fine-grained 2 , Tetsumaru ITAYA 4 References 39 r il e atrd n h salt. the in captured be will Ar É Y A, F A., NY, 3 Ó , IS I, AY G & G NAGY, I., RIZS,

39 Ar recoil in recoil Ar Ó TH, M. Á ------, Abstracts Book

Clay minerals assemblage in the Upper Albian carbonate succession (Tinjanska Draga, Istria, Croatia)

Uroš BARUDŽIJA1, Neven TADEJ1 and Jasna TADEJ2

Introduction other phyllosilicates, probably smectites, kaolinite and Several clay-containing layers within the Upper Albian chlorites, are also present. In the total heavy mineral sam- carbonate sequence (BARUDŽIJA et al., 2004) from Tin- ple there are transparent grains (up to 50% – predominatly epidote–zoisite–clinozoisite minerals, followed by pyrox- janska Draga area in Istria (Croatia) were analyzed. The enes [Cpx+Opx], garnets, hornblende and feroactinolite aim of the study was to connect their mineral assemblage and some zircons, tourmalines and glaucophanes), musco- with the contemporaneous diagenetic siliciﬁcation of car- vite (up to 40%), chlorite (up to 10%) and opaque minerals bonates appearing in the same sequence (BARUDŽIJA, and grains with limonitic cover as well. In the light mineral 2003; DURN et al., 2003). Therefore, 12 samples from the assemblage quartz and feldspar (plagioclase) grains are the four diﬀerent horizons were analyzed by X-ray powder dif- dominant components. fraction (XRD). Results were compared with petrographic analysis of heavy and light mineral assemblage from the Discussion same samples. Clay minerals assemblage in the Upper Albian carbonate 3r

Methodology and results succession from Tinjanska Draga is closely connected with d Mid-European Clay Conference – MECC 06 silicification developed within limestones and dolomites Bulk samples were analyzed by XRD. Samples were treated from that section. Determined mixture of illite and highly with NaAc/HAc and diffraction patterns of obtained air illite–smectite clays indicate diagenesis of clays within ma- dried and differently treated (with glycerine; with ethylene rine conditions. Mineral association present within heavy glycol; 2 hours heated at 600°C; dissolved for 24 hours in and light mineral fraction shows a significant composition hot 18% HCl) insoluble residues were also recorded. Clay and can indicate volcanic origin of source material for de- fractions (<2 µm) from insoluble residues were taken and velopment of determined clay minerals assemblage and diffraction patterns of non-oriented and oriented samples source of silica for silicification as well. were made. In order to determine clay minerals, samples were saturated with Mg2+ (oriented air dried samples, eth- References ylene glycol treated samples and samples heated at 300°C/ BARUDŽIJA, U. (2003): Quartz diagenetic sediments within the Up- + 2h and 550°C/2h were prepared) and K (oriented air dried per Albian shallow-marine carbonate sequences in Central Istria samples, ethylene glycol and DMSO treated samples, 2 (Croatia).– 22nd IAS Meeting of Sedimentology – Opatija 2003, Ab- hours heated samples at 300°C and 550°C were prepared) stracts Book, 11. and diffraction patterns were taken. BARUDŽIJA, U., TADEJ, N., ALJINOVIĆ, D. & VRKLJAN, M. (2004): Clay minerals within the carbonate sequences in Tinjan area (Istria, Samples have significant percentage of carbonates Croatia).– In: NEMETH, T. & TERBOCS, A. (eds.): 2nd MECC (35–95 wt.% of calcite in 10 samples, and 2 samples with – Miskolc 2004, Acta Mineralogica–Petrographica – Abstract Series, almost 95 wt.% of dolomite and less than 5 wt.% of cal- Univ. of Szeged, 12. cite). Insoluble residues contain from 10 wt.% to 90 wt.% DURN, G., OTTNER, F., TIŠLJAR, J., MINDSZENTY, A. & BARUDŽIJA, U. (2003): Regional subaerial unconformities in shallow-marine car- of quartz, as well as up to 5 wt. % of feldspars and variable bonate sequences of Istria: sedimentology, mineralogy, geochemistry content of phyllosilicates mainly present in clay fraction. and micromorphology of associated bauxites, palaeosols and pedo- Depending of sample, clay fractions mostly contain illite sedimentary complexes.– In: VLAHOVIĆ, I. & TIŠLJAR, J. (eds.): and/or mixed-layer illite–smectite dominated by illite lay- Evolution of Depositional Environments from the Palaeozoic to the Quaternary in the Karst Dinarides and the Pannonian Basin: 22nd ers, illite–smectites with higher amount of smectite layers IAS Meeting of Sedimentology – Opatija 2003 – Field Trip Guide- than previous and randomly interstratified minerals. Some book, Zagreb, 209–254.

1 Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, Pierottijeva 6, HR-10000 Zagreb, Croatia ([email protected]) 2 INA Oil Industry, Oil & Gas Exploration and Production, Šubićeva 29, HR-10000 Zagreb, Croatia 23 Abstracts Book Abstracts 24 3rd Mid-European Clay Conference – MECC 06 tions. Illite and chlorite were determined in small quantities forma Eocene Lower and Paleocene the amountslargein Middle Eocene series. Corensite and 14 and Cretaceous Upper the in mineral clay dominant the is Smectite fraction. clay the in determined were miculite done using geochemicalmethods. were fraction clay of analyses chemical and fractometry dif X-ray using by determined were samples the of erals and samples were collected along these sections. Clay min area study the in measured were sections Stratigraphical Tertiary.Lower and Cretaceous Upper between observed Kenozoic series and and continuous marine sedimentation Mesozoic was Paleozoic, of consists area study Ankara. The of town the nearHaymana, of south located is area Study Hacettepe University Geological Engineering Departmnet, Beytepe–Ankara,Hacettepe Turkey, Geological University Engineering Departmnet, ([email protected]) mcie crest, 14 corrensite, Smectite, Upper Cretaceous–Lower Tertiary clay mineral successions of southernHaymana region (Ankara, Turkey) S –14 C ilt, hoie n ver and chlorite illite, , S –14 C were found in Emel BAYHAN - - - - massive are sources the of clays area. inthis K and rocks ultramaphic that dicate rocks. which derivedterial from different fromminerals occurred the transformation of ma detrital clay interstratified and Smectites chlorites. and illites for source the are rocks metamorphicand minerals clay trital de were chlorites and Illites sources. ported from different analyses Chemical results show that sediments were trans Al in rich issamples of fraction Clay saponite. and beidellite as determined are smectites analyses chemical elements major to According that duringperiod. important was input detrital that indicated data These sediments. Eocene Lowerand Paleocene the in increases amount illite However,the sequence. the along Clay mineral chemistry and petrographical studies in studies petrographical and chemistry mineral Clay 2 O 3 –Fe ı r 2 ş O ehir metamorphic ehir 3 or MgO–Fe or

2 O 3 - - - - . Abstracts Book

Clay mineralogy of Tertiary sedimentary sequence from Gökçeada Island (northeast Aegean Sea, Turkey)

Hasan BAYHAN, Fatih GÜLEÇ, Emel BAYHAN, Abidin TEMEL and Halime HÜRYILMAZ

Gökçeada Island is located at Northeastern Aegean Sea, als were determined by X-ray diffraction. The whole rock west of the Çanakkale Strait and Gallipoli Peninsula (Tur- mineralogy is characterized by clay, mica, kaolinite, quartz, key). Study area covers Yenibademli village and its sur- feldspar, calcite and trace amounts of dolomite. In the clay roundings which is located at the northeast of Gökçeada fraction smectite, illite and kaolinite comprise the domi- Island. In this region many archeological studies have been nant minerals. In addition to these minerals, trace amounts carried out, but no detailed mineralogical studies were pre- of 14S–14C were also found in the clay fraction. In gener- sented yet. This study aims to determine the whole rock al, important mineralogical differences are not observed and clay mineralogy of the region. along the Tertiary sequence. However, in the upper part All of the rock formations in the study area are of Tertia- of the Oligocene sequence the content of smectite decreas- ry age. These Tertiary sedimentary units lie unconformably es, while illite becomes more abundant. These differences over the Paleozoic basement rocks. Eocene Tepeköy forma- suggest greater amounts of detritus transportation in the tion which is composed of blue–gray marls and siltstones upper parts of the Oligocene sequence that includes sedi- overlies the Paleozoic units. Oligocene Kaleköy formation, ments derived from different sources. 3r consisting of light brown sandstones–siltstones alterna- Petrographical studies indicated that feldspars were al- d Mid-European Clay Conference – MECC 06 tion, succeeds the Tepeköy formation. Bademli formation tered into clay minerals. It seems that great majority of clay conformably overlies the Kaleköy formation and consists minerals in the whole sequence occur as alteration prod- of brown-green marl and yellow sandstones. Kuzulimanı ucts of either feldspars or volcanic rocks. Illites, appear to formation unconformably overlies the Bademli formation. be detrital and they derived from the basement rocks. It At the top of Oligocene sequence volcanic rocks were ob- is concluded that these sediments have been transported served. from varius source areas, while the clay minerals derived Samples were collected systematically along measured from the basement rocks on the island and from Biga Pen- sections of these formations. Whole rock and clay miner- insula, located on the northwestern corner of Asia Minor.

Hacettepe University, Geological Engineering Department, Beytepe–Ankara, Turkey ([email protected]) 25 Abstracts Book Abstracts 26 3rd Mid-European Clay Conference – MECC 06 1 K of fixation and smectite of dehydration of time the represent ages these was <2 fraction metamorphism the within recorded This established. be can 1), (Figure Ma 85 around event(s) (thermal) metamorphic taceous samples K4and K7and pyrophyllite insample K4. in chloritoid K8, sample in found was Hematitesamples. with K-feldspar in all “K” samples and plagioclase in all “R” samples, all in chlorite and illite–muscovite quartz, yields dlovac metamorphic complex (R) determine mineral the composition. to (XRPD) method diffraction powderX-ray with studied radiogenic also were samples of All dilution. isotope amount by measured was the and photometry flame by <2 tion JAMI TriassicEarly (JAMI the tocambrian acteristics and age (Table 1) which char range from the Late Pre petrological different the of rocks of varieties ferent dif comprise samples Analyzed complex). metamorphic Psunj and rocks sedimentary (including transect Kutjevo the and complex metamorphic Radlovac the concerning (JAMI dlovac Ra and (Jankovac) Papuk(Kutjevo), Psunj region: vonia Sla the in distinguished be can metamorphism, and tion deforma of phases several with characterized complexes, Po of edge very the on re northeastern the located in Slavonia, Zagreb from east km situated200 Croatia, of gion a mountain is Papuk The 2 University ofZagreb, University Faculty ofGeology, ofScience, Department Institute forMineralogy andPetrology, Horvatovac bb, HR-10000 Zagreb, Croatia ([email protected]) Hungarian Academy ofScience, Institute ofNuclearResearch (ATOMKI), 4026Debrecen, Bemt18/c, Hungary h hl okXP nlsso ape rmteRa the from on samples analysis XRPD rock whole The K According to the measured K–Ar data (Table 1), Cre (Table1), data K–Ar measured the to According K 12 Quartz metasandstone Quartz Metaconglomerate K11 Metaconglomerate K12 K8A K8B R9 R1B R4 K4 (JAMI K7 (macroscopic determination) Sample – Č Ar dating was performed on whole rocks and frac and rocks whole on performed was dating Ar I Ć µ m. Concentration of potassium was determined was potassium of Concentration m. etal., 1987). Č K–Ar dating ofCretaceous metamorphismrecorded I in the eastern part ofMt. Papuk,in theeastern part Slavonia, Croatia Ć Vanja BI + 93.Tersac sbsdo studies on based is research The 1983). , cation in the crystal lattice of illite. The illite. of lattice crystal the in cation Chloritoid schist Metasandstone Metasandstone Chlorite schist Sandstone Rock type type Rock Phyllite

ž g Vle. he metamorphic Three Valley. ega Š EVAC µ

and Kutjevo transect (K) m i.e. m 1 , Dra Č I Ć “ Stratigraphic age illite fraction illite ž & BRKI & Č en BALEN I Ć & BRKI PCm C, P C, P C, P 2 1 1 D T PT PT PT

1 3

Ć Ć , 1987; , , 1987) ” 40 , so so , 1 Ar , Kadosa BALOGH, Kadosa ------JAMI JAMI JAMI older, components. detrital contain frequently types rock parametamorphic that fact known well the byexplained be canages rock whole older Fig. 1 Plot of K–Ar data (Ma) (whole rock and <2 µm) vs. stratigraphic vs. µm) <2 and rock (whole (Ma) data K–Ar of Plot 1 Fig. hl ok Fraction <2 Whole rock 113.6 112.6 120.8 130.0 86.0 Beograd, 72p.Beograd, Croatian). (in hovica Yugoslavia of Map Geological 1:100000,sheet Orahovica. scale 36,51 vjesnik, Croatian). Papuk(in Mt.of part eastern the and KrndijaMt. Kutjevo (<2µm) transect & BRKIĆ, age 1987) (JAMIČIĆ for samples from Radlovac (<2 µm) Č Č Č – – – – ± ± ± ± ± I I I 33 71.4 3.3 Ć Ć Ć Measured age . 91.6 85.0 4.9 4.6 83.1 89.7 4.3 4.4 , D., BRKI D., , , D & BRKI on rocks metamorphosed the of fabric Structural (1983): D. , K – Ar (Ma) – 94.0 92.3 79.4 99.3 2 72. Ć and Ć , M., CRNKO, J. & VRAGOVI & J.CRNKO, M., , , M. (1987): MapBasic Geological of Yugoslavia in ± ± ± ± ± ± ± ± ± 2.8 3.8 3.6 3.3 3.2 3.1 3.9 3.3 3.5 – µ Darko Darko TIBLJA Geol. zavod Zagreb (1986), Sav. geol. zavod geol. Sav. (1986), Zagreb zavod Geol. m References

● , and Kutjevo (wholerock) transect – – xlntr nts o set Ora sheet for notes Explanatory Table 1Generalinformation Sav. geol. zavod Beograd. <2 µm. of wholerock andfraction with measured K–Ar data about investigated samples Š 1 Ć , M. (1987): Basic Basic (1987): M. ,

– Geol. ▲

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A multispectral study of clay minerals: Mössbauer, reﬂectance, transmittance, and emission spectroscopy

Janice L. BISHOP1, Adrian J. BROWN1, Ed CLOUTIS2, M. Darby DYAR3, Takahiro HIROI4, Melissa D. LANE5, Ralph E. MILLIKEN4, Enver MURAD6 and John F. MUSTARD4

A collection of phyllosilicates are under study using a large Gusev regions contains a combination of ferrous and ferric number of spectroscopic techniques in order to coordinate minerals (e.g. KLINGELHÖFER et al., 2004; MORRIS et the spectral features among these different techniques with al., 2006). We hope through our study to be able to better each other and the mineral structures. Our collection in- characterize any clay mineral components that might be cludes examples of chlorites, kaolin–serpentines, micas, present in the Martian Mössbauer spectra. and smectites. We are measuring Mössbauer and visible/ near-infrared (VNIR) spectra in order to characterize the References Fe bonds in these samples. Mid-IR transmittance, reflec- BISHOP, J.L., MURAD, E. & DYAR, M.D. (2002): The influence of octahe- tance and emission spectra are used for measuring the dral and tetrahedral cation substitution on the structure of smectites fundamental vibrations due to Si (&other)–O tetrahedral and serpentinites as observed through infrared spectroscopy.– Clay Minerals, 37, 617–628. bonds, Fe (&other)–O octahedral bonds, structural O–H CHRISTENSEN, P.R., BANDFIELD, J.L., HAMILTON, V.E. et al. (2001): and interlayer/adsorbed H–O–H. The VNIR reflectance Mars Global Surveyor Thermal Emission Spectrometer experiment: 3r spectra also exhibit absorptions due to overtones and com- Investigation description and surface science results.– Journal of d Mid-European Clay Conference – MECC 06 binations of the fundamental IR absorptions. The samples Geophysical Research, 106, 23823–23871. in the study include allophane, celadonite, chamosite, KLINGELHÖFER, G., MORRIS, R.V., BERNHARDT, B. et al. (2004): chrysocolla, chrysotile, clinochlore, ferruginous smectite, Jarosite and hematite at Meridiani Planum from Opportunity’s Möss- bauer spectrometer.– Science, 306, 1740–1745. gyrolite, halloysite, kaolinite, lizardite, montmorillonite, MORRIS, R.V., KLINGELHÖFER, G., SCHRÖDER, C. et al. (2006): nontronite, phlogopite, picrolite, saponite, and talc. Mössbauer mineralogy of rock, soil, and dust at Gusev crater, Mars: VNIR spectra collected by OMEGA have shown the Spirit’s jounrey through weakly altered olivine basalt on the plains presence of clays on Mars (POULET et al., 2005). We ini- and pervasively altered baslat in the Columbia Hills.– Journal of Geo- physical Research, 111, doi:10.1029/2005JE002584. tiated the current study in order to prepare an archive of MURCHIE, S., ARVIDSON, R.E., BEDINI, P. et al. (2006): CRISM clay mineral spectra for the CRISM VNIR spectrometer (Compact Reconnaissance Imaging Spectrometer for Mars) on MRO (MURCHIE et al., 2006) that is en route to Mars, for the (Mars Reconnaissance Orbiter).– Journal of Geophysical Research, thermal emission spectrometer that is in orbit at Mars in revision. (CHRISTENSEN et al., 2001) and for the Mössbauer POULET, F., BIBRING, J.-.P., MUSTARD, J.F. et al. (2005): Phyllosilicates spectrometers that are currently on the Martian surface on Mars and implications for the early Mars history.– Nature, 438, 632–627. (KLINGELHÖFER et al., 2004). Identifying clay minerals on Mars provides information about the extent and duration of aqueous processes there. The VNIR andö M ssbauer spectra of Mars may enable the best opportunities for identification of clay minerals because of the nature of the spectral features and the sample sizes measured on Mars. VNIR spectra of a few samples are shown as an example in Fig. 1 in order to illustrate the variety of spectra observed for the samples in our study. The Fe bands in the 0.3 to 1.2 µm region of these spectra are being correlated with the Mössbauer spectra of these samples. The OH and

H2O bands near 1.4, 1.9 and 2.1–2.5 µm are overtones and combinations of fundamental vibrations at longer wavelengths. We are integrating the band centers of these overtones and combination bands with the mid-IR fundamental absorptions measured in the reﬂectance, transmittance and emission spectra as in a previous study (BISHOP et al., Fig. 1 VNIR spectra of 2002). The Martian surface measured in the Meridiani and a few samples.

1 SETI Institute/NASA–ARC, 515 N. Whisman Road, Mountain View, CA 94035 USA ([email protected]) 2 Department of Geography, University of Winnipeg, 515 Portage Avenue, Winnipeg, R3B 2E9 Manitoba, Canada 3 Dept. of Earth and Environment, Mount Holyoke College, South Hadley, MA 01075 USA 4 Dept. of Geological Sciences, Brown University, Providence, RI 02912 USA 5 Planetary Science Institute, 1700 E. Fort Lowell, Suite 106, Tucson, AZ 85719 USA 6 Bayerisches Landesamt für Umwelt, Leopoldstr. 30, Postfach 389, D-95603 Marktredwitz, Germany 27 Abstracts Book Abstracts 28 3rd Mid-European Clay Conference – MECC 06 4 3 2 1 1200 at even not expand significantly purposes. forcomparison parallel Madridregiontested in have been LWAproduce the to in used currently ARL2) and (ARL1 and dwelling time (10 min). Additionally, two clay samples temperature(1150–1200 maximum the considering designed were cycles thermal Fouragents.expansiveorganic of volume low a of use the without and pel with both disc, rotary a in water were with letized compositions The batches. the of components (LWA) has been carried out using mining wastes as unique usually has higherillite contents. fraction silt The wastes.Alberche the kaolinite-richandin smectite-rich in the wastes from Jarama, Henares and Tajo, is fraction wastes may reach clay occasionally more than 15%. The the to classify silty-clays allow as andminor clayey butsilts, particles sand-size distributions size particle The systems. river Jarama north and Alberche the in absent is it while respectively, 45%, and 55% to up of values reach deposits. gravel Calcite in the wastes and from the Tajo and Henares sand rivers may washing by the produced of wastes compositions chemical and mineralogical the bedrocks in variation significant the a of causes rivers heterogeneity different by the eroded The quarries. different 37 from 142 of total a of out samples seven selected have we On the basis of their mineralogy and grain-size quarries. distributionsaggregate from generated wastes of applications process. extraction the or by left ponds voids in tailing filling accumulated fine-grained of are volume sludges huge These wastes. the of view in systems, fluvial especially Alberche is and Tajo,HenaresJarama, the along aggregates important fluvial quarrying by generation Spain central GARC region, (BLANCO Madrid the volumes in large materials waste produces of aggregates natural of Mining 5 CNR–ISTEC, Istituto di Scienza eTecnologiaCNR–ISTEC, Istituto diScienza deiMateriali Ceramici, Via Granarolo 64,48018Faenza, Italy Castilla–La Mancha, Avd. Camilo JoséCela, 3.13071,CiudadReal, Spain Instituto deTecnología Química yMedioambiental. UnidaddeMineralogía yGeoquímica Ambiental. Facultad deC.C. Químicas, Universidad de Geology, Katholieke Universiteit Leuven, Celestijnenlaan 200E,Heverlee, B-3001 Belgium Facultad deC.C.delMedioambiente, Universidad deCastilla–La Mancha,Avd. Carlos IIIs/n,45071,Toledo, ([email protected]) deCristalografíaDpto yMineralogía, Facultad deC.C.Geológicas, Universidad Complutense deMadrid, CiudadUniversitaria, 28040Madrid, Spain hswr spr famjrsuyo h ceramic the on study a major of part is work This Wastesfromsouth-Jarama, Henares Tajoand riversdo aggregates lightweight synthetic of production The Jan ELSEN Iv á n BLANCO GARC Production ofsynthetic lightweight aggregates (LWA) 3 , Magdalena RODAS, Magdalena Í e a. 20) Tepolmo waste of problem The 2005). al., et A ° C), heating rate (20–60 rate heating C), Í A 1,3 , Javier LUQUE ° C, and initial melting 1 from miningwastes , RudySWENNEN ° C 1 · , Jos min -1 é - ) F. BARRENECHEA N–N 073 UEE 14–, N–N 1744–3), UNE–EN 1744–1, UNE–EN 1097–3, UNE–EN 1097–6/AC, ac (UNE–EN standards Spanish compositions the to cording these of study The materials. LWAraw north- and Alberche Jaramariverwastes,characteristics show which best as the the to agent expansive organic of with aggregates of g 1 below density production The additives. expansive without densities low reach an auto-expansive can they because behaviour, show wastes These spheres. fired the of sity reduction above 1200 atdices lower temperatures, increasing process the of den in expansion higher show wastes rivernorth-Jarama and Alberche destabilizationThe wastes. rich carbonate fast using a by achieved is and conditions, these more under became difficult process firing the of control carbonates.The ofdecomposition thermal the during released CaO the of is observed at higher temperatures, effect due to the fluxing UNE–EN 1744–3 (2003): Parte 3: Preparación de eluatos por lixivación por eluatos de Preparación 3: Parte (2003): 1744–3 UNE–EN UNE–EN 1744–1(1999):Parte 1:Análisis químicos. de densidad la de Determinación 6: Parte (2003): 1097–6/AC UNE–EN UNE–EN 1097–3 (1999): Parte 3: Determinación de la densidad aparente & M. DONDI, C.J., SÁNCHEZ, M., RODAS, I., GARCÍA, BLANCO MEC/FULBRIGHT. to Ministerio de Educaci 2002 (CAM) and (MEC), 2003–01247 REN Projects: of support financial Acknowledgements: qualityhigh synthetic lightweight aggregates. of production the in used be can riversnorth-Jarama and Alberche from wastes clayey that show ARL2, and ARL1 and their comparison with the reference industrial samples 3 , Carlos J. S de áridos. absorción yla partículas de agua porosidady la 283–295. Jarama river deposits middle-course (Central Spain).– Applied from Clay Science, by-products28/1–4, pit gravel of application ceramic ALONSO AZCÁRATE, J. (2005): BTE 2000/0340 (MCYT). Á · cm 1 NCHEZ hsrsac a enudrae ihthe with undertaken been has research This , Jacinto AlonsoAZCARATE ó -3 n y Ciencia for the postdoctoral fellowship is possible by adding a low volumelow a adding by possible is References Spain ° C, and maintaining the integrity 4 and Michele DONDI andMichele Technological characterization and I. Blanco Garc

07M/0028/ í a thanks 2 , 5

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Physical properties and behaviour during leaching of synthetic aggregates made with polluted dredged sediments from Flanders, Belgium

Iván BLANCO GARCÍA1,2, Rudy SWENNEN2 and Jan ELSEN2

Dredging is a necessary tool in removing contaminated tion of the external layer on these spheres increases as the sediments from rivers, harbors, estuaries, etc. Annually, maximum ﬁring temperature increases, but is high enough more than 9.000,000 m3 of sediments are dredged from to avoid the expansion process, even at 1225°C. The addi- waterways in Flanders, north Belgium (OVAM, 2003), tion of the clay-rich component (BC) improves the den- and only about 6–7% of these underwater materials are sity of the synthetic aggregates in all the wastes, due to a considered as non contaminated (DE COOMAN et al., decrease in the sintering temperature, lowering the gas 2004). In the past, dredged sediments have been disposed release. A dense glassy layer covers these samples, and a along the shores of the waterways without precautions for better density reduction is attained by adding inorganic ex- contaminants eventually present. As a result, many areas pansive agents. Slow thermal cycles (20°C·min-1) get higher containing elevated metal contents in relation to historical densities in all the tested compositions, and good LWA are sediment disposal have been identiﬁed along waterways in obtained at 1225°C, with fast thermal cycles. Leaching tests

Flanders (CAPPUYNS & SWENNEN, 2005). Nowadays, (EN 1744–3) show a low mobility of Zn, Cu, and Pb after 3r sediments dredged from inland waterways are mostly being firing. The tests now being carried out on size-reduced ag- d Mid-European Clay Conference – MECC 06 land disposed in confined facilities, reducing progressively gregates (EN 12457–3, NEN 7371) will assist with predic- the available disposal capacity. Thus, the use of polluted tion to the long term release of heavy metals. dredged sediments as building materials is two fold: first, preserving the disposal capacity for a longer period, and Acknowledgements: The authors thank the company DREDGING second, transforming waste materials in useful resources. INTERNATIONAL, N.V. for providing the sediments. Mr. Blanco García thanks to Ministerio de Educación y Ciencia for the MEC/ This work deals with four polluted sediments (Zn: 600– FULBRIGHT postdoctoral fellowship. 1380 mg·kg-1; Cu: 65–152 mg·kg-1; Pb: 97–276 mg·kg-1; -1 Cd: 3–21 mg·kg ), dredged in the Flanders waterways, that References have been studied at laboratory scale as raw materials in CAPPUYNS, V. & SWENNEN, R. (2005): Kinetics of element release the production of synthetic aggregates. The sediments were during combined oxidation and pHstat leaching of anoxic river sedi- tested as unique components of the batches and in mix- ments.– Applied Geochemistry, 20, 1169–1179. tures (1:1) with clay (BC) traditionally used in the produc- DE COOMAN, W., VOS G., D’HONDT, P., VAN ERDEGHEM, M., tion of lightweight aggregates (LWA) in Flanders. These MEERS, B., VAN WAUWE, P., WUYTS S. & PEETERS B. (2004): compositions were pelletized with water in a rotary disc, Kwaliteit van oppervlaktewater.– In: VAN STEERTEGEM M. (ed.): MIRA–T 2004. Milieumaatschappij en natuurrapport Vlaanderen: both with and without the use of a low volume of organic thema’s. Vlaamse Milieumaatschappij, Aalst, België, 303–314. and inorganic expansive agents. Five thermal cycles were EN 12457–3: 2002: Characterisation of waste. Leaching. Compliance test designed considering the maximum temperature (1150– for leaching of granular waste materials and sludges. -1 1200–1225°C), heating rate (20–60°C·min ) and dwelling EN 1744–3: 2003: Tests for chemical properties of aggregates – Part 3: time (10 min). Additionally, three BC samples were tested Preparation of eluates by leaching of aggregates. in parallel for comparison purposes. NEN 7371: 2004: Leaching characteristics – Determination of the availability of inorganic components for leaching – Solid earthy and stony The high water absorption and bulk density of fired- ag materials. gregates, made exclusively of dredged sediments, show the OVAM (2003): Ontwerp uitvoeringsplan Bagger– en Ruimingsspecie. inefficiency to trap the gases generated during the thermal Openbare afvalstoffen–maatschappij voor het Vlaamse Gewest.– Be- process, whatever the expansive agent. The porosity reduc- leidsdocumenten afvalstoffen D/2003/5024/11, 2003. 206 p.�

1 Dpto de Cristalografía y Mineralogía, Facultad de C.C. Geológicas, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain ([email protected]) 2 Geology, Katholieke Universiteit Leuven, Celestijnenlaan 200E, B-3001 Heverlee, Belgium 29 Abstracts Book Abstracts 30 3rd Mid-European Clay Conference – MECC 06 1 BrF 200 with at ﬂuorinated day 1 vacuum under heated wereﬁrstly samplesusing a classic silicate line with Nickel bombs. The performed were oxygen on measurements isotope Stable removed. is water interlayer all practically heating hours each heating step 24 IR spectrum was measured. Only after ples were heated for 2, 4, 12 sam and 24 hours at 200 The standard. smectite CMS a STx–1 on done were 200 atsamples sorption and interlayer water were removed by heating the of Forsmectites. isotopicthe composition composition measurements ab isotopic the determine and analyses cal chemi additional make to order in separated were levels <0.2 The morillonite. OH montis smectite indicatethe that spectra IR the in bands the of positions The wt.%). (2–4 kaolinite and wt.%), clay minerals present Other in very wt.%. small amounts are: 94 illite (4–10 to up with dominates smectite, fraction, bulk mineralogy dominated by layer silicates. In the <2 transsylvanicus areeggs thought to belong to a hadrosaurid the remains, these on Based found. were remains skeletal embryonic/hatchlingdinosaurssiteswithnestingtogether 1994). JAMES, them, abovelayer, justconcretion of some & with Associate (MACK calcisols as classified be can moderately developed soils (RETALLACK, 2001). Paleosols of calcretes with thickness and lateral continuity indicating a level with calcareous concretions. There are several levels burrowsandrootsand vertical developed wellpresenceof red mud horizon with blocky structure characterised by the coarse sediment supply, of were site of pedogenesis. The soils starved show a areas, inter-channel The fluctuations. discharge with flow channelized unstable indicate which crosscutting and alternating sandstones and conglomerates, to stratification. parallel The channel show bodies laterally trough-cross with deposits sorted poorly grained, coarse representedmudstonemassiveis red m a by followed4 by and cross-stratified sandstones. The bottom of the sequence ofmassive redmudstones intercalated conglomerateswith basin, into (1985) At unconformities. local STILLA by separated by groups, divided sedimentary was Cretaceous late Ha the Within 3 2 Department ofGeology andGeophysics, Bucharest University,Department Bd. Bălcescu 1,Romania Geology,Institute forApplied BOKU Wien, Peter Jordan Strasse 70,A-1190 Wien, Austria Sciences, GeologyandPaleontology,Institute ofEarth Karl-Franzens University, Heinrichstrasse 26,A-8010 Graz, Austria ([email protected]) Maastrichtian from calcisols theHateg Carpathians: basin,South uta quarry,Tustea -a aaye so ta al aesl ape hv a have samples paleosol all that show analyses X-ray

the 10 m vertical escarpment comprises two levels two comprises escarpment vertical m 10 the ° Ana–Voica BOJAR (GRIGORESCU etal., 1994). C for ~24 hours. Preliminary heating tests heating Preliminary hours. ~24 for C ţ eg basin (SW South Carpathians) the the Carpathians) South (SW basin eg mineralogical andstableisotopic investigations situated at the northern border of the the of border northern the at situated 5 at 550 at µ rcinfo ieetpaleosol different from fraction m ° C for ~ 1 day.1 The ~ for C 1 , Franz OTTNER Telmatosaurus ° ° C and than and C C and after δ 18 O com O µ m 2 - - - - - , DanGRIGORESCU fa luilfndrn odn vns h ihcontent high The events. flooding duringfan alluvial anof coarse sequence is interpreted as deposited in a feeder zone border.The basin the to de close terrace, stable probablya on veloped most soils, developed strong to moderate the indicate levels calcrete the ofdistribution and for thickness favourable The material. bone and egg were of preservation conditions These soils. well drained suggest also traces root vertical penetrating deeply The conditions. alkaline oxidizing, under table water the above formed soils the that indicate texture micritic with inAuguststarted 2005. been have water rain the of composition isotopic the on 166 The continuousin device flow. vacuum one day at 200 under heated also were samples the measurements topic positions are around 19‰ (SMOW). For the hydrogen iso STILLA, A. (1985): Geologie de la region de Ha de region la de Geologie (1985): A. STILLA, isotope hydrogen and oxygen The (1970): S. EPSTEIN, & S.M. SAVIN, paleope tointroduction An past. the ofRETALLACK, Soils G.J.(2001): distri JAMES,C.W. & global G.H. MACK, the Paleoclimateand (1994): oxygen- and Deuterium TAYLOR,(1971): H.P.Jr.& J.R.LAWRENCE, SECLAMAN, D.B.,NORMAN, D.,WEISHAMPEL,GRIGORESCU, D., TAYLOR, 1971). LAWRENCE& 1970, EPSTEIN, (SAVINworkers& early by evidence in put also was water rain meteoric present ent meteoric water line. Equilibrium between smectite and pres local the with equilibrium in are smectites the that indicate data isotopic the factors, fractionation propriate ap Using site. this at present material volcanoclastic the of presence the favoredby was wt.%, 98 to up smectite, in At TuAt efiia 6 92 66, Geofizica, meridionales). (Carpathes nita 35 Acta Cosmochim. Geochim. minerals.– clay of geochemistry dology.– Blackwell 404p. Science, bution of J. paleosols.– Geol.,102,360–366. 35, Acta, 993–1003. Cosmochim. Geochim. waters.– meteoric to soils compared Quaternary in hydroxides and minerals Clay correlation: 18 andeggs babies. Cambridge University Press, 75 Dinosaur (eds.): J.R. K.F.HORNER, HIRSCH, & K., CARPENTER, Late Ha the from (1994): eggs V.dinosaur Maastrichtian TEODORESCU, & A. BALTRES, M., RUSU, M., ‰ – 42. (SMOW). Also for the Hateg basin, measurements basin, Hateg the for Also (SMOW). ş tea, the red the tea, – 197. 3 andZoltan colour and the presence of calcretes of presence the and colour ° References C, and than measured on a TC/EA – Anuarul Institutului de Geologie si Geologie Institutuluide Anuarul δ D values vary from 143 tofrom 143 valuesvary D CSIKI ţ eg Basin (Romania). Basin eg ţ eg – multipleburied, 3 Cioclovina – 87. – Pui – – 34, , In: Ba ------Abstracts Book

Solid-state NMR study of stability of “geopolymers” prepared from alkaline activated metakaoline

Jiri BRUS1, Martina URBANOVA1, David KOLOUSEK2 and Jana ANDERTOVA3

Geopolymers defined as amorphous aluminum-silicates it was found out that 27Al MAS NMR spectra are fairly in- originate by the reaction of metakaoline with sodium or sensitive to long-term hydrothermal treatment (only con- potassium water glass. During the reaction the geopolymer version of residual octahedral sites to tetrahedral ones was gel is formed, which “structure“ is partially reminiscent to recognised), while 29Si MAS NMR spectra provide signifi- zeolite one. Current trends in geopolymer chemistry are to cantly deeper insight to changes occurring at atomic level. develop geopolymers systems without adding water glass. For our inorganic systems broad 29Si MAS NMR signals The absence of water glass makes fabrication of geopoly- indicates wide range of Si environments among them Q4 mers significantly cheaper. The aim of our work was to- ex (3Al) units predominate. As a consequence hydrothermal amine the structure of such prepared materials and their treatment we observed changes in 29Si MAS NMR spectra subsequent transformations at laboratory and hydrother- which correspond to formation of structure units reflect- mal conditions. ing increase in Si/Al ratio. Up to some level of this ratio Contrary to generation of “right geopolymers“, the first mechanical strength increase, then steep decrease was step of our preparation was calcination of metakaoline to- observed. NMR spectra also clearly revealed that during 3r gether with the mixture of NaOH and KOH. Surprisingly the hydrothermal period the second generation of “geo- d Mid-European Clay Conference – MECC 06 the structure of the resulting products is quite comparable polymer“ was formed. This period is characterized by the with standard geopolymers as was nicely confirmed by sol- dissolution of the quartz and the phillipsite with the par- id-state 27Al and 29Si MAS NMR. Hydrothermal treatment ticipation of the amorphous phase. The presence of phil- and similar experiments are important for the understand- lipsite was detected in the hydrothermally altered compos- ing of long-term stability of metastable substations. ites whereas zeolite X (FAU) was found in the composites All the samples during treatment were subjected to spontaneously aging as follow X-ray powder diffraction. measurement of the compressive strengths, X-ray powder Acknowledgements: This work was supported by the Grant Agency diffraction and analysis 29Si and 27Al MAS NMR. of Czech Republic (project No. 103/03/0506) and will be supported At first 27Al and 29Si MAS NMR experiments confirmed by Czech Ministry of Education, Youth and Sports (research project that structure of metakaoline was significantly altered only No. MSM 2B06120). by calcinations with hydroxides at ca. 550°C. Subsequently

1 Institute of Macromolecular Chemistry, Academy of the Czech Republic, Heyrovskeho sq. 2, 162 06 Prague 6, Czech Republic ([email protected]) 2 Department of Solid State Chemistry, Institute of Chemical Technology, Technická 5, 166 28 Prague 6, Czech Republic 3 Department of Glass and Ceramics, Institute of Chemical Technology, Technická 5, 166 28 Prague 6, Czech Republic 31 Abstracts Book Abstracts 32 3rd Mid-European Clay Conference – MECC 06 charge densities. low or medium of surfaces the at reactions deaggregation gregatescharge high ofat the surfaces densities,the or dye eral dispersions included min the formation of higher-orderin R6G/clay ag reactions The place. take assembliesdye the of re-distribution andre-organization complex where systems. troscopies were used spec for the characterization of the studied fluorescence and Ultraviolet/visible properties. cal opti different distinctly by characterized were assemblies molecular dye The densities. charge high with specimens mineral clay of surfaces on formed wereH-aggregates der large-or The H-dimers. and J-aggregates and H- as such distribu dye’sassemblies, the molecular cation of formation the and dye tion the controlled charge The tested. was 6G, rhodamine dye, cationic adsorbed the of properties optical the montmorilloniteon substratea of chargelayer ( oriented thin films mate mineral ( dispersions R6G/clay studied: were rials hybrid of types Two fixation. ion Nano from cor montmorillonite using the standard of method Li prepared was charge modified systematically dye, rhodamine 6G(R6G). tem mineral clay organic of cations adsorbed a of properties optical for plate of parameters of importance work confirm presented of results The papers. numerous in lished various pub and with studied been have dyes compounds solid ofinorganic rhodamine interactions The memory media. in and lasers solid devices, and sensors optical as such applications, various for candidates potential are matrix, inorganicsolid an in incorporatedorganicdyes of Hybrid nanocomposite materials, which contain molecules 2 1 NationalInstitute forMaterials Science, 1–1,Tsukuba Namiki Ibaraki 305–0044,Japan Institute ofInorganic Chemistry, Slovak Academy ofSciences, Bratislava, SK-84536, Slovak Republic ([email protected]) sre o rdcdcag mnmrloie wt a with montmorillonites reduced-charge of series A h y/iiaedsesosaednmcsystems, dynamic are dispersions dye/silicate The Clay mineral formation template-controlled ofmolecular

BUJD Á K Juraj BUJD ta. 03.Teeeto the of effect et al., 2003). The BUJD assemblies ofrhodamine6G Á K Á et al., 2004) and 2004) al., et K 1 , NobuoIYI + cat ------2 andAdriana CZ of dye the cations. arrangement heterogeneous the sensitiveenough to reflect not was plane of the clay mineral surface. X-ray diffraction the to respect with angleslow at cationsinclined were dye dichroism.stronglyisolatedpositiveAdsorbed a as served ob was which fashion, perpendicular nearly in oriented wavelengthswerelowat absorbinglight H-aggregatesand forming cations ily resolvable by the polarized spectra. The the in eas cations was which host, R6G mineral clay the of of spaces interlayer species several were There films. the in cationsdye orientationof molecular the of acterization byterized emission at broad range of wavelengths. the reaction system with the highest charge silicate and charac the gatesluminescentexhibitedin mainlyproperties weak H-aggre the Surprisingly,monomers. also of form the in adsorbed were which cations, dye adsorbed of properties BUJD BUJD layer the ize charge distribution. character to mineralogistsclay for useful be can minerals clay and dyes organic between interaction Moreover, the to tool a as achieve desired optical properties of adsorbed organic used dye. be can parameters optimal with plate tem mineral clay a of Choice assemblies. molecular dye of formation the in role key a playstemplate mineral clay Polarized UV–Vis spectroscopy was used for the char the for UV–VisPolarized used was spectroscopy luminescent the revealed spectroscopy Fluorescence icate dispersions.– Journal of PhysicalB, 108,4470–4477. Chemistry dye molecular aggregates, and reactions in rhodamine 6G/layered sil Chemistry Physical charge.– layer the Physics,Chemical 5,4680–4685. of effect The silicates: ered lay of films the cationsin arrangement6G Molecular rhodamine of a of charge layer the of distribution the summary, In Á Á K, J., IYI, N. & SASAI, R. ( J.,K, KANEKO,N., IYI, Y., CZ Í MEROV References 2004): Spectral properties, formation of Á 1 Í MEROV Á , A. & SASAIR. & A. , (2003): ------Abstracts Book

Spectroscopic study of interaction of porphyrin dyes with layered silicates

Alexander ČEKLOVSKÝ and Juraj BUJDÁK

Hybrid materials lie at the interface of the organic and We found out that adsorption of studied porphyrin dyes inorganic realms. These materials offer exceptional op- leads to the significant changes of their optical properties. portunities not only to combine the important properties The changes in absorption spectra in a visible spectral from both the fields but also to create entirely new com- region partially reflect the layer charge characteristics of positions with truly unique properties (YUI & TAKAGI, layered silicate templates. The position of a main Soret 2003). Generally, dye molecules tend to aggregate on the band is generally shifted to lower energies, even more clay surface or in the interlayer spaces. The layer charge of significant changes are observed in the spectral range of Q- layered silicates controls the molecular aggregation of the bands. Judging from these data, spectral analysis indicates dyes of various structural types (BUJDÁK & KOMADEL, the formation of J-aggregates of the dye on the silicate 1997; BUJDÁK & IYI, 2002). surfaces, characterized with head-to-tail intermolecular The objective of this study is to investigate the association. interaction of four representative cationic porphyrin dyes Formation of non-luminescent “pure” H-aggregates was

with layered silicates (layered silicate/porphyrin systems, not conﬁrmed in any reaction systems. This fact conﬁrms 3r

LSP). As layered silicate matrices, the series of reduced- the systems based on layered silicate/porphyrin composites d Mid-European Clay Conference – MECC 06 charge montmorillonites was used. These were prepared as perspective materials for photochemical applications. from one parent material (Nanocore) by Li+-saturation and thermal treatment. The effect of the layer charge is References investigated in detail. Molecular aggregation is expected BUJDÁK, J. & IYI, N. (2002): Visible spectroscopy of cationic dyes in to be suppressed due to high electrostatic repulsion forces dispersions with reduced-charge montmorillonites.– Clays and Clay between the dye cations. This paper studies in detail if the Minerals, 50, 446–454. molecular aggregation is sufficiently suppressed regardless BUJDÁK, J. & KOMADEL, P. (1997): Interaction of methylene blue with reduced charge montmorillonite.– Journal of Physical Chemistry B., the properties of silicate template. The study is based on the 101, 9065–9068. investigations of spectral characteristics of layered silicate/ YUI, T. & TAKAGI, K. (2003): Photochemistry of laminate type organic/ porphyrine systems (LSP) using UV–VIS and fluorescence inorganic hybrid compounds.– Journal of the Society of Photograph- spectroscopy. ic Science and Technology Japan, 66, 326–340.

Department of Hydrosilicates, Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, Slovakia ([email protected]) 33 Abstracts Book Abstracts 34 3rd Mid-European Clay Conference – MECC 06 2 1 af different has zeolite towardswhich forms ionic several in chromium and zinc of appearance of because problem complex a is solutionswater in ions metal with contact in & (RO ions metal and zeolite between processes change ex ion on influence great had parametersmentionedthat ofions lectivity investigated.removal been has It provedis se and capacity the on ligand) ofconcentration and type librium, concentration and pH value of metal ions solution, andric chemical treatment of natural zeolite, time of equi UV/VIS and AAS. by determined are species density.Metaland specific area surface of measurements analysis, thermal differential sis, analy structural diffraction X-rayincludes zeolite natural GROGOROPOULOU,characterizationof Detailed 2003). cations(CERJAN-STEFANOVI moval from water solution, what is shown in several publi ions and they found wide range of application metal for metal ions re the towards affinity show zeolitesNatural ters. compounds from galvanization and dye industry wastewa and chromium) (zinc, ions metal of moval re of process the in of natu mine Jesenje Donje from zeolite of application ral possibilities investigates study This 4 3 Faculty ofTextile Technology, ofZagreb, University Prilaz barunaF Vodotehnika d.d. Koturaška 49,Zagreb, Croatia Faculty of Chemical Engineeringand Technology, ofZagreb, University Marulićev trg 20,Zagreb, Croatia ([email protected]) National Institute of Chemistry, Hajdrihova 19,Ljubljana,Slovenia CERJAN-STEFANOVI h nuneo aua elt ramn (granulomet treatment zeolite of natural influence The Š ec CERJAN-STEFANOVI tefica Metal complex exchange innatural zeolites Ć 02.Tebhvo fzeolite of behavior The 2002). , Ć et al., 1996; VASSILIS1996; al., et Mario Mario

Ć their complex their Š 1 ILJEG , Natalija ZABUKOVEC-LOGAR 3 ilipovića 30,Zagreb and Branka andBranka VOJNOVI Ž I & Ć ------

PANSINI, M., COLELLA, C. PAPI KOPRIVANAC, N., CERJAN basis the forbe Paterson and Langmuir isotherm. will results investigated.Obtained be will of zeolite and zinc processes ion exchange on of ligand influence 1997). The ligand in metal on of ligand depending curtail, be influence The 2001). metal al., et (PANSINI finity VASSILIS,J.H. RO Ž 149. zeolite. using exchange ion by water from and Pigments, 35, 57 anddyeing properties ofcopper 2:2 complex azomethine dye. PARA 281 zeolites. natural by exchange ion Metal hnei xdbd fclinoptilolite.61, 273 of beds fixed in change al. remov ammonium for montmorillonite-richclinoptiloliteandtuffs I Ć – – , M. – Croat. Chem.Acta, 75,255 – , Croatia complex compounds on the metal ion removal can removalion metal the complexcompoundson - 289. elt budn srnt (ORVNC t al., (KOPRIVANAC et strength bounding zeolite STEFANOVI Ć – & -OSTERMAN, 279. CERJAN-STEFANOVI & GROGOROPOULOU,P. Ć Ć , – 4 Ć 58. 2 Š Đ , Karmen MARGETA, Karmen ., S, HERGOLD-BRUNDI S., , References & . Ć DE GENNARO, S. & URKOVI

GRABARI – 269. Ć , – Š ligand, metal ligand, . (2002) Ć – , (2003): Modeling of ion ex ion of Modeling (2003): Micropor. Mesopor. Mater.,Mesopor.Micropor. – Ć L . Z. , ra. hm At, 69/1, Acta, Chem. Croat. – & Desalination, 83, 145 83, Desalination, : Evaluation of Croatian

(2001): Metal removal (97: Constitution (1997): , FILIPAN, Ć A, AL A., NAGL, A., , – 1 zeolite and zeolite ,

. (1996): T. – Dyes Dyes – - - Abstracts Book

Energy transfer between cations of laser dyes in dispersions of reduced charge montmorillonites

Adriana CZÍMEROVÁ1, Juraj BUJDÁK1 and Nobuo IYI2

Fluorescence resonance energy transfer (FRET) is a phe- parent Li+-montmorillonite. High charge density on the nomenon of energy transmission between an energy do- surface of clay mineral induced formation of H-aggregates nor and acceptor molecules. The occurrence of the energy which quenched luminescence. The FRET was detected for transfer is limited by the properties of interacting compo- the reaction systems with lower charge montmorillonite nents and depends on intermolecular distances and spatial templates, prepared by Li+-fixation at 100, 110 and 120°C. molecular arrangement. FRET requires a spectral overlap The FRET was accompanied with a significant reduction of between emission and excitation spectra of energy donor the luminescence from energy donor, R3B cations, which and acceptor components, respectively (LAKOWICZ, initially received the energy from electromagnetic radia- 1983). The energy transfer does not normally proceed in tion and played the role of light harvesting antennas in dilute solutions due to large intermolecular distances, but this system. After excitation of R3B cations, the energy was may occur after the concentration of interacting molecules transferred to neighbouring Ox4 cations (energy accep- at interfaces. Smectites represent appropriate templates tors), which was followed by significantly enhanced fluo- to be used to concentrate cationic dyes on their surfaces. rescence from Ox4 cations. Reduction and increase of the

Moreover, the layer charge of smectites sensitively con- luminescence from R3B and Ox4, respectively, indicated 3r trols the cation distribution of dyes and formation of vari- the efficiency of an energy transfer process. The efficiency d Mid-European Clay Conference – MECC 06 ous types of supramolecular assemblies (BUJDÁK, 2006), was closely related to the layer charge and increased with which may be significant for the processes of FRET. the charge reduction achieving optimal values for the sys- + The objective of our work was to study the energy tem with a clay mineral template prepared by Li -fixation transfer between two cationic laser dyes, rhodamine 3B at 120°C. Further decrease of the layer charge resulted in (R3B) and oxazine 4 (Ox4), in dispersions of reduced lowering of the energy transfer efficiency. This could be in- charge montmorillonites (RCMs). The series of RCMs terpreted in terms of increasing intermolecular distances were prepared using a standard method of Li+-fixation between cations representing the energy donors and accep- (KOMADEL et al., 2005) in Nanocore montmorillonite tors. A substantial reduction of the charge (samples pre- at 100–300°C. The charge reduction was expressed as the pared at 140– 300°C) led to absence of the FRET. Probably, decrease of values of cation exchange capacity (CEC). The the adsorption sites for these cases were so far apart, that CEC, as well as the layer charge gradually decreased with large intermolecular distances did not allow the resonance increasing temperature of RCMs’ preparation. Li+-fixation between R3B and Ox4 molecules. Furthermore, lower ex- led in some cases (treatment at >130°C) to the loss of ma- pandability of clay minerals might have led to entrapment terial expandability due to the formation of non-swelling of a part of dye molecules isolating them from potential interlayer spaces. neighbours, thus reducing the yields of FRET. The FRET was investigated by means of fluorescence In summary, clay minerals can act as templates in ener- spectroscopy. The efficiency of FRET in studied system gy transfer processes. The significant result of this work is was found to be very sensitive to the layer charge and that the parameters of clay mineral templates, such as layer swelling of smectite. Dye species, which were formed on charge density and distribution or material expandability, montmorillonite surface, included isolated dye cations and play a crucial role for the overall efficiency of the process. molecular assemblies, such as H- and J-aggregates. The molecular assemblies were identified using ultraviolet/vis- References ible spectroscopy. H-aggregates, characterized with a sand- BUJDÁK, J. (2006): Effect of the layer charge of clay minerals on optical wich-type intermolecular association, are non-fluorescent. properties of organic dyes. A review.– Applied Clay Science, submitted. Moreover, they significantly quench luminescence of other KOMADEL, P., MADEJOVÁ, J. & BUJDÁK, J. (2005): Preparation and species and reduce FRET yields. On the other hand, J-ag- properties of reduced-charge smectites. A review.– Clays and Clay gregates of a head-to-tail intermolecular association are lu- Minerals, 53, 313–334. minescent. Fluorescence spectroscopy confirmed absence LAKOWICZ, J.R. (1983): Principles of Fluorescence Spectroscopy.– Ple- of energy transfer from R3B to Ox4 in dispersions with num Press, New York, 698 p.

1 Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 845 36, Bratislava, Slovakia ([email protected]) 2 Advanced Materials Laboratory, National Institute for Materials Science, 1–1 Namiki, Tsukuba, Ibaraki, 305–0044, Japan 35 Abstracts Book Abstracts 36 3rd Mid-European Clay Conference – MECC 06 conites and ferriillites satisfy experimental data obtained data experimental satisfy ferriillites and conites glau celadonites, for values these to according simulated the of Feheterogeneity local ofthe of dependence the including tion al et DRITS under study. mineral interpretation ofthe peculiarity spectrum andthe S components, blet CD reconstruction satisfying both the areas under the dou arrangements variouslocal around Fe on distribution (CD) characterized by w certain dou j bysimulationsolved be two-dimensionalofcanblets cati the of structure” “fine the determining of problem ∆ probabilities,w ments (3Fe ∆ splittings, quadrupole of range small a with blets presented as superpositions of individual quadrupole dou be can resolution, spectral by limited is which splittings,of number their with doublets quadrupole fitted the Therefore,sheets. environmentsoctahedral cation in local nuclei Fe sponsible for the variety of EFGs affecting approach our of idea principal al (DAINYAKet ago Wedevelopingbegan moresuchmodels decades two than short-range the to order methods cation ic in distribution. usingmodels which account for spectra the sensitivity Mössbauer of the spectroscop their refine to possibility unique tahedral dioc 2:1 of peculiarities structural and Crystal-chemical Geological Institute, RussianAcademy per., ofSciences, 7Pyzhevsky 119017,Moscow, Russia([email protected]) i i values to this or that local arrangement is known, the the known, is arrangement local that or this to values arrangecation local ofone nucleiin Fecorresponds to h sineto the of assignment The ∆ i pred trans A new approach to theinterpretation ofFe 3+ vle scnre ytefc htteCDs the that fact the by confirmed is values . , 3Al, 2AlFe (1997). It is provided by the empirical equa empirical the by provided is It (1997). -vacant Fe-rich phyllosilicates provide the the provide phyllosilicates Fe-rich -vacant i . When the quantitative assignment of the the ofquantitative assignment the When . doublets in Mössbauer spectra of dioctahedral ofdioctahedral doublets inMössbauerspectra j , and , . , 2004, and references therein). The therein). references and 2004, , 3+ ∆ ∆ , MgAlFe j i values is regarded both as the the as both regarded is values values for Fe 3+ evrnet h reliability environment. The trans is that the main factor re factor main the that is ∆ 2+ i pred , etc. 3+ on charge and size andcharge on andFe -vacant micaceous minerals 3+ ) with occurrence was reported by 2+ i values for hnthe Then . Lidia G.DAINYAK ∆ is their i ∆ . Each Each . j , the the , ------raig uduoe pitn ws on t b te same the be to found was splitting quadrupole creasing derived. individual the correlations, these on Based probabilities. occurrence Fearrangementsaroundcation local of sition Fe between correlations display leucophyllites and lites of collection a representative trans for CDs resulting The ture. tion of Fe interpreta the time, first the for provides, reconstruction CD two-dimensional for program the of version new the analysis (DRITS etal chemical and spectroscopies IR and EXAFS by DRITS, V.A., DAINYAK, F., L.G., MULLER, BESSON, G. & MANCEAU, Computer (2004): H. LINDGREEN, & V.A. DRITS, L.G., DAINYAK, meansal for controlling CDreconstruction. the with the new CD simulation program provide an addition at Fe Fe the Fe for both 2+ h re flclcto ragmnsi em ofin in terms arrangements cation local of order The the Combinationof spectroscopies.– Clay Minerals, 32,153–179. EXAFS and Mössbauer infrared, by determined Fe-illites and nites glauco celadonites, in distribution cation Isomorphous (1997): A. Mineral dioctahedral in components Mössbauer simulation of cationoctahedral distribution and interpretation of the of set The fitdt h orsodn pcr n aincompo cation and spectra corresponding the to fitted 2+ -vacant dioctahedral celadonites, glauconites, ferriil glauconites, celadonites, dioctahedral -vacant site. 2+ quadrupole splitting on the structural distortion structural the on splitting quadrupole 2+ . , 16,451–468. quadrupole doublets in terms of the local struc ∆ 3+ . i and Fe and tent , 1997). ∆ i o Fe for tent for Fe 2+ and implies a direct dependence of dependence direct a implies and 2+ References 2+ referred as “tentative” have been been “tentative” have as referred 2+ ∆ combined with i pred quadrupole values for Fe for values trans

-vacant micas.– Eur.J.micas.– -vacant ∆ 3+ i pred doublets with doublets 2+ for Fe with their their with

3+ ∆ and j of ------Abstracts Book

Inﬂuence of controlled mechanical deformation on structural, thermal and technological properties of commercial talc

Francesco DELLISANTI, Vanna MINGUZZI and Giovanni VALDRÈ

Layer silicates used in industrial applications generally un- The structural disorder induced by the mechanical dergo a grinding process which besides refining the particle treatment produced a generalized anticipation of about size can also induce significant changes in structural and one hundred degrees of the maximum temperature of de- physical properties which, in turn can affect the techno- hydroxylation of talc. Instead of the classical temperature logical application of the material. Because during grind- of about 930°C we observed the dehydroxylation at 840°C ing various parameters (temperature, pressure, mechanical for talc deformed for 20 hours. In addition, the dehydroxy- energy, etc.) can influence the structural modifications of lation occurs in two stages probably due to the presence of talc, mechanical deformation was performed in controlled different size and crystallinity of particles of talc or because environmental condition. Mechanical treatment, which some amounts of undeffective talc were still present. Fur- involves simultaneous compression and shear, was applied thermore, it was noted that the release of structural water to commercial talc through planetary ball milling by a spe- in deformed samples starts already at temperature lower cifically built apparatus working in controlled thermody- than 300°C in a continuous monotonic way as a function namic conditions, as already successfully applied to oth- of treatment time. The overall loss of OH at lower tempera- 3r

ers layer silicates (DELLISANTI & VALDRÈ, 2005). XRD, ture range progressively increases. Finally, the deformed d Mid-European Clay Conference – MECC 06 FT–IR, DTA–TG and BET analyses were performed for material is more thermo-reactive in respect to the untreat- the characterization of the material. Commercial talc (talc ed one, in fact the recrystallization of talc in enstatite is content higher than 95%) was mechanically treated for 1, 5, anticipated at temperature of about 850°C instead of the 10 and 20 hours at room temperature in vacuum. classical recrystallization at about 1000°C. As a non-linear function of the treatment time a pro- In conclusion, we reported that mechanical deforma- gressive reduction of structural order related to crystallite tion conducted in controlled conditions leads to a different size decrease and to an increase of both lattice deffects and grade of modification of structural, physical and thermal microstrain was observed. In particular, it is to be noted properties of talc. In particular, for short treatment times that mechanical treatment causes delamination for short delamination along ab plane was observed, followed from times (up to 1 hour), whereas a destabilization of all struc- maximum changes in the structure of talc after 5 hours and ture occurs for longer times. However, degradation of talc finally the degradation increases, but in a less relevant way, was not followed by amorphization of the mineral and also for longer treatment times. Further investigations involving after 20 hours of treatment the talc structure was main- particle size distribution, colour (measurements according tained. Initial stages (up to 5 hours of treatment) were also to the CIELAB system) and rheological properties are in characterized by increase of specific surface favouring wa- progress to evaluate if the different structural changes of ter absorption, whereas for longer times a re-aggregation commercial talc could be exploited in specific technologi- of material by a cold welding mechanism occurred. cal applications. Infra-red data showed that deformation mostly affects the Mg–OH bonds within octahedral layer leading to a References structural destabilization in the overall TOT structure, even CHRISTIDIS, G., DELLISANTI, F., VALDRÈ, G. & MAKRI, P. (2005): though lesser modifications were observed in the bands Structural modifications of smectites mechanically deformed under controlled conditions.– Clay Minerals, 40, 511–522. relative to the Si–O–Mg and Si–O bond. The destruction DELLISANTI, F. & VALDRÈ, G. (2005): Study of structural properties of of octahedra occupied by Mg could induce a variation of ion treated and mechanically deformed commercial bentonite.– Ap- layer charge and charge distribution similarly to that ob- plied Clay Science, 28, 233–244. served for Mg-rich montmorillonites by CHRISTIDIS et al. (2005), however specific measurements were not at the moment performed.

Department of Earth and Geo-Environmental Sciences, University of Bologna, Piazza Porta S. Donato 1, I-40126 Bologna, Italy ([email protected]) 37 Abstracts Book Abstracts 38 3rd Mid-European Clay Conference – MECC 06 5 4 3 2 1 extra-Alpine region as well as in the Tethyan taken basin is either be the in metallogenesis largely Alpine the continuum,whereas a as may metallogenesis Variscan The lotect. metal Alpine the into incorporated and metallogenesis Alpine during re-activated was metallotect Variscan the elements tointroduced be from sources. subcrustal Part of genesis”, when for a ofperiod time the system was open for successor shows all the hallmarks of an “ensimatic metallo moreorlessclosed-system conditions, Alpine whereasthe “ensialicmetallogenesis”,an as under denominated acting predominantlywith granitophileiselements Alps the side listthe of raw materials even by world standards. in up high rank to Europe Central render which modities com non-metallic rangeof wide a and salt coal, mainly is Poland,it in deposits metal base the Excludingstandards. world by deposit termed be longer no today can them of many although world, the in elsewhere deposits similar of origin the of understanding the to contributed cantly signifi have them Manyof (France). Baux Les (Slovakia), J ny), Kupferschiefer (Germany, Poland), Bleiberg (Austria), (Germa Rammelsberg e.g. earth, on depositswell-known most the of some host which units metallo-tectonic pine VariscanItaly, the between Al boundary andcoversit the northern to Denmark southern from and Russia western to France eastern from extends consideration under area The resources. energy and non-metallic of deposition and mineralization ore of Ma 500 than more of on yearsand mining 2000 than more on back looks Europe Central 7 6 IHS Energy, Perly–Geneva, Switzerland Sciences, ofModenaandReggio University Emilia,Modena,Italia ofEarth Department ofZagreb,University Faculty ofMineralogy andPetrography, ofScience, Department Zagreb, Croatia ([email protected]) Faculty of Mining, Ecology, Process Control and Geotechnologies attheTechnical ofKošice, University Slovakia Geological ofSlovak Survey Republic, Košice, Slovakia Geosciences ofApplied andGeophysics, ofLeoben, University Department Leoben, Austria Federal Institute forGeosciences andNatural Resources, Hannover, Germany á hmv Ceh eulc, dia Soei) Kremnica (Slovenia), Idrija Republic), (Czech chymov h aicnmtloeei nCnrlErp out Europe Central in metallogenesis Variscan The The originofmineral andenergy resources ofCentral Europe Ladislav A.PALINKA Harald G. DILL (accompanied by metallogenicmap1:2.500,000) Walter PROCHASKA 1 , Reinhard SACHSENHOFER Didier ARBOUILLE Š 5 , SibilaBOROJEVI 2 , Giorgio GARUTI 7 ------and Markus SCHULZ andMarkus Ć Š mum spreading in the Alpine Tethys during the mid-Juras maxi of period the with coincides mineralization related unconformity- of epochs Alpine early and late the tween be limit and hypogene mineralizations are associated. The geomorphological terms, peneplains with which supergene in orunconformities, of set a offormation the in resulted early Alpine and Subhercynian/Laramide/late Alpine uplift Variscan/ late the Variscan and Alpine metallogenesis. The during developed deposits collision-/granite-related and thrustbound deposits stratabound, of of sequence types A concerned. the are as far as different much very not are oce an of anic Penninic, inthe crust Meliata and Vardar formation zones. the by affected directly or indirectly terials wereterials shown on amap 1:2.500,000. on scale the ma raw constructionexcluding deposits, importantmost The Recent. the to Proterozoic late the from span time a andItaly northern to Denmark southern from andRussia western to France eastern from area an covering Europe as well as energy resources has been performed for Central Paleozoic.the during started already has trapping hydrocarbon craton Variscan the of edge eastern the At Cenozoic. and Meso- the along all trapped were hydrocarbons In Europe Central off. start to going is cycle new the a e.g., where Graben along, Rhein Cenozoic the during occurred type this of processes far-reaching most the cycles, metallogenetic Alpine andVariscan the of periods various during zones fault deep-seated along triggered wasRe-mobilization sic. O 2 Š h aicnadApn ealgntcsuccessions metallogenetic Alpine and Variscan The lsicto fnnmtli n ealcdeposits metallic and non-metallic of classification A , Pavol GRECULA TARI 6 , Federica ZACCARINI Ć 5 , SabinaSTRMI 7 3 , Tibor SASV Ć

PALINKA 2 ,

Á RI Š 4 , 5 ,

- - - - - Abstracts Book

Mineralogical transformations during ﬁring of some Plio–Quaternary clays from NE Slovenia

Meta DOBNIKAR1, Michele DONDI2, Breda MIRTIČ1, Duška ROKAVEC3 and Chiara ZANELLI2

Natural clayey raw materials differ in mineral and chemical tially for thin walled hollow bricks as we can predict from composition as well as in granulometric distribution and WINKLER (1954) diagram as well. therefore show different drying and firing properties that Samples were milled and homogenized, extruded, dried are of decisive importance for the quality of the end prod- and fired at different temperatures from 800°C to 1100°C, ucts (BAULUZ et al., 2003; DONDI, 1999). Mineral trans- with same soaking time and slow cooling. formations as well as formation of liquid phase in the firing Mineral composition of raw material (bulk and orient- process depend on raw material characteristics and can be ed <2 µm sample) and fired products as well as the amor- influenced by heating velocity and soaking time. phous phase content were determined by means of X-ray With the aim of studying the mineral changes occur- powder diffraction. Polished thin sections were prepared ring during firing of clays and ceramic bodies with differ- for mineralogical and textural analysis. The transforma- ent mineral composition and granulometry, composite tion temperatures of raw material minerals during firing samples of Plio–Quaternary clays from secondary deposit and the temperature of melting were determined. on Pannonian basin margin hills, NE Slovenia, were ana- 3r lyzed for their mineral and granulometric composition and References d Mid-European Clay Conference – MECC 06 fired at different temperature stages. BAULUZ, B., MAYAYO, M.J., FERNANDEZ-NIETO, C., CULTRONE, These clays are of illite–chlorite composition with dif- G. & GONZALES LOPEZ, J.M. (2003): Assesment of technological ferent smectite content. They are of intermediate plasticity properties of calcareous and non-calcareous clays used for the brick- with high quartz content. Feldspars (both K-feldspar and making industry of Zaragoza.– Applied Clay Science, 25, 121–126. plagioclase) are present in all samples, while carbonates DONDI, M. (1999): Clay materials for ceramic tiles from Sassuolo Dis- trict (Northern Apennines, Italy). Geology, composition and techno- (calcite and dolomite) occur in some samples as well. The logical properties.– Applied Clay Science, 15, 337–366. less then 2 µm particle size fraction varies in the 35–53% WINKLER, H.G.F. (1954): Bedeutung der Korngrössen-verteilung und range. According to particle size distribution, these raw des Mineral-bestandes von Tonen für die Herstellung grobkerami- materials belong to silty clay or clayey silt, and could be ap- scher Erzeugnisse.– Ber. DKG, 31, 337–343. propriate for roofing tiles and lightweight blocks and par-

1 University of Ljubljana, FNSE, Dpt. of Geology, Aškerčeva 12, 1000 Ljubljana, Slovenia ([email protected]) 2 ISTEC CNR, Via Granarolo 64, 48018 Faenza, Italy 3 Geological Survey of Slovenia, Dimičeva 14, 1000 Ljubljana, Slovenia 39 Abstracts Book Abstracts 40 3rd Mid-European Clay Conference – MECC 06 expressed as apparent chargeabilities of the medium. For medium. the of chargeabilitiesapparent as been expressed have data Measured used. was method IP domain time The spacing. electrode unit m 10 and array electrode terrain and Velika Jamni Velika in out Jamni set Manojlovi was was profile second the profile and Ogulin, near first the of Location profiles. two on out carried were measurements IP and Resistivity zones with clay. fractured from water with zones fractured distinguish to show IP anomalies and therefore it is theoretically possible can Clays zones.carbonate fractured in clay of presence a to due occur can resistivity of decrease com Similar rock. pact the than resistivities lower significantly showing are that zones fractured and faulted in found be usually can logical explorations in karst terrains. In such terrains water hydrogeo in interesting very be can Method method. IP using zones clay of discovering of possibility a Because is there that, 1997). (PARASNIS, potentials diffusion of up polarisa a membrane tion, as which is probably due to ionic exchanges and termed setting- been has effect This fects. ef IP strong anomaly show also can sediments clay ores, sulphide Besides exploration. ores sulphide dissipated in applied often been has method (IP) polarisation Induced Department ofGeophysical Exploration Surveying, Faculty and Mine Department of Mining, GeologyandPetroleum Engineering, ofZagreb, University Pierottijeva 6, 10000Zagreb, Croatia ([email protected]) h esrmnswr efre sn Wenner using performed were measurements The č ka near Zagreb. Manojlovi Resistivity andIPmeasurementsResistivity Application ofIPmethodfor discovering clay zones Introduction č Snje ka inaluvial terrain. ž ana DOMINKOVI ć vrelo is situated in karst in carbonate terrains ć Ć vrelo ALAVANJA - - - - a cnldd ht h fatrd oe wr fildwith filled were zones fractured the itthat concluded therefore was and profile of part this in increased not were chargeability of with values filled the However, clay. be with or may water zone fractured This lowzone. fractured of were there (200 profile resistivities resistivity of part middle the In (0 Manojlovi chargeabilityface distribution. subsur define to modelling inverse using chargeabilities had current the after ms 150 turned of.been to 100 interval, time first the during measured was Chargeability s. 2 was time on rent measurementeach werecycles and cur the threeused full AANS DS (97: rnils f ple Gohsc. Chapman Geophysics.– Applied of Principles (1997): D.S. PARASNIS, of and IPmethod resistivity method. combinedclayusingdistinguishedfromzonesapplication be can water with zones that indicate examples two these on results Measurement sediments. clay of presence low the of zones indicate with and location resistivities this match in resistivity on profile generally 50 anomalies than These (more ms). discovered were chargeability of values Jamni Velika the On water. – 5 ms), and there were no IP anomalies on this profile. this on anomalies IP no were there and ms), 5 Apparent chargeabilities were transformed into true true into transformed were chargeabilities Apparent and Hall, New York, 429p. i.1 nepee Ppol eiaJmik ihtomain two with Jamnička Velika Fig. 1Interpreted IPprofile andJasnaORE anomalies indicating clay zones. ć vrelo profileshowedlowvaluesofchargeabilities – 500 References Ω Š ) ht niae te presence the indicated that m) Results KOVI č a rfie(i.1 eyhigh very 1) (Fig. profile ka Ć

- - Abstracts Book

Mechanism of As sorption on Fe-treated clays

Barbora DOUŠOVÁ1, Tomáš GRYGAR2, Alexandr MARTAUS1, David KOLOUŠEK1, Lucie FUITOVÁ1 and Vladimir MACHOVIČ3

Adsorption of arsenic from aqueous environment on clay tetrahedrals to available Fe3+ particles (ion-exchangable or surfaces becomes more and more important for economic ferrihydrite) forming the stable inner-sphere surface com- reasons. Most of the considered natural aluminosilicates plexes (SHERMAN & RANDALL, 2003). The adsorption belong to low-cost and environmentally acceptable materi- of AsIII oxyanions, ran in a different manner; in the case of als. all metakaoline sorbents did not change the initial valence Two methods using FeII and FeIII salts were applied during the sorption process and were bound in trivalent forms. The sorption of AsIII on FeII-treated bentonite gave to the pre-treatment of natural clay minerals to improve III their sorption efficiency to AsV and AsIII species. Different the same results; the Fe -treated bentonite was able to bind types of clays, natural kaoline from the Merkur quarry, As only in a pentavalent form, which considered the oxidation of arsenites to arsenates during the sorption process. Czech Republic, calcined at 550°C, and a raw benton- The final oxidation state of adsorbed arsenites was prob- ite from mineral deposit in Hajek, Czech Republic, were ably connected to the character of available Fe3+ particles used. In the first process the initial material was exposed II . on the sorbent surface, steric effect and sorption kinetics; to concentrated solution of Fe (0.6 M FeSO 7H O) for 3+ II 4 2 small, single Fe particles (resulted from Fe -treatment) 3r

24 hours (BONNIN, 2000). In the second process the d Mid-European Clay Conference – MECC 06 appeared to be more suitable as arsenites binders keeping sorbents were treated with partly hydrolyzed FeIII (0.025 the trivalent state. The larger FeOOH aggregates (resulted M Fe(NO3)3·9H2O; 0.05 M NaOH) overnight. The results III II from Fe -treatment) were attracted to more porous ben- showed that the method with Fe was more appropriate for III V V tonite surface forming stable Fe -As inner–sphere com- the kaoline treatment (sorption efficiency of As ≈ 98/28 plexes. The unoccupied active3+ Fe particles on the sorbent %; AsIII ≈ 30/33 %), whereas for the bentonite treatment the III surface were transformed to more stable and/or crystalline procedure with Fe was excelent (>99% efficiency for both oxidic forms. the AsIII and AsV sorption). Metakaoline was more sensitive to the type of pretreat- Acknowledgements: This work will be supported by MSM (Re- ment, therefore only FeII-treatment was usable for AsV search project No. 2B06120) and was supported by GA CR (Project sorption. Both methods of treatment were applicable to No. 103/03/0506). bentonite, while FeIII-treatment was much more effective. References Arsenates were better adsorbed in all systems than arsenites. The appropriate reaction time for reaching the equi- BONNIN, D. (2000): Method of removing arsenic species from an aqueous medium using modified zeolite minerals.– U.S. Patent No.6,042,731. librium state was 24 hours for the sorption on the benton- DOUŠOVÁ, B., KOLOUŠEK, D., KOVANDA, F., MACHOVIČ, V. & ite and/or 72 hours on the metakaoline. NOVOTNÁ, M. (2005): Removal of As(V) Species from Extremely The mechanism of Fe-treatment and subsequent sorp- Contaminated Mining Water.– Applied Clay Science, 28, 1–4, 31– tion processes depended on the structure of raw material, 43. method of treatment, initial solution properties (pH, AsIII/ SHERMAN, D.M. & RANDALL, S.R. (2003): Surface complexation of arsenic(V) to iron(III) (hydr)oxides: Structural mechanism from ab V As concentration) and reaction time (DOUŠOVÁ et al., initio molecular geometries and EXAFS spectroscopy.– Geochim. 2005). It is evident, that AsV was entirely bound as arsenate Cosmochim. Acta, 67, 22, 4223–4230.

1 Institute of Chemical Technology in Prague, Department of Solid State Chemistry, Technicka 5, 166 28 Prague 6, Czech Republic ([email protected]) 2 Institute of Inorganic Chemistry AS CR, 250 68 Řež, Czech Republic 3 Laboratory of Molecular Spectroscopy, Technicka 5, 166 28 Prague 6, Czech Republic 41 Abstracts Book Abstracts 42 3rd Mid-European Clay Conference – MECC 06 1 etation which could easily “digest” excess the dust with the veg the by trapped was and season dry the during winds by deposition of site the to blown was material aggrading the of part that unlikely not is Itclimate. humid warm al, with silt.detrital Pedological features suggest mixed a strongly season material clayey preweathered probably fine, of amounts moderate receivingintermittently system, tional viation and soil formation. It seems as if it were an aggrada colluvial complex showing superimposed features of collu detrital grains. the of distribution both grain-size change in and quantity sudden in a upper indicates the which in event profile, the “detrital” of part the only is It clay. fine andtus constant quantity, implying is fairly a fairly constant supply of silt size detri groundmass and size grain of view of point the in the from both throughout, fraction detrital The conspicuous clayfeaturea profile.throughoutilluviation is the profile, the of part lowest the of exception the With inspection. visual by site on established horizons soil the presented.chemical be analyses will resultsof the micromorphologicalandresearchtionswith observa field compare attemptto An formation. soil and colluviation of features superimposed showing complex colluvial a above complex loess Pleistocene Upper composed an depression of karst of type complex uvala thick cm an in situated 850 an represents profile Sjenokoša The 3 2 Pogo Producing Co., 5Greenway 77046–0504,USA Plaza, Suite 2700,Houston, TX Eötvös Loránd University, &Environmental ofApplied Geology, Dept. Pázmány Péter sétány 1/c, 1117BudapestXI,Hungary ofZagreb,University Faculty ofMining, GeologyandPetroleum Engineering, HR-10000 Zagreb, Pierottijeva 6,Croatia ([email protected]) h ideadlwrpr fteSeooapol sa is profile Sjenokoša the of part lower and middle The with coincide nicely log textural the on bulges Clay Micromorphology of the pedo-sedimentary colluvial complexMicromorphology ofthepedo-sedimentary Goran DURN in Sjenokoša (Istria,Croatia) 1 , Andrea MINDSZENTY ------idepr ftepol hc aetelws ausfor values lowest the have which profile the of part middle the in Samples similar. very were thickness intervals) sampling of (and distances in sampling Namely, profile the of part 1996). that (DURN, profile Sjenokoša the of part middle the for studies independent two the of results the between existsagreement good quite a studies, phological micromor for sampling with simultaneous not was tion sition of covering the loess-complex (last glacial). as considered be may profile the developingdepo ofsemi-aridity, signs the in culminating of part upper the in influx a woodland. of that been “nurtured”havemust has complex soil luvial col of kind this which ecosystem the that suggest all ings of clay, the argillic horizons, and the voluminous clay coat amounthelp of moisture provided in the rainy season. The UN G (96: rgn cmoiin n gnss f er rsa in rossa terra of genesis and composition Origin, (1996): G. DURN, a possible A–E transition horizon. the highest values for weathering indices was recognised as logically recognised as Bt horizons. Also, sample which has Al (Na indices weathering 2 2 O andJudithGERMAN-HEINS Although sampling for chemical and textural composi detrital sheet-wash the anderosion soil episodic Both, 204 p. Zagreb, of University Croatian), (in Istria.– UnpublishedPhD Thesis 3 ] SiO , 2 /Al 2 O 3 n SiO and Reference 2 O/K 2 2 /Fe O, 2 [ O CaO+MgO+Na 3 wr micromorpho were ) 3 2 O+K

2 O/ ------

Abstracts Book

Clay minerals in Jurassic bauxites and associated cover “blue hole” sequence (Istria, Croatia)

Goran DURN1 and Franz OTTNER2

The Rovinj bauxite occurs at the contact of Upper Oxford- rite/vermiculite/illite. The mineralogy of the iron bearing ian–Lower Kimmeridgian and Upper Tithonian strata in phases and chemical composition clearly indicates that red an apparent stratigraphic gap of a relatively short duration bauxites were deposited under oxidizing conditions (va- (about 6 MY) and is considered that of a passive plate in- dose bauxites), while grey bauxite at the top of red bauxite, terior under interplate stress (Type 2 sensu D’ARGENIO formed in a reducing environment as a result of hydrologi- & MINDSZENTY, 1995). The uppermost 20 to 30 cm of cal change due to deposition of the coverbeds (phreatic the bauxite is heavily altered: its colour is greenish–grey bauxite). Since chlorite is present in similar amounts in to yellowish–white with vertical to subvertical extensions red and grey bauxite, its origin cannot be related solely to penetrating the underlying deep red bauxite. Above the al- the reducing processes which aﬀected the top of the red tered bauxite the lowermost part of the cover records the bauxite and converted it to grey bauxite, but also to burial establishment of a palustrine–lacustrine environment with diagenesis. The immediate cover of grey bauxite is yellow greyish, organic-rich marl and brecciated limestone, char- clay dominated by kaolinite, while chlorite and mixed layer acterized by a very restricted fauna and probably repre-

chlorite/vermiculite/illite are present in similar amounts as 3r senting a freshwater pond, formed as the groundwater ta- subordinate phases, and illitic material as traces. We tenta- d Mid-European Clay Conference – MECC 06 ble was pushed upwards by seawater rising through karstic tively propose that this clay represents redeposited mate- channels from below. Greenish–grey to yellow clay interca- rial introduced to the depositional environment from the lations in the coverbeds may be signs of ephemeral expo- kaolinitic and bauxitic blanket covering adjoining slightly sure or, alternatively, represent clay inﬂux from adjoining higher elevated areas. slightly more highly elevated areas (still exposed when the depositional environment was already inundated). Reference The dominant mineral phases in both red and grey D’ARGENIO, B. & MINDSZENTY, A. (1995): Bauxites and related pale- bauxite are kaolinite and boehmite. The main iron bearing okarst. Tectonic and climatic event markers at regional unconformi- phase in red bauxite is haematite and in grey bauxite pyrite. ties.– Ecl. Geol. Helv., 88/3, 453–499. Both bauxites also contain chlorite and mixed layer chlo-

1 University of Zagreb, Faculty of Mining, Geology and Petroleum Engineering, HR-10000 Zagreb, Pierottijeva 6, Croatia ([email protected]) 2 University of Natural Resources and Applied Life Sciences, Department of Applied Geology, Peter Jordan Strasse 70, A-1190 Vienna, Austria 43 Abstracts Book Abstracts 44 3rd Mid-European Clay Conference – MECC 06 1 while with area, in decreases sextet maghemite) or (magnetite The mm/s grinding. with changes fields fine hyper high with sextets the in Fe of percentage the ond, Sec grinding. the of heat the given result predictable a is This 13%. to Fe total the of 5% from slightly, increase to apparent. First, the areamount of Fe trends two However, difficult. interpretationis unique at lower temperatures (150and 12K). phase. In hopes of clarifying this issue we reran all samples amorphous an of representative a or artifact an be might ther magnetite or antigorite; we suspected that this doublet ei to assigned be cannot that parameters has (about position, terms of in constrained small poorly is and extremely area) total the is of 3% which doublet, remaining The Fe with doublet The (O species mineral serpentine haveparameters closely matching reportedfor those other & between Fe Fe the respond well to those published for magnetite corat 293K, with sextets the to magnetite and fits antigorite (Fig. 1). The (KLINGELH M to study our relate to order in cies were formed. Here we focus on the M addition, nanophase carbonate, Si–OH and iron oxide spe In grinding. with expected, as decrease, to found was size M and HRTEM, reflectance (BISHOP et al., 2003) and includes a combination of SEM, OLDS & BISH, of 2002) properties and antigorite( structure the affects grinding through orminutes10 30 vibrationa in grinder. Physical alteration 3, 1, for ground were Samples Mars. of surface the on miner als clay on processes physical of to assess the influence characterizechanges in the mineral grains resulting from grinding, and to is study this of purpose processes there. The durationinformationextentaqueousandof key aboutthe providesMarson alterationspecies aqueous other and als miner clay Characterizing 2005). al., et (POULET Mars Phyllosilicates have been found in small isolated regions on 3 2 The Clorox Company, 7200JohnsonDrive, Pleasanton, CA94588USA Road,SETI Institute/NASA-ARC, 515N.Whisman Mountain View, CA94035USA andEnvironment, MountHolyoke ofEarth Dept. College, Hadley, South MA01075USA ([email protected]) ONO, 97. w o te aaantc doublets paramagnetic the of Two 1987). JOHNSON, 2+ 3+ M hs o eprtr pcr r eycmlxada and complex very are spectra temperature low These , and the doublet with and the δ ≈ ö 0.30 mm/s sextet assigned to high-spin tetrahedral tetrahedral high-spin to assigned sextet mm/s 0.30 sae seta r dmntd y h peec of presence the by dominated are spectra ssbauer h nuneo hsclatrto nteMsburand Mössbauer the on alteration physical of The influence 2+ DRIEF & NIETO,1999) & DRIEF δ and Fe Ö ≈ eetnesetao nioieadapiain to applications and antigorite of spectra reflectance 0.67 mm/s sextet assigned to charge transfer FER etal., 2004). δ ≈ 3+ hspoetbid na nta study initial an on builds project . This 1.11 mm/s is assigned to octahedral octahedral to assigned is mm/s 1.11 on the B (octahedral) sites (MURAD δ M. Darby DYAR ≈ ö ssbauer spectroscopies. Grain 0.27 mm/s is Fetetrahedral ’ HANLEY & DYAR,1993). & HANLEY soil alteration processes onMars 3+ ö in the antigorite appears ssbauer spectra of Mars of spectra ssbauer and kaolinite ( kaoliniteand ö ssbauer spectra 1 , Janice L.BISHOP δ REYN =~0.32 3+ ------. IHP JL, RE, . DA, .. (2003) M.D. DYAR, & A. DRIEF,BISHOP, J.L., int es observed bauer as spectra a function of grinding with related chang that to issmall resolve too properly 295Kdata. inthe sextet incipient an be fact in might it that is doublet that of interpretation possible One temperaturefits. low the in appear not “amor phous” does apparent phase in the room temperature fits the Finally, occurring. be might phase oxide the in change actual an that indicate to seem does unconstrained) of are the changes (and the fact that the fits consistency tets are the simply swapping but area in the fits, sex these that possible is It grinding. with area in creases with sextet the ENLS J. .. BS, .. 20) Teeet fgidn on grinding of effects The (2002): D.L. BISH, & R.C. Jr. REYNOLDS, POULET,F.,J.-P., BIBRING, MUSTARD, PhyllosilicatesJ.F. (2005) al. et lizardite of O’HANLEY, composition DYAR,D.S.& The M.D.(1993): JOHNSON,J.H.Ironoxyhydroxides.–& MURAD,(1987): oxidesand E. KLINGELH on antigorite grinding dry of effect The F.NIETO,(1999): & DRIEF,A. We are integrating the changes observed in the M the in observed changes the integratingWe are 1626–1630. 87, Mineralogist, American kaolinite. low-defect a of structure the 632–627. 438, Nature,history.– Mars early the for implications and Mars on gist, 78,391–404. and the formation of magnetite in serpentines.– American Mineralo Chemistry. Plenum, 2,507–582. InorganicAppliedto MössbauerSpectroscopy (ed.): G.J.LONG, In: bauer spectrometer.– 306,1740–1745. Science, Opportunity’sfrom M PlanumMeridiani athematite and rosite from Mulhacen, Spain.– Clays and Clay Minerals, 47,417–424. Mars, on Conf. Int’l Sixth CD-ROM #3008(abstr.). Mars.– on Processes Iden Aqueous and of Clays tification of Detection on Influence its Grains, Dust Martian 2 andAhmedDRIEF Ö FER, G., MORRIS,G., R.V., FER, BERNHARDT, Ja(2004): al.B. et δ evsbeifae eetnespectra. he visible-infrared reflectance =~0.53 mm/s (magnetite or hematite)in or(magnetite mm/s =~0.53 References 3 : hscl leain of Alteration Physical Fig. 1Mössbauer

samples. and ground the initial of spectra ö ö ss ss 1T ------

Abstracts Book

Fluidised bed technology for drying and milling of clay minerals

Gunther FLECK1, Frank PUDEL1, Lothar MÖRL², Janitza RANGELOWA² and Gerhard KRÜGER²

A special kind of the fluidised bed process is the jet layer ing the adsorption of chlorophyll content of the vegetable process. The advantage of this technology is that in single oil. The necessary bleaching tests were accomplished in a equipment a drying process and a milling process for clay standardized procedure with rapeseed oil. minerals can take place at the same time. In the technical pilot plant clay/tone minerals with a The company Pilot Pflanzenöltechnologie Magdeburg grain spectrum up to 40–140 µm were processed. The hu- e.V., in co-operation with the University of Magdeburg, midity content for the final product in the cyclone could developed and tested a technology for the drying and cut- be lowered with very different output products (10–80% ting up of clay minerals. After an acid activation process water content) up to 2%. The throughput performances clay minerals can be also used as bleaching earth for the amounted 8 to 18 kg/h. Tests for the processing of chemi- refining process of vegetable oils. In a new pilot plant of cally activated aqueous clay/tone suspensions were also the PPM company the new jet layer technology was tested successful. in an extensive test program. In this technical pilot plant The result of the trials is the development of a technol- aqueous suspensions with a solid content of up to approx. ogy for drying and cutting up of bleaching earths and/or 30% were tested. their base products which can take place in very simple As raw material Friedländer clay/tone was used. The equipment without maintained rotary parts and large me- 3r d Mid-European Clay Conference – MECC 06 Friedländer clay/tone comes from Mecklenburg–Vor- chanical mills and dryer mechanisms. As processing prod- pommern in the north of Germany and is a mixed–layer ucts both solids and suspensions can be used. The high mineral with a high part of muscovite – montmorillonite, quartz portion in the clay mineral remains without prov- which is interesting particularly for adsorption processes able influence on the technology. The desired drying step for bleaching of vegetable oils. and grain spectra are adjustable in certain ranges by varia- The attempts were evaluated especially considering tion of the process conditions. the following quality indices: grain spectrum and humid- Presented results, obtained on Friedländer clay/tone, ity content of the final product, throughput performance, can be transferred also to other products with similar char- BET surfaces and especially the bleaching activity concern- acteristics.

1 Pilot Pflanzenöltechnologie Magdeburg e.V , Berliner Chaussee 66, D-39114 Magdeburg, Germany (fl[email protected]) ² Otto Guericke University of Magdeburg, Institute for apparatus and environmental technology, P.O.Box 4120, D-39016 Magdeburg, Germany 45 Abstracts Book Abstracts 46 3rd Mid-European Clay Conference – MECC 06 r apioe. te hay ieas s op as minerals and heavy Other amphiboles. amounts are small in very somelackin samples ofMinor twoolder paleosols. phases occur carbonates The mite). dolo and carbonates(calcite as well as chlorite,and spars feld mica, white quartz, areMajorphases sequences. osol fraction clay their compositionmineral samples of all is on as well (< as paleosols, different and loess samplesof bulk randomlyorientedpowdered ten on Cu with diffractometer Philips using fraction termination of pHand TOC. de and procedure Scheibler bycontent carbonate of tion chemical analyses of major and trace elements, determina fraction, mineral heavy and light of analyses microscopic aerometry); and (sieving analysis size grain analysis, tion brownish developed less are paleosols. soils two other The thick. m is well developed dark secondpaleosol brown soil, about 2 is paleosol followedbyThelaminated loess. sedimentand hydromorphic the alluvial oldest, The paleosols. all from A-horizonsC-horizons,andarerecognized. B- areeroded by represented levels, paleosol four section, the (interstadials). Throughout and interglacials periods during (stadial) developed paleosols glacial during formed of horizons length total a with profiles 16.2 vertical several the on investigated was section The Croatia. of part easternmost near River Danube the of bank south methods research (GALOVI laboratory and field using investigated was region, the in deposits loess oldest “Šarengrad”, the representing section loess/paleosol sediments Pleistocene Upper alluvial The Slavonia. Eastern Holocene of members lithological and dominant are loess Pleistocene The 2 1 Faculty ofMining, Geologyand Petroleum Engineering, Pierottijeva 6,HR-10000 Zagreb, Croatia Croatian Geological Survey, Sachsova 2,HR-10000 Zagreb, Croatia ([email protected]) 2 h iea opsto a eemndb -a dif by X-ray determined was composition mineral The diffrac X-ray included investigations laboratory The loess of interchange by characterized is section The µ 0 ) ht a sprtd y sedimentation. by separated was that m) m. Lidija GALOVI Ć , 2005). Investigated section is located on the the on located is section Investigated 2005). , loess/paleosol section inŠarengrad,loess/paleosol section Srijem,Croatia Mineralogical and geochemical characteristicsof Mineralogical andgeochemical Ć 1 , Marta MILEUSNI , Marta

typical oftypical loess/pale Š arengrad in the the in arengrad K â u miner que α radiation h bulk The Ć 2 ,

Zoran PEH ------pitted well-rounded surface. Paleosol horizons could be be could horizons Paleosol surface. well-rounded pitted by characterized grains spherical aeolian typical abraded oldest strongly show the analyses modal hydromorphyc is paleosol. The exception only The processes. accumulation and migration of consequence a as C-horizons and in BC- highest is content carbonate intensive.The was process pedogenic where soil developed well second, in especially horizons, paleosol in present is fraction clay contentof er layersmiculitic are present. also mineral interstratified chloriticandlayersveras well andillitic as smectitic with of amount Small paleosol. third the in lacks and amount, negligible in present is DMSO, of mainly byproved Kaolinite, smectite. and chlorite material, illitic composed are fractions clay The investigations. microscopic by only proved are chromite and apatite ite, garnet,kyanite, staurolite, tourmaline, zircon, titan rutile, biotite,chlorite,epidote–zoisite, als, amphibole,pyroxene, AOI, . 20) Gohmcl n mnrlgcl characteristics mineralogical and Geochemical (2005): L. GALOVIĆ, same population cannot rejected. be the to belong samples of means sub-groups two that and possibility variances of equality andAccordingly, lessin developed paleosols paleosols. of the criteria the fits Ba/Sr coefficient weathering that show t-tests and F- of results The development. soil of degree the to according selected on values, wecandistinguish TOC sub-groups the of samples Based TOC. of 0.5% and 0.1 between contain rizons ho paleosol profiles. while TOC, of <0.1% containhorizons Loess between composition chemical in difference cant signifi no shows statistics Elementary horizons. loess in then paleosol in higher areelements, trace as well as REE, (CaO+Na and Ba/Sr, coefficients, weathering on based extracted clearly h angansz rcini ersne ysl.High silt. by represented is fraction size grain main The aaj i rain. nul h hss nvriyo Zagreb, 278 p. of University Thesis, PhD Unpubl.Croatian).– and (in Baranja Slavonia eastern in profiles loess in paleosols Pleistocene the of 1 , GoranDURN 2 O+MgO+K 2 References and 2 O)/Al JosipHALAMI 2 O 3 rto h otn of content The ratio.

Ć 1 - - - - - Abstracts Book

Behaviour of carboxylic acids on NH4-smectites: pollution prediction in waste landﬁll

Mathieu GAUTIER, Fabrice MULLER, Patrick ALBÉRIC, Lydie LE FORESTIER, Jean-Michel BÉNY and Patrick BAILLIF

Waste storage induces environmental problems like soil and treatment to 1.25 nm (cation exchange proportion=53%) + + water pollutions by landfill leachates. Smectites are usually was observed, corresponding to a NH4 -to-H exchange. used as pollutant barriers at bottom of waste landfill. For These results are in accordance with the001 d reflection value this application, most interesting properties of smectites of SWy-2 montmorillonite saturated by protons: 1.26 nm at are their low permeability after compaction, expansion 40% relative humidity (FERRAGE et al., 2005). Besides, the ability and high Cation Exchange Capacity (CEC). Waste same general phenomenon was confirmed with the other decomposition leads to produce high amount of pollutants montmorillonites of various CEC we studied. and it is necessary to predict the long-term behaviour of the Interactions between ammonium SWy-2 montmo- clay barrier. Landfill leachates are first characterized by large rillonite and other short-chain carboxylic acids (formic amount of ammonium. Therefore a natural cation exchange acid, pKa=3.75; chloroacetic acid, pKa=2.86; oxalic acid, can be predicted in clay barriers. Moreover, high amount pKa=1.25) have also been investigated with the same proof acetic acid are observed in landfill leachates. For these tocol. At equal acid concentration, lower is the pKa of acid, 3r reasons we focused our study on acetic acid (pKa=4.74) d Mid-European Clay Conference – MECC 06 higher is the NH +-to-H+ exchange rate. Furthermore, this in interaction with ammonium montmorillonite, then 4 study indicates that cation exchange is directly dependent extended to others carboxylic acids to better understand on pH value for acid concentrations lower than 1 mol/l. carboxylic acids and ammonium smectites interaction Results showed that the behaviour of formic acid on am- mechanisms. Experiments were performed with the monium smectite is very close to the one of acetic acid. The reference SWy-2 montmorillonite totally exchanged with interaction is characterized by the absence of adsorption NH + cations and different carboxylic acids at several 4 and only by the NH +-to-H+ exchange. This exchange was concentrations but higher than found in landfill. 4 also found when chloroacetic acid and oxalic acid were in- NH -smectite samples were stirred during 7 days in 4 teracted with ammonium smectite. But in addition, we ob- acetic acid solutions, then rinsed and dried at 40°C. The pH served fixation on the clay with these two last acids, clearly was controlled during experiments. Analyses performed characterized by an increase of the carbon concentration by FTIR spectrometry indicate no adsorption of acetic acid in the solid phase. These observations were confirmed by onto montmorillonite. The main observed modification FTIR thanks to a stretching band in the C=O vibration is a decrease of the H–N–H-bending intensity after acid range. Besides, XRD patterns showed a significant increase treatment, which tends to decrease with the increase of acid of d reflections from 0.5 to 2.5 nm which may be attribu- concentration. Carbon, nitrogen and sulphur in the solid 001 ted to a fixation in interlayer space. Additionally, a decrease phase were quantified with a LECO CNS–2000 analyser. of the width at mid-height of the 00l reflections is observed Nitrogen quantitative analyses indicate that ammonium cations are partially exchanged during the interaction with for clay treated with oxalic acid, indicating a better stacking + of the layers which can be attributed to a structural modi- acetic acid. For example, 44% NH4 cations were exchanged with 0.1 mol/L acetic acid (pH=3.2), although no carbon fication of the interlayer space. was fixed. Ammonium concentrations in solution after Reference interaction were quantified with ionic chromatography, + + FERRAGE, E., TOURNASSAT, C., RINNERT E. & LANSON, B. (2005): and confirm the partial cationic exchange of NH4 by H . Moreover, d reflection values have been measured by Influence of pH on the interlayer cationic composition and hydra- 001 tion state of Ca-montmorillonite: Analytical chemistry, chemical X-ray powder diffraction. In room relative humidity and modeling and XRD profile modeling study.– Geochimica et Cosmo- temperature a shift from 1.19 nm for the sample before chimica Acta, 69/11, 2797–2812.

ISTO, UMR 6113, CNRS – Université d’Orléans, 1A rue de la Férollerie, 45071 Orléans Cedex 2, France ([email protected]) 47 Abstracts Book Abstracts 48 3rd Mid-European Clay Conference – MECC 06 s ly n hdoabn, s el s elgcl mapping geological as well as hydrocarbons, and clay as wasteexplorationdeposits, ofraw materialssuch deposits, andsiteprojectsveys tests onselection or disposal nuclear sur with deal reports FederalRepublic of Germany. These the of surveys geological state the and BGR the of chives mat (MS–Excel). band as forworksheetinto exported and in displayed presented be can data are values raw anisotropicrespective the cases Many these In values. mean and widths latter. to the regard of having effects even values, diffusion and sorption AEC, CEC, properties, mineral and geophysical, Moreover,geomechanical, database. the of part main the up make data hydraulic and mineralogical, geochemical, The sections. thin of photographs and images, REM ture, tex lithological data, sedimentologicale.g. data, grain size, vitrinite reflexion contains database The set. data each for gether with a site map and a to photo of an descriptionoutcrop are layerstored a and name rock the site, sampling location and stratigraphy. referenceto without spotor sequence anyfrom taken samples, no are There horizons. stratigraphic describing only data contain to is generally database cant illustrations. The signifi and maps descriptions, geographical and graphic stored in the database together with the lithological, strati are sets data Corresponding claystones. and clays of tics characteris technical the determine properties hydraulic ling, engineering civil and clay the working industry. It can also be used as a tool for site characterisation, model researchclaygroup. BGR the ofmembers the tocountries European other and Germany from de claystones or clay of been has characteristics barrier the about data 2004) provide to veloped (GERARDI, database BETTON The Federal Institute for Geoscience and Natural Resources Hannover, (BGR),Stilleweg 2,D-30655 Germany ([email protected]; www.bgr.bund.de) h egahcladsrtgahclpsto fthe of position stratigraphical and geographical The and mechanical physical, mineralogical, Geochemical, aa ore ae ueos eot soe i te ar the in stored reports numerous are sources Data Barrier characteristicsofclay andclaystone: the B Johannes GERARDI ETTON ------edol cins Pasblt cek ae automatically are and checks input- Plausibility data clients. guaranteed is as read-only constructed database clients hosted different using server by the of integrity The or MS–Word and other data formats. intoMS–Excel e.g. data, export to printor to user ena the bles This environment. MS–Office the in embedded well is databaseplatform, the 2000 Windows clienta on Server 2002/2003 MS–ACCESS an Using system. client/server a con of terms. used are database BETTON the in definitionsgives literatureglossary a A database.in tained data the research. of claystone sources and The clay the of field the in BGR the of in venturesjointinternational from and universities scientific stitutes, other by provided results scientific of reports open are database the in included sources Other surveys. GERARDI, J. (2004): Barrier Characteristics of Clay and Claystone: the the Claystone: and Clay of Characteristics Barrier (2004): J. GERARDI, of database, BETTON the web the presence is intended. the data or in form of a strata log. As a future development on overview general a outputof the foravailable are mats interest with respect to barrier rock properties. Special for for the horizons in a given area with the properties of most search a ofresults the forprovidedformatsare Other site. e.g. for data on a selected stratigraphic horizon at a selected used be of the results can of a search formats for data. These rameters. pa sensitive certain of magnitude of order correct the to regard with particularly input, data the during conducted database Data input by entitled users works with a client.special as works database BETTON the of version actual The lin, Kontec, Hamburg, 127–129. Conference on WasteRadioactive Disposal, April 26–28, 2004 – Ber Database.–DisTec2004 BETTON InternationalProceedingsof the – BETTON provides user-friendly formats for the output References

------Abstracts Book

1773: The year of the ﬁrst manufacture of porcelain in Portugal

Celso de Sousa Figueiredo GOMES

The Portuguese were the first to introduce and commer- graved moulds were used in the conformation of porcelain cialize in Europe the porcelain manufactured in China; pieces. however, within the European the Portuguese were the last Figures 1a and b show the front and the back views to industrially produce porcelain, in 1835, in the Fábrica de of one of the studied porcelain pieces produced by Bar- Porcelana Vista Alegre. In Portugal, the first experiments tholomeu da Costa which is made of high quality porce- of porcelain manufacture, at laboratory scale, were car- lain, consisting mainly of mullite, glass being an accessory ried out in Lisbon by the engineer Bartholomeu da Costa, component. Kaolin of high purity was used as main raw- starting on 1773. We had the chance to analyse by XRD material. and SEM several of the manufactured porcelain pieces (medals and cameos) which are stored in the Museum of Information relative to the composition of other porce- the Academia das Ciências de Lisboa. Mullite, cristobal- lain pieces and to the raw-materials (kaolin, quartz sand, ite, cordierite, diopside and glass were identified as high talc, calcite and dolomite) used in their manufacture will temperature phases, the maximum firing temperature was be disclosed. estimated at 1300C, coal was used as fuel, and metallic en- 3r d Mid-European Clay Conference – MECC 06

Fig. 1 Front (a) and back (b) views of the rectangular porcelain medal (5.5x4 cm) showing the Por- a b tuguese Royal Arms, the word Lisboa, and the date 1773.

MIA (Centro de Investigação “Minerais Industriais e Argilas” da FCT, Fundação para a Ciência e a Tecnologia), Universidade de Aveiro, 3810–193 Aveiro, Portugal ([email protected]) 49 Abstracts Book Abstracts 50 3rd Mid-European Clay Conference – MECC 06 external (topically) applications. Clay and mud have spe have mud and Clay applications.(topically) external and (orally) internal through state, health his improve to order prehistory,in the since man by used been have miner als other and mud Clay, asbestosis. and silicosis as, such system, respiratory the in instance for too, diseases hand, other certain the On systems. endocrinal and epidermal gastro–intestinal, cardiovascular, muscular–skeletal, the als supplements.However, both toprovided, life can be tial either ordiets, in nutritional in so-called The absorption. or inhalation ingestion, through happen solids inorganic both cludes of intake The response. dose/functional the upon depending cases both or in risks, health benefits, for responsible are health they when negative provide as they when positive as be classified can interactions These state. health the by determined are expected to occur conditioning the living quality highly elementsmanandchemical andminerals between actions inter Therefore, omnipresent. are minerals and elements in the natural environment where man lives, both chemical essential both to life and to the formation of minerals. are And, which elements chemical composition, their in mon, com in having systems chemical are minerals and Man Centro deInvestigação “Minerais IndustriaiseArgilas” daFundação deGeociências, para Universidade aCiência eaTecnologia Departamento (FCT), de Aveiro, 3810–193 Aveiro, ([email protected]) Portugal dfiinyadecs a rdc eiu iessof diseases serious produce can excess and deficiency ieas es rsrcu (s.r.) restrictu sensu minerals Clay-based formulations to beusedintopical applications mineralsalts minerals sensu restrictu (s.r.)restrictuminerals sensu ieas es lt (s.l.) latu sensu minerals ,

and the the and Celso Figueiredo deSousa GOMESandJoaoBaptistaPerteira SILVA and inorganic chemical elementschemicalinorganic traceminerals mineralsalts a poie serious provide can ,

which are essen are which and ocp ta in that concept meaning traceminer natural ,

can ------lar–skeletal diseases. In such formulations besides specific formulationssuch besides In lar–skeletaldiseases. plementary topical applications in the treatment of muscu com as use eventual for prepared been have which tions and of reformulating composition. their in naturallyraw-materials scarceused or of properties the currentimprovecomplextoa isprocessbut used essential Maturationperformed. be can methodologies application various and beneficiated be can to referred properties ral make otherapy, which natu dermopharmacy and dermocosmetics. The rate, cooling low them interesting products for topical and applications in balne heat specific high ity, bio-adhesivity,absorptioncapacities, high extensibil high cation and anion exchange capacities, high adsorption and structure, platy and size, chemistry hydrophylism, inertia, chemical high organophylism, high varied particle shape, small particle as fibrous or such properties, natural cific and S. Sr,Si Mg, Ca, act as, such elements, functional some manner which involved being controlled a in liberate can they minerals since principles, active spe as the investigated of previously properties the cific account into took These and formulations. the in participate amorphoussilica) organic sand carbonate biogenic water, minero–medicinal claysand chemicals, other resourcesmineral (for instance, pelotherapy. hspprsostoeape fca-ae formula clay-based of examples two shows paper This Recycling is another process of reusing the the reusingof process another is Recycling peloids for applications in applications for peloids peloidtherapy preparation, ------Abstracts Book

Physico–chemical and mineralogical characterization of the Hălmagiu clay (Arad county, Romania), a raw material for ceramic industry

Maria GOREA1, Marcel BENEA1 and Cristina MARIŞ2

Clays and kaolin represent the main raw materials for The physico–chemical transformations of the clay traditional ceramics, thus the identification of new re- under thermal treatment, i.e. dehydroxilation of the clay sources is an important research direction in Romania, minerals, carbonate decomposition, oxidation of Fe-rich and in general. Among the new clay deposits of interest in minerals and formation of new phases etc., at temperatures this respect, we focused on the Pannonian clays from the of 700, 800, and 900°C have been evidenced by X-ray dif- Hălmagiu (Arad county) area. fraction and IR spectroscopy. The mineralogy and chemistry of the clays in the study For testing the technological characteristics (rheology area were investigated, followed by the technological char- of the slurry, water adsorption capacity, open porosity and acterization for establishing their best way of usage. apparent density), samples obtained by the wet method were X-ray diffraction (on both unoriented and oriented thermally treated at temperatures of 900, 1100, and 1300°C. samples), IR spectroscopy and thermal analysis were com- At 1300°C the melting process was complete, pointing out to optimal firing temperatures of 1100–1150°C. The colour 3r

plementarily used in the view of establishing the mineral d Mid-European Clay Conference – MECC 06 components, i.e.: kaolinite, montmorillonite–vermiculite, of the fired product was brownish–red. muscovite/illite, chlorites, carbonates (calcite), quartz, pla- In conclusion, the Hălmagiu clay is recommended as gioclase feldspars, and Fe oxi–hydroxides. main raw material for the construction materials industry The grain size distribution analysed by a laser granu- (bricks), or, in smaller amounts, as additives for semi fine lometer has evidenced two fractions in the 0.5–10, and re- ceramics (wall and floor tiles). spectively 10–50 micrometers ranges, classifying the mate- The average chemical composition of the investigated rial as fine clay. clays is presented in the Table 1.

Table 1 The average chemical composition

Oxides LOI SiO2 TiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O of the investigated clays.

wt % 15.73 46.90 0.58 16.29 6.08 11.72 1.30 0.30 1.40

1 Babeş–Bolyai University, 400084 Cluj–Napoca, Romania ([email protected]) 2 Crissblok SRL, 407310 Gilău, Cluj, Romania 51 Abstracts Book Abstracts 52 3rd Mid-European Clay Conference – MECC 06 highly highly charged smectite. The illite/ mixed-layer interstratified randomly high-smectitic, as defined be can It dioctahedral. is marls Carpathian the ICP) and analysis thermal (DTA M were used: XRD (multispecimen technique), NMR, IR and and course the of diagenetic processes. origin its reconstruct to out carried were mineral features this of crystallochemical of studies Detailed form. flaky a contain units displays that mineral smectitic clay,by tectonic dominatedsimilar various from age different of marls examined. (<0.2 fractions carbonate-free ed (Sub-Cergowa unit Marls) and from Gryb the Dukla the from marls Oligocene as ( Ż (W one W Sub-Silesian and and Fucoid (Siliceous, unit Skole the from marls CretaceousUpper Beds), Cieszyn (Lower unit Silesian the from investigated:marlsTithonian/Berriasian pathian basins. Car the of parts deeper to material shelf of redeposition of effects the are sediments these since basins Carpathian the of shelves the on sedimentation of evolution the ing record are Moreover, they Carpathians. the of evolution age. among sediments of different tation. Similar lithologic varieties of marls appear cyclically sedimen flysch of end the Fore-Maguraindicating basins and Dukla Magura, the in Oligocene to Eocene from and basins Sub-Silesian and Skole the in both occur deposits marly Eocene till period Turonian. this in Frompearance the initial stage of and this sedimentation is marked Tithonian by their ap of turn Berriasian (Silesian basin). In the the eastern part (Skole basin) on sedimentation flysch of ing Outer Carpathians among sediments indicating the begin Marls appear in western part of sedimentation basin of the AGH andTechnology, ofScience University Faculty of Geology, Geophysics andEnvironmental Protection, al. ([email protected]) Łą gcn Mrs, oee al fo te aua unit Magura the from marls Eocene Marls), egocina ő cko, Budz cko, ssbauer spectroscopy, as well as chemical (FESEM/EDX, Natural samples and monoionic-saturated two separat were materials following the study present the In palaeotectonic the to related strictly are marls These h banddt niaeta mcii iea from mineral smectitic that indicate data obtained The complexinvestigations followingthese methods In the Carpathian the data, obtained the from follows As The anddiagenetictransformation structure ofillite/smectite ó w, Zembrzyce and Leluch and w,Zembrzyce from marlsofthePolish Flysch Carpathians ó ę gl w one (Gryb 27 ó k, rdk Jseia and Jasienica Frydek, wka, Al Al and – DTG µ m and 2 and m 29 – Si MAS NMR spec ó TG and EWA). ó w Marls). w Marls) as well as Marls) w ę – ira Marls) gierka 0.2 Katarzyna GÓRNIAK Katarzyna µ m) were m) ------iea. hyaecaatrsi o mcie omdby formed smectites for characteristic this are of properties They mineral. primary be to them indicate charge, layer the causing aluminium for iron and magnesium of in vacances of occurrences the cation, main the as aluminium of presence the as ied stud mineral the of sheet octahedral featuresof such that cations over octahedral of distribution 600 the above indicates curves, and EWA in below maxima the with effect Al of part Mg of substitution Al for the to due is charge layer This octahedral sheet, in allow to call the smectitic layers predominantly as montmorillonitic. charge of localization the Hofmann–Klemen’sresultsof the as well as indicatingtest tra showing aluminium mainly in octahedral environment, DRITS, V.A. (2003): Structural and chemical heterogeneity of layers sili layersheterogeneityof chemicalV.A. and DRITS, Structural (2003): Berlin, Verlag, Springer sedimentology.– Clay (1989): H. CHAMLEY, University o Acknowled of Carpathians. the evolution palaeogeographic of reconstruction the for tool useful very as considered be apparentlycan marlsmutely with volcanic phenomena. Consequently, these geological activity tectonic of relation the suggests strongly them in occurring minerals smectite examinationof tallochemical crys ofresultsTethys the the andof Ocean part northern the Flysch Carpathians with the stages of reconstruction of by compaction and shear. deformed sheets octahedral of geometry of change the of result bythe notonlyillitizationcausedprocess butis also featureslatter the that postulated also Itis 2003). (DRITS, of and trans-vacant non-swelling of presence The smectite. canogenic vol was marls Carpathian in occurring smectite/illite of precursor the that concluded is it DRITS, 2003). Therefore, transformation of volcanic material (e.g. CHAMLEY, 1989; h nlsso h bv rsne aaevidences data presented above the of analysis The cates and clay minerals.– Clay Minerals, 38,403–432. 623p. in marls of appearance the of coherence observed The 3+ . Moreover, the M Moreover, the . 3+ gments: gments: f Science and Technology grant no. 11.11.140.323. is substituted by Fesubstitutedby is lyr nissrcuei h ffc fdiagenesis layers of in its structure is the effect trans and hswr a nnilyspotdb AGH by supported financially was work This cis References Mickiewicza 30,30–059 Kraków,Mickiewicza Poland sites. ő ssbauer spectra indicate that a that indicate spectra ssbauer cis positions, the substitution the positions, 3+ . Double dehydroxylationDouble . o C, observed observed C, 2+ and Fe

2+ - - - - -

Abstracts Book

Thermal properties of illitic material from Lower Carboniferous black shales (Western Pomerania, N Poland)

Katarzyna GÓRNIAK, Krzysztof BAHRANOWSKI, Adam GAWEŁ, Tadeusz RATAJCZAK and Tadeusz SZYDŁAK

Lower Carboniferous black shales of Western Pomerania to 8 wt.%) and, locally kaolinite (up to 7 wt.%). The illitic are considered to be the source rocks of oil and gas de- material represents an ordered (Reichweite R=1–3), high- posits. The estimation of thermal maturity of these rocks illitic mixed-layer illite/smectite, containing from 30% to is necessary to evaluate the possibility of generation of hy- less than 10% swelling layers. In some samples the presence drocarbons within them. In this case the mixed-layer il- of discrete illite as admixture cannot be excluded. Chemi- lite/smectite can be used as mineral geothermometer. Its cal analyses indicate some substitution of Al for Si in tet- proper use is conditioned by correct evaluation of origin of rahedral sheets of I/S and Mg and Fe for Al in octahedral clay minerals contained in these rocks. ones. Apart from potassium, the main interlayer cation is Dinantian black shales of Western Pomerania were calcium. Mixed-layer illite/smectite from black shales in formed in marginal part of extensional back-arc basin de- Drzewiany block contains more swelling layers than that veloped at the southern shelf of Fennoscandia. According occurring in rocks of the Kołobrzeg block.

to MERRIMAN (2005), volcanic material is a significant The examination of thermal properties (EWA) of illitic 3r precursor of clay minerals in the basins of this type. In material of the black shales studied have evidenced two d Mid-European Clay Conference – MECC 06 DRITS (2003) opinion, volcanogenic origin of smectitic thermal effects at temperatures below and above 600oC, precursor of mixed-layer illite/smectite formed during which can be assigned to dehydroxylation of trans-vacant burial diagenesis is recorded in thermal properties of I/S, (tv) and cis-vacant (cv) octahedral sheets respectively in il- detected by evolve water analysis (EWA). This method was litic material. The presence of cv layers in diagenetic illite/ applied to confirm the primary presence of volcanogenic smectite is considered to be the evidence of volcanic origin smectite as the precursor of illitic material occurring in of its smectitic precursor. The formation of illite layers from the black shales studied. Volcanic origin of this precursor smectite ones during illitization of the latter mineral leads is suggested by common occurrence of volcanoclastic ma- to proportional increase of tv layers (DRITS, 2003). In the terial in the whole cross-section of Dinantian deposits of samples studied an interdependence between the content Western Pomerania. of swelling layers and the surface of the effects mentioned The black shales studied were sampled from two at the EWA patterns is observed. The surface of the peak at boreholes localized in tectonic blocks buried at various temperature above 600oC increases with growing content depth: Kurowo–1 in Drzewiany block and Żelazno–1 in of swelling layers. Kołoobrzeg one. Natural samples and Na+-saturated fractions (<2 µm and <0.2 µm) separated from them after re- Acknowledgments: This work was financially supported by AGH University of Science and Technology grant no. 11.11/140.158. moval of carbonates, were investigated using XRD, SEM/ EDX, XRF, ICP methods, as well as thermal and evolved References water (EWA) analyses. DRITS, V.A. (2003): Structural and chemical heterogeneity of layers sili- Illitic material compose 49 to 71 wt.% of the black shales cates and clay minerals.– Clay Minerals, 38, 403–432. studied from both the mentioned boreholes. It displays a MERRIMAN, R.J. (2005): Clay minerals and sedimentary basin history.– “cornflake” form. Some samples also contain chlorite (up European Journal of Mineralogy, 17, 7–20.

AGH University of Science and Technology, Faculty of Geology, Geophysics and Environmental Protection, al. Mickiewicza 30, 30–059 Kraków, Poland ([email protected]) 53 Abstracts Book Abstracts 54 3rd Mid-European Clay Conference – MECC 06 1 SHEPARD(1976). e.g. data, references with ty,compared thermal alteration, intensi i.e. vitrification–amorphization mine the ralogical changes of the from temper grains and from the matrix inferred were temperatures firing The ups. gro two into classified further weresamples ceramics the remnants,fossils as or clasts limestone as either present – on carbonatesFe-oxides.andBased feldspars,K-feldspars,micas, plagioclase quartz, minerals, clay of composed are shards ceramic the that show scopy Thenoticed. be can metimes transition of colours from brown–reddish to grey thick b) and one.-walled Shards thin-walled, colour is greyish or brownreddish. So a) categories: two into classified micro Macroscopically,(SEM). scopy electron scanning and (XRPD) X-Ray microscopy,diffraction powder light plane-polarized included techniques that analytical petrographical and mineralogical Dev the at found ceramic holds ho as either used were usehold ceramics or for ceremonies. burial they and hand-made all were They shanks. with are bowls and bowls shapes conical situlas, amphoras, vessel dominant The patterns. geometrical in their shape as well as for the carved and painted decoration NIKOV Czech Republic and the Sopron area in Hungary (STUDE in regionMoravia of part southern most the Austria, tual llstattiancultural complex whichoverlapped ac the partly Ha northeastern the to belonging B.C.) years (800–600 Culture Kalenderberg ceramics so-called Age the Iron to assigned Early artifacts are there these, Among Slovakia findings. southwestern the in located and represents a place of is several remarkable archaeological Castle Devin The 3 2

Archaeological Department ofSlovakArchaeological NationalMuseum,Žižkova Department 14,81436,Bratislava, Slovakia Bratislava Castle, Museum,Devín Muránska, City 84110,Bratislava, Slovakia Geological Institute ofFaculty ofNatural Science, Comenius University, Mlynsk wnyfu famns f aedregtp house Kalenderberg-type of fragments Twenty-four Á Mineralogical andpetrographical analysis ofKalenderberg 93.TeKlnebr eaisaetpclfor typical are ceramics Kalenderberg , 1993). The household ceramic from Devín Castle (Slovakia) Milo XR P D patternsmicroopticalD andthe š GREGOR the ceramic shards can be be can shards ceramic the í n Castle were studied by studied were Castle n the carbonatecontent the 1 , Katar í na HARMADYOV ------Acknowle and sands alluvial of Danube the and/or Moravia river. utcarbonates content, might come from clayish sediments On contrary, the raw materials used for the ceramics witho the Dev of sediments loess from likely most originate temper and & (IONESCU fingers GHERGARI, 2002). or fist the with opened lump clay a frommodeling by orform den woo a on lumps clay small several pressing as processes, mum 700 maxi reachead temperature firing the calcite, containing rangea of800–900 in red Most likely the ceramics without carbonates content was fi STUDENÍKOVÁ,Ironhalštatská(Early – železná Staršiadoba (1993): E. edition, 9th archeologist.– the for Ceramics (1976): O.A. SHEPARD, technology IONESCU,Modelingfiring and(2002): L. GHERGARI, & C. Cluj are gratefulvery to Dr. Corina Ionescu of Bratislava for permission to use XRD and SEM facilities. Also we tories for the Electric and Optic Methods from Comenius University logical Institute of Natural Science Faculty and the Central Labora á dolina G,84215Bratislava, Slovakia ([email protected]) For the ceramics with carbonate content, the raw clayscarbonaterawcontent, with the ceramics For the modeling indicates wall ceramic the of structure The p. (inSlovak). 375 Elán, Vydavateľstvo Bratislava). of History Oldest Bratislavy (The Age – Halstatian).– In: ŠTEFANOVIČOVÁ, T. (ed.): Najstaršie dejiny InstCarnegie Washington, 414p. ceram Issue. 53,Special Carpathica, the of Geologica mineralogy Transylvania(Romania).– in sites Neolithic the the from and ics features textural the in reflected – – Napoc Á í 2 nska Kobyla Hill, located nearby the Dev dgement: and Radoslav and Radoslav ° C. a, Romania) for her help. Inthis waywould we like thankto thetoGeo References ° C ( C Č AMBAL ± 50

single, almost sphaerical, almost single, ° (Babe C), while in the ceramic the in while C), 3 ş– Bolyai University of í n Castle. ------Abstracts Book

Experimental study of iron–bentonite and pyrite–claystone interaction at low temperature

Miroslav HONTY1, Vladimír ŠUCHA1, Peter KOMADEL2, Marek OSACKÝ1, Jana MADEJOVÁ2, Jana VALÚCHOVÁ2, Juraj BUJDÁK2 and Peter UHLÍK1

The principle of radioactive waste storage is based on a In the presence of metallic Fe powder, the experi- multi-barrier system consisting of two basic components ments resulted in mineralogical changes in both starting – a geological and an engineered barrier. The metallic con- bentonites. The XRD pattern of bentonites shows the ori- tainers filled with vitrified nuclear waste are placed in an gin of magnetite and significant decrease of smectite and engineered barrier which is surrounded by a geological bar- feldspar reflections during experiments. After 30 and 120 rier. The reactive components of the engineered and geo- days, a new reflection of metallic Fe is formed. During ex- logical barriers are clays (mainly smectites) while metallic periments with metallic Fe, the initial pH of the solution containers could made up of iron. To predict the long-term increases and redox potential (Eh) decreases considerably. properties of these clay barriers, it is thus essential to study The iron contents increase progressively in solution with the interactions between clay minerals and iron. the reaction time. Mössbauer spectroscopy demonstrates the consumption of metallic Fe powder in Fe-montmoril- Studies of the iron–clay interactions have shown the lonite whereas in Al–Mg montmorillonite 41% of total Fe partial destabilization of the initial clay material and subse- 3r is present as metallic Fe after experiments. d Mid-European Clay Conference – MECC 06 quent crystallization of reaction products (GUILLAUME et al., 2003; NEAMAN et al., 2003; WILSON et al., 2006). In the presence of steel plate the steel surface oxidation The nature of these reaction products depend on experi- was observed by SEM. In contact of the steel plate with Fe- mental conditions such as temperature, the nature of the montmorillonite the oxidation was more intensive than in Al–Mg montmorillonite. initial clay material and others. Finally the stability of bentonites and claystones in the The present study deal with the interactions between presence of pyrite was studied. Experiments were focused bentonites, and more especially smectite, and iron (metal- on the effect of pyrite on the claystone and bentonite stabil- lic Fe, steel plate) the last part of the study is focused on ity. Experiments were performed at 80°C during different interactions between claystones, bentonites and pyrite. time periods. The stability of bentonites in the presence of metallic Fe and steel plate was studied experimentally to simulate References the mineralogical and chemical reactions of bentonites in GUILLAUME, D., NEAMAN, A., CATHELINEAU, M., MOSSER-RUCK, contact with steel container in a nuclear waste repository. R., PEIFFERT, C., ABDELMOULA, M., DUBESSY, J., VILLIERAS, Bentonites from two Slovak deposits (Al–Mg motmoril- F., BARRONET, A. & MICHAU, N. (2003): Experimental synthesis of chlorite from smectite at 300 °C in the presence of metallic Fe.– Clay lonite and Fe-montmorillonite) were used as starting ma- Minerals, 38, 281–302. terials. Experiments were performed at 60 and 90°C for pe- NEAMAN, A., GUILLAUME, D., PELLETIER, M. & VILLIERAS, F. riods 5, 10, 15, 30 and 120 days, using bentonite, redistilled (2003): The evolution of textural properties of Na/Ca-bentonite fol- water, metallic Fe powder and steel plate. Both solid and lowing hydrothermal treatment at 80 and 300°C in the presence of Fe liquid phases were analyzed. Solutions coexisting with the and /or Fe oxides.– Clay Minerals, 38, 213–223. solid phases were analyzed by AAS, UV–VIS and pH mea- WILSON, J., CRESSEY, G., CRESSEY, B., CUADROS, J., VALA RAG- NARSDOTTIR, K., SAVAGE, D. & SHIBATA, M. (2006): The effect surements. Solid phases were characterized by XRD, SEM, of iron on montmorillonite stability. (II) Experimental investiga- FTIR and Mössbauer spectroscopy. tion.– Geochim. Cosmochim. Acta, 70, 323–336.

1 Department of Geology of Mineral Deposits, Comenius University, Faculty of Natural Sciences, Mlynská dolina, 84215 Bratislava, Slovakia ([email protected].) 2 Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská 9, 84236 Bratislava, Slovakia 55 Abstracts Book Abstracts 56 3rd Mid-European Clay Conference – MECC 06 Polymer-layer silicate composites were prepared by direct by preparedwere Polymer-layercomposites silicate cations. exchange (ODA) octadecylammonium and (OA) ion monium by prepared oleylam (ODTMA), octadecyltrimethylammonium were with derivatives organic The used. was g) meq/100 (119 capacityexchange cation high relatively of Industries) (Kunimine “Kunipia–F” (>98%) inter the increase to is modification layer spacing and hydrophobicity the of clay. the the of aim The ons. substituting by achieved is long-chaininorganicalkylammoniumcationscati forthe modification This modified. organicallymontmorillonite polymers,be in tosion needs the lateral dimensions. In order to improve the clay disper in nm and200–300 ofsilicatecomposedthick layers nm 1 used is often most which clay, natural common The well. improvingas are resistance abrasion e.g. properties, other vulcanizates; the of 100) modulus break, at strain and strength (tensile ties proper mechanical the of enhancement by expressed is rubbers of reinforcement to The properties. is certain improve addition filler for aim main withorganoclays. ber The rub solid mixing on based thermoplastics,for used those posites have prepared been using procedures derived from nanocom NR (NR). naturalappliedrubber to be canthat has nanocomposites polymer–clay creatinga been of development The 2 1 Polymer Institute, Slovak Academy ofSciences, Dúbravská cesta 9, 84236Bratislava, Slovakia Institute ofInorganic Chemistry, Slovak Academy ofSciences, Dúbravská cesta 9,84536Bratislava, Slovakia ([email protected]) cmeca hgl prfidNa-montmorillonite purified highly commercial A ucnzdrbe le ihmdfidmontmorillonite modified with Vulcanized rubberfilled

number of technologies and opportunitiesandtechnologies of number

as reinforcing agent, is montmorillonite, is agent, reinforcing as Jana HRACHOV Á 1 , Ivan CHOD , Ivan ------oie n noie le sosre ntepresence in the is observed filler with unmodified and materials modified the between with difference composites No matrix. rubber in filler the of effects plasticizing and ing reinforcaltered in resultsferent ammoniumorganicsalts dif by montmorillonite of matrix.Modification NR the in filler values unmodified to comparedelongation and strength higher of to leads modification filler The contents.ite montmorillon all for SiO values break at of stress the stantially % mass 15 but effect; negligible has montmorillonite in cation organic the silica, of presence sys the In materials content. clay increasing the with increases tematically of break at stress The silica. of presence valueshigher of mechanical properties the in are observed much expected, As tests. tensile the from evaluated were M100 modulus and break at strain break, at Stress ured. loading organoclay or from 1 up to 10 mass clay % on of the tensile properties was meas effect The filler. reinforcing conventional a as silica also contained clay mixtures and rubber of the cases some in intercalation; melt polymer terials. ma rubber/organoclayfor observed is M100 on presence silica the leads to higher of values of M100; negligible effect SiO % mass 15 with obtained are data break at strain the for trends similar results, break at stress the with As silica. of Á K 2 2 i h oye.Fle oicto xetfrODA for except modification Filler polymer. the in andPeter KOMADEL 1 2 increases sub increases ------Abstracts Book

Fast determination of CEC by Cu-trien method, its limitation and use

Michaela HRUSKOVA, Tomas GRYGAR and David HRADIL

Several methods have been suggested for estimation of cat- be easily explained by heterogeneous occupation of the ion exchange capacity of clays (CEC). All novel procedures interlayer space although careful conversion to homoionic to CEC estimation are focused on simplicity, low time de- form was performed. Difference is larger with decreasing mands, accuracy and repeatability. Cu-trien method was relative atomic mass of the interlayer cation. CEC deter- first proposed in 1999 (MEIER & KAHR, 1999). The meth- mined from the balance of Cu2+ is recommended. Com- od is based on interaction of highly charged small copper parison of CEC determined by UV–Vis spectroscopy with (II) cation with interlayer space of expanding clay minerals. CEC obtained by AAS of Cu2+ shows minor differences but During the exchange, the blue colour of Cu-trien complex attention should be paid at possible turbidity if UV–Vis is is lightening. Exchange is reported to be fast and irrevers- applied. The loads of stock solution influence the value of ible. Reaction time is short and consecutive treatment is CEC estimated by Cu-trien. Oscillations increase with the not necessary. Measurable signal is developed within the use of stock solution of higher overload of trien and 1+ exchange and easily measured – by UV–Vis spectrometry, charged cations in interlayer space when both CEC AAS of or by AAS to avoid possible instability of the Cu-trien com- Cu2+ and CEC UV–Vis have risen by 20 meq/100g. 3r plex at varying pH (AMMANN et al., 2005) and possible Cu-trien method is a handy method for large series of d Mid-European Clay Conference – MECC 06 problems with turbidity of the supernatant. samples (GRYGAR et al., 2005). It is recommendable to These advantages led to use of this method at our work- use exactly the same procedure of preparation of samples, ing place and test the influence of the type of cation in the ion exchange, and supernatant processing. For lower scat- interlayer space and stoichiometry and excess of the stock tering of results stock solution with 1:1 ratio of Cu-trien solution. Four homoionic (Ca, Mg, Na and Li) smectites should be prepared. UV–Vis spectroscopy is a quick way with size under 2 µm from Rokle, Czech Republic, were of determination of CEC, but possible turbidity can in- prepared by step saturation by desired cation in 1 M solu- fluence the results. AAS is powerful tool for determining tion, washed out by distilled water and finally followed by CEC by determination of Cu2+ consumption. CEC deter- dialysis. Powder samples were well mixed and water con- mined from cations released is reliable only if all possible tent was determined by drying at 110°C for 24 hours. Three cations present in the original sample are determined and stock solutions were prepared with 0, 19 and 49% overload free calcite or salts soluble in neutral aqueous solutions are of trien over Cu(II). The loads of the stock solution were absent. varied between 100 and 240% stoichiometry with respect to CEC of the samples. Reported UV–Vis detection was Acknowledgement: This work was supported by the Grant agen- used and additionally AAS/AES spectrophotometry was cy of the Academy of Sciences of the Czech Republic, project No. applied to evaluate the cation balance in supernatant. Sam- IAA3032401. ples were prepared by dispersion of 0.11 g of clay in 10 ml of distilled water using ultrasonic bath. Consecutively the References desired amount of stock solution was added and volume AMMANN, L., BERGAMA, F. & LAGALY, G. (2005): Determination of was fixed to 50 ml. After 15 min the suspensions were- cen the cation exchange capacity of clays with copper complexes revis- ited.– Clay Minerals, 40, 441–453. trifuged or filtered and supernatant/filtrate was taken to GRYGAR, T., BEZDICKA, P., HRADIL, D., HRUSKOVA, M., NOVOT- analysis. The filtration was later excluded from the sample NA, K., KADLEC, J., PRUNER, P. & OBERHANSLI, H. (2005): Char- preparation procedure; not only to save time, but mainly acterization of expandable clay minerals in Lake Baikal sediments by because it caused Na+ contamination and interaction of thermal dehydration and cation exchange.– Clays and Clay Minerals, solution with paper itself is disputable. General trends ob- 53/4, 390–401. served are as follows: MEIER, L.P. & KAHR, G. (1999): Determination of the cation exchange capacity (CEC) of clay minerals using the complexes of copper(II) Cationic balance in the supernatant is never reached ion with triethylenetramine and teraethylenepentamine.– Clays and which means that CEC determined by AAS/AES from Clay Minerals, 47, 386–388. cations sorbed and released is not identical. This fact can

Institute of Inorganic Chemistry, Czech Academy of Sciences, 250 68 Rez, Czech Republic ([email protected]) 57 Abstracts Book Abstracts 58 3rd Mid-European Clay Conference – MECC 06 1 by P-enrichment. chalcedony by marked are deposition, analcime replacing the volcanic glass alterations clasts and burial The well. as hematite, anorthite, leucite, K-feldspar, and wollastonite,melilite gehlenite,formed glass, as such phases New cracks. isotropic and the glassy, amorphous melt intruded into the became feldsparclasts ofParts grains. quartz of rims ened soft the into matrix the from migrated Fe processes. ing body, aretogetherbysintering–meltsticked particles the where rigid a forms which matrix, clayish the the is of and change important matrix most The clasts. the the with relationshipits mainly affecting sion–recrystallization, reveal melting–diffu analyses i.e. processes, EMP alteration and thermal intimate SEM OM, The one. semifine the to assigned be can 45% while ceramics coarse as classify 1 mm), Lg (large particles, over 1 mm), 55% of our samples and 0.5 mm), Md (medium size-particles, 0.5 between and 0.02 between particles, (small Sm amountof the on based present.Granulometrically,arebioclasts and ceramoclasts crystalloclasts, various as well the as lithoclasts, sedimentary In vitrification. and and metamorphic magmatic, of amounts variable sintering matrix, of degrees different its exhib and fabric amorphous and crystalline combined, regular-shaped pores and to microfissures. the ceramic elongatedir orthe to both porous,duegeneral in is body The noticed. be can hues, reddish into grading grey dark with zoningslight a seldomhomogeneous, only rather is colour the thickness, wall the Across potshards. brick-red as well as pebbles even and clast mineral fragments white ceramic The large by colour,spotted body materials. grey dark a general in show raw the and firing, the phasecomponents, the tify alteration thermal their during iden to order in (EPR) resonance paramagnetic electron and (EM) microprobe electron (SEM), microscopy elec tron scanning (DTA), analyses thermal (XRD), diffraction powder X-Ray (OM), microscopy optical light polarized plane- by studied were Transylvania(Romania) North in Ili of sitearchaeological the pottery,in exhumedmade (1400 Age Bronze Late of Potshards 3 2 Bistriţa–Năsăud County Museum,19 Gen.Gr. Bistriţa–NăsăudCounty BălanStr., Bistriţa,Romania RO-420016 Paris Lodron University, 34HellbrunnerStr., A-5020 Salzburg, Austria Mineralogy Chair, Babes–Bolyai University, 1Kogalniceanu Str, Cluj–Napoca, Romania([email protected]) RO-400084 h eaiscnit aial facaihmti with matrix a clayish of basically consists ceramics The Corina IONESCU Thermal alteration ofmineral phasesinBronze Age ceramics 1 , Lucretia GHERGARI from Transylvania (Romania – 20 .. hand- B.C.) 1200 1 , Volker HOECK ş ua ua ------w dffrn ore,ms ieylctda ad They Ili of surroundings the in occurring hand. clays ic–kaolinitic at located illit and kaolinitic–illitic Badenian the likely example, for were most sources, different least two at from came clays content.The carbonatecidentally ac only with clays or claysnon-calcareous were they that the as aswell well as indicates wollastonite and/or gehlenite matrix of scarcity fired the in calcite of lack content. The ( itic illitic–kaolin and kaolinitic–illitic of mixing by obtained was ceramics that indicate matrix the of features alogical 800–850 domains: Bronze Age ceramics approximated could be in three large Late the for conditions firing results, the experimental ous previ our with and etc.) 2003, FABRA, & BERTOLINO al et RICCARDI 1998; al et DUMINUCO 1982; (MAGGETTI, data reference with compared data EMP and EPR SEM, XRD, as well as RICCARDI,M.P., MESSIGA, B.DUMINUCO, & P. approachAn (1999): technology MAGGETTI M. (1982): for Phase analysis and its significance DUMINUCO,M.P.procP.,RICCARDI, Firing & B.(1998): MESSIGA, CULTRONE, G., RODRIGUEZ-NAVARRO, C., SEBASTIAN, E., CAZA tech ceramic Provenanceand (2003): FABRA,M. & BERTOLINO, S.R. 2005). Romanian Acknowledgement: site. the nearby from Somes the River flowing derived materials, tempering as sediments sandy alluvial the to points clasts the of composition mineralogical that and reveal pellets clay some soil was of added in petrographic the ceramic paste. The frequency high The settlement. Based on macroscopic and microscopic observations, microscopic and macroscopic on Based otednmc fca rn. ple lySine 5 393–409. 15, Science, Clay Applied to dynamics the of clay firing.– SmithsonianCeramics, Institute Press, Washington, D.C., 121–133. and origin.– In: J.S. OLIN & A.D. Archaeological(eds.): FRANKLIN 185–190. 321, Acta, tions. –Thermochimica composimicrotexturesrelatedphase andSome clays. natural of ess Mineralogy, of 13, 621–634. Journal European firing.– ceramic during reactions O. LLA, TORRE, DEM.J.LA & Carbonate(2001): and silicate phase valley, Argentina.– Applied Clay 24,1,21–34. Science, Ambato the at cultures Andean ancient from sherds pot of nology ± smectite) raw clays, with some iron- oxihydroxidesiron- some with clays, raw smectite) 2 , Viorica SIMON iity f dcto ad eerh Gat 1762/ (Grant Research and Education of Ministry Th , 850–950 , s td ws nnilyspotdb the by supported financially was study is ) References . 19; UTOE t al et CULTRONE 1999; , 1 and 950–1000 and and Marius HORGA andMarius ° .Teminer The C. . 2001; ,

3 ş ua ua . ------, Abstracts Book

Cement suspensions for slurry cut-oﬀ walls with ultra ﬁne ground Na-bentonite from Lieskovec and Jelšový potok deposits

Ivan JANOTKA1 and Igor GALKO2

Slurry cut-off walls are used as vertical barriers to con- pensions. Compressive strength varied between 0.72 and trol groundwater flow or to keep contaminants captured 0.88 MPa (cubes: 20x20x20 mm) after 28-day basic curing in waste containment systems. They consist typically of in water (20±1°C). a mixture of selected bentonite, cement, additives and wa- Investigation of the effect of aggressive solution on ter. There is still a little information on long-term perform- hardened cement–bentonite suspension was performed ance of cement–bentonite slurry cut-off walls. This paper using next principles: a) mixing the material with ap- is concerned with the research of rheological and utility propriate volumes of contaminants; b) evaluating utility properties of cement–bentonite suspensions and the exam- properties (changes in weight, dynamic modulus of elas- ination of their durability potential. Laboratory immersion ticity and strength); c) analysing reaction products (XRD, tests were performed to assess their chemical resistance. TG–DTA–DTG, SEM, chemical analysis) and d) immers- The following materials were used for the tests: finely ing specimens in the solution of combined contaminants ground (d<45 µm) Lieskovec and Jelšový potok sodium {0.05% MgCl2 and 0.03% (NH4)2SO4 solution contain- bentonite and Portland cement of type CEM I 42.5 R. The 2+ ing following concentrations of aggressive ions: Mg – 3r suspensions were adjusted on the constant cement content 127 mg.l-1, Cl- – 372 mg.l-1, NH + – 82 mg.l-1 and SO 2 – d Mid-European Clay Conference – MECC 06 per 1 m3 and flow ability measured by the Marsh cone be- 4 4 218 mg.l-1). Compressive strength of the specimens tween 39 and 43 seconds. They were prepared by mixing (20x20x20 mm) kept in reference water (W) and aggressive water and bentonite until bentonite particles were fully solution (AS) for one year is reported in Table 1. hydrated. Cement was added afterwards and cement–bentonite suspension was constantly circulated until cement The specimens showed negligible signs of attack – only particles were fully dispersed. Bentonite portion differed some discolouration and fine softening of the surface on between 16.5 and 13.2 mass % of the cement and showed the edges of specimens (20 mm3 and 20x20x120 mm) were varying percentage portions: the first comprises bentonite observed after one-year exposure to aggressive solution; from Lieskovec (reference), while other mixtures con- regularly restored. Valuable utility properties and high sist of Jelšový potok and Lieskovec blends in the ratios of chemical resistance of suspensions to the combined con- 15 to 85, 22 to 78 and 30 to 70 mass %. Jelšový potok has taminant were proved by the tests. The suspensions with higher swelling (WL=625%) than Lieskovec (WL=300%) ultra fine bentonite have been prepared for field applica- and served as upgrading agent. Water decantation was less tions. than 1.5 vol. % per 24-hour sedimentation of the fresh sus-

Table 1 Compressive strength of cement– Suspension Compressive strength, MPa bentonite suspensions kept in water (W) No. Curing 28 days (basic) 180 days 365 days and aggressive solution (AS). Specimens were kept for next 180 and 365 days in W 0.88 0.91 1.02 both liquids after basic curing. 1 AS 0.81 1.20

W 0.72 0.98 0.97 2 AS 0.88 1.00

W 0.78 1.03 1.01 3 AS 0.78 0.99

W 0.75 1.01 0.94 4 AS 0.94 0.99

1 Institute of Construction and Architecture, Slovak Academy of Sciences, Dúbravská 9, Bratislava, Slovakia ([email protected]) 2 Envigeo, a.s., Kynceľová 2, 974 11 Banská Bystrica, Slovakia 59 Abstracts Book Abstracts 60 3rd Mid-European Clay Conference – MECC 06 2 1 230 100– temperaturesof peak by characterized was sequence tures200–250 between m ophiolitic 390–460 Jurassic ca. of temperatures gave mometers R and indicators T cal 300–420 ca. of temperatures complex (Paleozoic–Mesozoic) Eoalpine the from metapelites“thermometers”. anchi-epizonal For organic and inorganic empirical by calculated peratures geothermobarometerthe of and thermometers Al(IV) empirical chlorite the of results andlattice strainvalues obtained byVoigt the and method K (illite chlorite indices “crystallinity” the phyllosilicate with correlated were data maturity Organic (2005). (2002), al. et of equations the on based parameters spectral of (R equation the reflectance using vitrinite random were on Paleo-temperatures as calculated indicators. used maturity were (CM) thermal material carbonaceous dispersed fine- the of parameters spectroscopic Raman ( and 1971) “ordering” graphite (XRPD)-based diffraction DIK by earlier presented were which of parameters linity” phyllosilicate“crystal microand paragenetic mineral structural, the series, rock these of evolution metamorphic diagenetic the on data additional providing 1998) ( Croatia Medvednica, Mt. of m olitic the Eoalpine (Paleozoic–Mesozoic) on complex, the obtainedJurassic ophi indicators grade metamorphic organic esis and low-T metamorphism. the phyllosilicate reaction progresses acting during diagen and maturation the organic with the of controls dealt physico-chemical papers numerous years 40 ca. last the In 4 3

Institute ofMineralogy andPetrology, ofGeology, Department Faculty ofScience, ofZagreb, University Horvatovac bb, HR-10000 Zagreb, Croatia OMV Exploration &Production 151,A-1210 Vienna, GmbH,Gerasdorfer Austria Geosciences ofApplied andGeophysics, ofLeoben, University Department Peter Tuner 5,A-8700, Leoben, Austria Institute forGeochemical Research, HungarianAcademy ([email protected]) ofSciences, Budaörsi45,H-1112 Budapest, Hungary o ti proe irnt rﬂcac,Xrypowder X-ray reﬂectance, vitrinite purpose this For and inorganic to correlate was work this of aim The Fairly good correlation was proven between the tem the between proven was correlation good Fairly ° etal. (2004). . vle icesd ytmtcly rm youngest, from systematically increased values T C. Correlation oforganic andinorganic temperature indicators – Katalin JUDIK Katalin é Á a case studyonlow-temperaturea case metamorphicrock series ag ad ae Cretaceous Late and lange rkai indices), apparent mean crystallite thickness ° C were estimated on the basis of mineralogi of basis the on estimated were C RANTITSCH é ag R lange 1 ° o , Gerd RANTITSCH .TeLt Cretaceous–Paleocene Late The C. BARKER aa Hwvr te aa ther Raman the However, data. et al. (2004) and (2004) al. et VIDAL &PARRA PAMI o aus ugse tempera suggested values from Mt. Medvednica, Croatia 18) n o Raman on and (1988) Ć – aecn sequence Paleocene & TOMLJENOVI & RAHL 2 (2000). , Thomas M.RAINER ° ü C. In the the In C. BEYSSAC LANDIS, lr and bler o values ) – low-T et al. et JU Ć ------,

BARKER, C.E. (1988): Geothermics of petroleum systems: Implicationssystems: petroleum of Geothermics (1988): C.E. BARKER, titsch and Katalin Judik and Peter to (T049454) OTKA Acknowledgement: series. rock these in caution with therapplied be only Raman can mometer the Therefore, generations. CM diﬀerent the of bands Raman the of superimposition by were characterized rocks altered diagenetically The zone. diagenetic the of part temperature high the to well fairly corresponded Paleocene towards data the oldest, Cretaceous rocks. These VIDAL, O. & PARRA, T (2000): Exhumation paths of high pressureme high PARRA,VIDAL,ExhumationofO. paths & (2000): T W., F.,GROGGER, TEICHERT, HOFER, EBNER, G., C., RANTITSCH, FASSOULAS,C. M.T.& BRANDON, K.M., ANDERSON, J.M., RAHL, PAMI Carbonaceous Dispersed the of Graphitization (1971): C.A. LANDIS, JUDIK, K., GOFF BEYSSAC,O., PetroleumSystems of United the States. U. Bul Survey Geological S. In temperature.– peak at brief duration heating a geologically after maturation kerogen of stabilization the of blages.– Journal, Geological 35,139–161. chlorite–phengiteforassem equilibria local fromobtained tapelites Alps.– Eastern the Int. J. 93,959–973. Sci., Earth of Zone Greywacke the withingraphite to material carbonaceous of Conversion(2004): M. TOTH, MAUER,SCHAFFER,& B.C., E.M., Letters, 240,339–354. to application Science Planetary and Earth Greece.–Crete,exhumationtectonic in and Calibration rocks: metamorphic low-grade of thermometry material carbonaceous spectroscopic Raman (2005): Hungarica,logica 41,389 Zagorje the of Croatian part Petrology, 30,34 rocks. Metamorphic in Material 47, 151 blages and phyllosilicate characteristics. perature metamorphism of Mt. Medvednica, Croatia: Mineral assem D., TOMLJENOVI thermometer.– geoofcarbonaceous new metasediments:materiala in man spectra 1870,26–29. letin, Ć , J. & TOMLJENOVI & J. , Á – 3 176. RKAI, P., HORV ,

Darko Darko TIBLJAŠ Journal – É h rsn okwsspotdb ud from funds by supported was work present The 45. , B., CHOPIN, C. & ROUZAUD,(2002): J.N.& C. CHOPIN, B., , Ć , B.& PAMI o References Á f Ć –

Metamorphic TH, P., DOBOSI, G., TIBLJAŠ, D., BALEN, Á , B. (1998): B. , 400. MZO ki OA (61 OMAA rkai, – Mid-TransdanubianZone. Ć 4 – Š , J. (2004): Diagenesis and low-tem andP Contributions to Mineralogy and Mineralogy to Contributions (0119412) to Dra Basic geologic data from the the from data geologic Basic –

Geology Acta Hungarica, Geologica é ter MAGOON ö 9 t Gr Ran Gerd to u9) , 20,859–871. Á RKAI ž en Balen – LB (ed.): L.B. ,

Acta Geo Acta

Ra . ------Abstracts Book

The structure and chemistry of natural takovite and synthetic analogue of takovite

Alexey E. KAPUSTIN1, Roman A. KOZLOVSKIY2 and David L. BISH3

. The mineral takovite (Ni6Al2CO3(OH)16 4H2O) is an im- showed pronounced preference for carbonate over other portant nickel-containing phase in low-silica weathering anions, which is also true for other minerals of pyroaurite deposits. Takovite and related minerals in the hydrotalcite and hydrotalcite groups. This makes the task of synthesiz- group have structures in which brucite-like layers carry a ing non-carbonate samples difficult. net positive charge due to the substitution of trivalent for X-ray diffraction study reveals that ion-exchange of divalent cations (BISH, 1980). takovite with nitrate and chloride anions causes only mi- The synthetic analogs of takovite, pyroaurite, and hy- nor changes in the structure, with minor increases in basal drotalcite are active heterogeneous catalysts of basic cata- spacing. However, ion-exchange with sulfate anions leads lytic processes, such as oxialkylation, aldol condensations, to considerable change in basic structure and to formation etc. (KAPUSTIN, 1991). One can assume that natural of two different structures. minerals should have the similar properties. However, the The catalytic activity of both natural and synthetic ta- distinction in the origin may have substantial influence on kovite was investigated in the reaction of alcohol oxialkyl-

the ion-exchange and catalytic properties of natural and ation. The reaction proceeds by a serial-to-parallel route 3r synthetic takovites. resulting in the formation of a mixture of alkylene oxide d Mid-European Clay Conference – MECC 06 To compare the structure, physical–chemical proper- addition products: ties, and catalytic activity of natural takovite and its syn- CH CH thetic analog, the latter was obtained by precipitation. This 2 2 + ROH RO (CH CH O) H O 2 2 n method involves the mixing of a concentrated, aqueous solution of Ni2+ and Al3+ with aqueous hydroxide–car- Our results show that in the kinetic region the reaction bonate to yield an amorphous gel. At a final pH of 9–10, of takovite and alkylene oxide is first order. In the presence the carbonate concentration exceeded the stoichiometric of both types of takovites the alkoxylation reaction proceed- requirements by a factor of approximately three. Follow- ed similar to a basic-heterogeneously catalyzed reaction. In ing precipitation, the heavy gel was allowed to crystallize order to determine the influence of takovite’s steric structure by heating for 24 h at 65°C. The aged gel was investigated on its catalytic efficiency, the composition of reaction prod- by elemental analysis, thermal analysis and X-ray powder ucts was investigated. Both natural and synthetic takovite diffraction, and results were compared with those for the provided narrower product distribution in comparison with natural takovite. The presence of basic sites was examined a homogeneously catalyzed reaction that is more typical of on the surface of both natural and synthetic takovite by ti- heterogeneous catalysis. These results can be considered in tration with benzoic acid in the presence of Hammett indi- light of similarities and distinctions in structure and chem- cators. Because takovites have green color, the titration was istry between takovite and its synthetic analogue. carried out in the presence of white etalon for comparison. Bronsted basic sites of moderate strength were found on Acknowledgement: This work was carried out with financial the surface of both synthetic and natural takovites, and the support from the Ministry of Education and Science of Ukraine site distribution was dependent on the heat treatment. and Federal Agency on Science and Innovations of Russia. The ion-exchange behavior was also studied for both natural and synthetic takovite. During the study of takovite References we found that treatments with various dilute acid and salts BISH, D. (1980): Anion-exchange in takovite: applications to other miner- solutions did not destroy the basic structure. The order of als.– Bulletin de Mineralogie, 103, 170–175. preference to inorganic ions was obtained from anion ex- KAPUSTIN, A. (1991): Inorganic anion-exchangers.– Successes of Chem- change experiments; synthetic and natural takovite both istry, 60, 2685–2717.

1 Azov Sea State Technical University, University Street 7, 87500 Mariupol, Ukraine ([email protected]) 2 Mendeleyev University, Miusskay sq. 9, 125047 Moscow, Russia 3 Indiana University, East Tenth Street 1001, Bloomington 47405, USA 61 Abstracts Book Abstracts 62 3rd Mid-European Clay Conference – MECC 06 n ae. oe f hm ieae lrfieclod which colloids ultrafine liberate them of Some water. in water, representing most the simple aqueous solution. deionized with contact in behaviourbentonite of ferences ers) play arole. oth (amongst components different between intergrowth and (quasi)crystals of morphology smectites, of position content, layer charge density (distribution), chemical com smectite the addition, In properties. bentonite determine to known is Ca/Mg) or Na either (commonly cation able exchange dominating The significantly. vary deposit a of parts different or deposits bentoniteproperties ofdifferent bentonitesinvestigated.are However, thatknown well is it drying, etc.). In some concepts only a few possible extensivesalinity, candidate high pH, high (e.g. processes alteration possible of scenarios ies are available dealing with different Accordingly,studconditions. several expected the under prerequisite for application this is stability the of bentonite The solutions. aqueous with contact in capacity swelling vourableproperties are cation exchange capacity wellasas wasteHLRWin e.g. repositories ( applicabilityradioactive forsealing geotechnicalbarrier as the to respect with investigated currently are Bentonites BGR/LBEG, Stilleweg 2, D-30655 Hannover,BGR/LBEG, Stilleweg 2,D-30655 Germany ([email protected]) As expected, Na dominated smectites readily disperse disperse readily smectites dominated Na expected, As dif the to identify in order conducted was study This Detachment ofcolloids from bentonites inwater Stephan KAUFHOLD DOHRMANN andReiner PUSCH 92.Terfa Their 1992). , ------(b) reduces mass the of geotechnical the itself. barrier are (a) complexescolloidalandradionuclides transportas to able which: colloids liberate to tend they since tories reposi HLRW in barrier geotechnical as application the higher reactive area surface of Na smectites insuspension. the by and pH) on depending silicates of solubility to ing (accord value pH high the by caused bonds chemical of weakening to due colloids liberate to tend water with tact phases might present. be amorphous X-ray of amounts minor although smectites, mainly are colloids the that prove methods three All IR. were enriched by evaporation and analyzed colloids by ESEM, XRD, and The separated. was colloids the containing supernatant the centrifugation After >9. values pH having bentonitesdominated Na of suspensions w/w % 2 of case in Suchobserved colloidswereU/min. particularly 20.000 cannot be centrifuged even by using an ultracentrifuge with PUSCH We conclude that such bentonites are less suitable for suitable less are bentonites such that Weconclude We propose that bentonites which react alkaline in con products.– Clay Minerals, 27,353–361. R (92: s o bnoie o ioain f aiatv waste radioactive of isolation for bentonite of Use (1992): R. , Reference - - -

Abstracts Book

Geochemical studies on pore water from two diﬀerent clay types in the frame of radioactive waste disposal researches

Sándor KELE1, Mieke DE CRAEN2, Maarten VAN GEET2 and Wang LIAN2

Argillaceous formations ranging from plastic clays (Boom the above mentioned parameters under undisturbed in situ Clay, Belgium) to highly consolidated claystones (Boda Boom Clay conditions. Claystone Formation, Hungary) are considered as prom- In the case of the Boda Claystone, piezometer-derived ising host-rocks for the geological disposal of high-level pore water is not available. Furthermore, the squeezing radioactive waste. technique could not be used because of the low pore water In the last decades important research efforts and anal- content in this claystone (1 wt %). Therefore, the leaching yses were made both in Belgium and Hungary in the field technique is used to study the pore water composition of of radioactive waste disposal. To assess the safety of the the Boda Claystone. This study started recently and only clays as a geological barrier, a good understanding of the preliminary results are available yet. mineralogical and geochemical composition of the clays, The aim of this work is to present and compare the ex- as well as the mechanisms controlling the geochemistry of periences of sampling techniques and geochemical analyses their pore waters are essential as it reveals the geochemical of pore water from two different clay-rock types to provide stability of the host rock and influences the migration/re- information for the radioactive waste disposal researches. 3r tention of radionuclides. d Mid-European Clay Conference – MECC 06 Geochemical studies conducted in the last years on the References Boom Clay at the SCK·CEN (Mol, Belgium) used different DE CRAEN, M., WANG, L., VAN GEET, M. & MOORS, H. (2004): The pore water extraction techniques: in situ sampling using geochemistry of Boom Clay pore water at the Mol site, status 2004.– piezometers in the HADES Underground Research Facility SCK·CEN Scientific Report. BLG 990. (Mol, Belgium), and laboratory extraction techniques KELE, S., VAN GEET, M. & DE CRAEN, M. (2006): Geochemistry of such as squeezing and leaching (DE CRAEN et al., 2004). Boom Clay pore water and its dissolved gasses. – SCK·CEN Internal Beside the determination of the chemical composition, Eh, Report, 33 p. pH and pCO of Boom Clay pore water, studies started on MOORS, H., DE CRAEN, M., VAN GEET, M. & WANG,L. (2005): In 2 situ pCO2 measurements in Boom Clay: The PEGASUS experiment. the composition and stable isotope composition of the dis- Clay in Natural & Engineered Barriers for Radioactive Waste Con- solved gasses in the Boom Clay pore water (KELE et al., finement.– International Meeting, March 14–18, 2005, Tours, France, 2006). Using the PEGASUS experimental set-up (MOORS abstract, 423–424. et al., 2005) it was possible to take samples and measure

1 Hungarian Academy of Sciences, Institute for Geochemical Research, Budaörsi út 45., H-1112 Budapest, Hungary ([email protected]) 2 Belgian Nuclear Research Centre (SCK·CEN), Waste and Disposal Department, Boeretang 200, 2400 Mol, Belgium 63 Abstracts Book Abstracts 64 3rd Mid-European Clay Conference – MECC 06 1 measured by nitrogen adsorption at 77 K: BET ratehigh phenol oxidation and low the leaching iron ions. the adjectives: technological best the possesses Fe/Al–M Thus, catalysts. in iron content to according those (1.5%) Fe/Al–M and (2.0%) Fe/Al–T on than more was (13.3%) Fe/Al–Z on ions iron leaching Fe/Al–T.Whereas > Al–Z Fe/ > Fe/Al–M order: following a in decreased oxidation of phenol on all catalysts achieved 100% and rate of phenol of phenol oxidation by hydrogen peroxide. Fe/Al–Z –3.6%and Fe/Al–M –1.6%. 1.9%, – Fe/Al–Taverage: to was catalysts these contentof 500 filtered at calcined water, and air with in dried washed suction, by was clay pillared The kHz. 22 at min 3 during ultrasound by treatedpreviously was clay The temperature. room at overnight stored was mixture 80 at (1%) clay the of dispersion the to added was polyoxocations, Fe/Al containing Solution, 2. was metal OH/ ratio final molar a obtain The 1/10. = Fe/Alratio molar solutionof to NaOH 0.1M with chlorides Al and Fe were Fe/Al of appropriatemixingprepared by 0.1M aqueous volumesof solutions pillaring The structure. Keggine [FeAl aluminum and by iron out carried was exchanging interlayer ions with polyoxocations clay containing of (Transbaikalia, modification The accordingly. Mukhortala Fe/Al–M, and andFe/Al–Z Fe/Al–T, called located were and Russia) Zagustai montmorillonites, Taryat, occurring in naturally from (GUELOU etal, 2003;CARRIAZO etal, 2003). compounds organic toxic of oxidation for catalysts neous heteroge as used were montmorillonites, as such clays, voluminous swelling of pillaring layers structural between by complexes metallic prepared clays Fe/Al-modified 2

Chemical Department, Buryat State Buryat University,Chemical Department, Smolina Str., 24a,670000,Ulan–Ude, Russia ([email protected]) ofEngineeringEcology,Laboratory Baikal Institute ofNature Management,Sakhyanova Str. 8,670047Ulan–Ude, Russia The synthesis ofiron-containing pillared clays from natural clays h eA-oie ly aayt eesynthesized were catalysts clays Fe/Al-modiﬁed The h antxua hrceitc fF/lMwere Fe/Al–M of characteristics textural main The wet reaction the in studied were catalysts obtained The of Transbaikalia andresearch in oftheircatalytic properties Sesegma Ts. KHANKHASAEVA wet oxidation ofphenol by hydrogen peroxide 12 O 4 (OH) 24 (H 2 O) Th 12 1 and Ulya V. DOBOLOVA ° , SayanaV. BADMAEVA ] e conversion

. h iron The C. surface surface area 7+ ih like with ° C, the the C, - of iron ions in the solution, increased with the increasing the with increased solution, the in ions iron of leaching the as well as reaction, the of rate initial the that established was It oxidation. phenol the and pH influenced tempera reaction hydrogencatalystconcentrationphenol,ture, the peroxide, of as that determined shown was were It products. water the final and dioxide carbon The acids. carboxylic and catecholhydroquinone, were HPLC by ed detect products intermediate The g/l. catalyst0.5–5.0 and mmol/l 0.25–4.0 concentrationphenol mmol/l, 0.25–25.0 40–60 from temperature reaction the varying by Fe/Al–M catalyst on that interlayer was 18 Å – 219 m ULU E, ARUT J, ORIR J & AIOE, J.-M. TATIBOUET, & J. FOURNIER, J., BARRAULT, E., GUELOU, & TATIBOUET, BARRAULT, J.-M. J., E., GUELOU, J.G., CARRIAZO, Foundation for Basic Research Grant 06–08–01064 Acknowledgements: catalystperspective for treatment sewage from phenols. a as it consider to us allows conditions reaction the in M catalystthe content 1g/l. t=50 established: were oxidation phenol of reaction of ditions con optimal rate The 3.7–3.9. = pH at achieved was phenolof oxidation maximum The reagents. of concentration h d The . h ieisbhvoro hnloiainwsstudied was oxidation phenol of behaviour kinetics The 44, 1–8. phenol over pillared clays containing iron.– (2003): 303–308. 22, Science, Clay Applied clays.– Al–Cu or Al–Fe modified MORENO, S. (2003): Catalytic wet peroxide oxidation of phenol over Fe/Al– of stability high and activity catalytic high The ° , H3739 [PhOH]:[H pH=3.7–3.9, C, 2 /g, /g, pore volume – 0.270 cm 001 Active iron species in the catalytic wet peroxide oxidationperoxideofwet catalytic the in Activespecies iron -spacing, determined by XRD analysis, showedanalysis, XRD by determined -spacing, 1 ° , Elvira Ts. DASHINAMZHILOVA 2 C, pH 2–6, hydrogen peroxide concentrationperoxidehydrogen 2–6, pH C, hswr a upre by supported was work This Å References . 2

O 3 /g, /g, pore diameter – 37 2 =:4 o/o and mol/mol ]=1:14 Applied Catalysis B: Env., 1

Russian

- - -

Abstracts Book

Structural heterogeneity of alkylammonium-exchanged synthetic swelling ﬂuoromicas

Zenon KŁAPYTA

Swelling fluoromicas can be synthesized from the mixture within the mica interlayers. As a consequence, the organo- of suitable oxides and fluorides melted at 1300–1500oC or TSMs contain several phases consisting of randomly and from talc using an intercalation procedure. These silicates regularly interstratified layers differing in terms of the are produced on the industrial scale and, in comparison to amount of the alkylammonium ions adsorbed. The larg- natural clays, show a greater degree of crystallinity. Their est basal spacings (40.8–50.4 Å) indicate the presence of a chemical composition and physico–chemical properties superstructure, composed of two different layers. However, can be controlled in a wide range. these layers swell in ethylene glycol in the same manner Alkylammonium derivatives of clay minerals have been and form new interlayers with identical spacings. From the extensively studied. In contrast, surprisingly few investiga- XRD patterns it is clear that the organo-TSMs do not con- tions have been reported on the adsorption of organic am- tain the Na-TSM phase and the interlayers are presumably monium ions on synthetic layered silicates. In this work, filled with both organic and Na+ ions in various ratios. two synthetic swelling micas: Na-fluorotetrasilicic mica The maximum amount of the alkylammonium ions ad- (TSM) and Li-fluorotaeniolite (TN) were used as starting sorbed on the TN was 124 meq/100 g. By reacting the mica 3r materials. Their cation exchange capacities (CECs), deter- with an excess of the C16 and C18 salts, the surfactants d Mid-European Clay Conference – MECC 06 mined by adsorption of alkylammonium ions are 92 and were adsorbed in both cationic and molecular forms as it 124 meq/100 g. was found for TSM. Thus, the interlayer Li+ ions were also Organo-micas were prepared by ion exchange with do- only partially replaced by the alkylammonium ions. decyl-, tetradecyl-, hexadecyl- and octadecyltrimethylam- The XRD patterns of the organo-TNs show a series of monium (C12, C14, C16 and C18) bromides. Concentra- reflections suggesting that the samples obtained are poly- tion of the ammonium salt varied from 0.25 to 4.0 CEC of phasic. The strong peaks in the range 23.3–28.7 Å may be 23 the mica. The products were characterized using Na MAS ascribed to the random interstratifications of the TN layers NMR spectroscopy, X-ray diffraction (XRD) and C and N with diversified amount of adsorbed alkylammonium ions. determinations. The peaks with very low intensity corresponding to the As shown by 23Na MAS NMR, up to 25% of the total basal spacings of 42.3–51.2 Å indicate that small amounts + amount of Na ions in the TSM were non-exchangeable, of regularly interstratified layers are present. even if a large excess of the organic salt was used. The This study also shows that adsorption of ethylene gly- maximum amount of the alkylammonium ions adsorbed col, well known and widely used in clay mineralogy, may on the mica was 92 meq/100 g. However, at high concen- be successfully applied to XRD characterization of alkyl- trations of the C16 and C18 surfactants, it was found that, ammonium-exchanged silicates, especially those with except for organic ions, the salt molecules were addition- mixed-layer structure. ally adsorbed on the silicate, resisting washing with water but being removable with ethanol. Acknowledgments: This work was supported in part by the AGH– The XRD patterns of the samples obtained show that University of Science and Technology (Kraków, Poland), the re- the alkylammonium ions are distributed inhomogeneously search project 11.11.140.158.

1AGH–University of Science and Technology, Faculty of Geology, Geophysics and Environmental Protection, al. Mickiewicza 30, 30–059 Kraków, Poland ([email protected]) 65 Abstracts Book Abstracts 66 3rd Mid-European Clay Conference – MECC 06 Table 1 Characteristics of intercalated montmorillonite samples with methylene blue. (1.5 Ca–Cheto for higher much is that CEC with agreement good in are data trationof dyeaqueous in solutions. These concen increasing with MB–Cheto for mol/mol 1.124 to increases MB/montmorillonite fromtomol/mol0.536 0.685 for MB–SWy and from 0.896 ratio molar these The samples. of analyses total from calculated was MB–Cheto) MB in of intercalatedmontmorillonite fully samples(MB–SWy and amount adsorbed monomer/ The ratio dimer/trimer/tetramer. various of solutions aqueous MB with intercalated fully were Ca–Cheto) (Na–SWyand samples montmorillonite The concentration. analytical MB ferent dif with solutions aqueous for calculated were tetramer monomer,and dye dimer, trimer ofdistributions the data β constants aggregation equilibrium the solutions aqueous in (MB) blue methylene of spectra Vis-absorptionUsing 2 1

Faculty ofMathematicsandPhysics, Prague, CharlesUniversity Ke Karlovu 3,121,Czech VŠB–Technical Ostrava, University 70833Ostrava–Poruba, Republic([email protected]) Czech Zdenek KLIKA q

of the the of of Na,KandCa (meqAlk/gNa–SWy ormeqAlk/gCa–Cheto); Cheto; and MB or SWy and MB between ratio molar q – 0

– mean – meq.g q- -1 th dye aggregates were evaluated. From these these From evaluated. were aggregates dye th necltdmnmrloie ydﬀrn aggregates Intercalated montmorillonites by diﬀerent q ) in comparisonin ) Na–SWywith meq.g (0.88 BCeoV) .01- 23 18 114 .2 .2 1.74 1.53 0.99 0.22 0.97 0.32 0.90 0.18 1.52 0.99 0.19 1.21 1.05 0.13 0.91 1.124 0.78 0.22 0.896 0.34 0.77 0.685 1.86 0.70 0.585 1.71 2.39 1.58 0.71 0.581 1.10 1.55 0.528 5.00.10-3 2.39 1.54 5.00.10-5 0.536 2.05 MB–Cheto(VI) 5.00.10-3 1.53 1.59 MB–Cheto(II) 2.00.10-3 1.51 1.34 MB–SWy(VI) 5.00.10-4 1.10 MB–SWy(V) 2.00.10-4 MB–SWy(IV) 5.00.10-5 MB–SWy(III) MB–SWy(II) Sample -th MB -th 1 q+ , Pavla aggregate in aqueous solution; aqueous in aggregate Č APKOV mll (m (o/o) mqg (e/) (meq/g) (meq/g) (meq/g) (mol/mol) (nm) (mol/l) c Á 1 , Petra HOR of methylene blue q d MB q – 001 01 M/M qB Ak qsum qAlk qMB MB/MMT d001 – intercalated amount of MB (meq MB/g Na–SWy or meq MB/g Ca–Cheto); Ca–Cheto); MB/g meq or Na–SWy MB/g (meq intercalatedMB – of amount – basal spacing of fully intercalated montmorillonite sample; montmorillonite intercalated fully of spacing basal –

q Á sum -1 KOV ). - - =q Alk of Education of the Czech Republic, project No. MSM 6198910016. Acknowledgement samples. MB–Cheto in luminescence no almost and MB–SWy in spec luminiscence the strong the exhibits blueMethylene rillonite. on charge layer silicate troscopic behavior of MB the of effect strong the showed measurements Fluorescence montmorillonites. MB of arrangement the interlayer in differences the revealed modelling molecular with MB–Cheto). intercalatedmontmorillonite fully samples(MB–SWy and spacing MB/montmorillonitebasal ratioand molar Moreover there is a very good positive correlation between + q Á 1 Alk , Marta , Marta VAL Structure analysis using combination data of diffraction .

Notes: c Republic – analytical concentration of MB in aqueous solution : ÁŠ We acknowledge KOV q+ Á guests intercalated in montmo 1 and Miroslav POSP q+ guests in SWy and Cheto SWyand in guests the support from the Ministry MB/MMT

– calculated – q Alk ÍŠ d

– sum – 001 IL of 2 - - ;

Abstracts Book

Sorption of arsenic on clay minerals – a theoretical approach

Goran KNIEWALD and Željka FIKET

The mobility of arsenic species in the environment is largely model and competition between arsenic and other ions controlled by solid phase sorption reactions (LANGMUIR, for sorbing phases for a finite number of sites was allowed. 1997; WILKIE et al. 1998). Quantitative evaluations of the Both mineral assemblages were allowed to come to equi- solid phase/water partitioning of many toxic metals, in- librium by simulating the flushing of many pore volumes cluding arsenic, are best accomplished by a surface com- through the sediment–mineral surface assemblage. The plexation approach (CHERRY et al., 1986; SADIQ, 1997). model output was evaluated using the ratio “R” of mod- Equilibrium-based thermodynamic modelling is currently elled vs. expected arsenic concentrations. one of the most appropriate methods to evaluate the com- Small differences in the conceptual model and data ac- petitive geochemical processes that affect the transport and quisition techniques can have a large effect on the simula- toxicity of arsenic, including predictions regarding arsenic tion error. The error of neglecting competition by common persistence and mobility in the environment. compounds such as bicarbonate or silicic acid can equal The numerical computer code PHREEQC was used to or exceed the bias resulting from inappropriate choice of simulate arsenic surface complexation from a small water- mineral phases. The continued development of field and shed with naturally high levels of arsenic on clay mineral analytical protocols to support surface complexation mod- components (kaolinite and montmorillonite) of a stream elling is clearly needed. 3r sediment. Surface complexation mass-action coefficients d Mid-European Clay Conference – MECC 06 were obtained from the literature in the generalized two- References layer model form, or from linear free energy relationships. CHERRY, J.A, MOREL, F.M.M., ROUSE, J.V., SCHNOOR, J.L. & WOL- A reasonable simulation of expected arsenic concentrations MAN, M.G. (1986): Hydrogeochemistry of sulfide and arsenic-rich tailings and alluvium along Whitewood Creek, South Dakota.– In: is obtained using competitive complexation, literature-de- Mineral and Energy Resources: a review of developments. Colorado rived sorption constants and the PHREEQC model. School of Mines Publication 29(4), 44–56. The USGS computer code PHREEQC version 1.6 was LANGMUIR, D. (1997): Aqueous Environmental Geochemistry.– Pren- used for all simulations. The WATEQ4F thermodynamic tice Hall, New Jersey, 601 p. database formed the core to which surface complexation SADIQ, M. (1997): Arsenic chemistry in soils: an overview of thermodynamic predictions and field observations.– Water, Air and Soil Pol- parameters were added. The code was used for the calcula- lution, 93, 117–136. tion of saturation indices, sensitivity analysis of parameters WILKIE, J.A. & HERING, J. (1998): Rapid oxidation of geothermal such as Eh, pH and temperature, modelling the mixing of arsenic(III) in streamwaters of the eastern Sierra Nevada.– Env. Sci. stream water of different compositions. The surface com- Technology, 32, 657–666. plexation routine was used in the generalized two-layer

Center for Marine and Environmental Research, Ruđer Bošković Institute, POB 180, 10002 Zagreb, Croatia ([email protected]) 67 Abstracts Book Abstracts 68 3rd Mid-European Clay Conference – MECC 06 5 4 3 2 1 lite P and analcime in addition to the metastable zeolites X stablezeolitezeo formsformed, e.g. have kinetically been temperatureInhigher the observed. hasnot been systems, at100 experiments found. the In ed water a higher enrichment in the zeolite phases has been aqueouswithoutenvironmentsystemadd the the in then in more decreases strength sample the Although biguous. am is relationhowever, phases, their zeolite offormation compressive strength of geopolymer can be correlated with 100 atday one after alreadybutlongest experiments, the in MPa 4 to com pressive strength the of the Na composites gradually decreased exposition, hydrothermal the respectively.After Na the in MPa about26 and MPa 14 were strengths compressive original The hours. 168 environmentforaqueous in or hours, 24 for medium ous 180 and 140 100, at autoclave an in exposition hydrothermal to also but ageing, normal to Al (1.1–1.2)Na systems in alkali and water-glass metakaolin, of mixtures DAVIDOVITS, 1999) ( time that at available materials raw of reactions simple on based pyramids building in materials accordingto his hypothesis, these evenold Egyptians used but agents, bonding cement ofsubstitution full-value a as only not considered be can geopolymers the patents, original of author the Davidovits, to According of water-glass. presence the in produced relicts metakaoline tivated alkali-ac of structures network represent Geopolymers 7 6

Institute ofRockStructureandMechanics ASCR,VHolešovi ZPSV a.s., Krizikova 68,66090Brno, Republic Czech ofMolecularSpectroscopy,Laboratory Institute ofChemical Technology, Technická 5,16628Prague, Republic Czech ofGlassandCeramics, Department ofEnvironmental Protection Engineering,Department Tomas Republic inZlin,76272Czech BataUniversity Institute ofMacromolecular Chemistry, Academy Republic, oftheCzech Heyrovskeho sq. 2,16206Prague, Czech State Chemistry, ofSolid In Department 2 O Roman SLAVRoman Blocks with dimensions 2x2x2 cm werepreparedfromcm dimensions 2x2x2 with Blocks 3 David KOLOU Tecmoiemtraswr ujce o only not subjected were materials composite The . ° C it decreased to half of the original value. The value. original the of half to decreased it C 2 O–(3.6–4.4)SiO Í K 3 . Š , JanaANDERTOV EK Hydrothermal ofgeopolymers stability 1 , Jind 2 Institute ofChemical Technology, Technick –Al 2 O and K and O stitute ofChemical Technology, Technická 5,16628Prague, Republic([email protected] Czech ° 2 O C, zeolite mineralizationzeolite C, ř ° ich VOREL 3 wt/ihu aque with/without C and 1.2K 2 DAVIDOVITS& O environments,O Á 2 4 O–4.4SiO , Vladim 1 è , Barbora DOU k á ch 41,18209Prague Republic 8,Czech 2 í – ------r MACHOVI ae hs en oﬁmdb T uvs nthe In signal (3Al) Q4 curves. the of intensity DTA the spectra, NMR by MAS conﬁrmed been has water bound zeolite the of presence from 28 MPa to 14 MPa. The decreased strength compressive original 60 environment. The at exposition autoclave year half hydrothermal exposition. the after compressivestrength higher their for reason the been probably has this and K-geopolymers, of products syn expressed cantheses be following inthe way: hydrothermal of result The chabasite. and (faujasite) DAVIDOVITS, J. & DAVIDOVITS, F. (1999): Archeological analogues Archeological (1999): DAVIDOVITS,F. & DAVIDOVITS,J. lic ( 2B06120) and was supported by the Grant Agency of Czech Repub MSM No. project (research Sports Youthand Education, of istry Acknowledgements: associatedsignals with higherSi/Al ratios increased. P-zeolite the of intensities the while decreased strength) characteristic for geopolymers (as well as their compressive á 5 project No. 103/03/0506). , 16628Prague, Republic Czech h agooyeswr ute ujce oa nearly to subjected further were Na-geopolymers The the in found been has mineralization zeolite No ference Geopolyére ‘99,283–296. Con International Second Geocistem.– project research european the from Result maerials. geopolymeric of stability long-term and Š 180/+/24 h:zeolite P, analcime 140/+/24 h:zeolite X,zeolite P -/24 h:chabasite, zeolite P +/24 h:zeolite X,zeolite P OV Á Č 5 1 , Vlastimil B , Martina URBANOV , Martina hswr ilb upre yCehMin Czech by supported be will work This Reference Í LEK

Republic 180 180 6 a o o C C nd Á zeolite P, analcime zeolite P, analcime Pavel H 2 ° i te aqueous the in C , Ji ří ří BRUS analcime ) analcime Á JEK 2 ,

7 29 Si - - - - Abstracts Book

Iron phases occurring in Fe-rich bentonite from Lieskovec, Slovakia

Peter KOMADEL1 and Joseph W. STUCKI2

Fe-montmorillonite of relatively low charge is the domi- The hyperfine parameters of theö M ssbauer spectra nant mineral in Lieskovec bentonite (Central Slovakia) for raw bentonite L3 (Fig. 1) are consistent with structural developed from andesitic pyroclastics. Admixtures of ka- Fe(III) in an aluminosilicate phase mixed with an Al- olinite, quartz, cristobalite and plagioclase are present in substituted hematite. The hematite did not undergo the all samples, while muscovite/illite and orthoclase occur in Morin transition, as evidenced by the negative values most samples. The Lieskovec bentonite deposit is relatively for the quadrupole splitting of -0.264 mm/s at 30 K and homogeneous as demonstrated by quantitative analysis us- -0.158 at 6 K. The intensity of the sextet relative to the ing Rietveld refinement, though some differences in the doublet increased from about 10% to about 15% between samples obtained from different parts occur. Size fraction- temperatures of 30 and 6 K. The magnetic hyperfine field ation failed to separate pure smectite. The <2 µm fractions of >52 T at both temperatures is consistent with an Al- contain smectite, kaolinite and traces of crystalline non- substituted hematite but it is too high for ferrihydrite, clay minerals. Total contents of SiO2, Al2O3 and Fe2O3 in goethite, or maghemite (MURAD, 1988, 1989). the raw bentonite samples are 53–65, 16–22 and 5–9 %, respectively. The Fe2O3 content in Lieskovec bentonite is References higher than in most other Slovak bentonites. Preliminary ANDREJKOVIČOVÁ, S., MADEJOVÁ, J., CZÍMEROVÁ, A., GALKO, I., 3r data obtained from Mössbauer spectra taken at room and DOHRMANN, R. & KOMADEL, P. (2006): Mineralogy and chem- d Mid-European Clay Conference – MECC 06 liquid nitrogen temperatures show that Fe(II) content is low istry of Fe-rich bentonite from Lieskovec deposit, Central Slovakia.– and Fe(III) occurs dominantly in smectite. Goethite and/or Geologica Carpathica, in press. hematite, containing up to 26 % of total Fe, are present in MURAD, E. (1988): Properties and behavior of iron oxides as determined some samples (ANDREJKOVIČOVÁ et al., 2006). by Mössbauer spectroscopy. – In: STUCKI, J.W., GOODMAN, B.A. & SCHWETMAN, U. (eds.): Iron in Soils and Clay Minerals. D. Re- Results of most recent variable temperature Mössbauer idel, 309–350. spectroscopic assay of Lieskovec bentonite and its <2 µm MURAD, E. (1989): Poorly-crystalline minerals and complex mineral as- fraction will be discussed. semblages.– Hyperfine Interactions, 47, 33–53.

a b

Fig. 1 Mössbauer spectra of Lieskovec bentonite sample L3 at 30 K (a) and 6 K (b).

1 Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-84536 Bratislava, Slovakia ([email protected]) 2 Department of Natural Resources and Environmental Sciences, University of Illinois, Urbana, IL 61801, USA 69 Abstracts Book Abstracts 70 3rd Mid-European Clay Conference – MECC 06 pacity. ca absorption smaller the period, immersion longer the leachate: the into time immersion sample of increase the with capacity absorption of decrease the indicate results liquid as atest fluid. ex of series last periments IV) was conducted(series using the site specific using The performed fluid. test were a as water tests demineralized index what after III), series and (II two for time of periods leachate the duringdifferent into immersed wascomponent (bentonite)mineral GCLs samples (series I), three other series of tests were also made. Jakuševac near Zagreb. site disposal waste solid municipal a of basin retentionleachate the from collected was leachate real i.e. liquid site-specific capacity The conducted. werebentonite absorption of tests water and loss fluid index, swell tion, composi mineral of series A liquids. to compatibility cal recommenda ASTM fortestedchemi shouldbe GCL a ofclay portion the tion with line In landfills. for liners clay compositein used frequentlyare (GCLs) liners clay thetic Geosynthetic materials such as geomembranes and geosyn Faculty ofMining, Geologyand Petroleum Engineering, 10000Zagreb, Croatia ([email protected]) Table 1 Swell index [ml/2g]. Legend: series I (“as-received”); series II series (“as-received”); I series Legend: [ml/2g]. index Swell 1 Table 3 2 1 Sample no. Series I Series II Series III Series IV Series III Series II Series I Series no.Sample Water absorption test results are shown in Fig. 1. The 1. Fig. in shown are results test Waterabsorption Besides the baseline testing performed on “as-received” (immersion time – 7 days); series III (immersion time – 60 days); 60 IV(leachateseries astest fluid). – time (immersion III series days); 7 – time (immersion Biljana KOVA Chemical compatibilityChemical ofGCLmineral component 4 4 3 16 16.5 16 43 43 44 34 34 35 34 33 34 Č EVI Ć ZELI Ć , Dubravko DOMITROVI ieseicliquid site-specific ------yatrimrinbcueterslso eisI (7 days) II series of and III(60days) series do not show almost any difference. results the because immersion after ly interesting to note that these changes occurred immediate is noticed for samples immersed into the leachate. It is also spacing basal of change of the minerals being smectite. The the majoritywith minerals clayof that 75% containssampleabout indicate analyses XRD (XRD). diffraction powder index. swell lower much show IV) (series fluid test as contrary, the liquid tests performed with site specific of immersion comparing to baseline testing (series I). On a and III) show increasethe of swell index with durationthe II (series liquid forsamples intoimmersed site the specific liquid. son with samples immersedinto site the specific “as-received”with compariobtained valuesin samples in atiflec flaht otebentonite. the to leachate of cant signifi influence showed fluid test a as leachate using the site specific the to bentonite behaviour. However, swell leachate index tests conducted of different influence some showed during time of periods leachate specific site the into immersed iea cmoiin a be dtrie b X-ray by determined been has composition Mineral results Tablein shownareThe results test 1. swellFree difference significant no yield loss Testfluid forresults XRD analysis and index tests conducted on specimens onconducted tests index andanalysis XRD Ć , Marta MILEUSNI , Marta Fig. 1 Water capacity. absorption Ć andNeven TADEJ

- - - Abstracts Book

Geochemistry and weathering of the Late Cenozoic red clays in the Pannonian Basin

János KOVÁCS

During the past decade little attention has been paid to the Al/Na and low Sr/Ba ratio, which indicate strong chemical red clays in the Pannonian Basin. Important key forma- weathering because Na and Sr are more mobile than Al, K, tions in the Late Cenozoic stratigraphy are the red (silty) Rb, and Ba and consequently easily removed from parent clays. Litho-, bio-, chemo- and magnetostratigraphic data rocks during chemical weathering. show that they formed in different periods (SCHWEITZER The results show that chemical weathering was intense & SZÖŐR, 1997; VICZIÁN, 2002; KOVÁCS, 2003). The in the Pannonian Basin in the Late Neogene. youngest red paleosol (reddish clay) is of Early Pleistocene The CIA and MIA values suggest that warm and humid age. The older one (red clay) was formed in the Early and climate was predominant and responsible for the intense Middle Pliocene (PÉCSI, 1985; KRETZOI, 1987; SCH- chemical weathering. The weathering values suggesting WEITZER & SZÖŐR, 1997; KOVÁCS, 2003). that the Neogene palaeoclimate in the Pannonian Basin Geochemical study was carried out on 50 samples from was more humid and hotter (thus favoring intense chemi- 14 red clay sequences. The red clays are primarily com- cal weathering) compared to the present climate regime. posed of silt and clay (KOVÁCS, 2003, 2006). Degrees of 3r chemical weathering during the Pliocene were estimated References d Mid-European Clay Conference – MECC 06 by using geochemical proxies including CaCO contents, 3 DING, Z.L., SUN, J.M., YANG, S.L. & LIU, T.S. (2001): Geochemistry chemical index of alteration (Al2O3+CaO+Na2O+K2O) of the Pliocene red clay formation in the Chinese Loess Plateau and diagrams (NESBITT & YOUNG, 1982) and mineralogical implications for its origin, source provenance and palaeoclimatic index of alteration (MIA) (VOICU et al., 1997). The degree change.– Geochim. Cosmochim. Acta, 65, 901–913. of silicate weathering can be estimated by the chemical in- KOVÁCS, J. (2003): Terrestrial red clays in the Carpathian Basin: a dex of alteration (CIA). These values are 60 to 90, which paleoenvironmental approach.– Geomorphol. Slovaca, 3, 86–89. show a strong weathering process. The mineralogical index KOVÁCS, J., (2006): Wind-blown origin of the Neogene red clay in the of alteration evaluates the degree of mineralogical weather- Pannonian Basin.– Geophys. Res. Abstracts, 8, 04182. ing, i.e. the transformation ratio of a primary mineral into KRETZOI, M. (1987): Remarks on the correlation between European and Asian Late Cenozoic local biostratigraphies.– Vertebr. Palasiat, 25, its equivalent alteration mineral. It has the advantage of in- 145–157. dicating the degree of weathering for each analyzed sample, NESBITT, H.W. & YOUNG, G.M. (1982): Early Proterozoic climate and independently of the depth of sampling. The MIA values of plate motions inferred from major element chemistry of lutites.– Na- our samples (60–100%) indicate intense to extreme weath- ture, 299, 715–717. ering. The value of 100% means complete transformation PÉCSI, M. (1985): The Neogene red clays of the Carpathian Basin.– Stud- of a primary mineral into its equivalent weathered product ies Geogr. Hungary, 19, 46–60. and, by extrapolation, complete weathering of the parent SCHWEITZER, F. & SZÖŐR, Gy. (1997): Geomorphological and strati- rock. graphical significance of Pliocene red clay in Hungary.– Z. Geomor- phol. Suppl., 110, 95–105. The degree of chemical weathering can be estimated by VICZIÁN, I. (2002): Typical clay mineral associations from geological geochemical proxy indicators. Elemental concentrations formations in Hungary: A review of recent investigations.– Geol. Carpathica, 53, 65–69. such as K, Na, Ca, Sr, Ba and CaCO3 as well as element ratios of K/Na, Al/Na, Rb/Sr, and Sr/Ba have been widely VOICU, G., BARDOUX, M. & VOICU, D. (1997): Mineralogical norm used to study the degree of chemical weathering based on calculations applied to tropical weathering profiles.– Mineral. Mag., 61, 185–196. the fact that these elements commonly display remarkably different mobility and are fractionated to different degrees YANG, S.Y., LI, C.X. & CAI, J. (2006): Geochemical compositions of core sediments in eastern China: Implication for Late Cenozoic palaeoen- through chemical weathering (DING et al., 2001; YANG et vironmental changes.– Palaeogeogr., Palaeoclimatol., Palaeoecol., al., 2006). Our data show high ratios of K/Na, Rb/Sr, and 229, 287–302.

Department of Geology, University of Pécs, Ifjúság u. 6, H-7624 Pécs, Hungary ([email protected]) 71 Abstracts Book Abstracts 72 3rd Mid-European Clay Conference – MECC 06 1 30 about of tures tempera decomposition and dehydration both exhibited 350 above phase NiO-like of formation gradual a and temperatures these at structure LDH of destruction a showed measurements H of evolution simultaneous 320–380 at observed was effect endothermic second The analysis. thermal ofresults 50 about of temperatures found at was measurements XRD HT by in line formerly (003) diffraction of reported shift was corresponding The LDHs (1999). STANIMIROVAal. et of heating after phases spacing.formation A basal of such low-temperature meta decreased slightly with structure hydrotalcite layered the retained samples dehydrated interlayerwater.ofThe lease by H accompanied tion was found at 200–250 effect endothermic first The DTAcurves. in observed were compoundsdrotalcite-like significant. not was treatment hydrothermal of effect the 4, of ratio molar Ni/Al with sample the For samples. treated hydrothermally or coprecipitated in phases found were crystalline other No phase. LDH of crystallinity dif hydrotalcite improved of an indicate which observed, were lines values fraction FWHM of decrease andsignificant intensity integral of increase an treatment, thermal hydro After products. coprecipitated the in present was XRD) and Raman spectroscopy. (HT (TG/DTA/EGA),diffraction high-temparatureX-ray analysis thermal using studied were oxides mixed Ni–Al transformationformedphase ofpreparedand products of hydrother 180 at was h 20 samplesfor treated mally prepared of part A solutions. nitrate ofcoprecipitation by prepared were 4 and 3, 2, of composi chemical Ni of with tion clays anionic takovite-like Three to precursors as oxidesapplicableheterogeneousmixedobtain in catalysis. used often are structure drotalcite-type Anionicclays(layered doublehydroxides, LDHs)hy with 3 2 Institute of Inorganic Chemistry AS CR, 250 68 Řež, Czech Republic ASCR,25068Řež,Czech Institute ofInorganic Chemistry ofMolecularSpectroscopy,Laboratory Institute ofChemical Technology, Technická 5,16628Prague, Republic Czech State Chemistry, ofSolid Institute ofChemical Technology,Department Technická 5,16628Prague, Republic ([email protected]) Czech Thermal behaviour ofsynthetic takovite-like anionicclays studied w mjr nohri eet hrceitcfrhy for characteristic effects endothermic major Two crystallinity lowrelatively of hydrotalcite-likephase A yhg-eprtr -a ircinadRmnspectroscopy Raman and by high-temperature X-ray diffraction 1-x Franti Al x (OH) ° ° . h yrtemlytetdsamples treated hydrothermally The C. C higher in comparison with coprecipiwith comparison in higher C š ek KOVANDA 2 (CO ° 3 ) C and it was accompanied by a by accompanied was it and C ° x/2 C and to re itthe was ascribed ° · C lower in comparison with comparison in lower C yH 2 ° ad CO and O .Temldecomposition Thermal C. 2 O and Ni/Al molar ratio molar Ni/Al and O 1 , Tom 2 . The HT XRD The . áš ROJKA 2 O evolu O 1 , Vladim ------aa pcr ftkvt-ieLH.Tecmlxband in complex also The LDHs. takovite-like of found spectra Raman were bands corresponding The ordination. cm 550 about at band major The oxide. nickel reference of spectrum with dent 400 at calcined samples of spectra 400 of temperature low relatively at even a indicated patterns obtainedsamples the in phase spinel-like ofamount XRD trace of fitting full-profile the hand, 900 abovetemperatures samples high at of calcined patterns XRD powder in NiO with together NiAl The lattice. NiO the in ions Al with of presence by comparisonexplained be can which in NiO,reference lower slightly of was phase parameter NiO-like lattice The LDHs. takovite-like of position molarAl ratio. Ni/ increasing with decreased LDHs prepared of stability Thermal treatment. hydrothermal without samples tated STANIMIROVA, TS., VERGILOV, I., KIROV, G. & PETROVA, N. (1999): Nos. 104/04/2116and 106/05/0366). republic(projectsCzech Grant of Agencythe by and 6046137302) MSM No. project (research Sports Youthand Education, of istry Acknowledgements: at highertemperaturesobserved above 800 spinelisof markedcrystallization butspinel-likea phases, of amounts trace by accompanied probably oxide, mixed 300–400 between decomposed are claysanionictakovite-like that concluded be Itcanfound. 60 atband ca. new the 800 at calcined samplesof tra calcination temperature wasIn observed. the Raman spec of increasing these with sharpening gradual spectra their and bands three using Raman fitted The also were LDHs bands. takovite-like calcined separate three using fitted cm 550 at maximum with h i-iepaewsfre fe hra decom thermal after formed was phase NiO-like The o-eprtr mtpae. Junl f aeil Sine 34, Science, 4153–4161. Materials of compounds: Journal hydrotalcite-like metaphases.– low-temperature of products decomposition Thermal í r MACHOVI Č hswr a upre yCehMin Czech by supported was work This 2 andPetr BEZDI 0 -1 References is related to Ni in octahedral co octahedral in Ni to related is cm -1 -1 characteristic for NiO can be be can NiO for characteristic , ascribed to spinelto phase,was ascribed , ° C and higher temperatures,higher and C 2 O ° C were nearly coinci nearly were C ° 4 t fr NiO-like form to C spinel was detected detected was spinel Č ° C. On the other the On C. ° KA ° . h Raman The C. C. 3 - - - - - Abstracts Book

Smectites from Ziryanovskoe deposit (Kurgan Region, Russia): Relation between composition, structure and technological properties

Viktoriya KRUPSKAYA1, Leonid VOEVODIN2, Georgij PILOYAN1 and Maximilian NIKOLSKIJ1

This work was carried out to optimize technological pro- IR-spectroscopy testify to increase structure Fe3+ in yel- cessing of bentonites from Ziryanovskoe deposit, situated low bentonites. Also, mixed layers kaolinite–smectite was in the Kurgan region on south-eastern part of the Eastern- found in this type. Destruction of smectites structure starts Siberia lowland. Recently this deposit is actively exploited. during 300°C heating caused by octahedral Fe oxidation. Clays from it are used for drilling fluids, foundry sands and All investigated bentonites have good rheological be- iron-ore pellets. haviour and quality of suspension in activated state, but For investigation of relation between composition and they have not enough thermal stability. Temperature of structure of smectites and technological properties of ben- second endoeffect is about 510–530°C. Only bentonites of tonites the following methods were used: X-Ray diffraction, I group have a small effect at 675°C. Smectites of group thermal analysis, IR-spectroscopy, EMR-spectroscopy. III have lowest order but they have the best quality of sus- Technological properties were tested by specification API pension. Processes of Ca–Na replacement take place faster 13A and VGD–69. The XRD patterns were collected from than in I and II bentonites. The best technological prop- 3r d Mid-European Clay Conference – MECC 06 oriented preparations of natural in air-dried and ethylene erties reach under 2% of soda. Activation in brown–grey glycol-solvated states and after 100, 300 and 550°C heat- and brown bentonites happens in other way. In the begin- ing and from activated samples (2, 3 and 4% of Na2CO3) in ning (at 2–3% of soda) disordered is increased. Then, in air-dried and ethylene glycol-solvated states. XRD patterns the moment of Ca–Na replacement maximum, ordering calculation and spectrum analysis were used for smectites increasing is observed. The subsequent activation results structure study. in decrease of structure and technological properties. Bentonites can be subdivided into brown–grey (I), So, activation of smectites from Ziryanovskoe deposit brown (II) and yellow (III) clays. Among non-clay miner- considerably improves their technological properties. als quartz and feldspars were registered in extrinsic quanti- Ca–Na replacement is going faster in smectite which have ties (<5%). The main components are ferriferous, poorly more disordered structure. At the moment of maximum of ordered montmorilonites. Predominant interlayer cations replacement smectite have the best ordering and techno- are Ca–Mg, but Na–K cations are also present. Content of logical properties. Fe in octahedral position decrease ther- montmorilonite is about 65–75%. Complicated composi- mal stability but increase quality of suspension. tion of cations content is confirmed by thermal data and results of exchange capacity study. In addition to montmo- Acknowledgement: This work was supported by grant of President rilonite, illite and kaolinite are present in small amounts. of Russian Federation МK–8651.2006.5 and Russian Federation Content of FeO oxide is varying from, 8.6% in type I clays Fundamental Research grant 05–05–0869_ofi. to 6.9% – in clays of type III by the XRF analysis. Date of

1 Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry, Russian Academy of Science, Staromonetny per. 35, 119017, Moscow, Russian Federation ([email protected]) 2 Bentonit Scientific Industrial Company, Tverskaya 12/1, 125009, Moscow, Russian Federation 73 Abstracts Book Abstracts 74 3rd Mid-European Clay Conference – MECC 06 the the northern part where the clayey rocks were transformed age of the secondary deformation K–Ar textures falls to 20 Ma. Inprofile of part southern the in But foldbelt. ranean tonic phase in the tec Caucasus and other areas of Eocene the Mediter an reflects which Ma, 50 age demonstrate the to south along profiles. the north from increases minerals clay the of transformation The age. K–Ar calculated of changes and minerals clay of transformation the of degree between correlationpositive a is there samples studied all In Rivers). KoysuAvarskoe Caucasus were studied (along the Terek, the Belaya and the post- first the fix Ma event.sedimentary 600 about age The 2003). al., et DOV phase of diagenetic changes first and illitisation of rocks (VINOGRA the for typical is correlation 900 to 600 Ma. This from age calculated the of reduction by accompanied was samples lies900 andbetween 600 Ma. same Increase of K from 2 to 4.5% the of dating K–Ar platformThe sediments. ofHercynian beginning transformationresponds the to of 380 boreholes all from of samples show age of 600 systems from isotopic Rb–Sr taken The Early in Kepina. were Nevel, Soligalitch, Yam, samples later, Gavrilov boreholes: the and studied Cambrian The Early in time. Devonian eroded and lifted tinental margins. con passive the of Taman rocks peninsula are the low-lithified of the Neogene of of clays schists GreaterCaucasus were folded. The clayey and argillites Jurassic The vironment. en platform within transformed and accumulated were clays Vendian The different. is sediments investigated the Taman the peninsula. of Neogene and Caucasus Greater the of in the sic data isotopic Rb–Sr Vendian and from RussianrocksPlatform,clayeyJuras the of K–Ar with deals paper The Geological Institute ofRussian Academy per. ofSciences, Pyzhevsky 7,119017Moscow, Russia h eda lydpst fteRsinPafr were Platform Russian the of deposits clay Vendian The of transformation of degree and regime Geodynamic –radR–riooi ytm ftepol Terek profile the of systems isotopic Rb–Sr and K–Ar Greater the of deposits Jurassic the of profiles three The The oftheisotopic possibility dating stagesofpostsedimentary ± transformations ofclayey terrigenous depositsinthedifferent 0M nteuprpr.Teaeo 380 of age The part. upper the in Ma 40 ± 0M ntelwrpr ftepol and 50 Ma in the lower ofpart the profile Yulia V. KUSHCHEVA, I.GOLOVIN Dennis andMargot I.BUJAKAITE geodynamical situationsgeodynamical ± 40 Ma cor Ma 40 ------tion of Greater the Caucasus. reconstruc structural of beginning the age,Jurassic Early north isotopic these systems manifestsourceSo rocks. age ofthe the from the group to correspond second data ern part gives the age 240–260 Ma. They The the alike Belaya. age profile the stratigraphic of to close Early–Middle are with They Jurassic. associates distin first can The we groups. two guish Ma) 165–260 Koysu, Jurassic Avarskoe Middle profile (the the in Caucasus 180 – Greater the of tion reconstruc- structural of phase only the indicate systems (BU Ma JAKAITE 180 etal., 2003). about Caucasus, Greater the of struction recon structural the of age the keep they lowergrade a to VINOGRADOV, V.I., GOLOVIN, D.I., BURZIN, M.B. & BUJAKAITE, & M.B. BURZIN, VINOGRADOV,D.I.,V.I., GOLOVIN, KUSHCHEVA,Yu.V., LATISHEVA, I.V., GOLOVIN, D.I.GAVRILOV, & BUJAKAITE, M.I., GAVRILOV, Yu.O., GERTSEV, D.O., GOLOVIN, D.I., samplesthe proves our observation. of composition chemical the of investigation and vations obser section sedimentary redistribution of material. Thin post- the with connected is ages K–Ar rejuvenation the of the of process We the Ma.that sure13 are and 11 8–10, is deposits clay the within beds ash the from samples of age sec the Ma.K–Ar ~260 todemonstratetions ~90 fromages K–Ar all from samples whole-rocks The Kamen.Popov line: the along studied were h lyyNoeedpst fteTmnpeninsula Taman the of deposits Neogene clayey The K–Ar transformation. least the shows profile Belaya eral Resources,eral 2,209–214. Min and investigations.– Lithology isotope-geochemical K–Ar and rocks from the central East European Platform: Evidence from Rb–Sr M.I. (2003): Stages of the epigenetic alteration of Upper Precambrian River).–Belaya and Lithology Mineral Resources (inprint). North-Western (alongthe Caucasusof deposits terrigenousJurassic Yu.O.datingisotopicTextural–structural, and (2006): mineralogical Greater Caucasus.– and Lithology Mineral Resources, 6,613–621. isotopic systems in rocks from the Jurassic terrigenous complex Rb–Sr of the and K–Ar PANOV,KUSHCHEVA,& Yu.V.D.I., The (2003): ± 1 5 Ma (KUSHCHEVA et al., 2006). In K–Ar data K–Ar In 2006). al., (KUSHCHEVAet Ma ([email protected]) References Саре Tuzla, Zhelezni Rog, Rog, Zhelezni Tuzla, ------Abstracts Book

Evolution of swelling and hydration properties of a compacted hectorite percolated by nickel solutions

Lydie LE FORESTIER, Patrick BAILLIF, Chantal PROUST and Fabrice MULLER

Nowadays, subsurface waste disposal is based on the con- A mechanical unloading after 45 days of experiment cept of compacted clay barriers, characterized by a low with pure water shows that the equilibrium is already permeability and high cation retention. The aim of this ex- reached, since the swelling strain is 44%, identical to that perimental study is not only to reproduce at the laboratory obtained after 180 days. Similarly, the Ni2+ exchanged hec- scale the in-situ compaction of saturated clays, but also to torite with KNa+=0.19 exhibits a swelling strain of 38% after focus on the evolution of the clay properties. Therefore, unloading. By contrast, the swelling strain of the same hec- percolation experiments have been performed using an torite with KNa+=0.32 stands to the same value, 23%. These oedometer cell equipped with an injection system under results highlight that the swelling ability of hectorite has constant pressure (JULLIEN et al., 2002). been significantly reduced by the Na+–Ni2+ exchange. The chosen clay is the hectorite from Hector (Cali- The microstructural evolution of hectorite has also fornia, USA), with the structural formula (Na0.25Ca0.04) been investigated, in order to better understand the influ- . (Mg2.74Li0.31)Si3.97O10(OH,F)2 nH2O. This hectorite is associ- ence of nickel on macroscopic properties. For this purpose, ated with minor calcite. For all experiments, the hectorite a diffractometer equipped with a controlled atmospher cell 3r sample was compacted at 0.5 MPa, and then soaked at was used. The three hectorite samples (soaked with water, d Mid-European Clay Conference – MECC 06 2+ 0.3 MPa with deionised water or Ni(NO3)2 0.01 M solution. soaked with Ni solution with KNa+=0.19 or KNa+=0.32, Some mechanical unloadings were also performed along respectively) have undergone the same treatments: on the the experiments, in order to test the swelling behaviour of one hand, a thermal cycle (50°C, 100°C, 150°C), and on the the clay at different exchange rates. Axial strain variations other hand, anhydration cycle (relative humidity at 50%, were monitored during testing. Moreover, output solutions 70%, 80%, 90%, with a constant temperature of 30°C). from the oedometer, i.e. leachates, have been regularly ana- When increasing temperature, dehydration of interlayer lysed for Ni2+, Na+, K+, Ca2+, Mg2+ and Li+. These analyses space is delayed when Na+ is exhanged by Ni2+. Indeed, allowed to calculate the exchange ratio, KNa+, defined as the d(001) reaches 10 Å since 100°C for hectorite soaked with fraction of Na+ released to the solution, compared to the water, whereas the same value is obtained at 150°C for hec- + bulk Na content in the starting clay, in atomic proportion. torite with KNa+=0.32. Besides, when increasing relative hu-

Two samples, run in the oedometer with Ni(NO3)2 solu- midity, hectorite with KNa+=0.32 swells less than both other tion, were also obtained, during 180 and 230 days, with an samples. exchange ratio KNa+ of 0.19 and 0.32, respectively. What- When increasing the interaction with nickel solution, 2+ + ever the run duration, neither Ni nor Li have been de- the macroscopic behaviour of hectorite, a smectite known + tected in the leachates, and the Na content in the solu- for its swelling properties, is getting close to that of a non- 2+ 2+ + tions is around 100 times higher than Ca , Mg and K : expansive clay. Moreover, nickel has significantly changed 2+ Ni has been totally fixed by hectorite and exchanged to hydration properties of hectorite layers. So, evolution of + Na . Hydraulic conductivity, k, was calculated from the swelling properties at a macroscopic scale can be linked to Darcy law, using the expression elaborated for a saturat- evolution of hydration properties at a nanoscopic scale. ed medium: k=Q/iS, with Q the measured volume flow (m3.s-1), i the hydraulic gradient and S the section area of Reference 2 the oedometer (m ). The obtained hydraulic conductiv- JULLIEN, A., PROUST, C., LE FORESTIER, L., & BAILLIF, P. (2002): Hy- ity k of the compacted hectorite drops in the same range, dro–chemio–mechanical coupling effects on permeability and swell- 4.2 10-13 m.s-1 to 4.9 10-13 m.s-1, when soaked with water ing behaviour of a Ca smectite soaked by Cu solutions.– Applied Clay or Ni2+ solution, respectively. Swelling strain values deter- Science, 21, 143–153. mined at the permanent regime are similar: 28% with water and 23% with Ni(NO3)2 solution.

ISTO (UMR 6113 CNRS–Université d’Orléans), 1A rue de la Férollerie, 45071 Orléans Cedex 2, France ([email protected]) 75 Abstracts Book Abstracts 76 3rd Mid-European Clay Conference – MECC 06 1 Fe-oxyhy an that is result this of interpretationprobable most the totaliron contents oforder the Thus, ofCEC. the tion, the lowest intensity for being observed solutions with concentrawith intensityvaries its Onlysolution. calating independentobserved of the Fe concentration in the inter for larto that ferrihydrite. observed Such isalways sextet a simi quite is that sextet intercalateda exhibitsamples the M the K Atmm/s.4.2 about0.6 of ting vermiculites, while the other original one shows the a these quadrupole split in doublet the of of that practically one is doublets of splitting The samples. exchanged ion the Fe two by represented better is material, starting the in splittings quadrupole electric of which can be represented by a single Gaussian distribution Fe the fact, In mm/s). 1.06 (0.89 of instead mm/s vermiculite untreated the in than lower is ponent Fe the of splitting quadrupole average doubled. The Fe total the while vermiculites, ing start the to compared reduced strongly is spectra bauer sityofFe the droxide precipitation. ironoxyhyshowsomeday lutions a storedmoreforthan so since used, been havesolutions prepared freshly Only clays. the treatmentof the during further decreases which of acid attack. problem However, the even these reduce solutions show to a pH of CEC) 2.6 10 to up 1CEC in solution Fe of amount total M; 0.002 M, (0.02 concentrations isolated hydrated Fe than ratherintercalated be to expected is that species this hydratecationdimer dominatingoxo-bridged the solution the in be species will acid attack on the clays may occur. Despite this low pH, the FeCl of solutions aqueous 1M using studied been usually has exchange ion literature, the in reported As spectroscopy. we studied the iron uptake of these by XRD and M ver uses miculites from Santa andOlalla Oj here report will we which on investigation est. The lated Fe The 3 2 Instituto de Ciencia de Materiales de Sevilla, Instituto deCienciaMateriales deSevilla, E15,TechnischePhysik-Department Universität München,85748Garching, Germany Walther MeissnerInstitutBayerische fe ramn tro eprtr,terltv inten relative the temperature, room at treatment After FeCl lower used therefore we experiments ﬁrst our In electron mediator and catalytic properties of interca of properties catalytic and mediator electron 3 . Such solutions have a pH of about 2, at which some atwhich about2, ofSuchsolutions pH . havea 3+ oxyhydroxides? AMössbauerspectroscopic investigation in the interlayer space Fe Anton LERF 2+ component room the in temperature M 3+ intercalation into vermiculite ordepositionofiron 3+ ions. [(H 2 O) 1 , Friedrich E. WAGNER 4

Fe-O Akademie derWissenschaften, Walter-Meissner Strasse 8,85748Garching, Germany ([email protected]) of clays is of general inter 3+ quadrupole doublets in doublets quadrupole 2 é -Fe(H 3+ ,San saﬁs step n, Spain. As a ﬁrst (UNSE–CSIC/Am content has roughly has content ö ssbauer spectra of ssbauerspectra and Jos 2 O) 3+ 4 ] component, 4+ hsi is it Thus . é ö rico Vespucio Spain s/n,41092Sevilla, é ssbauer 3+ L. P com ö 2 , JuanPOYATO ss É ------3 REZ-RODR

l 20) h ae pcn fteitraae n dried and intercalated the of spacing layer The (2005). al. FeCl of solution methanol a of Feintercalate to pH Wetried therefore7. below range the in oxyhydroxides iron various of formation the Fe of hydrolysisbehaviour intercalated. can be they ace tate trimers get destroyed on the vermiculite the surface before that indicates This amount. smaller a in although oxyhydroxide, iron finds also one trimers, acetate the like clusters iron polynuclear charged positively of insertion negatively charged clay surfaces. charged oxidic iron nuclei which interact strongly with the particles. droxide is deposited on the outer surface of the vermiculite LETAÏEF, iron ARANDA,S., P. of RUÍZ-HITZKY,& Influence (2005): E. lem. probsame the face intercalatingof will pillarsFe trials all also seems to conclusion be valid for similar reactions in smectites and This oxyhydroxide. an of deposition taneous anaqueous solution always this because results simula in in intercalationcompoundsironprepare to impossible be to appears it the external surfaces of the vermiculites. Thus aqueousparedin solutionprecipitates duetois formedon pre samples in K 4.2 at mag observed phase ordered netically the that conclusion earlier our confirms phase dered or magnetically a of absence the and ordering magnetic quite similar to that of starting material. the looks spectrum sextet The phase. ordered magnetically no a to due is there Now different. quite look K 4.2 at taken However, spectra case. aqueous the in than higher is tent samples obtained with aqueous solutions, but the Fe M LETA with ment specimen obtained in this way amounts to 13.8 ö ssbauer spectra look very similar to the spectra of the the of spectra the to similar very look spectra ssbauer Tedsrbdpolm a edet h complex the to due be may problems described The by deposition oxyhydroxide iron avoid to tries one If Applied Clay 28,183–198. Science, nanocomposites.– polypyrrole–clay conductive of formation the in Fe intercalated that shows result This Í GUEZ hsmyb u otefraino positively of formation the to due be may This 3 , Ver 3 Ï ó Fe l 20) h omtemperature room The (2005). al. et EF nica RAM References 3+ ions in aqueous solution and solution aqueous in ions Í 3 REZ- according to LETAto according V ALLE 3+ cannot induce cannot 3

Å in agree 3+ 2+ Ï from EF et EF con ------Abstracts Book

Point of zero charge and surface acidity constants of Fe(OH)2 Diana LIEBER and Helge STANJEK

Green Rust (GR), a group of Fe(II)–Fe(III) layered double of excess protons and hydroxyl ions respectively is varied. hydroxysalts, is a prevalent phase generated by steel cor- Remaining ions represent the background electrolyte. Af- rosion (ABDELMOULA et al., 1996). To predict the re- ter equilibration the difference between the measured pH tardation behaviour of actinides by GR, it is important to in the solution and the pH calculated from the surplus of investigate ferrous hydroxide, Fe(OH)2, as well, for it is hydroxyl ions after synthesis is determined. Subsequently, known to be a common precursor in the formation of GR the surface acidity constants are calculated by modelling and has a similar structure (GENIN, 2004). Presumably, the titration data with the computer program FITEQL elements adsorbed onto ferrous hydroxide might easier get (HERBELIN & WESTALL, 1999). incorporated into GR. Adsorption of ions and molecules on a mineral surface References depends on the charge of both. The ability of a substance ABDELMOULA, M., REFAIT, Ph., DRISSI, S.H., MIHE, J.P. & GENIN, to develop a certain surface charge as a function of pH is J.M.R. (1996): Conversion electron Mössbauer spectroscopy and characterized by the point of zero charge (PZC) and the X-ray diﬀraction studies of the formation of carbonate-containing green rust one by corrosion of metallic iron in NaHCO and surface acidity constants. YOON et al. (1979) proposed an 3 (NaHCO3+NaCl) solutions.– Corrosion Science, 38, 623–633. approach to calculate these values from crystallographic 3r GENIN, J.M.R. (2004): Fe(II–III) hydroxysalt green rusts: from corrosion d Mid-European Clay Conference – MECC 06 data for various minerals. With that, they estimated a pHPZC to mineralogy and abiotic to biotic reactions by Mössbauer spectros- of 11.87 for ferrous hydroxide. copy.– Hyperﬁne Interactions, 156/157, 471–485. For testing this value in the present work the PZC of HERBELIN, A.L. & WESTALL, J.C. (1999): FITEQL – A computer pro- ferrous hydroxide is determined experimentally via po- gram for determination of chemical equilibrium constants from experimental data.– Report 99–01, Department of Chemistry, Oregon tentiometric titration. To prevent oxidation of ferrous iron, State University, Corvallis, OR 97331. experiments are conducted in a multibatch setup strictly YOON, R.H., SALMAN, T. & DONNAY, G. (1979): Predicting points of closed to air. Synthesis of ferrous hydroxide and titration zero charge of oxides and hydroxides.– Journal of Colloid and Inter- are conducted in one step: by using bases of different con- face Science, 70, 483–493. centration in the synthesis of ferrous hydroxide the amount

Institute of Mineralogy and Economic Geology, RWTH Aachen, Wüllnerstr. 2, 52062 Aachen, Germany ([email protected]) 77 Abstracts Book Abstracts 78 3rd Mid-European Clay Conference – MECC 06 1 similar is Cr#=0.40–0.84) (Mg#=32.5–64.0, composition Spinel albite). adularia, epidote, pumpellyite, actinolite, (quart crystaloclasts Fs (Di TiO (Mg#=57.4–63.4; (Or [sanidine An crystaloclasts volcanic the distinguish to us The allow tephra analysed the from minerals chemistry. residual mineral of composition chemical and morphology crystaloclastic grain their by lavas position. de tephra of time the at Pinjevica in established already wereconditions pedogenetic and climatic similar that ing or wet systems with good drainage ( moist highly in ash volcanic vitric of product weathering early-stageimogoliteindicativeforareand Allophane lite. imogo and/or allophane mineral(s), clay poorly-ordered to non-crystalline as recognized be may phase(s) the ples, Due to the absence of carbon and volcanic glass in the sam <32 saturatedetilenglycoleheated and dried, air the ofanalyze XRPD sample.The bulk the of wt% around98 makes tion to separated <32 the samples all were In fractions. light and heavy which fractions grain larger several <32 fractions and sieved wet were aliquots The layer. entire the represent to intervals equal wind W by transported Late to recent the position (BOGNARetal., 1992). recurrently as distal were that deposits interpreted fluvial are sands The infillings. by sandy marked loose with channels bioturbation and wide cm lithified 1 to up slightly is layer tephra The 1995). PENCINGER, & (KRKALO largest tephra vitric thick cm 35–40 the by interlayered sand quartz-dominated is of tons mega 1.4 pit Pinjevica of amountestimated containing island, the The on excavation past. of the deposits in exploited sand aeolian medium-grained thick to by fine- filled be may depressions these part, lakes SE the In island. the shallow of part NW the formingin (blata) water fresh retain forms karstic These valleys. karst and dolines deep by characterized is Croatian carbonate the Mesozoicatofmorphologyisland surface,the the rocks exposed prevailing of the to pearl Due southeasternmost archipelago. the is Mljet 3 2 Institute ofMineralogy andPetrology, ofGeology, Department Faculty ofScience, ofZagreb, University Horvatovac b.b., HR-10000 Zagreb, Croatia Croatian Museum,Demetrova Natural History 1,HR-10000 Zagreb, Croatia HR-10000 Zagreb, Croatia ([email protected]) Institute ofMineralogy, Petrology andMineral Faculty Deposits, ofMining, GeologyandPetroleum ofZagreb, EngineeringUniversity Pierottijeva 6, 35.3–38.8 0.8–5.6 46.9–49.4 ape eesrpdo rmtetpr ae nthree in layer tephra the from Samples were scraped off Altered tephras can be correlated to coeval distal distal coeval to correlated be can tephras Altered µ Mineralogical signatures ofweathered Late Holocene ashlayer m fraction revealed only XRD “amorphous” phase(s). , lgols (Or plagioclase ), ) and Ti-magnetite (8.7 wt.% TiO En 34.7–38.6 Fs 13.1–17.9 z > 2 pnl dosd/uie enstatite, diopside/augite, spinel, Bo 4448 t%, clinopyroxene wt.%), =4.4–4.8 ), orthopyroxene (Di 5.1–9.4 š ko LUGOVI , Ab hc ws commercially was which from theislandMljetinCroatia 38.6–53.2 µ WADA, m was separated from separated was m 2 An )] from the aeolian Ć 38.0–56.2 1989) suggest 1 51.5–86.4 , Marta CRNJAKOVI , Marta 1.6–2.4 , biotite ), µ Ab En m frac m 11.7–45.2 59.6–63.2 ü rm rm - - - - -

the deposition of analysed tephra, we search for the south the for search we tephra, analysed of deposition the BOGAARD, 1998). Since the soil formation interferes with ( onsettlers Roman introduced or Greek been by Mljet has to supposed is which Pinus particularly of pollen, arboreal of predominance the from and 1992) al., et (BOGNAR complex the of be bottom the at may as BP ka the from 3.115 inferred around to BC ka 3.776–3.363 from formation soil of onset shows complex” “pedologic it as sands Pinjevica of was constrained by source BOGNARetal. (1992). potential as flysch confirm ( Bosnia central m Jurassic the to (L NW km 450 around located basins flysch Eocene Lateto Creataceous Upper of sandstones the from spinels the to WADA,K KAMENETSKY,D.,LENAZ, V.S., CRAWFORD,PRINCIVALLE, & A.J. otoka sirovine Mineralne (1995): V. PENCINGER, & E. KRKALO, S. JAHNS, S., VITA,DE A., BOGNAR, AMS the to source. relatedtephra an signalize another unidentified still not are which orthopyroxene and the of plagioclase candidate volcanicHowever, abundanttephra. source Pinjevica best the are 1999) al., et VITA (DE BP ka 4.100 to of dated eruption (AMS) Spina magnitude Agnano–Monte highest the with BP ka 3.800 to 4.800 from period eruptions the in caldera Flegrei Campi recurrent the from The tephras. dispersed NE with BP ka 3.0 and 5.8 around between erupted volcanoes Italian n h ajcn Spuaa a a el developed well a Bay Saplunara adjacent the In . (d.: ieas n ol niomns Si Si Sc o Amer., of Madison, WI,1051–1087. Soc. Sci. Soi. Environments. Soil in Minerals (eds.): S.B Contrib. Mineral. Petrol., 139,748–758. enia): A new approach to provenance studies of sedimentary basins.– F.Melt(2000): inclusions spinel fromdetrital SE Alps(Italy–Slovin Zagreb. 147–154, 6, Mljeta.– Ekološke monografije, 219–234. is Veget.Croatia.– Dalmatia, south Mljet, Archaeobot.,7, Hist.of land the on lagoons salt two of investigations tephrostratigraphical (Italy).– J. Volcanol. 91,269–301. Res., Geotherm. caldera CampiFlegreirestless the in BP) years (4100 Spinaeruption Za greb. 99–110, 22–26, September Lošinj, Mali Sea, and morphology Geo symp.Internat. Proc. island.– Mljet the of part south-eastern Ć ENAZ . (1989): Allophaneimogolite.–and(1989): . In:DIXON, J.B. WEED,& 2 & and Vanja BI é VANDEN ORSI, G., CIVETTA, L. CIVETTA, G., ORSI, lange from the Dinaride Ophiolite Belt in the the in Belt Ophiolite Dinaride the from lange KLEIN, V.,MESI KLEIN, et al., 2000) and from the matrix of Upper of matrix the from and 2000) al., et MIKES 14 BOGAARD, C. (1998). New palynological and palynological New (1998). C. BOGAARD, cretd g o Gsrpd shells Gastropod on age corrected C References Š upbihd. hs findings These unpublished). , Ć EVAC , I. , et al. (1992): Quaternary sands at sands Quaternary (1992): al. et ta.(99:TeAgnano–Monte The (1999): al. et 3 JAHNS & VANDEN - - - -

Abstracts Book

Geological prospecting of kaolin and kaolinite clays deposits on territory of the Western Carpathians (Slovakia)

Michal MAJDÁN1, Ivan KRAUS2 and Igor GALKO1

The main phase of kaolinization in the Western Carpathi- it which formed by redeposition of the primary weathering ans (Slovakia) took time from Badenian to Pontian. We crust on the longer distance. Surveying and prospecting distinguished primary (weathering and hydrothermal) and of kaolin and kaolinite clays deposits is quite diﬃcult on secondary (sedimentary) genetic types of kaolin deposits the territory of the Western Carpathians. This is the reason in the Western Carpathians. The weathering genetic type is why we suggested simple prospecting criteria for geologi- mainly the result of alteration of diﬀerent type of metamor- cal survey. The most important prospecting criteria are: (1) phites and granitoids. The sedimentary deposits are repre- Geological position, (2) Mineral composition; (3) Intensity sented by kaolin silts, sands and gravels. They are usually of alteration; (4) Palaeoclimatic; (5) Technological; and (6) formed by redeposition of the primary weathering crust on Commercial (economic). the short distance. We also recognise kaolinite clays depos- 3r d Mid-European Clay Conference – MECC 06

1 Company ENVIGEO, a.s., Kynceľová 2, 97411 Banská Bystrica, Slovak Republic ([email protected]) 2 Department of Geology of Mineral Deposits, Faculty of Natural Sciences, Comenius University, Mlynská dolina G, 84215 Bratislava, Slovak Republic ([email protected]) 79 Abstracts Book Abstracts 80 3rd Mid-European Clay Conference – MECC 06 2 1 Fe M the and features the normal the 4 minutes keep for grinding After sites. ropole doublets assigns to one Feoctahedral mate starting the quadinterpretedthreeof superposition be bythe can rial of spectra The solids. treated acid and M a undertook we id neite according to XRD. probablyakaga very oxide–hydroxideironis an which of (S area surface high very a with silica amorphous an in sults re HCl 1M with However,treatment HCl. M 0.5 and M 0.25 with attack acid forminutes4 keepsits structureafter ground Vermicullite treatment. acid the due increases after resi the contentof iron the butsamples, the of attack the favours mill) vibratory the (with Grinding hours). 24 with during attack acid 80 at (1M, work this in concentration acidused highest the after remains still vermicullite Nevertheless, solid. residual the in contentsilicium the of increase an with accompanied occurs iron and minium alu magnesium, of decrease remarkable a 1M to up tion concentra acid the Increasing lattice. vermicullite the of layer octahedral the from iron and magnesium partially acid attack. the favouring mineral the of producemodification surface effects These materials. amorphous grinding progressive (mainly after yielding structure, atoms the “prototropy”)within protons of diffusion and polyhedra coordination Additionally,produces rearrangementalso grinding the of ing of layers and aggregation of the newly formed particles. (delamination and lateral size reduction), folding and glid reduction size particle in results vermicullite of Grinding 4 3 Physik Department EI5,TechnischePhysik Department Germany Universität D-85748, München,Garching Walther Meissner InstitutBayerische Akademie derWissenschaften, Walter-Meissner Germany Strasse D-85748, 8,Garching Americo Vespucio Spain s/n,41098Sevilla, (UNSE–CSIC) Instituto deCiencia deMateriales deSevilla Instituto deRecursos Naturales yAgrobiolog BET Celia MAQUEDA h cdteteto nugon apeleaches sample unground an of treatment acid The To get more insight in the fate of iron species in the sol =720.2 6 Mössbauer spectroscopy investigation ofground and m 2 g -1 ). It is coloured yellow due to deposition ö ssbauer investigation of the ground the investigationof ssbauer 1 , Agua SANTAS ROMERO Anton LERF í a (CSIC) Apdo 1052, 41080 Sevilla, Spain ([email protected]) 1052,41080Sevilla, Apdo a (CSIC) 2+ acid treated vermicullite /Fe ö 3+ ssbauer spectra spectra ssbauer ratio remains ratio 3+ and two Fe 3 andFriedrich Ernst WAGNER 1 , Esmeralda MORILLO ° C 2+ ------

h apegon o iue n rae ih02 M 0.25 M with vermicullite typical treated the still and shows HCl 4 minutes for ground sample The quadrupole splitting due to the presence of an Fe–O–(OH). Fe vermicullite Fe of splitting pole Fe the of decrease slight a is there but vermicullites, of spectra typical the to M The solution. the iron as Fe some alteration of mineral. the fected. Just a slight line broadening of indicates the spectra from grinding whereas the local ordering is not stronglystrongly af suﬀers order range long the and size particle the that means That vermicullite. the of structure the on tack atshowsevere data XRD unchangedthe althoughalmost akaganeite precipitates on amorphous the SiO an acid after attack with the only highest acid concentration destroyed applied and only completely is Fe vermicullite The some but of iron, dissolution andFe to leads attack acid The M the to according sample our in occur during step essential grinding since an the vibratory mill is very energetic, does not as considered been has which akaganeite. of splitting magnetic hyperﬁne at4.2 samples taken these of droxides. Spectra Fe-oxyhy for indicative mm/s 0.6 about to dropped ting M 1M the with to according treated and orangecompletely are and solution HCl 4 minutes 2 or for ground samples The with aFetrum ö ssbauer spectra only Feonly ssbauerspectra During treatment During of unground the vermicullite (7.50% xdto o te tutrl rn n h vermicullite, the in iron structural the of Oxidation 3+ remains in the structurally damaged remainsvermicullite. structurally the in 2 O 3 ) with 1M HCl almost half of the iron is lost to 2+ 3+ /Fe ie ih oe te Fe other some with site 2+ 3+ 3+ 1 ö , Jos otn.Tedces ftequadru the of decrease The content. site indicates a superposition of the the of superposition a indicates site ssbauer spectrum is still very similar very still is spectrum ssbauer ratio similar to untreated the sample. 4 é 3+ L. P remains.Itssplitquadrupole É REZ-RODR ö 3+ ssbauer results. ssbauer ö ie o lower of sites ssbauer spec ssbauer 2

Í . K show the K GUEZ 2 , 2+ ------

Abstracts Book

Particularities of Mössbauer spectroscopy for the archaeological potsherds dating

Oleg B. MILDER, Alex I. PIKULEV, Vladimir A. SEMIONKIN and Evgeny G. NOVIKOV

The possibility ofö M ssbauer spectroscopy for dating of components is estimated, that allows us also to make some the ancient pottery based on the evaluation of absorbed suggestions concerned on pottery production technology. dose has been demonstrated (EISSA et al., 1979). The lin- Alternative parameter received from spectrum fitting ear dependency estimated (EISSA et al., 1979) between which characterized the dose absorbed by potsherd is of- the relative intensity of peaks corresponding to Fe(III) fered – a relative degree (RD) of overlapping for Fe(III) and the dose absorbed by sample was confirmed also quadrupole components peaks. (AMULEVICHIUS et al., 1989). Dating of 10 archaeological potsherds has been per- Number of potsherds excavated on the territory of his- formed by means of building “RD vs. absorbed dose” de- torical memorials of Hanty–Mansi national district were pendencies. Received results are in good agreement with studied. We have used both a discrete spectrum descrip- radiocarbon data. tion and P(Qs) quadrupole distribution restoration method. The principal particularity of any observed spectra is References the presence of at least four nonmagnetic components: two EISSA, N.A., SALLAM, H.A. & MORCY, M.H. (1979): Estimation of doublets associated with Fe(II) and two doublets associated natural radiation dose and of the age of ancient pottery by Mössbauer with Fe(III). Mutual overlapping of left peaks of all Fe(III) effect.– J.de Phys C2., 40, 462–463. 3r d Mid-European Clay Conference – MECC 06 and Fe(II) doublets occurred. This greatly influences upon AMULEVICHIUS, A., DAVIDONIS, R., BALCIUNIENE, M. & VIT- KEVICHUS, G. (1989): Radiative damage in archeological ceramics the parameter informative for dating – relative intensity of and its dating by means of Mössbauer spectroscopy.– ICAME’89, Fe(III) doublet peaks. The nature of each of the spectrum Book of Abstracts, 12.3b.

Ural State Technical University (USTU–UPI), Mira Street 19, 620002 Ekaterinburg, Russian Federation ([email protected]) 81 Abstracts Book Abstracts 82 3rd Mid-European Clay Conference – MECC 06 Fig. 1Pore size for distribution thesampleKG1. range of relative pressure 0.8–0.99, the higher uptake in the the in them Comparing materials. nonporous for more typical is KG1 of sample kaolinite in case of structure ordered isotherms well the of shape The isotherms. sorption linite mineral. fa disorder dissolutionkao of selective higher in bacteria ofrole cilitates the the that indicates This kao (Table1). KG1 ordered poorly ordered well the the from than higher from are KG2 sample Fe linite and Si of extractions The comparable. are Al of extractions the only KG2, KG1and spitecontentsof almostequal samplesand ofboth Al Siin samples. in disordering of degree the of influence the emphasize to order in evaluated were residua solid the of of distribution structure size pore and propertiesadsorption minerals, distribution, size particle composition, cal in chemi changes duringdays100 lastingincubation. The the process of elements Fe, Al and Si dissolution monitored active role of bacteria on the kaolinite was investigated and Lu in deposits kaolin the Bacillus cereus kaolinite of rates dissolution mineral. the on influence important an has microorganisms reducing silicate and iron of ing us the (2001) al. MAURICEet of paper the from As follows ions. iron of removal biological changes structural after Claytheir Minerals) were aimtodescribe studied the with HandbookforKG1KG2 the andaccording(designatedto orderedkaolinitesamplespoorlyTwo and well samplesof Institute ofGeotechnics ofSlovak Academy of Sciences, Watsonova 45,04353Košice, Slovakia ([email protected]) KG2–bacterially activated KG1–bacterially activated ofelements [%] Extraction te hne eeietfidfo h adsorption–de the from Other changes were identified in that show experiment a100-days after results The of mixture with inoculated were samples kaolinite The Characterization ofchangeslow andhighordered kaolinite Fe Al Si and Bacillus purilus č eneck Annamária MOCKOVČIAKOVÁAnnamária andIveta ŠTYRIAKOVÁ á Kotlina in Slovakia. The Slovakia. in Kotlina , originally isolated from 8.24 0.95 1.6 after bioleaching after ------12.04 2.21 sible for nitrogen molecules. It can be concluded that the the that concluded be can It molecules. nitrogen for sible ties from KG2 makes more pores, meso- and macro- acces of impuri to the well ordered dissolution sample KG1. The comparison in different quite is sample disordered highly bio-activation. of mineral after structure the in changesindicating increases volume pore gregation may be also present. In contrary to that, the total ag of were surfaces formed during process.the Moreover, an effect new no that explaining bioleaching, slightly decrease after very area surface specific of values bioleaching. The S area volumeV pore total the as well surface specific the describe measurements adsorption the from determined Parametersmacropores. and mesopores of presence the indicates loop hysteresis narrow the and activation biological nite sample KG2 after amount of nitrogen atwas observed the low ordered kaoli Fig. 2Pore size for distribution thesampleKG2. MAURICE, and No–2/5035/5. No–3/6189 projects the supportingAgency VEGA by and 006304 APVV–51–No.contract the underTechnology AgencyAssistance Acknowledgements: more disordered structure. of case in effective more is disorder of degree ferent bioleaching of iron ions from samples of kaolinite with dif 1.7 As follows from Figs. 1 & 2, the distribution of pores for Journal, 18/1,21–35. bacterium.– mendocina Pseudomonasaerobic an & FERRYMAN, P.A., VIERKORN, A. ( A. Table ofSi,AlandFe 1Extraction from kaolinite hswr a upre ySineand Science by supported was work This 2001):

samples KG1 andKG2. References M.A.,

Enhancement of kaolinite dissolution bydissolution kaolinite ofEnhancement HERSMAN, 0 of samples prior and afterandsamplesprior of L.E., Geomicrobiology FULGHUM, BET

as , J.E. - - - - - Abstracts Book

Intercalation of aniline in Wyoming montmorillonite exchanged with diﬀerent cations

Fabrice MULLER, Jean Michel BÉNY and Mathieu GAUTIER

Intercalation and deintercalation of organic molecules aniline spectra shows that all the characteristic bands of in the interlayer space of phyllosilicates represent an im- aniline are found in the intercalated with aniline montmo- portant interest in the development of new materials with rillonite spectra. The N–H stretching wavenumbers are desirable properties (catalysts, sorbents, ...) and in envi- lower for the aniline–montmorillonite complex than for ronmental protection and rehabilitation (waste deposits, the dilute state (or like gas state) aniline (3388 cm-1 and polluted soils, ...). In this work, we turn one’s attention to 3312–3324 cm-1 for the aniline–montmorillonite complex; the interaction of aniline with montmorillonite. Firstly, be- 3480 cm-1 and 3395 cm-1 for the dilute state); this implies an cause this compound serves as a model for the sorption of increase of the N–H bonds length in the complex because aromatic amines by expanding layer silicates, and secondly, of a strong hydrogen bridge formation between aniline and because aniline is a very dangerous polluting molecule. water molecule. Aniline anchorage seems to require the The interaction of aniline with SWy2 Wyoming presence of interlayer water. montmorillonite (structural formula: (Na0.14Ca0.05K0.01)(Al1.56 O  H --- NH2  C6H5 Fe Mg )(Si Al )O (OH ).nH O) exchanged with 0.21 0.23 3.95 0.05 10 2 2  3r + + 2+ 2+ 2+ different interlayer cations (Na , K , Mg , Ca , Ba and H d Mid-European Clay Conference – MECC 06 + NH4 ) is obtained by placing the sample in aniline vapour. Mass measurements of the sample versus time show that The C–N band wavenumber shifts from about 1275 saturation of adsorption process is obtained after 16 hours cm-1 in the liquid state or dilute state to 1250 cm-1 in the of exposure. complex which proves a length increase for this bond in Carbon and nitrogen were quantified after interaction the complex consistent with the strong hydrogen bridge with a LECO CNS–2000 analyser. The results confirm that formation. aniline molecules are adsorbed. The quantity of adsorbed The structural changes have also been investigated. For molecules is more important than the CEC (Cationic Ex- this purpose, a diffractometer equipped with a control- change Capacity) of the sample. For example, for 100g of led atmosphere cell was used. The patterns have been re- Na–SWy2, 0.088 mole of aniline are adsorbed after 16 hours corded with the relative humidity of 50% at 30°C. For Na of exposure, while the CEC value equals to 0.065 mole/ ≅ and NH4-samples an increase of 0.3 nm in the d-value of 100 g. The interlayer cation type influences the amount the 001 reflection after aniline treatment confirms clearly 2+ 2+ of aniline taken up by clay. For Mg and Ba cations, the the fixation of the molecule in the interlayer space of the proportion of adsorbed aniline is approximately equal to montmorillonite. A systematic decrease of the width at + 4CEC, whereas this value is lower with Na (≅1.5CEC) and mid height is observed for the adsorbed samples indicating + NH4 (2.5CEC). a better stacking of the layers which can be attributed to a Characteristics of the absorption (localisation of ani- structural reorganisation of the interlayer space. For all of line molecules, type of bonding between layer and mol- studied samples, the basal spacing after the adsorption is ecule) have been studied using infra-red spectroscopy. The ≅1.5 nm. This result is compatible with an orientation in comparison between the original material spectra, interca- which the plane of the benzene ring is practically perpen- lated with aniline montmorillonite spectra and liquid state dicular to the silicate surface of the sample.

ISTO (UMR 6113 CNRS–Université d’Orléans), 1A rue de la Férollerie, 45071 Orléans Cedex 2, France ([email protected]) 83 Abstracts Book Abstracts 84 3rd Mid-European Clay Conference – MECC 06 prepared from synthetic Na-saponites (trioctahedral clay (trioctahedral Na-saponites synthetic from prepared (0.75–0.30 charge layer decreasing ally troneutrality. elec preserve to order in space interlamellar the occupy the layer.tetrahedral Exchangeable cations such as sodium in orlayer octahedral the in substitutionmorphouseither iso cation of result a as charged, negatively are Clay platelets Al(III). with filled sites octahedral three of two have phyllosilicates dioctahedral Mg(II), by occupied sites dral trioctahe three layers.Trioctahedral their showclays dral tetrahe two between sandwiched being layer the octahedral condensation, 2:1 from result clays cation.Three-sheet (OH) Si(O,OH) linked of sheets of condensation by formed layers of consists cates, cations to form intercalated clay–surfactant hybrids. interlamellar with ion-exchangedare surfactants Cationic treatmentmineral. surface the of the is steps critical the of op economic nanocomposites,oneTo and clay–polymerportunities. obtain technological new offer and materials conventional by shared not properties unique with them endows that nanometers few a of order clay the of (e.g. minerals) dispersion phase ultrafine inorganic an with als materi of class new a Nanocompositesconstitutemance. naturalcompoundssyntheticand improve to perfor their both of variety a with admixed commonly are Polymers 2 1 Institute ofInorganic Chemistry, Slovak Academy ofSciences, Dúbravská cesta 9,SK-84536 Bratislava, Slovakia ([email protected]) ofLi University Robert M Robert he eiso necltdca ieaswt gradu with minerals clay intercalated of series Three phyllosili named also clays, of structure lamellar The 6 octahedra, where M is either a divalent or a trivalent è Ü ge, Institute of Chemistry B6a, CERM, COSM, Sart Tilman, B-4000 Li Tilman, B-4000 B6a,CERM, COSM,ge, Institute ofChemistry Sart LLER Structure and dynamics of cationic surfactants anddynamicsofcationicStructure surfactants 4 tetrahedra with those of linked M linked of those with tetrahedra 1 , Jana VAL intercalated insynthetic clays Ú CHOV

e/O Á 10 2 (OH) , C é dric CALBERG dric 2 were ) 2-3 ------

h yrxty hi nune h ogcanconforma chain long the the hydroxethyl chain inﬂuences and 0.60, to upgrows chargesaponite the progressivelyas shown that amount of the all-trans conformation decreases have results surfactant the andsilicatetween the layer. The the gauche/trans conformational as ratio and suchinteraction sites be level molecular the at information dynamic tent and CECof clay. ex cation conorganic the between ratio a as calculated the was change of degree The analysis. thermogravimetric of means by mineral clay the in cations alkylammonium from the weight loss of the decomposition of the remaining or determined the was exchanged-clay cation the in phase ganic of content The (DHEMHA). iodide lammonium methylhexadecy di-(2-hydroxyethyl) and (HEDMHA) iodide dimethylhexadecylammonium (2-hydroxyethyl) bromide, (HDTA) mineral), hexadecyltrimethylammonium clay using (dioctahedral Na-laponite and mineral) number. conformer trans the and intercalation surfactant the fect ef location its and chargesize interlayerthe anddistance, ly packed gauche conformation leads to the increase of the dense less spectroscopyFTIR appended results. these The and analysis packing and the all-trans XRD conformer. The layer silicate anchoring,chainsurfactantfavouringincrease couldalkyl the of atoms oxygen and surfactant the of group hydroxyl the between bonding hydrogen and tion, 13 è ge, Belgium C CP MAS NMR studies provided the structural and structural provided the studies NMR MAS CP C 1 , Robert J , Robert É R Ô ME 1 andJeanGRANDJEAN

1 ------Abstracts Book

Dating of fault clays of the North Anatolian Fault Zone, Turkey

Halim MUTLU1, Erhan ALTUNEL1 and I. Tonguc UYSAL2

The North Anatolian Fault Zone (NAFZ) is one of the main following the collision of the African plate with Anatolia. active tectonic structures of the world which defines the The variation in old ages could indicate that margins of the border between the Anatolian block and Eurasian plate. Neotethyan Ocean were irregular before the collision. A Although the age of the fault zone is under discussion, it is relatively younger age from the Resadiye area might indi- agreed by previous works (based on relative dating) that the cate that the initiation age of the NAFZ is as old as 26.6 Ma initiation age of the NAFZ is mid or late Miocene (BARKA which is nearly consistent with the age of collision between et al., 2000; BOZKURT, 2001; ŞENGÖR et al., 2005). This Anatolian block and Arabian plate in southeastern Turkey study is the first attempt to provide new geochronologi- (ŞENGÖR et al., 1979; ŞENGÖR & YILMAZ, 1981). How- cal data on the NAFZ on the basis of age dating (K–Ar) ever, further dating is needed to obtain a precise age for the and stable isotope (18O/16O) tracing of illite and other au- commencement of the NAFZ. thigenic minerals (in various clay size fractions between <0.2 to >4 µm) formed during the near surface faulting. It References was determined from the mineralogical studies that fault BARKA, A., AKYUZ, H.S., COHEN, H.A. & WATCHORN, F. (2000): gouge samples are completely altered as pseudotachylytes Tectonic evolution of the Niksar and Tasova–Erbaa pull-apart basins, North Anatolian Fault Zone: their significance for the motion of the and that authigenic minerals such as illite, smectite, kaolin- 3r Anatolian block.– Tectonophysics, 322/3–4, 243–264. ite, mixed layered illite/smectite and chlorite are generally d Mid-European Clay Conference – MECC 06 found in fine grained size. BOZKURT, E. (2001): Neotectonics of Turkey – a synthesis.– Geodin. Acta, 14/1–3, 3–30. Among the clay-rich fault gouges collected along the ŞENGÖR, A.M.C. & YİLMAZ, Y. (1981): Tethyan evolution of Turkey – a NAFZ, only four samples were suitable for authigenic illite plate tectonic approach.– Tectonophysics, 75/3–4, 181–241. development and dating. Illite samples from Gerede and ŞENGÖR, A.M.C., TÜYSÜZ, O., IMREN, C., SAKİNÇ, M., EYİDOGAN, Mudurnu in western section of the NAFZ yielded K–Ar H., GÖRÜR, N., LE PİCHON, X. & RANGİN, C. (1979): The North ages of 56.5 and 58.7 Ma, respectively. On the contrary, Anatolian Transform Fault: its age, offset and tectonic significance.– J. Geol. Soc. London, 136, 269–282. the ages obtained from Koyulhisar and Resadiye areas from eastern part of the fault zone are younger and they ŞENGÖR, A.M.C., TÜYSÜZ, O., IMREN, C., SAKİNÇ, M., EYİDOGAN, H., GÖRÜR, N., LE PİCHON, X. & RANGİN, C. (2005): The North yielded ages of 34.5 and 26.6 Ma, respectively. The old ages Anatolian Fault: a new look.– Annu. Rev. Earth Planet. Sci., 33, 37– are believed to be heritage from strike-slip faults developed 112.

1 Eskisehir Osmangazi University, Dept. of Geological Eng. 26480, Eskisehir, Turkey ([email protected]) 2 Queensland University, Department of Geology, Queensland, Australia 85 Abstracts Book Abstracts 86 3rd Mid-European Clay Conference – MECC 06 By this method, applying complex forming agents, palladi Pd(0).to reduced be can clay the of surface the on sorbed palladium(II) the that show analysis thermal the od sults re The sites.sylanol surface concentration the of the with the palladium(II) ionssorbed is in a fairly agreementgood the of quantity on deprotonatedsylanolsitesclay of rock.The the sorbed mainly are that They montmorillonite.of space show interlayer the studies into introduced not are analytical ions palladium(II) thermal and diffraction ray [Pd(NH charged positively as applied was clay,Pd(II)of destruction acidic the and Pd(II)hydrolysis dium-bentonite.ofTo the avoid microscopy. electron scanning measurementsandpotential redox ysis, anal thermal diffraction, X-ray spectroscopy, fluorescence X-ray by studied were properties their and preparedwere tochemistry.In work this and palladium- silver-bentonites pho in catalyst important an is silver and processes hydrogenation for used is palladium states: oxidation different the for significant e.g. be can cation the transformations and of organic matter innature. Noble metals, clay the of effect simultaneous the so conditions, geological natural, foundunder be can forms exchanged cation are applied. also The clays exchanged cation chemicallytreated forms. Different Clayrockscatalystsareas natural in widely used wellas as Isotope Laboratory of Department ofColloid andEnvironmental Chemistry,Isotope ofDebrecen, ofDepartment Laboratory University Egyetem Square 1,H-4032Debrecen, Hungary ([email protected]) silver and palladium, are widely applied as catalysts in catalysts appliedas widely are palladium, and silver h opino aldu(I o a tde nso on studied was ion palladium(II) of sorption The Preparation ofnoblemetalbentonites for catalytic purposes 3 ) 2 ] 2+ n [Pd(en) and 2 ] 2+ opee. h X- The complexes. Noémi M.NAGY andJózsef KÓNYA ------greater than the average concentration of the ions. These ions. the of concentrationaverage the than greater significantlyis palladium as wellconcentration as silverof the bentonitesexchangedwhere cation both on places are neglected. be cannot process this low is ion silver of concentration the cation exchange process in the clay/solution system. When of the solution. Hydrogen ions participate in a competitive concentra hydrogenconcentration ionthe to silver equal or smaller is tion the when uncertainties significant show data experimental the measurements: sorption to dencies rillonite. interlayer the montmoofin exchangeplace processtakes ion sodium-silver pure a concentrationssilver low at and desirable from catalytic the point of view. more is which bentonite, in phase amorphous the of tion concentra the increases treatment thermal However, the produced. be can state oxidation 0 or 2 with catalysts um n eoe ihe fe h ettreatment. heat the and becomes lighter after grey dark originally is which silver-bentonitecolor the of silver,oxidation metallic change provedofthe toas the by 361 atbentonitereaction exothermal shows an silverof study silver can also take place. Thermoanalytical content.It shows that reduction the of silver to(I) metallic silver of 100% to up be can SEM by studied enrichments areconsidered ion metal enrichments. as local Scanning electron microscopic studies show that there thatshowmicroscopicstudies electron Scanning In the system of silver(I) ion/sodium-bentonite at pH=4 Redox potential measurementspotentialRedox tenshowsimilar Somesilver ° C. ItrefersC. - - - - Abstracts Book

Nature and alteration of clay minerals in brown forest soil proﬁles (Luvisols) of Cserhát Mountains (North Hungary)

Tibor NÉMETH and Péter SIPOS

Brown forest soils cover significant proportion of Hunga- profile with considerable calcite content in the BC and C ry’s area, therefore they are very important from the point horizons. Soil chlorite or chlorite/vermiculite exhibits only of view of the ecosystem, of the environment and of the ag- a restricted expansion upon ethylene glycol solvation, does riculture. It is well known that the physico–chemical prop- not swell after Mg-saturation and glycerol solvation, and is erties of soils depend on their clay mineral composition. partially resistant to heat treatment and K-saturation. Results of earlier studies within the frame of a regional en- The major product of soil formation in a clayey, well vironmental geochemical research project of the Cserhát developed, deep soil on siltstone parent material is a typi- Mountains in North Hungary confirmed that due to their cal soil smectite with heterogeneous charge distribution adsorption capacity clay minerals play an important but between the layers, but originating dominantly from oc- variable role in the distribution of trace elements within tahedral substitution (montmorillonite). This soil smectite a soil profile among the different soil horizons (SIPOS et contains considerable amount of iron. Mobilization and al., 2005a, b). As the adsorption properties of clay minerals accumulation of iron in different oxi-hydroxide forms in are influenced by variable and sensitive parameters such

the studied soil profiles is a common process. Some con- 3r as their layer charge and swelling characteristics, alteration version of octahedral to tetrahedral charge, and the slight d Mid-European Clay Conference – MECC 06 of clay minerals in pedogenic processes affects the distri- increase of total layer charge in these horizons could be the bution of heavy metals in soils. Clay mineralogy findings consequences of pedogenic processes. including the detailed characterization of clay minerals in four brown forest soil profiles developed on different bed- The characteristic clay minerals in the soil formed on rocks, but influenced by similar pedogenic processes (e.g. limestone are smectite and illite/smectite with evident clay illuviation) and a suggestion on the possible genesis charge reduction and degradation of illite and smectite and evolution of clay minerals in Luvisols of the Cserhát during the weathering. In this profile the illite/smectite Mountains will be presented. interstratification seems to be the result of a polyphase process, even including reaction pathways with opposite The clay mineral composition of less than 2 µm fraction directions. of 17 soil samples was studied and characterized by X-ray diffraction (XRD) and transmission electron microscopy Dominance of low layer charged smectite (montmoril- (TEM) using the following diagnostic treatments: ethyl- lonite) in the C horizon suggests its formation from feld- ene glycol and glycerol solvation, Mg- and K saturation, spars and volcanic glass in a soil developed on andesite Green–Kelly test, alkyl-ammonium layer charge determi- parent rock. This smectite alters to high charged vermicu- nation, and analytical electron microscopy for chemical lite during pedogenesis in the B and A horizons. analyses. References Brown forest soils (Luvisols) formed on various parent rocks show differences in the details of their clay miner- SIPOS, P., NÉMETH, T. & MOHAI, I. (2005a): Distribution and possible immobilization of lead in a forest soil (Luvisol) profile.– Environ- alogy and consequently are characterized by different clay mental Geochemistry and Health, 27, 1–10. mineral alteration processes. A common feature in all four SIPOS, P., NÉMETH, T., MOHAI, I. & DÓDONY, I. (2005b): Effect of soil studied soil profiles is the predominance of swelling clay composition on adsorption of lead as reflected by a study of natural minerals. Siltstone bedrock weathered to chlorite/ver- forest soil profile.– Geoderma, 124, 363–374. miculite and vermiculite in a less developed, shallow soil

Institute for Geochemical Research, Hungarian Academy of Sciences, Budaörsi út 45, H-1112 Budapest, Hungary ([email protected]) 87 Abstracts Book Abstracts 88 3rd Mid-European Clay Conference – MECC 06 2 1 deeper the ofvermiculitein andincreaseofanillite crease de a show soils the general Incouldn’t found.chlorite be and smectite rare; are minerals layer mixed and miculite – as mainthe clayly minerals crystallized in soils.the Ver documents position the of a“dense clay-layer“. the maps one shows the depth of the soils and another one arboretumthe “Putevima Mira”. as served and animportant decidingfactor for presented the concept for analyzed was relevance ecological Their files. soil properties were andcollected evaluated in six soil pro Data on mineralogical, physical, chemical and hydrological an to concept.a new tool fundamental a be swer to these ecological hypotheses and was meant to seemed support research soil tific Scien conditionsmaintenance lessecological with efforts. present the under developed be should improvedconcept the initiators of the arboretum is sustainable or whether an of idea general the whether hypothesis the proof to dent condition.bad a in is arboretum the careabandoned and war the to Due lomatic activities of the former Yugoslavian President Tito. dip lively the document to examples as from countries various areas floristic different completely from shrubs and trees on as well a floris as Mediterranean onthe flora overview tic to give was idea basic infrastructure was established in 1987. The costly a with arboretum equipped well A situated.are objects new important most the and heritage most important island, where the major part of the cultural paral Pula, lel to the peninsula of Istria. Veliki of Brijun is the southwest largest and located is Brijuni archipelago The 4 3 University ofZagreb,University Faculty ofMining, Geology andPetroleum Engineering, Pierottijeva 6,HR-10000 Zagreb, Croatia wte Wassertechnik Platz, Austria A-2344 GmbH,EVN MariaEnzersdorf, Austria stra University Peter-Jordan-stra University h roeu a apdi aiu set:among aspects: in various mapped was arboretum The Luvisols. chromic as classified generally are soils The out carried wasby diplomaa survey stu ecological An Mineralogical Mineralogical analyses show illite and kaolinite – poor ß e 82,A-1190 Wien, Austria of Natural forForest- Resources LifeSciences, Sciences, andApplied Vienna, Institute andSoil Department ofForest Ecology, Peter-Jordan- of Natural ofCivilEngineeringandNatural Resources Hazards, LifeSciences, andApplied Geology, Vienna, Institute of Applied Department Franz OTTNER Clay ofsoils mineralsecological aspects andselected ß e 70,A-1180 Wien, Austria ([email protected]) 1 on theisland Veliki Brijun,Croatia , Monika SIEGHARDT, Monika 2 , Tomislav ERSTI ------fine soil. In general, a sufficient amount of water can be be can water of amount vegeta Mediterranean sufficient adapted the for soils a the in stored general, In soil. fine with filled limestones between cracks into penetrate they “exotic” plants. the and forunfavorable are structure deposits) clay to (similar porosity low dense This cm. 50 about of depth a in and naturally buried the developed A-horizon. cm of a terra rossa soil was deposited onto the existing soil 50 to 30 plantsexotic for improvequality siteto visible: is influence anthropogenic the 6) and (5 coast. In two profiles the to downwards island the of parts higher from moved situated at coast. It the that seen, past cansoil inthe the be the on processes surface.soil illitisation by caused profiles the of part diversity of Mediterranean woody and herbaceous species. attractive the on rely Mira”should “Putevima Arboretum without additional irrigation. A sustainable concept for the met be cannot plants indigenous non of requirements ter 14 than more of temperature mean annual an and mm 800 about ofprecipitation annual an assume we If arboretum. the in displayed be should conditions site ecological respective the to adapted shrubs and trees only not Therefore,soil. the of hydrologicalpropertiesimprove the did material soil heaped-up additionally care.siveThe waterrequirementssituationcover their to without exten pedologic and climatic the to adapted species woody only allows and available plant is water the of amount small a only that tension high a such with soil the of pores the in forBrijuni the samples soil proof thatwater the retainedis curves content potential/water water the However, tion. Woody species can hardly root in these shallow soils; shallow these in root hardly can species Woody layer clay the of density high the show Technicaltests is which 4, profile in visible are processes Solifluction Ć 3 and Marta MILEUSNI andMarta Ć 4

° C, the wa the C, - - - Abstracts Book

Inﬂuence of the synthesis conditions on the physico–chemical characteristics of porous clay heterostructures

Helena PÁLKOVÁ1,2, Małgorzata ZIMOWSKA1, Ewa M. SERWICKA1 and Fathi KOOLI3

Successful synthesis of mesoporous solids from layered In the second step of synthesis neutral amine (alterna- clays by GALARNEAU et al. (1995), resulted in the for- tively decylamine or dodecylamine, differing by the length mation of porous clay heterostructures (PCH), and proof carbon chain) and TEOS (tetraethylorthosilicate) as sili- vided link between microporous pillared clays and ordered ca source were added to organoclay. Two different ratios of mesoporous silica-based materials. In the synthesis of a organoclay/amine/TEOS were used: 1/10/75 and 1/15/75. PCH the clay is first opened up by the introduction of a XRD analysis showed that intercalation resulted in a sig- cationic surfactant via an ion exchange reaction, thus al- nificant increase of the basal spacing and both the ratio of lowing easier access to the interlayer region. Subsequently, reactants and the chain length of the neutral amine influ- neutral amine surfactant molecules and the silica source enced the structure of the resulting solids. E.g., in the case

(TEOS) are intercalated into the interlayer region, where of HDTMA–M intercalated with decylamine the d001 value the self-assembly of the silica species leads to the formation increased to 32.8 Å for the ratio 1/10/75 and to 33.2 Å for of a porous network. The ﬁnal properties of such materials the ratio 1/15/75. Materials obtained with the use of dodecylamine showed even larger basal spacing of 35.7 and

may be inﬂuenced by the synthesis conditions (BENJEL- 3r

LOUN et al., 2002). 36.4 Å for the ratio 1/10/75 and 1/15/75, respectively. FTIR d Mid-European Clay Conference – MECC 06 The aim of this study was to investigate the role of vari- spectra of the intercalated solids showed that the major changes were associated with the complex absorption band ous synthesis parameters in the preparation of porous clay of Si–O stretching vibrations, whose broadening reflected heterostructures derived from natural montmorillonites. the hydrolysis of TEOS. Among the studied factors were: To complete the synthesis the intercalated clays were – the origin of clay; subjected to calcination in air at 650°C. The absence of – the carbon chain length of neutral amine; any vibrations characteristic of organic groups in the – the molar ratio of reactants. FTIR spectra confirmed that thermal treatment removed completely the organic templates. The materials obtained The montmorillonite clays used in this study were the from Ca–JP showed slightly higher specific surface area, as sodium form of montmorillonite from Milowice deposit compared to those prepared from Na–M, e.g. for the solids (Poland), and the calcium form of montmorillonite from templated with dodecylamine at the reactant ratio of 1/15/ Jelšový Potok deposit (Slovakia), referred to as Na–M and 75 the specific surface areas of JP and M-based materials Ca–JP, respectively. were 810 and 842 m2/g, respectively. Dominant pore radius In the first step of PCH synthesis, inorganic cations in was 24 Å in both cases. the interlayer space of Na–M and Ca–JP were exchanged with hexadecyltrimethylammonium cation (HDTMA+). Acknowledgment: This work was financially supported by EU proj- The XRD patterns of organoclays HDTMA–M and HDT- ect Transfer of Knowledge TOK–CATA, contract No. MTKD–CT–

MA–JP showed an increase of basal spacing d001 to 21.2 Å, 2004–509832. as compared to parent montmorillonites (12.1 Å for Na–M and 15.1 Å for Ca–JP). This value points to the pseudotri- References molecular configuration of alkyl chains in the interlayers BENJELLOUN, M., COOL, P., VAN DER VOORT, P. & VANSANT, E.F. of both clays. FTIR spectroscopy also confirmed the pres- (2002): Template extraction from porous clay heterostructures: Influ- ence on the porosity and the hydrothermal stability of the materi- ence of organic cations in the smectite structure. Stretch- als.– Physical Chemistry Chemical Physics, 4, 2818–2823. ing and bending vibrations of CH and CH groups of alkyl 3 2 GALARNEAU, A., BRODAWALLA, A. & PINNAVAIA, T.J. (1995): Po- -1 chains were observed at 2923 and 2851 cm and 1488 and rous clay heterostructures formed by gallery-templates synthesis.– 1470 cm-1, respectively. Nature, 374, 529–531.

1 Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Niezapominajek, 8, 30-239 Kraków, Poland ([email protected]) 2 Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 845 36 Bratislava, Slovak Republic 3 Institute of Chemical and Engineering Sciences A*STAR, I Pesek Road, Jurong Island, 627833 Singapore 89 Abstracts Book Abstracts 90 3rd Mid-European Clay Conference – MECC 06 aeilfrbikmkn.Tredffrn lithostratigraph different material for brick making. Three were outcarried in order to the qualitydescribe of the clay mainly distribution,compositionrockwhole andclaymineralogy are They covered by aeolian sediments sediments. (loess). Analyses of grainsize fluviatile and marine prise for used als brick-making area. inthis ting and the petrographic characteristics of the raw materi and kilns most the ownership. all their al of history the reconstruct to it possible was bricksit produced, the on kiln each by impressed seals distinctive handcraft area. inthe in use on based a result of this process nowadays only a single kiln remains mainly formerly changed step by step to an almost totally automatic one. As production The changed. dramatically has industry brick the WarWorld 1780–1980 (PAPP et al., 2003). Since the end of the Second period the during district Hollabrunn the in operating as and loess loam.ternary Qua by partly covered are units tectonic Both (granites). western – parts to the eastern ofpart the Bohemian Massif Molas its of some with the to – as well as sediments),(Neogene sezone belongs district Hollabrunn The setting. cal clay materials for brick–making is given due to the geologi different of abundance wide a Austria Lower northern In Geological ofAustria, Neulinggasse 38,A1030Vienna, Survey Austria h egn eoiso h olbundsrc com district Hollabrunn the of deposits Neogene The set geological the to paid was attentionConsiderable the and sources historical of variety great a on Based claypitsarerecordedeightand kilns brick 150 totalIn Helga PAPP Brick kilns of northern Lower ofnorthern Brick kilns Austria: and geology History † , Mandana PERESSON , Mandana , Reinhard ROETZEL ( [email protected]) ------a constant quality. little variation over distances, wide an important factor for show distribution grainsize and Mineralogy mogeneous. ho very be to tend sediments the origin marine its to ing pelitic and sandy sediments of the Laa Formation. Accord by represented is It age. Karpatian of is brick-production productionthe of lightweight insulating bricks. for used are which intercalated, are diatomites laminated tents during firing. pyrite Gypsum, negatively. and behaviour their weathering products result in increased SO drying the fluence in may smectite by dominatedcomposition mineral clay The silts. clayey to clays silty of consists and carbonate of Lower Ottnangian to Pleistocene age. ic formations were found to be most suitable, ranging from PAPP, H., ROETZEL, R. & WIMMER-FREY, I. (2003): Die Ziegelöfen des reason for rather the heterogeneous quality of historical bricks. the is variability.This great show distribution size grain the as well as composition mineralogical the ation, used for all sediments kinds of bricks. Due commonto the local geological situ most the were deposits loess loamy From a historical point of view the Pleistocene loess and for formation geological important most the Today finely Formation Zellerndorf the of part upper the In is free (Ottnangian) Formation Zellerndorf marine The sch. Geol.B.-A.,sch. Band 24,117–191,Wien. Bezirkes Hollabrunn: Geschichte und Geologie.– Arch. f. Lagerst.for and Ingeborg andIngeborg WIMMER-FREY Reference 2 -con ------Abstracts Book

Acid treatment of clay minerals: a FTIR spectroscopic study

Martin PENTRÁK and Jana MADEJOVÁ

Clays are widely used materials in various industrial vibrations absorbing in the 950–800 cm-1 region (AlAlOH applications either in their original or in adapted forms. near 915 cm-1, AlFeOH near 880 cm-1, AlMgOH near Some properties of clay minerals can be modified, e.g. by 845 cm-1 and FeFeOH near 820 cm-1) and the band near acid activation, to increase their efficiency for selected 520 cm-1, attributed to deformation vibration of Si–O–Al. utilization. Inorganic acid treatment causes partial or Increasing intensity of the band near 800 cm-1 reflected complete destruction of the clay minerals structure growing amount of amorphous SiO2. The bands present depending on the reaction conditions and on the availability in the NIR region result of overtones and combinations of the interlayer space. During the acid attack the central of fundamental stretching and deformation vibrations. atoms from the octahedral as well as tetrahedral Al are Strong band at 7060 cm-1 was assigned to the 2ν-OH removed from the clay structure. The final reaction product overtone of the OH-stretching vibrations. The decrease of is a microcrystalline, protonated SiO2 (MADEJOVA et al., OH overtone signalized loss of octahedral atoms from the 1998). Acid activation of clays is an effective method for structure. On the other hand, the appearance and rising preparation of advanced adsorbents, catalysts or catalyst intensity of Si–OH overtone near 7315 cm-1 provided carriers (ADAMS, 1987; BROWN, 1994). evidence on protonization of Si–O groups. Acid treatment

The aim of this investigation was to follow the caused different level of structural decomposition of 3r changes in the clay minerals structures during treatment the clay minerals. The trioctahedral smectite (SHCa–1) d Mid-European Clay Conference – MECC 06 in hydrochloric acid. The fine fractions of four mont- was very unstable in the acid. Si–O stretching band was -1 morillonites SAz–1 (Cheto, Arizona, USA), SWy–2 shifted to 1098 cm after 8 h dissolution even in 0.5M (Wyoming, USA), Kunipia (Japan), Lastovce (Slovakia), HCl at 30°C. The dioctahedral smectites (SAz–1, Kunipia, one nontronite SWa–1 (Washington, USA), a hectorite SWy–2, Swa–1 and Lastovce) were more stable during acid (SHCa–1, California, USA), an illite/smectite (Dolná Ves, dissolution. Their Si–O stretching bands were shifted to 1095 cm-1 (Saz–1), 1056 cm-1 (Kunipia), 1065 cm-1 (SWy–2), Slovakia), a kaolinite (Gold Field, Tanzania, Africa) and a -1 -1 pyrophyllite (Vígľašská Huta, Slovakia) were studied. The 1094 cm (Swa–1) and 1100 cm (Lastovce) after dissolution was performed in 0.5M and in 6M HCl for 1 to dissolution in 6M HCl at 80 and 95°C for 8 h. On the other 36 hours. The first group of the samples (Kunipia, SWy–2, hand, pyrophyllite, kaolinite and partially illite/smectite Lastovce, Dolná Ves, Vígľašská Huta and Gold Field) was were more resistant to acid attack than smectites under the treated with 6M HCl at 95°C, the second group with 6M same conditions. Si–O stretching bands of pyrophyllite, HCl at 80°C (SAz–1, SWa–1) and the third group was kaolinite and illite/smectite after 8h HCl treatment were at dissolved in 0.5M HCl at 80°C (SHCa–1). the same positions as in the spectra of the original samples. No isomorphous substitutions of central atoms and thus no The solid reaction products were studied by infrared negative charge on the layers of pyrophyllite and kaolinite -1 (IR) spectroscopy in the mid-IR (MIR, 4000–400 cm ) and as well as partially collapsed interlayers of illite/smectite -1 the near-IR (NIR, 11000–4000 cm ) regions. This method restricted the attraction of protons to penetrate into the provides unique evidence on the depopulation of the layers and attack the OH groups. octahedral sheets and on the amount of SiO2, the reaction product of acid treatment. References The MIR spectra of original clay minerals contain a ADAMS, J.M. (1987): Synthetic organic chemistry using pillared, cation- complex band near 1030 cm-1 due to characteristic stretching exchanged and acid-treated montmorillonite catalysts.– Appl. Clay vibrations of Si–O groups. An upward shift of this band Sci., 2, 309–342. -1 BROWN, D.R. (1994): Clays as catalyst and reagent supports.– Geol. Car- to the position of amorphous SiO2 (near 1100 cm ) was observed as a result of acid treatment. Depopulation of the pathica, Ser. Clays, 45, 45–56. octahedral sheets was confirmed by decreasing intensities MADEJOVÁ, J., BUJDÁK, J., JANEK, M. & KOMADEL, P. (1998): Com- parative FT–IR study of structural modifications during acid treat- of the bands related to vibrations of the octahedral atoms, ment of dioctahedral smectites and hectorite.– Spectrochimica Acta, i.e., OH stretching vibrations near 3620 cm-1, OH bending Part A, 54, 1397–1406.

Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-84536 Bratislava, Slovakia ([email protected]) 91 Abstracts Book Abstracts 92 3rd Mid-European Clay Conference – MECC 06 model better than the Freundlich one for batch and column plicability of for method. each type isotherm aparticular ap the indicates 1 Figure surfaces. particle zeolitic ternal internalexandionsmechanism the on bindingof lead of Langmuir the and Freundlich isotherms, in order to define ofequations linear with tested wereperformances both of points equilibrium The method. column the for constant remaining while ions, lead increase of concentration the initial the with of decreases method batch the for efficiency (VUKOJEVI 2610.3 mg/l; for the column method: method: batch the (for ions lead of centrations temperature same (t=20 the at out carried were Experiments column method. batchthe byand the performancesby tal experimen different two from givenclinoptilolite, zeolite ex results perimental for ion exchange ionsof lead on natural equilibrium the compares paper This method. column the by or method batch the by performed be can process exchange ion The solutions. water from ions metal heavy with ions Mg and Ca K, Na, hydrated own its of change ex ion of property the has clinoptilolite zeolite Natural Faculty ofChemical Technology, ofSplit,Teslina University 10/V, 21000Split, Croatia ([email protected]) h xeietlpit tteLnmi isotherm Langmuir the fit points experimental The The equilibriumisothermfor leadremoval by natural zeolite– ° ) ihauossltoso ieetiiilcon initial different of solutions aqueous with C), clinoptilolite: acomparison ofbatch andcolumn methods Ć MEDVIDOVI Jelena PERIĆ, Nediljka Jelena PERIĆ,Nediljka VUKOJEVIĆ MEDVIDOVIĆandMarina TRGO Ć et al., 2006) al., et γ o =212.5 h removal The . – 520.5 mg/l) γ o =103.5 – ------VUKOJEVI immobilized by phenol of Biosorption F.(2004): GONEN, & Z. AKSU, treatment ( wastewater in application practical of its advantages for of method latter one is which method, column the for and are somewhat higher and equal 175.44 mg Pb/g zeolite batchfor the method Pb/g mg capacities149.25 that equal Langmuir comparisonandforcalculationexchange of used is model The ions. bound between interaction no with and sites, identical of particle number surfaces, with a finite external and internal on sorption homogeneous monolayer by a surface, on occurs clinoptilolite zeolite natural by ions lead of removal that Langmuir indicates equation isotherm the of fit better The performance. experimental through curve.– Process breakthrough Biochemistry, curve.– 39,599–613. of prediction bed: packed continuous a in sludge activated Technology, 49,237 clinoptilolite. zeolite natural of bed fixed by solutions aqueous from removal lead of performance umn Ć Fig. a,b–Langmuir model; isotherm 1Comparison of: AKSU &GONEN, 2004) MEDVIDOVI od; b, d–column method. c, d–Freundlich model;a,c–batch isotherm meth – 244. Ć References , N., PERI N., , Ć – , J. & TRGO, M. (2006): Col (2006): M. TRGO, & J. , eaain n Purification and Separation .

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Clay mineralogy and crystallochemistry of the Douro Carboniferous Basin (Early Stephanian C; NW Portugal)

Ary PINTO DE JESUS1 and Fernando ROCHA2

The Douro Carboniferous Basin [DCB] (NW Portugal) is terpretation, the obtained results were submitted to mul- an intramontane basin from the Early Stephanian C and tivariate statistic analysis, namely principal components occurs in the geological setting of the Central Iberian Zone and discriminant analysis. The results obtained for the KI (CIZ). The DCB is the major Carboniferous basin present and the good correlation with those obtained by organic in the Douro–Beira Carboniferous Trough [DBCT]. With petrography, namely the vitrinite reflectance, related to the an extension of 53 km, the DCB extends in a narrow strip, sedimentological and tectonic evolution of the DCB, lead always less than 500 m wide. The main tectonic structure is us to conclude about the two main phases of coalification. a duplex related with the tectonic deformation phase from The first one occurred before tectonic deformation and the late Hercynian orogeny (PINTO DE JESUS, 2001). In good late and more intense one related to a post-tectonic stage. relation with the granitoids occurring in the region, the coalification reached the meta-anthracite rank (LEMOS References DE SOUSA, 1978; PINTO DE JESUS, 2001). In this work KISCH, H.J. (1991): Illite crystallinity: recommendations on sample prep- we present the results and conclusions about the research aration, X-ray diffraction settings, and interlaboratory samples.– J. Metamorphic Geol., 9, 665–670. 3r

on the clay mineralogy of the several lithofacies of the DCB, d Mid-European Clay Conference – MECC 06 and also from the studies on illite crystallinity (Kubler in- KUBLER, B. (1964): Les argiles, indicateurs de métamorphisme.– Rev. dex [KI]). For those purposes, 24 samples (whole sample Inst. Fr. Pétrole, 19, 1093–1112. and <2 µm) were studied by X-ray diffraction, applying cri- LEMOS DE SOUSA, M.J. (1978): O grau de incarbonização (rang) dos carvões durienses e as consequências genéticas, geológicas e estru- teria and methods of MELLINGER (1979), and PEVEAR & turais que resultam do seu conhecimento.– Comun. Serv. Geol. Por- MUMPTON (1989), and, for KI those of KUBLER (1964) tugal. 63, 179–365. and KISCH (1991). MELLINGER, R.M. (1979): Quantitative X-ray diffraction analysis of clay Quartz and mica/illite are largely represented. Pyro- minerals. An evaluation.– Saskatchewan Research Council, Canada, phyllite is also present in several samples, sometimes in SRC Report G–79, 1–46. relevant amounts. Correlation between KI and the vertical PEVEAR, D.R. & MUMPTON, D.R. (1989): Quantitative mineral analysis of clays.– CMS Workshop Lectures, 1. The Clay Minerals Society, succession was carried out with very good results. From Colorado (USA). these results, we were able to establish sedimentologic and PINTO DE JESUS, A. (2001): Génese e Evolução da Bacia Carbonífera do stratigraphic subdivisions in the total series. It was also Douro (Estefaniano C inferior, NW de Portugal); Um Modelo.– PhD possible to confirm the position of the coalification as be- thesis, Univ. Porto. ing in the transition from diagenesis to low-grade metham- PINTO DE JESUS, A., ROCHA, F., GOMES, C. & SOUSA, M.J.L. (1997): orphism domains (PINTO DE JESUS et al., 1997; ROCHA Mineralogical parameters used as lithostratigraphic markers: Ser- rinha formation of the Douro Carboniferous Basin (Portugal).– Bol. et al., 2000). KI values clearly show the rising of illite crys- Soc. Esp. Mineralogia, 20–A, 119–120. tallinity in good relation with the increase of the coal rank. ROCHA, F., BOBOS, I. & GOMES, C. (2000): Clay minerals assemblage From these results, duplication on stratigraphic record was in anchimetamorphism from the Douro Carboniferous Basin, Portu- confirmed. Aiming a more refined sedimentological in- gal.– Abstr. 37th Annual Meeting Clay Minerals Society (USA), 99.

1 Dep. e Centro de Geologia, Fac. Ciências, Rua do Campo Alegre, 687, 4169–007 Porto, Portugal 2 MIA, Dep. Geociências, Univ. Aveiro, 3810–192 Aveiro, Portugal ([email protected]) 93 Abstracts Book Abstracts 94 3rd Mid-European Clay Conference – MECC 06 Fig. ofthephosphate isotherm aniononMg 1Sorption 1 The samples (25 temperature constant 1 at g/l. maintained were was ratio solid/liquid The anion. phate phos containing solutions aqueous of volumes identical with contacted were solids synthesized of amounts tical activated iden equilibrium,atretention capacity the study to order on performed were Mg experiments sorption The cites. Mg on anionphosphate of librium tions content with high of anionic pollutants. solu aqueous of treatment advanced the for used compounds be can these Therefore, 2005). al., et SEFTEL 2003; so hydrotalcites are good anionic exchangers (LAZARIDIS, anions, other with exchanged be can molecules water and anions interlayer The anions. of variety a host can which pairs, M(I)M(III), M(II)M(III), M(II)M(IV), M(III)M(IV), Mg of that to similar radius cationic the have to is the rule only clays; anionic hydrotalcite-type form of cation can that pairs variety large a is There molecules. water and ion interlayeran the by neutralized are which layers,droxide hy octahedral brucite-like charged positively of consists crease of phosphate concentration to stipulated limits. to leads water surface in de the requireeutrophication, problemswhich of serious anion phosphate of presence The 2

Faculty ofChemistry, “Al. I.Cuza” ofIasi, Blvd. University ([email protected]) Faculty andEnvironmental Engineering, ofIndustrialChemistry “Politehnica” University ofTimisoara, Victoriei Sq.No.2, 300006Timisoara, Romania x 2+ h i fti oki oivsiaetesrto equi sorption the investigate to is work this of aim The (LDHs) hydroxides double layered the of structure The Rodica PODE Rodica Zn cations. As a result there is a wide variety of cation of variety wide a is there result a As cations. 3-x Al Al hydrotalcite samples, where x=3; 2; 1.5; 1; 0. In 1 , Eveline POPOVICI Experimental Introduction Sorption equilibriumofphosphateSorption anion on Mg x Zn 3-x Al-type hydrotal Al-type x Zn 2 Copou, No. 11,700506Iasi, Romania , Laura COCHECI 3 Al sample. ± 3-x 1 ° ) n a in C) Al-type hydrotalcites

------Fig. 2 Sorption isotherm of the phosphate anion on Mg on anion phosphate the of isotherm Sorption Fig.2 Mg > Mg was: order selectivity sized samples. The synthefororder selectivity the establish to allowedanion capac Mg type adsorption the of the ity for values obtained The equations. Langmuir–Freundlich and/or Langmuir purpose general samples tion equilibrium of phosphate anion on two of synthesized sorp the show 2 and 1 Figures solids. synthesized all for tionof phosphate anion and ordertoestablish selectivity a to determine adsorp the for oxides mixedwas the of capacity sorption experiments the equilibrium the of aim The sorption equilibrium. the reach to order in hours 12 forthermostat Bath Shaker SEFTEL,DVININOV,M., E. LUTIC,E., D., POPOVICI, CIOCOIU,& E. (2003): K. N. LAZARIDIS, supporting this research. for No.1/S1–2005) (Project Authority Scientiﬁc TECH Acknowledgments: for Zn Mg for mg/g 108 between ranged These determined. were capacity adsorption the of values ple. h dopineulbimmdl sdwr the were used models equilibrium adsorption The biomolecules.– (2005): C. talcite.– single batch systems by uncalcined and Mg–Al–CO calcined 1 , Erika REISZ , Erika 1.5 3 Al sample,Al respectively. Zn . Water, Air, Pollution, 146,127–139. 1.5 l MgZn > Al ytei o hdoact-ye noi cas containing clays anionic hydrotalcite-type of Synthesis J.O.Adv.Mat., 7,2869–2879. Results andDiscussion h uhr iht hn h MATNAN the thank to wish authors The x 1 Zn and Elena Mihaela SEFTEL andElenaMihaela 3-x opin eoa o ain ad ain in cations and anions of removal Sorption References 2 l Zn > Al l ie oie fr h studied the for oxides mixed Al 3 l As, h maximum the Also, Al. 3 Al sample and 74 mg/g 74 and sample Al

3 Al Al > Mg 1.5 Zn 1.5 3 Al sam Al 2 hydro ZnAl ZnAl 2 ------Abstracts Book

The TOT layer silicate of the lacustrine green clay, Rona limestone, Romania

Dana POP1, Erzsébet TÓTH2, Tamás G. WEISZBURG2, Emanoil SĂSĂRAN3 and Sándor STICHLEUTNER4

The IMA nomenclature of micasRIEDER ( et al., 1998) strong adsorption bands (3557 and 3525–33 cm–1) in the offered a chemical framework for standardised species OH-stretching region, corresponding to ν Fe3+–Mg–OH definitions, containing formal borders between glauconite and ν Fe3+–Fe2+–OH vibrations in celadonite–XC (for the and celadonite, as well as borders and gaps between the suffices see WEISZBURG et al., in prep.). Theö M ssbauer Al- and Fe-rich phases of the system. Recent investigation spectrum is rather simple, it can be fitted for two doublets, of uncommon occurrences of green TOT phases (e.g. assigned to octahedral environments of Fe3+ and Fe2+, re- HOVER & ASHLEY, 2003; TIBLJAŠ et al., 2004) challenge spectively. The crystal chemical formula – the IMA phase limits. More likely, these minerals occupy 3+ 2+ K0.71Na0.02Ca0.05(Fe 0.89Mg0.62Al0.27Fe 0.25Ti0.01)(Si3.89Al0.11 a continuous crystal chemical space (WEISZBURG et al., O10(OH)2) (assuming the presence of 3 wt% quartz) – dein prep.). fines a glauconite–GC mineral, close to the border with The green clay occurrence under study is hosted by the celadonite–CC. Rona Member of the Paleocene Jibou Formation (COD- Few studies are currently available on the mineralogy 3r d Mid-European Clay Conference – MECC 06 REA & SĂSĂRAN, 2002), a lacustrine lens-shaped body and genesis of lacustrine green clays. According to the IMA of local extension within the thick pile (over 1500 m) of criteria, the TOT component of such clays plots in the non- continental red siltic clays. The classical profile of it is lo- defined field between illite and glauconite (PORRENGA, cated in the Rona village, near Jibou town (Sălaj district, 1968; HOVER & ASHLEY, 2003), in the aluminoceladonite Romania). The succession consists of a lacustrine and a and celadonite fields (HOVER & ASHLEY, 2003) or in that palustrine association; dolomitisation processes identified of glauconite (present study). It seems that the lacustrine in several carbonate sequences point to an advanced de- environments provide a wide range of physical, chemical gree of diagenesis. and possibly biologically-mediated mechanisms that may The Rona Member contains, at several levels, local direct neoformation of green TOT clays of a wide range of centimetre-size accumulations of green clays, mainly re- chemistries. lated to cracks and fractures in the host rock. In the basal References part of the Rona profile, in a 40 cm thick limestone level – consisting of dominant calcite and subordinate dolomite, CODREA, V. & SĂSĂRAN, E. (2002): A revision of the Rona Member.– as proven by the bulk XRD pattern – beside void-filling, Studia Univ. Babes–Bolyai, Geologia, XLVII, 27–36. the green clay forms coatings, in average 0.5–1 cm thick, HOVER, V.C. & ASHLEY, G.M. (2003): Geochemical signatures of pale- odepositional and diagenetic environments: a STEM/AEM study of around nodular cherts. The silica nodules, 4–20 cm in size, authigenic clay minerals from an arid rift basin, Olduvai Gorge, Tan- are polychromatic and inside exhibit “septaria”-like net- zania.– Clays and Clay Minerals, 51, 231–251. works of whitish radial and polygonal cracks. The studied PORRENGA, D.H. (1968): Non-marine glauconitic illite in the Lower samples originate from these coatings. Oligocene of Aardeburg, Belgium.– Clay Minerals, 7, 421–430. RIEDER, M., CAVAZZINI, G., D’YAKONOV, Y.S., FRANK-KAMENET- Powder XRD revealed that the green clay represents SKII, V.A., GOTTARDI, G., GUGGENHEIM, S., KOVAL, P.V., a mixture of dominant Fe-rich 10 Å phyllosilicate, calcite MÜLLER, G., NEIVA, A.M.R., RADOSLOVICH, E.W., ROBERT, J.- (~30%) and quartz (~5%). The Fe-rich mica was separated L., SASSI, F.P., TAKEDA, H., WEISS, Z. & WONES, D.R. (1998): No- from the green clay by careful decarbonation procedure menclature of the Micas.– The Canadian Mineralogist, 36, –905 912. (applying 5% acetic acid), and then investigated by XRD, TIBLJAŠ, D., ŠĆAVNIČAR, S., MOLIN, G. & SLAVKOVIĆ, R. (2004): Authigenic mica in Early Miocene volcanoclastic rocks of the Macelj IR and Mössbauer spectroscopy, TEM and ICP–AES. In area, Hrvatsko Zagorje, Croatia.– N.Jb.Miner.Mh., 69–82. the XRD pattern, the symmetric 001 reflection and the WEISZBURG, T.G., TÓTH, E. & POP, D. (in preparation): The continu- d060 value (1.509 Å) point to the celadonitic nature of the ous crystal chemical space of dioctahedral iron-rich micas and re- studied material. The IR spectrum is characterised by two lated phases (celadonite, glauconite, Fe-illite).

1 Museum of Mineralogy, Babeş–Bolyai University, 1 Kogălniceanu St., RO-400084 Cluj–Napoca, Romania ([email protected]) 2 Department of Mineralogy, Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117 Budapest, Hungary 3 Department of Geology–Paleontology, Babeş–Bolyai University, 1 Kogălniceanu St., RO-400084 Cluj–Napoca, Romania 4 Research Group of Nuclear Methods in Structural Chemistry of the Hungarian Academy of Sciences, Pázmány Péter sétány 1/A, H-1117 Budapest, Hungary 95 Abstracts Book Abstracts 96 3rd Mid-European Clay Conference – MECC 06 Fig. 1 1 the to fordetermine samples hydrotalcite the of was capacity sorption experiments the equilibrium the of aim The SCN was performed for an aqueous with concentration of study 75 mg kinetics at25 The hours. 12 for thermostat Bath Shaker a studied was equilibrium sorption The 0. usingMg 450 at samples activated the on performed 80 at ing heat by followed temperature room and pH constant at co-precipita by solutions,nitrate Al(III) and prepared Zn(II) and/or Mg(II) of tion were samples hydrotalcite The on Mg anion thiocyanate of process sorption the of acterization pollutants advanced the anionic ofcontent high for with wastes aqueous of treatment used be can compounds these Therefore, oth exchangers. anionic with good are be exchanged hydrotalcites so anions, er can anions interlayer The 1998). (GUPTA,properties catalytic and sorption to due niques, tech abatement pollution in importance large a gained priority dangerous pollutant. a as well-known is anion this since must froma is wastewater thiocyanates of removal The etc. electroplating, rea, thiou of manufacturing production, fibre acrylic duction, of variety a in industrial processes such as: herbicide and proinsecticide result wastewaters containing Thiocyanate 2 ([email protected]) Faculty andEnvironmental Engineering, ofIndustrialChemistry “Politehnica” University ofTimisoara, Victoriei Sq.No. 2,300006Timisoara, Romania Faculty ofChemistry, “Al. I.Cuza” ofIasi,Blvd. University hsppramdtetemdnmcadkntcchar kinetic and thermodynamic the aimed paper This have compounds hydrotalcite type clays anionic The - Sorption isotherm of the thiocyanates aniononMg ofthethiocyanates isotherm Sorption /l. x Zn ° x o 8hus h opineprmnswere experiments sorption The hours. 18 for C Zn 3-x Sorption kinetics and equilibriumofthiocyanate anion kinetics Sorption Al-type hydrotalcites.Al-type 3-x Al-type hydrotalcites, 1; Al-type 1.5; 2; 3; = wherex Results andDiscussion Eveline POPOVICI Experimental Introduction on Mg Vasile PODE x 1 , Rodica PODE , Rodica ° Zn C for 2 hours 2 for C Copou, No. 11,700506Iasi, Romania ± 3 3-x Al sample. 1 ° 2 C using C and Al-type hydrotalcites Elena Mihaela SEFTEL Elena Mihaela ------2 , Erika REISZ , Erika Fig. of curve 2Kinetic netic rate constant, h q where: expressed as: reached based on Lagergren tion isotherm Mg i.e., anion, studied for materials ised synteth of serie forZn selectivity the determine to mg/g allowed ties 12.7 3 from to ranged capacity sorption data. The equilibrium experimental the for suitable were els Variousmod anions.theoretic thiocyanate of adsorption AAII, .. (2003): N.K. LAZARIDIS, (1998): V.K.GUPTA, supporting this research for No.1/S1–2005) (Project Authority Scientific TECH Acknowledgments: La gergren equation. the with satisfactory fitted were results sorption netic Mg on thiocyanate of 1.5 process sorption the corresponding curve kinetic The were data experimental kinetic the of results The talcite.– single batch systems by uncalcined and Mg–Al–CO calcined low-cost adsorbent a slag, activated using wastewater and solutionaqueous from nickel and copper of removal the for operations column anddevelopment 7 Zn gg o Mg for mg/g 1.5 t – sorption capacity at the time t, mg g mg t, time the at capacity sorption – Al > Al MgZn Water, Air, Pollution, 146,127–139. for Mg 2

q , Laura COCHECI t h uhr iht hn h MATNAN the thank to wish authors The = qiiru utk, opin yais process dynamics, sorption uptake, Equilibrium thiocyanates anion sorption anionsorption thiocyanates .– Ind. Eng. Chem.Res. q 3 -1 2 3 l Tevle fsrto capaci of sorption values The Al. e Al > Al Zn 3 Al sample.Al . 1 li hw nFg .Teainki anion The 2. Fig. in shown is Al opin eoa o ain ad ain in cations and anions of removal Sorption ] [ References 1 − ex

equation (LAZARIDIS, 2003), p 3 Al. Figure 1 shows the sorp ) ( − kt 2

, Mg , 37,

(1) 3 192–202. Al > Mg > Al on Mg 3

Al sample. -1 ; k – ki – k ; 2 ZnAl > ZnAl 3 hydro 3 Al Al ------Abstracts Book

Use of Romanian clays for textile wastewater depollution

Eveline POPOVICI1 , Aurelia VASILE1, Rodica PODE2, Emiliana DVININOV1 and Erika REISZ2

Introduction (1–14 mmol Ti/g clay) in a hydrochloric acid medium Synthetic azo-dyes are extensively used for dyeing and (MOGYORÓSI et al., 2003). The structure and properties printing in textile industries (YANG, 2005). The traditional of the obtained materials were studied by X-ray diffraction, textile finishing industry consumes about 100 l of water to FTIR spectroscopy and thermal analysis. process about 1 kg of textile materials. Wastewater from Results and Discussion textile industries creates great problem of pollution due to the dyes contained therein. The dyes contribute to the or- The adsorption of dye on the sodium montmorillonite ganic load and toxicity of the textile industry effluents. In shows a strong dependence on the pH and follows a Lang- the same time, the dyes are normally present in dyehouse muir adsorption model. Photodegradation process was de- effluent at concentrations of 10–50 mg/l, color being no- pendent on the effect of the initial concentration of dye, table at concentrations above 1mg/l. titania content and pH reaction medium. The reaction rate Generally, chemical, physical, biological, catalytical and was ascertained and optimum conditions for maximum photocatalytical methods have been used for removal or degradation were determined. The disappearance of the dye destruction from dye containing wastewater (ZHOU studied dye follows approximately a pseudo-first kinetic & SMITH, 2002). order according to the Langmuir–Hinshelwood model. 3r d Mid-European Clay Conference – MECC 06 In this study, the adsorption and photodegradation Acknowledgments: The authors are grateful for the support of the of Congo Red dye using natural and modified Romanian MATNANTECH, Project CEEX No. 1/S1–2005. clay has been examined for the purpose of identifying the ability of these materials in removal of colored textile dyes References from wastewater (YERMIYAHU et al., 2003). MOGYORÓSI, K., DÉKÁNY, I. & FENDLER, J.H. (2003): Preparation Experimental and characterization of clay mineral intercalated titanium dioxide nanoparticles.– Langmuir, 19, 2938–2946. In this study raw Romanian clay (63% smectite) coming YANG, Y. (2005): Nanoclay and modified nanoclay as sorbents for ani- from Valea Chioarului area was used. In view of titanium onic, cationic and nonionic dyes.– Textile Research Journal, 75, intercalation, sodium-clay form having the following com- 622–627. position (% wt): SiO –72.87; Al O – 14.5; MgO – 2.15; YERMIYAHU, Z., LAPIDES, I. & YARIV, S. (2003): Visible absorption 2 2 3 spectroscopy study of the adsorption of Congo Red by montmorillo- Fe2O3 – 1.13; Na2O – 0.60; K2O – 0.60; CaO – 0.90; PC nite.– Clay Minerals, 38, 483–500. – 5.70 and cation exchange capacity determined by am- ZHOU, H. & SMITH D.W. (2002): Advanced technologies in water and monium acetate method, of 82 meq/100 g, as matrix, was wastewater treatment.– Journal of Environmental Engineering Sci- used. For the preparation of the TiO2 – pillared clay, the ence, 1, 247–264. alkoxide molecules were adsorbed onto/into clay samples

1 Faculty of Chemistry, “Al.I.Cuza” University of Iasi, Blvd. Carol I, No. 11, 700506 Iasi, Romania ([email protected]) 2 Faculty of Industrial Chemistry and Environmental Engineering, University “Politehnica” of Timisoara, Victoriei Sq., No. 2, 300006 Timisoara, Romania 97 Abstracts Book Abstracts 98 3rd Mid-European Clay Conference – MECC 06 1 optimi geometry and minimization energy the on based (CERIUS Studio Material and & (KOUDELKA program SUPRAMOL modified using solved was acid sulphonate preparation. of cost low and layer modifications possible preparation, simple also is layers hydrotalcite of andstrong bondsamong atoms layer. the in Bigadvantage interlayer weak interactions a to due suitablelayerstructure has Hydrotalcite hydrotalcite. of charge layer positive the compensate to anions organic desirable by replaced are anions, carbonate usually anions,Interlayer teraction. ties. properdesirable with materials new of design tionshipin of determination forpropertiesand understanding of structure-properties rela crucial is structure of Knowledge measurements). gravimetric thermo and (X-ray diffraction methods experimental and simulations) (molecular ods Structureanalysisintercalatesof meth includetheoretical pyrenetetrasulphonateacid. with intercalatedhydrotalcite of analysis structure complex on focused is work Present 2 pyrenetetrasulphonate acid, molecularsimulations andexperiment University ofPardubice,University State Chemistry, ofSolid JointLaboratory Studentská 84,53210Pardubice, Republic Czech ([email protected]ff.cuni.cz) Charles University, Faculty ofChemical Physics ofMathematicsandPhysics, and Optics, Ke Department Karlovu 3, 12116Prague Republic 2,Czech Structureof hydrotalcite intercalated pyrenetetrawith in exchange ion on based is case this Intercalationin Structure analysisStructure ofhydrotalcite intercalated with Miroslav POSP Č APKOV 2 20) Cluain are Calculations 2000). , ÍŠ Kl Á IL , 2002) and Cerius and 2002) , á 1 , Marek VETE ra MEL Á NOV Š Á ------KA 2 2

and V 1 , Pavla the resultantthe structure was investigated. crystal on water of interlayer influence imetric measurements. The amount of water molecules determined from thermo grav probablyunstable. Individual werewith models calculated 12.8 11.7 spacing: and sample basal 3 with two significant 9.8 spacing: with basal 1 Sample samples: different three for solved were els mod Structuredata. experimental on based spacing basal wereandmodelsoptimized for minimized initial different These SUPRAMOL. from models initial of series a tained of intercalate were created. rametersandsuitable minimization strategies fortype this pa field force empirical by described is Structure zation. CERIUS & KOUDELKA,B. Combining modelling and experimental results we ob lecular Simulationslecular Inc., San Diego. structure of VOPO the simulations: molecular using intercalates of analysis structure í Å t ě h eut fmdligso htsml 3 was sample that show modelling of results The . 2 (2000): Cerius zslav Z Č APKOV Č Í MA APKOV Å 4 Á 2 .C srGie ocfil ae iuain. Mo Simulations.– Based User Guide. Forcefield , sample 2 with basal spacing: 13.6 spacing: basal with 2 sample , 1 2 6 , Ludv H References 4 Á O , P. (2002): SUPRAMOL – a program for program a – P.SUPRAMOL , (2002): 2 – J. Mol Model, 8,184–190. í k BENE Š 2 ,

Å and Å - - - - -

Abstracts Book

Modiﬁcation of the montmorillonite surface with cationic surfactants

Petr PRAUS1, Martina TURICOVÁ1, Soňa ŠTUDENTOVÁ1 and Gabriela KARTOŠOVÁ2

Phyllosilicates can be modified with quaternary salts surface charge and thus eliminate the repulsive electrostatic including cationic surfactants in order to obtain new forces. In this way the large macropores were originated as materials with exceptional properties for the retention of demonstrated in Table 1. various organic contaminants (WEISS & KLIKA, 1994), The MMT surface modification was verified bya oils and amines (BEALL, 2003), and even inorganic study of moisture adsorption and desorption isotherm + oxyanions (LI & BOWMAN, 2001). In this study a Na - plots obtained using a dynamic vapour sorption (DVS) rich montmorillonite (MMT) type Wyoming (Al Mg ) 3.4 0.6 method. Moisture sorption was expressed as the percent- (Si Al )O (OH) was used for the MMT modification 7.8 0.2 20 4 age moisture content as a function of relative humidity. In with cationic surfactants, such as cetyltrimethylammonium comparison with natural MMT, both CTMB–MMT and bromide (CTMB) and cetylpyridinium chloride (CPC). CPC–MMT exhibited very similar but significantly small- Both surfactants were dissolved in water–ethanol (50:50, er amount of water taken up. The plots hysteresis loops of v/v) solutions in which MMT was added. Such prepared CTMB–MMT and CPC–MMT were narrower than that of suspensions were shaken for two hours to reach adsorption

MMT. It is surprising that only a slightly lower content 3r

equilibrium. The centrifuged and dried MMTs saturated d Mid-European Clay Conference – MECC 06 of water was sorbed on CPC–MMT in spite of its about with CTMB (CTMB–MMT) and CPC (CPC–MMT) were twofold increase of surface area (Tab. 1). This effect can examined by the surface area and pore area measurements, be explained by the higher amount of CPC attached to the electron scanning microscopy (SEM) and moisture MMT surface forming the more hydrophobic surfactant adsorption. coverage. It was also confirmed by construction of the Using the BET method, total surface areas of MMT, CTMB and CPC adsorption isotherms from which it fol- CTMB–MMT, and CPC–MMT were determined (Table 1). lowed that MMT was saturated with the higher amount The 5–50 µm and 50–1000 µm pore size areas were estimat- of CPC. ed by means of a Dollimore Heal isotherm (DOLLIMORE & HEAL, 1964). The 0–5 µm pore area was calculated as a Acknowledgement: This work was supported by the Ministry difference between the total and the 5–1000 µm pore area. of Education, Youth and Sport of the Czech Republic (MSM The MMT pores of 0–50 µm were significantly reduced by 6198910016). the surfactant adsorption. On the contrary, a number of the 50–1000 µm pores in the modified montmorillonite References samples increased. BEALL, G.W. (2003): The use of organo-clays in water treatment.– Morphology of the natural and modified montmorillo- Applied Clay Science, 24, 11–20. nite was examined by SEM. The SEM micrographs DOLLIMORE, D. & HEAL, G.R. (1964): Improved method for calcu- showed that the surface of MMT was equalized, covered lation of pore size distribution from adsorption data.– Journal of Applied Chemistry, 14, 109–114. by small and well separated particles. The CTMB–MMT and CPC–MMT surfaces exhibit a grain-like structure LI, Z. & BOWMAN, R.S. (2001): Retention of inorganic oxyanions by organo-caolinite.– Water Research, 35, 3771–3776. of agglomerated particles. The modified particles gather WEISS, Z. & KLIKA, Z. (1994): Modified clays and their utilization for together more easily than the unmodified ones because immobilization the waste materials from water solution. Ceram- the surfactants adsorbed compensate the MMT negative ics.– Silikáty, 38, 201–207.

Table 1 Natural and modiﬁed montmorillonite pore size distribution.�

MMT CTMB–MMT CPC–MMT

Total area (m2/g) 28.50 4.40 8.83 0–5 µm pore area (m2/g) 21.79 0.37 2.61 5–50 µm pore area (m2/g) 6.37 2.81 4.40 50–1000 µm pore area (m2/g) 0.34 1.22 1.82

1 Department of Analytical Chemistry and Material Testing VSB–Technical University Ostrava, 17. listopadu 15, 708 33 Ostrava, Czech Republic ([email protected]) 2 Institute of Material Chemistry VSB–Technical University Ostrava, 17. listopadu 15, 708 33 Ostrava, Czech Republic 99 Abstracts Book Abstracts 100 3rd Mid-European Clay Conference – MECC 06 eseá ad uzaifl Lmsoe omtos, in Formations), Limestone Pusztakisfalu and Kecskehát Sandstone, (Mecseknádasd bodies limestone and ments sedi redeposited of intercalations occasional show posits matter. organic and carbonate of proportions Marl to Komló Calcareous Marl Formations) with variable Calcareous Hosszúhetény facies, (Allgäu mudstones lagic Mec hemipe predominantly of the composed are Mountains of sek successions Sinemurian–Bajocian upper The mateand supply high a of terrigenous clastics tobasin. the cli humid subtropical the in a suggest Formation Coal Mecsek berthierine and kaolinite of proportions relative The chlorite.and/or berthierine of presence the with minerals olinite (kao), illite and(ill) illite/smectite (I/S) mixed-layer posited. Vasasand Formations)Marlde wereCoal Mecsek facies, and shallow marine coal-bearing siliciclastic rocks (Gresten a well-developed succession of Jurassic sediments. haveand Mega-unit(Hungary) Tisza the of nappe known source area. the in palaeoclimate and conditions weathering interpreting for tool powerful a be is to considered successions widely sedimentary ancient of mineralogy Clay 2 1 Department ofPetrology andGeochemistry,Department E and Environmental Sciences, ofEarth Pannon University,Department Egyetem utca 10,8200Veszpr In the Early Jurassic (Hettangian–Sinemurian),ﬂuvial Jurassic Early the In the Hettangian–Bajociansuccessions oftheMecsekMountains

h eskMutismk ato h lowermost the of part make Mountains Mecsek The

h lyasmlgscmrs rdmnnl ka predominantly comprise assemblages clay The Climato- environmental controls onclay mineralogy of (Tisza Mega-unit, Hungary) ö tv B ö é s L.University, P la RAUCSIK

hs de These á zm 1 andAndrea VARGA á ------ny P. s f / mxdlyr ieas n ilt wt sas occur sparse with illite and minerals mixed-layer I/S of proportions high contain sediments Komló Bajocian the weathering related to the oceanic anoxic event. In contrast, continentalintense and climate humid a suggesting ill>1) Siltstone(ÓbányaFormation;dominant mineral kao/clay the becomes Toarcian,kaolinite Towards the formations. underlying the to relative clastics terrigenous of input ate moder a and conditions climatic (monsoon-like) humid seasonally and warm represent to interpreted is interval Pliensbachianresults, time the these on proportion. Based small in present kaoliniteare minerals mixed-layer of I/S (kao/ill<1). amounts subdominant with illite of nantly predomi composed are Formations Kecskehát and dasd Hosszúhetény,PliensbachianMecsekná the of suites eral and min changes clay level The basin. depositional of sea subsidence intensive eustatic of effects with accordance ugra cetfi eerhFud(TA rjc 415to Béla Raucsik. 047195 T project (OTKA) Found Research HungarianScientific Acknowledgement: rigenous clastics from a relatively distant source area. conditionswith seasonal climaticdroughts and aminor humid input of ter and warm mineralassemblageclayreflects rence of kaolinite and chlorite (kao/ill=0 or kao/ill<1) é t á ny 1/C, 1117 Budapest, Hungary ny 1/C,1117Budapest,Hungary hssuywsfiacal upre ythe by supported financially was study This é m, Hungary ([email protected])m, Hungary 2

. This ------Abstracts Book

Mineralogy of Latosols along a regional toposequence across the Central Plateau (Brazil): First results

Adriana REATTO1, 2, Ary BRUAND2, Eder S. MARTINS1, Fabrice MULLER2, Euzébio M. SILVA1, Edi M. GUIMARÃES3 and Michel BROSSARD4

The Brazilian Central Plateau is constituted of the two main <2 µm fraction was also determined by using X-ray diﬀrac- geomorphic surfaces: the South American surface and the tion and results conﬁrmed those recorded after chemical Velhas surface. These surfaces were developed during the dissolution. The relations Ki and Kr that are weathering in- Cretaceous Superior and Tertiary and are covered by deep- dices (EMBRAPA, 1997) were computed as following: ly weathered Latosols. The South American surface is the Ki = 1.7 (SiO2/Al2O3) oldest and occupies the highest position in the landscape and (950 to 1,200 m altitude) with smoothly convex plane portions. The Velhas surface is composed by irregular and Kr = 1.7 (SiO2)/(Al2O3+0.6375×Fe2O3). slightly sloping planes and occupies in the landscape (750 The Latosols studied showed Ki and Kr that ranged to 950 m altitude). It is connected to the South American from 0.32 to 1.36 and from 0.26 to 1.06 respectively. The surface by areas of steep hillsides. averaged Ki and Kr were 0.50 and 0.40 respectively on the

Latosols cover about 40% of the Central Plateau surface South American Surface with Latosols whose parent mate- 3r area. Most Latosols in the Brazilian Soil Taxonomy corre- rials were originated from lateritic crusts and saprolites of d Mid-European Clay Conference – MECC 06 spond to Oxisols in the Soil Taxonomy and to Ferralsols detritic and mafic granulite rocks. The averaged Ki and Kr in the International Reference Base System. In the Central were 1.10 and 0.86 respectively on the Velhas Surface with Plateau, the Latosols can be Red Latosols (Acrustox, ~28%), Latosols whose parent materials originated from colluvial Yellow Red Latosols (Acrustox, ~10%) and Yellow Latosols pediments from South American Surface and saprolites of (Haplaquox, ~2%). The main characteristics of Latosols are pelitic rocks. The ratio kaolinite/kaolinite+gibbsite (RKGb) a poor differentiation of the horizons, a weak macrostruc- ranged from 0.24 to 0.78, and the averaged RKGb was 0.35 ture and a strong submillimetric granular structure result- on the South American Surface and 0.70 on the Velhas ing in microaggregates 50 to 300 µm in size (REATTO et Surface. The ratio hematite/hematite+goethite (RHGt) al., 2000). The objective of this work was to discuss the first ranged from 0 to 1, and the averaged RHGt was 0.36 on results of the mineralogical characterization of Brazilian the South American Surface and 0.74 on the Velhas Sur- Latosols located along a regional toposequence across the face. The kaolinite content ranged from 20 to 65 g.kg-1 for Central Plateau. the Latosols studied, the averaged content being 28 g.kg-1 Ten Latosols (L) developed in different parent materials for Latosols located on the South American Surface and -1 were selected along an approximately 350 km long regional 55 g.kg for Latosols located on the Velhas Surface. The -1 toposequence across the South American Surface (L1 to gibbsite content ranged from 22 to 63 g.kg , the averaged -1 L4) and Velhas Surface (L5 to L10). Samples were collected content being 52 g.kg for Latosols located on the South -1 in the diagnostic horizon (Bw) of these Latosols. Basic soil American Surface and 27 g.kg for Latosols located on the characteristics were determined on the air-dried <2 mm Velhas Surface. material according to the Brazilian standard procedures References (EMBRAPA, 1997). Thus, the particle size distribution was determined using the pipette method after dispersion EMBRAPA (1997): Manual de métodos de análise de solo.– 2 ed. Empresa Brasileira de Pesquisa Agropecuária, Rio de Janeiro, 212 p. with NaOH 1N. Chemical composition obtained after dis- REATTO, A., MARTINS, E.S., GUIMARÃES, E.M., SPERA, S.T. & COR- solution in sulfuric acid was used to estimate the kaolinite, REIA, J.R. (2000): Variabilidade mineralógica de latossolos da área gibbsite, goethite and hematite content. Goethite and he- da Embrapa Cerrados em relação aos do Bioma Cerrado.– Boletim matite content was also estimated using the soil color (hue, de Pesquisa Embrapa Cerrados, 20, 1–29. value and chrome). The mineralogical composition of the

1 Empresa Brasileira de Pesquisa Agropecuária (Embrapa Cerrados), BR 020, km 18, 73310–970, Planaltina, Distrito Federal, Brazil ([email protected]) 2 Institut des Sciences de la Terre d’Orléans (ISTO) UMR6113 CNRS/Université d’Orléans 1A, rue de la Férollerie 45071 Orléans, Cedex 2, France 3 Instituto de Geociências – Universidade de Brasília (UnB), 70910–000, Brasília, Brazil 4 Institut de Recherche pour le Développement (IRD), Unité Valpédo, BP 64501, 34394 Montpellier, Cedex 5, France 101 Abstracts Book Abstracts 102 3rd Mid-European Clay Conference – MECC 06 tionsamong and someclaymetals heavy content, between by r with and some are strongvery (Clay/Cr with r Clay/Cd) Clay/Zn, Clay/Cu, (Clay/Pb, cients are significant coeffi correlation clay the of Manycontent. metals heavy between and correlation a strong is There soils. in centage relationship between the elements investigated and clay per tion analysis was carried out to determine the extent of the (sedimentation).pipette by the Correlamethod termined spectively). contentclaycorrelationcant(r with signifi a show factors Both Ni. and Cr on loadings factor ex factor, plaining 18.50% of the total variance, showed high positive second The Cd. and Hg Zn, Cu, Pb, to related positively and strongly was variance, total the of 38.46% explaining factor, first by The determined components method. principal was topsoils in elements of associations 35.6 20.50 Ni obtained 0.415 (mg/kg) Cd were: concentrations average The elements. these of concentration clay the content generally influences ( composition material parent geological the on primarily depends soil with percentage the of clay insoils. fraction connection in measured metals heavy these in variations WAY,1995 heavy metals and soil parameters ( between exists correlation Significant topsoil. agricultural ters (pH, organic matter and carbonates) in were quantified Cr, (Cd, metals heavy Cu, Hg, Ni, and andPb other Zn) parame seven of content the composition, granulometric lected from an 8 km samplescontentswork624 In werethis metal col soils. in Soil clay plays an important role in the explanation of heavy I.N.I.A. CIFOR. Ctra. 7,5,28040 Madrid,I.N.I.A. delaCoruña Km, Spain([email protected]) BOLUDA Jos The natural concentration of heavy metals in arable metals heavy of concentration natural The h ly(<2 clay The ± 42.05 2 03) hs eut eesmlrt hs obtained those to similar were results These =0.35). é ± Antonio RODR 22.71, Pb 17.54 Pb 22.71, .Ti td hw h pta orltosand correlations spatial the shows study This ). µ (98 h eosrtdsgicn correla (1988) who demonstrated significant /g h itiuinmne of individual manner distribution The g/kg. DE TEMMERMAN DE ± µ .6, r 20.27 Cr 0.163, m) andsiltm) (2–63 2 Relationship between metalsandclay heavy terrain in the Ebro basin (Spain). The ± 10.41, Zn 17.53 Zn 10.41, Í GUEZ MART in Spanishagricultural topsoils ± BOLUDA, 1988; ALLO 32, u 17.33 Cu 13.21, et al., 2003). However,2003). al., et µ 2 m) fractions werefractions m) de =0.24 and r and =0.24 2 =0.42 or Clay/Ni ± Í N 24.19 and Hg and 24.19 , Diego MORALES HERRAIZ , DiegoMORALES 2 =0.39 re =0.39 ± 14.97, ------to the cation exchange duecapacity of organic probably material ( is effect this soils; in absorption metal heavy influence to found been also has matter Organic topsoils. grassland the in only observed was matter organic of age age 1.9%; range between 0.2% and 13.1%). Higher (averpercent content matter organic low a has and agricultural predominately is matter soil and heavy metals content. The although not for Cd. Cu, and Zn Ni, Cr, of values background for result same soil. loam or sand than soil clay for higher were concentrations als met heavy to heavy metal concentrations as expected. The through sand from loam to clayranged and these granulometric fractions were classes related textural The 2003). al., ( soils peaty and chalk over soils shallow sandy, with associated is carbonates.with Metal deficiency and metals organic these matter and negativea correlation TICHY, R., NYDL, V., KUZEL, S. & KOLAR, L. KOLAR, & S. V.,KUZEL, NYDL, TICHY, R., NICHOLSON,F.A., ALLOWAY, SMITH,S.R., B.J., CARLTON-SIMITH, MARTIN, H.W. & KAPLAN, D.I. VANONGEVAL,L., TEMMERMAN, DE W. BOON, L., HOENIG,M. & BOLUDA, R. ALLOWAY,J B. et al., 1997; Another high relationship was found between organic between found relationshipwas high Another Air, and Pollution, Soil 94,361–372. mium availability to crops on a sewage-sludge amended soil.– Water, total the Environments, 311,205–219. of Science Wales.–The and England in soil agricultural to B.J CHAMBERS, & C. 399–410. 101, Pollution, Soil and Air, Water, conditions.– field phytoavailabiltyunder and soil in mobility vanadium and thallium, Water, Air and Pollution, Soil 148,61–76. (2003) 47, 1503–1524. de Requena – Utiel (Valencia).– Anales de Edafología y Agrobiología, orgánica, carbonatos totales y arcilla de suelos de la comarca La Plana sados Co,(Cd, Cr, Cu, Ni, Pb cony Zn) el pH, contenido en material gow, UK. : Heavy metal content of arable soil in Northern Belgium.– Belgium.– Northern in soil arable of content metal Heavy : (1988): Relaciones estadísticas de los valores de metales pe DE TEMMERMAN DE MARTIN &KAPLAN . (1995): Heavy metals in soils.– Chapman & Hall. & Chapman soils.– in metals Heavy (1995): . andJos . (2003): An inventory of heavy metal input metal heavy of inventory An (2003): . References (1998): Temporal changes in cadmium, é Manuel GRAUManuel CORBI et al. et , 1998). (2003) obtained the the obtained (2003)

(1997): Increased cad Increased (1997): NICHOLSON TICHY

Glas et ------

Abstracts Book

Phase transformations of Co–MIII layered double hydroxides (MIII = Al, Cr, Fe, or Mn) during thermal treatment

Tomáš ROJKA, František KOVANDA, Barbora DOUŠOVÁ and David KOLOUŠEK

Layered double hydroxides (LDHs), also known as hydrotal- heating rate was used). Thermal decomposition accompa- cite-like compounds or anionic clays, are decomposed to nied by collapse of LDH structure resulted in a formation form well-dispersed homogeneously mixed oxides suitable of nanocrystalline spinels. Spinel was formed also after for application in heterogeneous catalysis. Therefore it is thermal decomposition of the Co–Mn sample. Based on of interest to understand in detail the thermal behaviour the XRD data processing the lattice parameters and mean of these materials. Four LDH precursors containing Co in coherence length were evaluated. With increasing calcina- combination with various trivalent cations (Al, Cr, Fe, or tion temperature, a gradual crystallization of spinel-like Mn) were prepared by coprecipitation of corresponding mixed oxides was observed but the composition of spinel nitrate solutions, where the Co/MIII molar ratio of 2 was phases was partially changed. The ratio of integral inten- adjusted. Thermal decomposition of prepared LDHs and sity of (111) and (220) diﬀraction lines can be taken for phase transformations of related mixed oxides were stud- evaluation of the occupancy of tetrahedral cationic sites ied using thermal analysis (TG/DTA/EGA), powder X-ray by a lighter component (WOLSKA et al., 1997). XRD diﬀraction including high-temperature measurements data processing showed that the occupancy of tetrahedral 3r

(HT XRD) and Raman spectroscopy. A well-crystallized cationic sites by light component (e.g. Al) increased with d Mid-European Clay Conference – MECC 06 hydrotalcite-like phase was detected in Co–Al and Co–Fe increasing calcination temperature. Raman spectroscopy samples, the Co–Cr sample exhibited a lower crystallin- confirmed the presence of Al cations in the tetrahedral sites ity. The lattice parameters evaluated from diffraction data of spinels obtained already at low calcination temperatures increased with increasing MIII cationic radius, which indi- (the characteristic band at 727 cm-1 was detected in the Ra- cated an incorporation of MIII cations into the hydroxide man spectra of these samples). layers of hydrotalcite-type lattice. In the XRD pattern of III The Co-rich spinels, i.e. Co3O4 or slightly M -doped Co–Mn sample, an unidentified phase with d~0.665 nm III (Co1-xM x)3O4 exhibit four characteristic sharp bands at was found. Two major endothermic effects, characteris- 300–800 cm-1 and therefore they can be easily identified by tic for hydrotalcite-like compounds, were found in DTA Raman spectroscopy. A segregation of Co-rich spinels was curves. The first one was ascribed to release of interlayer observed in samples obtained at lower calcination tem- water. The second endothermic effect, accompanied by si- peratures (300–600°C). In some cases, this phase segrega- multaneous H2O and CO2 evolution, was ascribed to de- tion cannot be detected by XRD because the lattice param- hydroxylation of hydroxide layers and destruction of LDH eters of formed spinels are very close to each other. With structure. The dehydration and dehydroxylation processes increasing calcination temperature, a recrystallization of partially overlapped, especially in the case of Co–Fe sam- the primary formed Co-enriched spinels took place and an ple. Thermal stability of prepared LDHs increased as fol- incorporation of MIII cations into the spinel lattice can be lows (temperatures of endothermic minima corresponding considered. The mixed oxides with spinel structure were to LDH thermal decomposition are written in parenthesis): detected in powder XRD patterns of samples calcined up Co–Fe (190°C) < Co–Al (260°C) ≈ Co–Cr (265°C). Dur- to ca. 900°C. At high temperatures above 900°C, the phase ing heating of Co–Mn sample, also two major endother- transformation was observed, when CoO was formed to mic effects with minima at approximately 100 and 245°C the detriment of spinels. were observed and the course of DTA curve was similar to that measured with LDH samples. However, both these Acknowledgements: This work was supported by Czech Min- minima were associated with evolution of water, which can istry of Education, Youth and Sports (research project No. MSM be explained by dehydroxylation of unidentified, probably 6046137302) and by the Grant Agency of Czech republic (projects hydroxide- and/or oxohydroxide-type phases. Nos. 104/04/2116 and 106/05/0366). According to XRD results, the prepared LDHs were Reference decomposed at temperatures up to 200°C. The HT XRD WOLSKA, E., STEMPIN, K. & KRASNOWSKA-HOBBS, O. (1997): X- measurements showed a slight decrease of LDH basal ray diffraction study on the distribution of lithium ions in LiMn O / spacing due to a partial dehydration, but the dehydration 2 4 LiFe5O8 spinel solid solutions.– Solid State Ionics, 101–103, 527– temperatures indicated by HT XRD were of about 30–40°C 531. lower than those detected by thermal analysis (the same

Department of Solid State Chemistry, Institute of Chemical Technology, Technická 5, 166 28 Prague, Czech Republic ([email protected]) 103 Abstracts Book Abstracts 104 3rd Mid-European Clay Conference – MECC 06 1 0.5 (Mg#=55.8 biotite crystalloclasts. nic Bunari carbonatethe platform. relativelyfor withinthe typical settingmarine pH~8, deep around at diagenesis suggests measurement) microprobe (Ca family ite exclusivelymontmorillonite and zeolite from heuland the ples, respectively. d d d showing maximums diffraction from samples oriented in treatment wt%, respectively. by Montmorillonite is defined bonate ptilolite and cristobalite in Gornji and biotite in the Bunari quartz (albite?), plagioclase cristobalite, calcite, by panied accom samples both in mineral principal the as rillonite herein. reported are briefly properties mechanic soil bentonite and mineralogy layers Ž layersbentonite ated the from sampled been has gations Leme hinterlandDalmatianintercalate typical the within in lage intraplatformthe troughs connected to open the sea. along moulded been have to assumed is It Mesozoic. the Adriatic facies development than different regularlythose being formed within the deciphers clearly succession The calations. limestonesdolomiteand (BRAUN,inter chert with 1991) (VELI limestones platy are the sedimentary succession comprised of light coloured Dinarides External the in deposits Lemeš Jurassic Upper 3 2 Institute ofMineralogy andPetrology, ofGeology, Department Faculty ofScience, ofZagreb, University Horvatovac bb, HR-10000 Zagreb, Croatia ofGeotechnics, FacultyDepartment ofCivil EngineeringandArchitecture, ofSplit,Matice University hrvatske 15,HR-21000 Split,Croatia HR-10000 Zagreb, Croatia ([email protected]) Institute ofMineralogy, Petrology andMineral Faculty Deposits, ofMining, GeologyandPetroleum Engineering, ofZagreb, University Pierottijeva 6, (001) (001) (001) aj h rlmnr eut forrsac nbentonite on research our of results preliminary danj. The 8 h R nlsso lblsmlsrvasmontmo reveals samples global of analysis XRD The vil Maovice of vicinity the in layers bentonite Two In the grain size fraction 63 fraction size grain the In =9.59 =16.62 =14.84 t% ad aiie (Or sanidine and wt.%) š

ć eois(RU,19) h aeilfrinvesti for material The 1991). (BRAUN, deposits contents were determined to 8.06 wt.% and 26.49 and wt.% 8.06 to determined were contents – Altered tephra layers intheUpperJurassic Lemeš deposits otis oprtvl hg aon o volca of amount high comparatively contains iai croae ltom el throughout realm platform carbonate Dinaric Å near Maovice (Dalmatia, Croatia): clay mineralogy and Å Å (heated) for Bunari for (heated) d , 0.54 ehln gyo strtd, d saturated), glycol (ethylene

(001) Na Alteration of tephra to assemblage the of –

13 TiO 61.3; 0.08 =15.02 The most abundant are euheadral are abundant most The on the localities Bunari localities the on Branimir K Ć ć 0.09 sample and calcite, quartz, clino t l, 95 ado dolomitic and/or 1995) al., et Ba Å 0.03 2 =4.2 ar re) d dried), (air – [Al 125 ć basic soilmechanicproperties Š Ž 65.9 and Gornji and – EGVI 1.63 danj sample. Total car . w., BaO=0.18 wt.%, 4.7 more despicably situ despicably more – µ Vanja BI 74.9 Si m, the sample fromsample the m, 7.46 Ab Ć O 1 24.4 , Aleksandar TO 18 ] ć – (001) (001) * 33.5 Ž 6H and Gornji and Š danj sam danj =16.6 An EVAC =9.79 2 after O 0.65 – 9 1.34 3 Å Å andBo – ------) , , % ncasfiainshm fe OT (1969). KONTA after scheme 2%) inclassification gravel 6%, sand 40%, silt 52%, (clay clay silty calcareous Gornji and 3%) gravel 1%, sand 66%, silt Bunari calcite gional source. re single a fromeruption(s) the inputtephrarelatedto of indicatoran be might crystalloclasts volcanic the of sition sourcetephra.ofApparently the arc asnic composimilar volca (rhyolitic?) calc-alkaline high-K a suggest strongly Leme the of chemistry mineral and samples.Volcanoclastic both abundantin composition mineral are fossils Radiolarian observed. occasionally are (Wo (Wohyperstene augite subcalcic quartz, whilst EI, . TŠJR J & LHVĆ I. VLAHOVIĆ, & J. TIŠLJAR, I., VELIĆ, of classification petrological analytical Quantitative (1969): J.KONTA, Mineralogical (1991): K. BRAUN, range of plastic state of analyzed bentonites. wide and aptitude swell compressibility, high clearly high imply data tests mechanic soil Overall MPa. 2.5 nearly and MPa 3.8 nearly kPa 200 to kPa 100 from increment stress forcompression of modulus showed test solidation the con oedometer after swell free test are up to and87% The 92%. volume soil of Increases 104.82%. and 86.85% to set limits liquid with 36.65%, and 45.54% are material kN/m 25.43 are Mg/m 2.59 to set Gornji and Š EVSKI According to the grain size composition and content of gress, Abstract Zagreb, Book, 96. l (eds.): I. VELIĆ, & I. VLAHOVIĆ,In: deposits”?– “Lemeš Kotar Gorski the of JurassicUpper the in chert rocks.– Actasedimentary Univ. Carol., 1,175–253. Geologica, abstract). Poljanskaand Luka. genesis of the bentonite deposits of Maovice, Gornja Jelenska, Bednja Soil mechanic properties are being reported for Bunari š ko LUGOVI 2 , Danijela Ž danj respectively. Measured dry densities aredensities respectively. danj dry Measured ć apei lsie scae it(ly30%, (clay silt clayey as classified sampleis 3 1.6 and 25.91 kN/m 25.91 and 3 En Ć and 2.64 Mg/m 2.64 and – 1 59.2 Acta Geol., 21, 1 21, Geol., Acta Š References Fs TEVANI 39.2 ) and potassium tschermakite potassium and ) – ergahcl hrceitc and characteristics petrographical Ć 3 3 19) Ae ietns with limestones Are (1995): – . Plastic limits of tested of limits Plastic . 2 , while weight densities weight while , 34 (in Croatian with EnglishCroatian with (in 34 , st Croatian Geological Con Geological Croatian st š

deposit tephra layers tephra deposit 36.5 En Ž 41.1 danj sample as sampledanj – 41.5

22.0 – 22.3 ), ć ------

Abstracts Book

Properties of clay mineral surfaces modiﬁed by intensive physical disintegration

Ivan SONDI and Neda VDOVIĆ

Previous studies have shown that surface and bulk prop- mation of an amorphous phase followed by changes in the erties of minerals can be modiﬁed by physical wear caus- morphology, structure and surface properties of clays. ing particle size diminution (SONDI & PRAVDIĆ, 1997, The milling approach simulates processes that take

2002). These processes, often called “physical weathering”, place in nature – the processes of intensive physical disin- continuously occur in nature and result in alteration of size, tegration which produce nanosize clay particles of unde- morphology, and bulk properties of mineral components. termined structure and of unique surface properties. Such The present study reviews research on the effect of physi- particles are the most reactive mineral phase in natural en- cal disintegration on the alteration of the structural and surface properties of three different types of clay minerals vironments and this characteristic governs physico–chem- – kaolinite, Otay-montmorillonite and chlorite–ripidolite. ical interactions at mineral surface/aqueous medium interfaces in soils and aquatic sediments. The structural properties of milled samples were examined by X-ray diffraction (XRD) and high resolution References

transmission electron microscopy (HRTEM). Their sur- 3r face properties were determined by measuring the electro- SONDI, I. & PRAVDIĆ, V. (1997): Surface properties of ripidolite and d Mid-European Clay Conference – MECC 06 phoretic mobility (EP, m2s-1V-1), speciﬁc surface area (SSA, beidellite clays modiﬁed by high-energy ball milling.– Colloids and Surfaces, 127, 141–149. m2g-1), and cation exchange capacity (CEC, meqv/100g). SONDI, I. & PRAVDIĆ, V. (2002): Electrokinetic of clay mineral surfac- This study has shown cases where physical disintegra- es.– In: HUBARD, A.T. (ed.): Encyclopedia of Surface and Colloid tion leads to size diminution, alloying processes, and for- Science. Marcel Dekker, Inc., New York, 1887–1893.

Center for Marine and Environmental Research, Ruđer Bošković Institute, Bijenička cesta 54, 10000 Zagreb, Croatia ([email protected]) 105 Abstracts Book Abstracts 106 3rd Mid-European Clay Conference – MECC 06 esrmns aons o 19% f hs as Q val Q mass. this of 81–92% to amounts measurements) 110 to up 200 above to200 up the monomolecular lost coverage of the clay surface. Water water lost of amount The dehydroxylation. of onset the above even smectites some surement on water based and EGMEsorption. mea TSA of techniques calibrate to used were formulae chemical from obtained Q and TSA performed. also were measurementssorption EGME and method Co-hexamine at 47% RH. Standard CEC measurements were made by the 900 temperatureto room from out carried experiments TGA–MS by studied was Ca-smectites Waterbyobtained. retention were clays the of areas surface total and densitiesXRD, by measured and formulae structural the and From calculated. were oxide formulae structural their ICP,and iron remove to treated carbonate impurities, Ca-exchanged, analyzeddialysed, by were samples The Q). (TSA/CEC/ density area, charge andcapacity, exchange surface cation total the between relationship data the these for refining use to and temperatures, different at heldwater of layer charge was undertaken to investigate the amount of A study of 12 smectite clays (<0.2 2 1 Total charge area,density, surface surface cation exchange capacity Chevron ETD, 3901 Briarpark, Houston, TX 77042, USAChevron ([email protected]) ETD, Houston, TX 3901Briarpark, Institute ofGeological PAN, Sciences Senacka 1,Kraków, 31002,Poland ([email protected]) G–S aa hw ht oeua wtr s ed by held is water molecular that show data TGA–MS ° ° C (conventional temperature of CEC and TSA TSA and CEC of temperature(conventional C C is close to 11% of this mass, and water lost water and mass, this of 11% to close is C ° ,atrtesmlswr equilibrated were samples the after C, b parameter of the unit cell, unit the of parameter and water retention insmectites µ m fractions) with a range Jan ° C approaches closely approaches C Ś RODO Ń 1 and Douglas K. McCARTY K. andDouglas - - culations (applicable when the structural formulaearenot structural culations(applicable the when cal unrefined the for and 3%, exceed not did combined TSA of error average the calculations fined correlated, not are calculations so they are decreased if the different results are averaged. For the re the of errors The these two parameters by two equations with two unknowns. dependentboth on and TSA Q, were to calculate used also H H and CEC between Q. and retention relations EGME experimental the using fined TSA mg/m H culate culate CECto completely the clay basis. dry watereliminatedalmost recal the todatawere when used were than differences Q obtained from the formulae. These ues calculated from CEC and TSA were substantially lower ter than conventional the EGMEmeasurement. precisionbet comparableorwithsample the of TSA sure mea content,wateropportunityprovidestofrom thusan porosityrock total measuring in step necessary a is which known) it increased to 4.5%. S fo te tutrl omle ee sd o cal to used were formulae structural the from TSA TGA measurementTGA waterof200 claysontoheldup EGME 2 . rm h aeae aus band TSA obtained, values average the From ). wr acltd h acltoswr ute re further were calculations were calculated.The 2 ad GE eetos n ly ufcs (in surfaces clay on retentions EGME and O 2 2 rtnin being retention, O H2O and TSA H 2 O and O 2 O and EGME ° C, ------

Abstracts Book

Krzysztof STARZEC and Michał SKIBA

Most X-ray diffraction (XRD) studies of glauconitic mate- Random powder XRD patterns revealed that glau- rial (green pellets called glauconite) are based on XRD of conitic grains of each sample represent the evolved and random powder mounts. Despite the structure of glauco- highly evolved stages of glauconitization (sensu ODIN & nite (GL) seems to be close to that of illite–smectite mixed MATTER, 1981), i.e. end member of glauconite–smectite layer minerals (I–S), the papers concerning diffraction pat- (GL–S) family. It suggests that in the structure of studied terns obtained for oriented mounts are relatively rare (e. g. material the glauconite layers predominate. It is confirmed THOMPSON & HOWER, 1975; WIEWIÓRA & ŁĄCKA, by diffraction patterns of oriented preparations. The air- 1980). It is widely accepted that XRD patterns of oriented dry and glycolated patterns of high and middle density mounts prepared for mixed layered clay minerals are most fractions only slightly differ in the shape and the position useful in characterization of the nature of component lay- of glauconite peaks which indicates highly glauconitic ma- ers, and the ordering in c direction. The information ob- terial. Nevertheless, all samples contain some admixture of tained using this procedure is potentially useful in interpre- expandable layers as evidenced by Ir index >1. On the pat- tation of the minerals origin, and their growth mechanism. terns of low density fractions changes are larger. 3r

The main idea behind this paper is to examine whether or d Mid-European Clay Conference – MECC 06 Simulation in NEWMOD program allows us to precise not a computer simulation method using the NEWMOD© identification of GL–S ratio and type of ordering. The esti- program (REYNOLDS, 1985), commonly used in case of mated amount of GL layers in studied samples ranges from I–S, is an effective way to reveal the structural details of 86% to >95%. The GL/S ratio increases with increasing of glauconitic material. the density of the glauconites, only samples of the lowest Samples were collected from sandstones of the Ma- density fractions are characterized by smectite content gura Beds of the Polish Flysch Carpathians. After disag- higher than 10% and the R1 type of interstratification, the gregation of rocks, a magnetic separation was used to other samples exhibit the R3 type of ordering. The prelimi- produce concentrates containing only glauconitic grains. nary results we obtained clearly shows that the simulated The material was then purified using acetate buffer and patterns well correspond with the experimental ones. Thus, ultrasonic treatment. Cleaned glauconites were separated the computer simulations seem to be an effective method by heavy-liquid fractionation into three density fractions: in determining the structure of GL–S. By applying this 2.8–2.7 g/cm3, 2.7–2.6 g/cm3 and 2.6–2.5 g/cm3. The grains method some additional information to glauconite–smec- of each fraction were pulverized (to ~2 µm) and random tite mineralogy may be added. oriented mounts were prepared for XRD analyses. Glass slides preparation was preceded by submitting the pow- References dered samples to carbonate and divalent cations removal using acetate buffer and saturation with Ca followed by ODIN, G.S. & MATTER, A. (1981): De glauconarium origine.– Sedimen- tology, 28, 611–641. dialysis. Oriented slides were prepared only for separated REYNOLDS, R.C. Jr. (1985): NEWMOD© a computer program for the <2 µm fraction. XRD analyses were performed with the use calculation of one-dimensional diffraction patterns of mixed-layered of Philips X’Pert diffractometer. The random mounts were clays.– R.C. Reynolds, 8 Brook Rd., Hanover, NH. scanned from 2–64° 2Θ and the oriented mounts from SATO, T., WATANABE, T. & OTSUKA, R. (1992): Effects of layer charge, 2–52° 2Θ (in air-dry and after ethylene glycol treatment). charge location, and energy change on expansion properties of dioc- For every sample the Ir index was measured (ŚRODON, tahedral smectites.– Clays & Clay Minerals, 40, 103–113. 1984) and numerous computer simulations with the use of ŚRODOŃ, J. (1984): X-ray powder diffraction identification of illitic ma- NEWMOD program were performed. During simulations terials.– Clays & Clay Minerals, 32, 337–349. lognormal crystallite size distributions (N= 4–10) were THOMPSON, G. R. & HOWER, J. (1975): The mineralogy of glauconite.– Clays & Clay Minerals, 23, 289–300. assumed. Fe3+ and K+ contents for glauconite were changed according to the EDS data obtained for single pellets. The WIEWIÓRA, A. & ŁĄCKA, B. (1980): Genesis of the glauconite pellets in the Ordovician deposits from Podlasie Depression. Part II: Crys- different values of smectite d(001) were also applied ac- tallochemical characteristics (In Polish).– Arhiwum Mineralogiczne, cording to SATO et al. (1992). 35, 57–86.

Institute of Geological Sciences, Jagiellonian University, Oleandry 2a Street., 30–063 Krakow, Poland ([email protected]) 107 Abstracts Book Abstracts 108 3rd Mid-European Clay Conference – MECC 06 using geotechnical methods. performed was testing approach.Indirect direct a as used was ultra magnifications thin sections observed at different directly or indirectly. Transmission electron microscopy of ticles and/or crystals. par smectite orientationof the oncompaction of role the on focused is tonite study processing and compacting. This ben during entation significantly which may be influenced ori particle smectite to connected parametersdirectly are bentonite, Mostthese tobentonite ofetc. size,initial grain tortuosity,additives bentonite, function of density dry porosity, a as is such bentonite parameters, or properties structural in pore various of nuclides radio of diffusion the surrounding rocks. It is well known from other ofstudies that and forms movement waste the between region the the in radionuclides retard to and flow groundwater inhibit to is waste radioactive high-level of disposal geological a in material buffer bentoniteofimportanta An function as 2 1 ENVIGEO a.s., Kynceľová 2,974 11Banská Bystrica, Slovakia Faculty ofNatural Sciences, Comenius University, Mlynská 84215Bratislava, Dolina, Slovakia ([email protected]) h ffc fteca atceoinainwstested was orientation particle clay the of effect The ffc fbnoiecmato nteorientation the on compaction bentonite of Effect Igor STR ÍČ EK 1 , Peter UHL M á ria ria of smectite particles of smectite Č APLOVI Í K 1 , Vladim Č OV - - - Á 1 es motn dffrne eeietfidbtenthe orientation the between in Difference identified origin. bentonites of different were differences important Less fractions. size their on depending andsamples on applied pressureof type the on depending samples in determined to up pressure with 35 technique isostatic an with along technique uneasily standard a samples:bentonite to plied g/cm 1.9 15 µ and 45 <250, fractions the to milled were bentonites volca andesitic of is nism and composed of product Fe-montmorillonite (55 alteration tuffs, the is ryolite of one second The alteration Al the by of mostly composed originated first, The using bentonite barriers. repositorieslong-term the of construction in accountinto propertiescompactedofbentonite, taken shouldbe which of particles has the implicit impact on the physico-chemical í andIgorGALKO r m and compacted to dry density between 1.6 g/cm 1.6 between density dry to compacted and m 0 Š infiatdffrne noinaino atce were particles of orientation in differences Significant Two types of Slovak bentonites were used for the study. UCHA MPa. 3 w ieetcmato ehiuswr ap were techniques compaction Twodifferent . 1 , Ren á ta ADAMCOV 2 – gmnmrloie (65 Mg-montmorillonite Á 1 ,

– 60%). The – 70%). 3 and - -

Abstracts Book

Eﬀects of in situ biostimulation on iron mineral speciation in a sub-surface soil

Joseph W. STUCKI1, Kangwon LEE1, Bernard A. GOODMAN1 and Joel E. KOSTKA2

The in situ alteration of Fe redox states in subsurface soils droxide mineral forms. Compared to the non-biostimulat- by bacteria, otherwise known as bioreduction or biostimu- ed soil, the spectral components assigned to goethite were lation, may play a key role in the immobilization of hazard- appreciably diminished in intensity in the samples that had ous redox active metals such as U, Tc, and Cr. The objective been biostimulated, whereas the hematite component was of this study was to characterize changes in Fe mineralogy greatly increased. The Fe(II):Fe(III) ratio in the non-oxide occurring in a subsurface soil as a result of biostimulation, phase (aluminosilicates) also increased, indicating that the in order to evaluate the bioremediation potential of this ap- bioreduction processes in the soil also affected the redox proach. Biostimulation was achieved by injecting glucose state of Fe in the constituent clay minerals. into the soil through a small well next to a sampling well. Cores taken from the sampling well were analyzed by vari- References 57 able-temperature Fe Mössbauer spectroscopy. Iron in the GOLDEN, D.C., BOWEN, L.H., WEED S.B. & BIGHAM, J.M. (1979): non-biostimulated soil was dominated by goethite (Fig. 1) Mössbauer studies of synthetic and soil-occurring aluminium-sub- with 0.12% Al substitution, mean crystallite diameter of stituted goethites.– Soil Science Society of America Journal, 43, 2 802–808. 3r 10.5 nm, and specific surface area of 133 m /g. These prop- d Mid-European Clay Conference – MECC 06 erties were determined from the magnetic hyperfine fields, MURAD, E. (1988): Properties and behavior of iron oxides as determined B , at 77 K and 4 K using the methods of GOLDEN et al. by Mössbauer spectroscopy.– In STUCKI, J.W., GOODMAN, B.A. hf & SCHWERTMANN, U. (eds.): Iron in Soils and Clay Minerals, D. (1979), MURAD & SCHWERTMANN (1983), and MU- Reidel Publishing Company, Dordrecht, 309–350. RAD (1988). Results further revealed that biostimulation MURAD, E. & SCHWERTMANN, U. (1983): The influence of aluminium (Fig. 1) resulted in an overall loss of Fe from the system and substitution and crystallinity on the Mössbauer spectra of goethite.– major changes in the distribution of its oxide and oxyhy- Clay Minerals, 18, 301–312.

Fig. 1 Mössbauer spectra of non-biostimulated (left) and biostimulated (right) soils.

1 University of Illinois at Urbana–Champaign, Department of Natural Resources and Environmental Sciences, Urbana, IL 61801 USA ([email protected]) 2 Florida State University, Department of Oceanography, Tallahassee, FL 32306 USA 109 Abstracts Book Abstracts 110 3rd Mid-European Clay Conference – MECC 06 Table1 methacrylate- poly(2-hydroxyethyl magnetic nonporous group-containing carboxyl with repurified and From inhibitors. PCR sediments, ofDNA was isolated using presence the to due problem difficult is sediments from DNA PCR-ready of Isolation study communities microbial complex fortechniques powerful are (PCR), reaction chain merase andria clay insediments lake. inthe bacte of concentration weathering the and it can influence interglacial during carbon organic in richer is suspension the largest tributary running riverinto the Lake Baikal. The is River Selenga Baikal. Lake of water cold deep vourable by ported sedimentation the of to lakeparticles less the fa in Table 1. arePosolskygiven the Bank in and Delta layersSelenga of the in found microorganisms of concentrations Bank). The Posolsky and Delta (Selenga Baikal Lake of positions two from taken were cores Sediment sediments. of formation dation of organic matter which suppose biochemical trans oxi microbial duringdiatomite and smectite of struction biode in sediments of activity microbial the study to was work this of aim tem peratureand organic carbon sources. The on dependence in bioformation mineral clay/iron and biodestruction silicate understanding for essential is Knowledge of microbial numbers and activity in sediments 2 1 05 m 18cfu/g 49cfu/g 32cfu/g 50–54cm 40–50cm 420cfu/g Posolsky Bank 30–40cm 20–30cm 10–20cm Delta Selenga 0–10cm Depth Department ofBiotechnology,Department Institute ofGeotechnics oftheSlovak Academy ofSciences, Watsonova 45,04353Košice, Slovakia PhysiologyInstitute ofAnimal oftheSlovak Academy ofSciences, Šolt o-utvto bsd oeua mtos a poly as methods, molecular based Non-cultivation trans were bacteria attached the that supposed was It Delta andinthePosolskyDelta Bank. The concentration of microorganisms in the layers of Selenga Selenga of layers the in microorganisms of concentration The Bacterial destruction of smectite and bacterial DNAbound andbacterial ofsmectite destruction Bacterial Igor ŠTYRIAK 730 cfu/g 9 cfu/g at 4 ° C 1 , Iveta ŠTYRIAKOV in smectite-bearing sediments in smectite-bearing Soil DNASoil Isolation Kit in clay sediments. clay in 195 cfu/g 470 cfu/g 70 cfu/g at 4 0 0 ° C co -ethyl Á 2

é , sovej 4–6,04001Košice, Slovakia ([email protected]) Alena ŠPANOV ------

Agency under the contract No. APVV–51–006304 and by Slovak by and APVV–51–006304No. contract Assistance the under TechnologyAgency and Science by and EVK2–2002–00538 Acknowledgements: cells with smectite.bacterial live of association via proceeded Destruction reduction. microbialironwith and Si Mg, of extraction with sociated in given Figure 1. are results The obtained. were products PCR bp 284 and bp 160 two strainspsychrotrophic of case the in PCR mesophilic strains one 284 bp PCR product was amplified, using of case the In sediments BcAPR1. and BcAPF1, BcFF2, primers lake the in identified were strains Psychrotrophic buffer. TE strength ionic low a in spheres Prague). CAS, Chemistry, Macromolecular of Institute (D.Horak, ene Fig. 1 DNA Agarose gel from electrophoresis of PCR products amplified Academy of Science No. VEGA2/5033/5.

h xeiet nsett idsrcinwr as were biodestruction smectite on experiments The tion, respectively (without thestep withmagnetic microspheres). extrac phenol or kit the using isolated cm) 0–10 Delta, (Selenga samples sediment Lake Baikal from DNA 14: and 13 lanes of DNA); instead (water control negative 12: lane ng); (10 depth cm 30 mycoides CCM19 mesophilic 9: lane ng); (10 DNA control CCM145 psychrotrophic 8: lane DNA ladder); 7: bp and (100 6 standard lanes respectively; depths, cm 40–50 and 30–40, 20–30, pH 10–20, EDTA, 0–10, from samples mM Delta Selenga 1 1–5: Tris-base, Lanes 8.0). mM 45 acid, boric mM (45 gel, TBE buﬀer agarose % 1.5 Conditions: microspheres. magnetic using isolated ehcyae (P(HEMA- methacrylate) Teasre N a eesdfo h micro the from released was DNA adsorbed The

T control DNA (10 ng); lanes 10 and 11: psychrotrophic 11: and 10 lanes ng); (10 DNA control sltd rm akl ae eiet a 01 ad 20– and 0–10 at sediments Lake Baikal from isolated Á 2 and hssuywsfne yteEU-project the by funded was study This Bohuslav RITTICH co EM) microspheres -EDMA)) 2

B. Bacillus

thuringiensis

cereus by

B - - - .

Abstracts Book

Bacterial removal of Fe(III) impurities from clay: A potential new technology

Iveta ŠTYRIAKOVÁ1 and Igor ŠTYRIAK2

Bioleaching is a technology applicable to iron removal tion indirectly through microbially promoted pH changes from non-metallic raw materials. Improvement of non- and production of organic acids. AQDS stimulated bacte- metallics can involve the action of bacterial assimilatory or rial iron reduction and Fe2+ concentration in solution was dissimilatory iron reduction. higher than Fe3+. However, NTA did not stimulate iron re- The reduction of Fe3+ for the purpose of intracellular duction but increased bacterial iron dissolution in form of incorporation into protein is called assimilatory iron re- Fe3+. The results presented in Table 1 showed that chela- duction. In contrast, dissimilatory iron reduction serves tors might be added to iron-contaminated non-metallics the generation of energy to fuel cell propagation (SCHRO- during bioleaching processes for stimulation of rate of iron DER et al., 2003). Dissimilatory Fe reducing bacteria re- removal. The concentration of carbon source in medium quire mM concentration of Fe (LOVLEY, 1991), in contrast is found to be crucial for the iron dissolution and metabo- to assimilatory bacteria only require µM concentration of lite production. Alternative cheap molasses and food-sugar Fe (MAURICE et al., 2000). have been used to optimize the cost of the bioleaching of

Naturally occurring iron oxides are often coating the iron on industrial scale. The low toxicity of chelators and 3r silicate surface of grains or are impregnated in the matrix in bacterial metabolites (pH 4) makes bioleaching an attrac- d Mid-European Clay Conference – MECC 06 silicates of industrial importance. That is why they cannot tive alternative way of quality improvement of non-metal- be removed by electromagnetic separation. These Fe-rich lics over chemical leaching (pH 2) which also improves impurities can be removed from industrial minerals such quality of non-metallics but needs complex operation con- as kaolinite through biodissolution. This process involves ditions and environmentaly hazardous chemicals. a siliceous matrix, which is why silicate heterotrophic assimilatory bacteria of the genus Bacillus are of potential use Acknowledgements: This work was supported by Science and in our experiments. Bioleaching resulted in a 17% decrease Technology Assistance Agency under the contract No. APVV– 51–006304 and by VEGA Agency supporting the projects No– in Fe content of kaoline raw material from Rudník. Fe2O3 content decreased from 1.103% to 0.9128%. 2/5033/5. The removal of oxidic Fe-phases from industrial sili- References cates via bioleaching needs to be optimized with regard to the rate of iron reduction and dissolution in order to make LOVLEY, D.R. (1991): Dissimilatory Fe(III) and Mn(III) reduction.– Microbiol. Rev., 55, 259–287. the removal competitive against the chemical leaching. MAURICE, P.A., LEE, Y.J. & HERSMAN, L.E. (2000): Dissolution of Al A new role for chelators as the low addition of AQDS or substituted goethites by an aerobic Pseudomonas mendocina.– Geo- NTA during bacterial quality improvement of non-metal- chim. Cosmochim. Acta, 64, 1363 – 1374. lics, resulted in enhancing Fe(III) reduction or stimulating SCHRODER, I., JOHNSON, E. & VRIES, S. (2003): Microbial ferric iron Fe dissolution under non-controlled anaerobic conditions. reductases.– FEMS Mic. Rev., 27, 427–447. Our experiment showed that bacteria enhance Fe dissolu-

Table 1 The highest concentration of iron in solution after 5–12 days bioleaching without and with chelators (AQDS – anthraquinone-2,6-disul- fonate, NTA-nitrilotriacetic acid).

Organic source without chelators AQDS NTA Fe2+ Fe3+ Fe2+ Fe3+ Fe2+ Fe3+

50 g/l food-sugars (after 5 days BL) 94.48 27.08 100.48 34.54 17.05 178.83 100 g/l food sugars (after 12 days BL) 134.46 36.76 180.9 53.22 81.45 195.45 Molasses (after 9 days BL) 106.54 93.8 154.26 100.35 50.5 219.26

1 Department of Biotechnology, Institute of Geotechnics of the Slovak Academy of Sciences, Watsonova 45, 043 53 Košice, Slovakia ([email protected]) 2 Institute of Animal Physiology of the Slovak Academy of Sciences, Šoltésovej 4–6, 040 01 Košice, Slovakia 111 Abstracts Book Abstracts 112 3rd Mid-European Clay Conference – MECC 06 .a neeto ieetfli o ntesnsoelayer; sandstone the in flow fluid different crystallization, of of effect anas 2. conditions different 1. ways: different in with hydrothermalnected growth (cf. BRUEL, 2000). con be can contact) the from distance bigger at collected samples in (noted SON et al., 1996). illite Growth of fibrous high amount of iron and to potassium in relatedstudied probablyrocks (LAN was I/S of formation Direct (I/S). als miner formed newly by replaced are BAUER (1983). They trusion as it was described by BRAUCKMANN & F in to vicinity close the in metamorphism contact during presence of potassium inmargins of kaolinite crystals. by manifested is process of stage Initial contact. the from of illitisation of kaolinite was atobserved 8 meters distance fromalteredminerals areordered. rocks R0 Firstevidence and 75% of smectite in 10 meters I/S distance. All identified smectite decrease to 80% in 4.5–5 meters from the contact, 90% of smectite layers. With increasing distance amount of illite was identified. the contact) by illite was observed. In some samples fibrous to close absent is kaolinite(which replacementprimary of basanite with contact the from Further contact. the from distance increasing with decreases minerals I/S in illite to smectite of Ratio mica. and (I/S) illite/smectite illite, tains of vicinity close intrusion.Pelitic basalt alteredof sandstones fraction con in collected samples studied in mined used. were diffraction X-ray and microscopy electron scanning cathodoluminescence, microscopy, Optical comparison. for collected also were rocks alteredNon(Poland). Silesia Krzeni sandstone were collected in two quarries (Wilcza G Triassic metamorphosed of Samples studied. were phism Clay minerals in sandstones subjected to contact metamor Jagiellonian University, Institute of Geological Science, ul. Primary clay minerals in sandstones are decomposed are sandstones in minerals clay Primary Close to the contact I/S contains about 10% of illite and deter mineral high-temperature only the is Sanidine Variable amount of illite in I/S minerals can be explained Clay minerals (I/S,kaolinite)incontact metamorphismrelated ó w) in vicinity to Tertiary basalt intrusions in Lower to Tertiary basaltsintrusions inLower Silesia(Poland) Oleandry 2a, 30–063Kraków,Oleandry Poland ([email protected]) Wojciech SZELIGA Ü ó ra and CHT ------of I/Sminerals. Skiba,SpecialthanksPh.D.M. helpNEWMODforinto modeling 24. 035 3P04D No. grant (KBN) Researches Committee of Scientific Acknowledgements: stages?)ity (several resulted information of I/Sminerals. ture zone in studied rocks. Subsequent hydrothermal activ tempera high in sanidine offormation and minerals clay composition, chemical temperature and pH. different of fluids with connected hydrothermalisactivity. retrogressiveminerals of Growth and metamorphism contact of case in both 2005), al., et authors numerous by(T described well was process third The activity?). hydrothermal of stage second with nected lower 3. temperature(retrogressive(con metamorphism?)growth model, (1987) NORTHROP & WHITNEY i.e. WHITNEY,NORTHROP,& G. H.R. T NIETO,F., MATA, PILAR BAULUZ,M., B., GIORGETTI,G., LANSON, B., BEAUFORT, D., BERGER, G., BARADAT, J. & LACHARP BRUEL, D. (2000) F F.J.BRAUCKMANN,& Ó Ó MASSON, J. & KRISTMANNSD Contact metamorphism caused decomposition of all all of decomposition caused metamorphism Contact American Journal of 287,353–382. Science, sandstone.– in minerals clay of composition isotope stable and ogy mineral regionalJuanzonationNewMexico Santhe – Basin, in the butions and to Petrology, Mineralogy 36,123–134. Iceland.–Reykjanes,brines, alteration Contrithermal andminerals ess on aregional Clay scale.– Minerals, 40,93–104. PEACOR,D.R.(2005) & Sedi of Journal Researchmentary Netherlands.– the of Offshore reservoir,sandstone versionlate–stage series: diagenesislower of the Permian Rotliegend AGNE J-C. Abstract, New Orleans Louisiana area, Alwyn the Viking Graben, AnnualAAPG North Meeting Sea.– Greenland).– Geology, Sedimentary (N 35,193–213. contacts basalt near sandstones and siltstones taceous ASN KRISTMANNSD & MASSON (1996): Illitization of diagenetic kaolinite–to–dickite con infiac fca eyrtto noepesrsin overpressures on dehydratation clay of : Significance , h eerhwr a upre yState by supported was work research The 66,501–518. Ü CHTBAUER References : Retrograde diagenesis, a widespreadprocdiagenesis,a Retrograde : Ó (97:Daeei n udflwin flow Diagenesis(1987): and fluid , TTIR, H. TTIR, (1972) 1–7. , H. (1983): Alterations of Cre of Alterations (1983): H. , Ó TR 17; NIETO 1972; TTIR, : High temperature Á RKAI,P. û gssuaq,

------Abstracts Book

Glauconitic materials from Lower Miocene Macelj Formation (NW Croatia) – new data

Darko TIBLJAŠ1, Radovan AVANIĆ2 and Darko HANŽEL3

The Macelj formation, situated in the northwestern part bends, they differ in the appearance of the OH-stretch- of Croatia, in the Hrvatsko Zagorje region, as well as in ing region. Those from Čemernica member samples have the adjacent eastern Slovenia, is composed of Vučji Jarek, more pronounced band at 3603 cm-1, which can be as- Čemernica, Lipni Vrh and Vrbno members (AVANIĆ et cribed to Al–Mg cationic environment of the OH groups al., 2005). The Vučji Jarek is the lowermost member of (BESSON & DRITS, 1997) in addition to bands at 3557 the Macelj formation laid transgressively on an erosional (Mg–Fe3+ and Al–Fe2+) and 3530 cm-1 (Fe3+–Fe2+) that are unconformity over Eggerian sediments. The Vučji Jarek practicaly the only visible in Vučji Jarek samples. In two sediments were deposited within a marine, nearshore envi- samples from Vučji Jarek sediments potassium content ronment under tidal influence. The sediments are charac- (7.75 and 8.03 wt% K2O) was higher than in two samples terized by horizontal-bedded and cross-bedded glaucony from Čemernica member having 5.58 and 6.24 wt% K2O sandstones and tuffs. The Čemernica member succeeds respectively, what is in accordance with observed differ- the Vučji Jarek member. It consists of clayey and silty sedi- ences in XRPD patterns. According to VELDE & ODIN ments affected by intensive bioturbation, and silty marls (1975) the content of expandable layers in Vučji Jarek and 3r

rich in ichnofossils. The deposits were formed in the- off Čemernica samples is approximately 5 and 20% respec- d Mid-European Clay Conference – MECC 06 shore-transition zone between shoreface and offshore. The tively. Mössbauer spectra recorded at room temperature, Macelj formation deposits were formed in Eggenburgian fitted with four doublets with Lorentzian line shape, show and in the earlier Ottnangian. The formation builds up an differences in site populations for samples belonging to dif- elongated syncline, plunging towards the east (ŠIMUNIĆ ferent members. et al., 1995). Glauconitic materials from Macelj-sandstones have References been already investigated in detail (SLOVENEC et al., AVANIĆ, R., PÉCSKAY, Z., WACHA, L. & PALINKAŠ, L. (2005): K–Ar 1997; TADEJ et al., 1997) but during recent investigations dating of glauconitic sediments in Macelj Mt. (NW Croatia).– In: VELIĆ, I., VLAHOVIĆ, I. & BIONDIĆ, R. (eds.): Third Croatian glauconitic materials belonging to different members, Geological Congress, Opatija, Abstracts Book, 5–6. Vučji Jarek and Čemernica, of the formation were investi- BESSON, G. & DRITS, V.A. (1997): Refined relationships between chemi- gated. Two samples of glauconitic materials were separated cal composition of dioctahedral fine-grained mica minerals and their per member and investigated by X-ray powder diffraction infrared spectra within the OH stretching region. Part I: Identifica- (XRPD), infrared (IR) and Mössbauer spectroscopy, and tion of the OH stretching bands.– Clays Clay Miner., 45, 158–169. by chemical methods. ŠIMUNIĆ, An., AVANIĆ, R., ŠIMUNIĆ, Al. & HEĆIMOVIĆ, I. (1995): Lithostratigraphic division of Lower Miocene clastic rocks in Hrvat- Performed analyses revealed that investigated glau- sko Zagorje.– In: VLAHOVIĆ, I., VELIĆ, I. & ŠPARICA, M. (eds.): conitic materials from two members differ significantly. First Croatian Geological Congress, Opatija, Abstracts, 88. XRPD patterns showed that no impurities were present in SLOVENEC, D., POPOVIĆ, S. & TADEJ, N. (1997): Heating products of investigated materials. Diffraction pattern of Čemernica glauconitic materials.– Neues Jahrbuch für Mineralogie, Abhandlun- gen, 171/3, 323–339. samples have broader diffraction maxima, this is best seen TADEJ, N., SLOVENEC, D., TIŠLJAR, J. & INKRET, I. (1997): Glauconit- for 001 peak, indicating higher expandable layer content. ic materials from Lower Miocene Macelj-sandstones of the Hrvatsko The observed d(060) for these samples of 1.510 Å in com- Zagorje, North-Western Croatia.– Geologia Croatica, 50/1, 17–25. parison to 1.516 Å for Vučji Jarek samples indicates higher VELDE, B. & ODIN, G.S. (1975): Further information relted to the origin Al content in them. In spite of the fact that IR spectra of of glauconite.– Clays Clay Miner., 23, 376–381. all samples are characterized by poorly resolved broadened

1 Institute of Mineralogy and Petrology, Department of Geology, Faculty of Science, University of Zagreb, Horvatovac bb, HR-10000 Zagreb, Croatia 2 Croatian Geological Survey, Sachsova 2, HR-10000 Zagreb, Croatia ([email protected]) 3 “Jožef Stefan” Institute, Jamova 39, SI-1001 Ljubljana, Slovenia 113 Abstracts Book Abstracts 114 3rd Mid-European Clay Conference – MECC 06 3 2 1 et EHRENBERG to according dependant is temperature sub-group, the to belonging polytypes two present dickite, to kaolinite were of minerals transformation clay The rocks. investigated the in sub-group kaolinite as sified dicating anchizonal, low-grade i.e. metamorphism. very K (K by expressed results obtained The used. were standards rocks polished Kisch purposes calibration the For (1991). KISCH of recommendations the fol lowing used was rocks bearing phyllosilicate in conditions metamorphism grade very-low of evaluation for methods fea These visible. are tures inspired study. history thermal further solution pressure of effects grains, quartz the in points contact At cleavage. crenulation the and fibres quartz slightlycurved in preserved arealso tory hisdeformationof stages Distinct (metamorphism). tion temperaturelowindicatingshape a external deformaand internal their both in history Strain deformation record sandstone.fringes Gorica Marija for feature crotextural mi common a is pyrite framboidal elongate an around andfraction, IR-spectroscopy). dif powder X-ray microscopy, (polarizing methods tary complemen several by studied been have rocks the event metamorphic possible reveal to and rocks the of history thermal determine to intentionHaving sediments. of ties cording to these authors the varie rocks comprise different per Palaeozoic rocks can be found ( Upoutcropsof few Croatia) (NW Hills Gorica Marija In 5 4 Laboratory forGeochemicalLaboratory Research, HungarianAcademy of Sciences, Budaörsi ú INA, Corporate Processes Research Sector, andDevelopment Lovinčićeva 1,HR-10000 Zagreb, Croatia ofInorganic TechnologyDepartment &Metallurgy, Faculty ofChemical Technology, ofSplit,Teslina University 10/V, HR-21000 Split,Croatia Croatian Geological Survey, Sachsova 2, HR-10000 Zagreb, Croatia ([email protected]) Institute ofMineralogy andPetrology, of Geology, Department Faculty ofScience, ofZagreb, University Horvatovac bb, HR-10000 Zagreb, Croatia Ü Clay minerals ofPalaeozoic asindicators ofthermalhistory rocks h lie“rsalnt”mto,a n ftebasic the of one as method, “crystallinity” illite The shadow strain a in quartz grown Syn-deformationally According to the results of XRD method minerals clas BLER, BLER, 1968) were in the range 0.33 Darko Darko TIBLJA Š 1 , Dra from Marija Gorica Hills,from MarijaGorica NWCroatia Darko Darko ž en BALEN Š IKI Š – Ć PANI 0.38 ü et al., 1979). Ac bler index (KI) index bler ° 1 2 , SmiljanMAHE Ć Θ 4 , Katalin JUDIK , Katalin CuK α in ------leet fvrosfcos(ukrc n udchemistries, etc.) having been fluid responsible for the and unusual persistence of rock (bulk factors various of al effects present. per polytype lower dominant the with was kaolinite which rocks in meability, i.e. rocks, grained fine in especially complete,not observed transformationwas dickite to kaolinite that was it Nevertheless determinationdifficult. rather polytypes of the made illite of presence The 1993). al., et (EHRENBERG regionOH-stretching in appearance trum spec on based was polytypes between Distinction copy. and <2 the therefore method, XRD by present polytype about on answerunequivocal give to possibleItnot performed. was information to obtain was determination polytype rocks, the of history thermal in order Therefore, (1993). al. Š K sample on recommendations crystallinity: Illite (1991): H.J. KISCH & A.R. FRASER, M.J., WILSON, P., AAGAARD, S.N., EHRENBERG, kaolinite at relatively (anchizonal) high temperatures. IKI Ü LR B (98: vlain uniaie u m du quantitative Evaluation (1968): B. BLER, Č Further research is planned in order to clear the eventu (in Croatian). 33 MapYugoslaviaof 000 1:100 000 1:100 SFRJ 385 cristallinit la sam interlaboratory and ples.– Journal of Metamorphic Geology, 9,665–670. settings, diffraction X-ray preparations, Clay Minerals, 28,325–352. shelf.– continental Norwegian the of sandstones in dickite to linite kao of transformation Depth-dependent (1993): D.M.L. DUTHIE, Ć t 45, I 5 , K., BASCH, O. & O.BASCH, K., , Ć – andPeter – 80). 1 µ 397.

, Marijan KOVA, Marijan H-1112, Budapest, Hungary m – Geol. zavod Zagreb (1972), Sav. geol. zavod Beograd, 81 p. 81 Sav.Beograd, zavod(1972), geol. Zagreb zavod Geol. rock fractions were investigated by IR spectros é de l’illite. de – Tuma Á Š RKAI IMUNI – References č Bulletin Centre Recherche Pau Recherche Centre Bulletin a it arb 33 L Zagreb list za Č 5 – Ć Explanatory notes for sheet Zagreb L Zagreb sheetnotesfor Explanatory I Ć , A. (1979): Osnovna geolo Osnovna (1979): A. , 2 , Dra ž an JOZI – 80 (Basic Geological Geological (Basic 80 é aopim par tamorphisme Ć 3 – , SNPA, 2, SNPA, š

ka karta karta ka <4 ------Abstracts Book

Comparing surface charge heterogeneity of 1:1 with 2:1 type clay particles in aqueous suspension

Etelka TOMBÁCZ and Márta SZEKERES

An analogous study to 2:1-type montmorillonite (TOM- able to form only below pH~7 in kaolinite suspensions. Co- BÁCZ & SZEKERES, 2004) was performed on 1:1 type agulation kinetics measurements at different pHs provided kaolinite obtained from Zettlitz kaolin. Clay minerals are undisputable proofs for heterocoagulation of kaolinite par- built up from silica tetrahedral (T) and alumina octahedral ticles. Similarly to montmorillonite, heterocoagulation at (O) layers. These lamellar particles have patch-wise surface pH~4 occured only above a threshold electrolyte concen- heterogeneity, since different sites are localized on definite tration, which was much smaller than that for montmo- parts of particle surface (VAN OLPHEN, 1963). pH-de- rillonite (only ~1 mmol l-1 NaCl for kaolinite) due to the pendent charges develop on the surface hydroxyls mainly substantial difference in particle geometry. The electrolyte at the edges, in addition to the permanent negative charges tolerance of both clay suspensions increased with increas- on silica basal plane caused by isomorphic substitutions ing pH, pH~6–6.5 range was sensitive, and even a sudden (JOHNSTON & TOMBÁCZ, 2002). Electric double layers change occurred above pH~6 in kaolinite. There was prac- (edl) with either constant charge density on T faces (silica tically no difference in the critical coagulation concentra- basal planes) or constant potential at constant pH on edges tion of kaolinite and montmorillonite (c.c.c. ~100 mmol l-1 3r

and O faces (hydroxyl-terminated planes) form on patch- NaCl) measured in alkaline region, where homocoagula- d Mid-European Clay Conference – MECC 06 es. The local electrostatic field is determined by the crystal tion of negatively charged lamellae takes place. structure of clay particles, and influenced by the pH and Rheological measurements showed shear thinning dissolved electrolytes. flow character and small thixotropy of suspensions at The acid-base titration of Na-kaolinite suspensions and above pH~6.7 proving the existence of repulsive showed analogous feature to montmorillonite (TOMBÁCZ interaction between uniformly charged particles in 0.01 et al., 2004). The initial pH of suspensions and the net pro- M NaCl for both clays. The appearance of antithixotropy, ton surface excess vs. pH functions shifted to the lower the sudden increase in yield values, and also the formation pH with increasing ionic strength indicating the presence of viscoelastic systems only at and below pH~6 verify the of permanent charges in both cases, but these shifts were network formation due to attraction between oppositely smaller for kaolinite in accordance with its much lower charged parts of kaolinite particles. Under similar layer charge density. The pH-dependent charge formation conditions the montmorillonite gels were thixotropic with was similar, positive charges in the protonation reaction significant elastic response. of (Si–O)Al–OH sites formed only at pHs below ~6–6.5, considered as point of zero net proton charge (PZNPC) References of kaolinite particles (SCHROTH & SPOSITO, 1997). So, JOHNSTON, C.T. & TOMBÁCZ, E. (2002): Surface chemistry of soil oppositely charged surface parts on both clay particles are minerals.– In: DIXON, J.B. & SCHULZE, D.G. (eds.): Soil Mineral- only below this pH, therefore patch-wise charge heteroge- ogy with Environmental Applications. Soil Science Society of Amer- ica, Madison, Wisconsin, USA, 37–67. neity exists under acidic conditions. SCHROTH, B.K. & SPOSITO, G. (1997): Surface charge properties of Electrophoretic mobility measurements, however, kaolinite.– Clays Clay Min., 45, 85–91. showed negative values for both clays over the whole range TOMBÁCZ, E. & SZEKERES, M. (2004): Colloidal behavior of aqueous of pH showing the dominance of permanent charges, and montmorillonite suspensions: the specific role of pH in the presence only certain decrease in absolute values, much larger for of indifferent electrolytes.– Applied Clay Science, 27, 75–94. kaolinite was observed with decreasing pH below pH~6. TOMBÁCZ, E., NYILAS, T., LIBOR, Zs. & CSANAKI, Cs. (2004): Surface charge heterogeneity and aggregation of clay lamellae in aqueous sus- The charge heterogeneity was supported by the pH- pensions.– Progress Colloid Polymer Science, 125, 206–215. dependent properties of dilute and dense clay suspensions VAN OLPHEN, H. (1963): An Introduction to Clay Colloid Chemistry.– with different NaCl concentrations. Huge aggregates were Interscience, New York, 301 p.

Department of Colloid Chemistry, University of Szeged, Aradi Vt.1. H-6720 Szeged, Hungary ([email protected]) 115 Abstracts Book Abstracts 116 3rd Mid-European Clay Conference – MECC 06 t l, 04. h erhda lsbttto sdecreas is WEISZBURG Al-substitution see tetrahedral The suffixes 2004). al., (for et celadonite–CC to finally and glauconite–GG to region lite and an IMA-non-defined FeoverAl-smectite Fe containing containing il dioctahedral from space chemical crystal continuous a cover they eral or a textured rock fragment. Concerning composition, min may elongated even exhibit some an relic texture after grains The inhomogeneous.and porous pore-free, orhomogeneous, compact, be may They zonation. colour exhibit biogenicsubstrate. are elongatedthey Sometimes andmay primary of signs rounded any show not traditional do and grains glauconite resemble not do They susceptibility. magnetic and density increasing with grains glassy translucent green, bluish finally and green grass into gradually yet incomplete due to lack the of Fe data on the studied layer silicates. Crystal chemical data are for chemical (EPMA, SEM+EDX) and structural (XRD, IR) sample only part of the density fractions could be analysed g/cm (2.43–2.03 magnetic still g/cm (>2.78–2.08 regiondensity identified: ments of same the mineral constituents. frag rock metamorphic and albite), (mainly feldspar ole, mica, greenish detrital contain fractions These separation. density size fractions (6 wt%) were residuesubjected to magnetic as well as insoluble The (1 acid. acetic 5% by decarbonated on “glauconite the grains” of formation. the focussed research Our 2001). (HAAS, basin pelagic deep a of part inner the in formed It beds. marl the of du rability low the to due profiles burrowedgeological in studied be only can outcropand natural no has it because mation for known little a is It beds. marl loose with alternating layers limestone nodular sometimes compact, of up built H of neighbourhood the In 1964). glauconite-bearing a formation from the Bakony Mountains, Hungary as (F described S was Formation Aptian) Marl (Barremian–Early Cretaceous Lower The Department ofMineralogy,Department Eötvös Loránd University, Pázmány Péter ([email protected]) sétány 1/c, H-1117Budapest,Hungary 5 Additionally, and crushed been has sample limestone white The In the the In wt% of the bulk rock) was sieved and the >63 w noe w ieetgacnt eisfo h aerock, same the from series glauconite Two inone:two different – elws hoie cainlyfiru amphib fibrous occasionally chlorite, yellowish a green grain series re gan series grain green

ignc cast biogenic 3 ). Due to the extremely small amountsof small extremely the to Due ). w series two Sümeg MarlFormation, Lower Cretaceous, i te oe dniy region density lower the in , f O lyr iiae were silicates layer TOT of elws gen ris turn grains green yellowish covering almost the complete 3 ) and ) á Bakony Mountains, Hungary Erzsébet Erzsébet TÓTH and Tamás G. WEISZBURG 2+ rsk /Fe ú whitish–palegreen, t, the formation is formation the t, 3+ ratios. µ m grain Ü ü L meg Ö P, ------calcite. A big portion of the grains, in spite of the whitish the of spite in grains, the of portion big A calcite. formed during dissolution of (partly euhedral; diagenetic?) From thin sections it became evident that these pores were rounded, sometimes angular pores (3 with structure, pronouncedspongy a chromite);havetite, TiO albite, quartz, (e.g. inclusions mineral contain may They fragments. echinoderm of pores cephalopods, gastropods/ tests, foraminifer fill They wet. when smeared sheet of celadonite–XC. and 3557 (3602, 3534 cm sharp well-defined, have composition) grains denser g/cm (>2.78–2.68 the while fractions, density lower the for cm 3560 around shoulder broad a shows spectra IR of the region OH-stretching The density.increasing with ing WEISZBURG,T.G., T F Buda Press,University Hungary.–Eötvös of Geology (2001): J. HAAS, Wildner and Eugen Libowitzky. Vienna,versityof specialthanksAnton areto due Beran,Manfred 3-monthMariea framestayUniCurieofthethe at in performed facilitiesof the (London).NHM Infrared spectroscopic studies were Project and especially SYNTHESYS Terry Williams the for the via access to Actionthe Infrastructureanalytical Research EC’s the to Acknowledgement: chemical characteristics, within same the sediment. and physical in both different series, glauconitic Al-substitution. tetrahedral increasing slighly and charge octahedral ing decreas with glauconite–G0, in into glauconite”)turns cent the to according (“nas Al-smectite series: dioctahedral rich iron density creasing grain series, green evolution the a chemical from different also form casts whitish These Fe wt% 10–17 contain may and magnetic is colour, Ü L The gary.– Acta Mineralogica–Petrographica Szeged, 45/1,65–80. HunÚrkút,ore, carbonate manganese the of mineral clay green Å Hungarica, Geologica 13,1–194. Geologica, ry).– Series summa German Hungarianwith in Mountains,Bakony – Hungary the of formations (Berriasian–Aptian) Cretaceous (Lower Gebirges 317p.pest, two of presence the demonstrated observations These Ö , . (1964 J. P, hts casts whitish –1 ) peaks, ) characteristicpeaks, for the ordered octahedral : neked [era–p] idne ds Bakony- des Bildungen [Berrias–Apt] Unterkreide ): Ó 3 h uhr iht xrs hi gratitude their express to wish authors The , of celadonite–CC and glauconite–GC and celadonite–CC of , TH, E. TH, are unconsolidated, i.e. they can be be can they i.e. unconsolidated, are References

& BERAN, A. (2004): Celadonite, the 10- Celadonite, the (2004): A. BERAN,

– 15 µ m in diameter). 2 , apa , 2 O 3tot –1 ------.

Abstracts Book

Mineralogy of glauconite-rich sand deposits in the Southern Slovakia

Peter UHLÍK1, Juraj ČIHÁK1, Ľubomír TUČEK2, Pavol MALACHOVSKÝ3 and Ján DERCO2

Several glauconite-rich sand deposits are located in Slovak both significant oxides for glauconite identification in- part of the Western Carpathians. They occur predominantly creased in magnetic concentrate to about 20% of Fe2O3 and as green unconsolidated marine sands of Eggenburgian age about 5% of K2O. in Cerova vrchovina Mts. (the Southern Slovakia). Some Clay fractions contain dioctahedral mica (probably geological and technological explorations were performed glauconite) and smectite as main clay minerals and trace in the area in the past. Because of low glauconite content amount of chlorite. Quartz, feldspars and clinoptilolite (2–6%), the glauconite-rich sands are not used from glau- were observed as nonclay minerals in the fraction. conite point of view. The greensands are exploited only occasionally for local building and less demanding foundry The first results of XRD quantitative mineral analy- purposes. sis by RockJock application (EBERL, 2003) showed that amount of glauconite is little bit more than 10% in some The main scope of the contribution is detailed miner- studied samples. The main mineral of glauconite-rich sand alogical study of the greensands. Investigations were per- is quartz (60–70%). The other minerals are albite (8–9%), formed on whole rock, clay fraction and several fractions K-feldspars (4–6%), Fe-smectite (1.5–7.5%), muscovite 3r obtained by electromagnetic separation. The samples were d Mid-European Clay Conference – MECC 06 (4%) and trace amounts of carbonates. studied by XRD, chemical analysis, electron microscopy and spectroscopic analyses (IR, Mössbauer and UV–VIS). Our preliminary results confirmed previous works (review in ODOM, 1987) about mineralogical heterogeneity The green glauconite grains and pellets are present in of greensands. the grain scale from 0.1 to 1 mm. Amount of magnetic fractions range from 4 to 8% of whole rock mass. The mag- References netic concentrates were obtained by electromagnetic separation of several fractions from 0.1 to 1 mm at current from EBERL, D.D. (2003): User’s guide to RockJock – a program for determining quantitative mineralogy from powder X-ray diffraction data.– 8–12 A. From 25 to 90% of glauconite in concentrates were U.S. Geological Survey, Open-File Report: OF 03–78, 40 p. determined by optical microscopy and XRD. ODOM, I.E. (1987): Glauconite and celadonite minerals.– In: BAILEY,

The amount of Fe2O3 in whole rock fraction varies from S.W. (ed.): Micas. Reviews in Mineralogy, 13, 545–572.

2 to 5% while K2O varies from 0.5 to 2%. The amount of

1 Dept. of Geology of Mineral Deposits, Comenius University, Mlynská dolina G, 842 15 Bratislava, Slovakia ([email protected]) 2 ATNS Department, Geological Survey of Slovak Republic, Košice, Slovakia 3 Kerko, a.s., Tomášiková 35, Košice, Slovakia 117 Abstracts Book Abstracts 118 3rd Mid-European Clay Conference – MECC 06 2 1 of sites acidicboth and active basic character of (HORV types different contains surface treated The properties. controllable of surface “superactive“ so-called tercalation dein thermal andintercalation grinding), (dry activation mechanochemical way this In well. as process, modifying analytical equipment can be considered as a kind of surface thermo a in sample the Heating (DRIFT). spectrometry diffraction infrared Fourier-transform X-ray reflectance (TG–MS), diffuse and (XRD) spectrometry mass with coupled CRTA) analysis, thermal controlled-rate DTG, thermogravimetry, derivative TGA; (thermogravimetry, analysis thermal techniques: instrumental following the in ananostructured mineral. surface internal kaolinite through complexing via hydrogen bonding, but the also results modifies only not calation (KRIST sheets dral octahe and tetrahedral of arrangement two-dimensional the of consisting or layers kaolinite the formamide between hydrazine) (e.g. compounds organic weight mo low lecular of insertion the via i.e. intercalation, by tested kaolinite structure (FROST etal., 2001). surface the on properties as well, due to the OH-group effect degradation in the of significant a kind has This modification surface area. surface specific its mineral increase to order in the delaminate to ground mechanochemically are kaolinites Veryproperties.often surface and reactivity its to related closely is industry) in pharmaceutical and mer an important poly paper, the in additive as (e.g. of kaolinite, material raw dustrial application industrial The 3 2434 Brisbane, 4001, Australia Queensland Inorganic Materials Research Program, ofPhysical School andChemical Sciences,ofTechnology, University Queensland 2George Street, G.P. O. Box ofEnvironmental Engineering andChemical Technology,Department Pannon University, Egyetem 10,H-8200Veszprém, Hungary ofAnalytical Chemistry, PannonDepartment University, Egyetem 10, H-8200Veszprém, ([email protected]) Hungary h aoope hsfre a eivsiae by investigated be can formed thus nanocomplex The be can surfaces internal kaolinite the of reactivity The together Surface reactivity investigation reactivity Surface ofmechanochemically Veronika V Ó oe ehi aal fpouiga producing of capable technic a offer F et al., 1999; 2002). However,inter 2002). 1999; al., et F Á GV Ö LGYI 1 Á , J TH etal., 2005). á nos KRIST activated kaolinite Ó F ------1 , Erzs FROST, R.L., MAK FROST, R.L., ments, as well as stability and ageing tests. measure area surface tigations are completed with specific inves These butane.and pyridine ammonia, as molecules probe using made is kaolinites ground-and-intercalated) (ground, activated mechanochemically of properties tion produced. be potentially can properties surface tailored with bents prop surface adsor clay,environmentally friendly natural, the of the erties on parameters treatment the of the effect of study systematic a Withtreatment). heat of conditions the as well as agent,intercalating time, grinding (e.g. tion modifica surface of parameters the on depends surface KRISTÓF, J., J.,KRISTÓF, É. MAKÓ, E., JAKAB, R.L., FROST, J., E.,KRISTÓF,HORVÁTH, J.T.(200 adsorp the of study detailed a work present the In clay active the of nature chemical and physical The rt itraae koiie y otoldrt teml analysis.– thermal Langmuir, 18,1244–1249. controlled-rate by kaolinite intercalated drate intercalatedhydrazine–hyandhydrazine in adsorbed ofSeparation Analysis and Calorimetry, 56(2),885–891. formamide,dimethyl sulphoxide and hydrazine.– Journal of Thernal M. BOR, and Interface 289,132–138. Science, Colloid of Journal kaolinite.–formamide-intercalated treated mally ther in centers VÁGVÖLGYI, superactive V. of (2005): Identification treatmen é bet HORV 1): t FROST, R.L., R.L., FROST, FROST, R.L., R.L., FROST, . 19) Temlbhvoro alnt necltdwith intercalated kaolinite of behaviour Thermal (1999): – Langmuir, 17(16),4731–4738. oicto fkoiiesrae ymechanochemical by surfaces kaolinite of Modification Ó , Á É TH ., KRIST ., 2 ATN,WN & HORV W.N. & MARTENS, LPOG, J.T., KLOPROGGE, References and Ray L.FROST andRay Ó F,HORVJ., Á TH, E. & KLOPROGGE, & E. TH, OVT, . & HORVÁTH, E. Á 3 TH, E. (2002): E. TH,

GÁ & ------Abstracts Book

Iron oxides on Mars: their characterization from MER Mössbauer spectra

Caroline VAN CROMPHAUT1, Valdirene G. DE RESENDE1, Eddy DE GRAVE1, Göstar KLINGELHÖFER2, Antoon VAN ALBOOM1,3 and Robert E. VANDENBERGHE1

A number of backscatter Mössbauer spectra (MS) acquired The alternative calibration/pseudo-folding processing by the Mars Exploration Rover Spirit (MER–A) from tar- of raw MER data was successfully applied to the MS of the gets at Gusev Crater, Colombia Hills, have been selected for selected targets, being Clovis (four ∆T windows), Ebene- characterization of the magnetic iron-bearing phases pres- zer–Cratchit (two ∆T windows), Ebenezer–Ratchit 2 (two ent in these targets. Non-processed sets of data, consisting ∆T windows), Wooly Patch (one ∆T window) and Uchben of 512 channels of the 14.4 keV γ-ray backscatter counts (three ∆T windows). Preliminary results derived from some for the rock target and an equal amount of channels for the of these MS have been reported earlier (KLINGELHÖFER corresponding transmission MS of the reference absorber, et al., 2005). All spectra were found to be a superposition were downloaded from the web site http://iacgu32.chemie. of ﬁve distinct components: (i) two relatively sharp sextets uni-Mainz.de/mer/. The reference absorber is a mixture of arising from antiferromagnetic and weakly ferromagnetic

α-Fe, α-Fe2O3 and Fe3O4. Spectra accumulated during suc- spin states of hematite, respectively, (ii) two sextets due cessive sols (Martian days) for a given target and spanning to respectively octahedral and tetrahedral Fe species in 3r a given temperature window ∆T, were added together. magnetite, (iii) a hyperfine-field-distributed component d Mid-European Clay Conference – MECC 06 Summed target spectra and corresponding reference spec- attributable to goethite, (iv) a ferric doublet, and (v) a fer- tra that were both thought to be of reasonable statistical rous doublet. The two doublets are believed to be due to quality were then considered for further processing and Fe-bearing silicates, either crystalline or amorphous. The interpretation. spectral components of the magnetic iron oxides could be The MER–MS are recorded using a triangular reference fit adequately imposing a minimum of constraints, and signal for the source motion, implying that they are com- their adjusted parameter values are very consistent and posed of two complimentary halves. For a near-perfectly generally perfectly in line with the parameters observed linear drive system (as in use in most laboratories), the two for laboratory oxide samples, implying that structure and halves are mirror images with respect to a central, so-called morphology of the Martian Fe oxides are in essence no dif- folding channel. In that case, the two halves can be folded ferent from their terrestrial counterparts. together and subsequent velocity calibration (velocity versus channel number) is then achieved from a (folded) spec- References trum of a reference absorber. The MIMOS spectrometers AGRESTI, D.G., DYAR, M.D. & SCHAEFER, M.W. (2006): Derivation (KLINGELHÖFER et al., 2003) of the MERs’ instrumental of velocity scales for Mars Mössbauer data.– LPSC XXXVII, Abstract payload, however, exhibit a significant velocity non-linear- #1517. ity, making a laboratory-conventional folding/calibration DYAR, M.D., ROTHSTEIN, Y., SCHAEFER, M.W. & AGRESTI, D.G. processing of the raw MS data impossible. Earlier efforts (2006): Mössbauer spectroscopy of outcrop at the Meridiani Planum site.– LPSC XXXVII, Abstract #2382. to establish a workable folding/calibration procedure for KLINGELHÖFER, G., MORRIS, R.V., BERNHARDT, B., RODIONOV, the MER–MS are partly relying on the “drive error signal” D., DE SOUZA, P.A., SQUYRES, S.W., FOH, J., KANKELEIT, E., of the MIMOS driving feed-back system (AGRESTI et al., BONNES, U., GELLERT, R., SCHRÖDER, C., LINKIN, S., EV- 2006; DYAR et al., 2006). In the present work, an alterna- LANOV, E., ZUBKOV, B. & PRILUTSKI, O. (2003): Athena MIMOS tive approach in that respect has been developed. It is based II Mössbauer spectrometer investigation.– J. Geophys. Res. 108 (E12), 8067–8082. on the adjusted peak positions of the eight most prominent KLINGELHÖFER, G., DE GRAVE, E., MORRIS, R.V., VAN ALBOOM, lines of the calibration spectra and on the corresponding A., DE RESENDE, V.G., DE SOUZA, P.A.Jr., RODINOV, D., velocity values obtained for a proper mixture of α-Fe and SCHRÖDER, C., MING, D.W. & YEN, A. (2005) ICAME2005, Ab-

α-Fe2O3 for which the MER acquisition sequences in the stract #T4–P2 (full paper to be published in Hyperﬁne Interactions). ten-Kelvin ∆T windows were mimicked in the lab.

1 Department of Subatomic and Radiation Physics, University of Ghent, Proeftuinstraat 86, B-9000 Gent, Belgium ([email protected]) 2 Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg University, Staudinger Weg 9, D-55128 Mainz, Germany 3 Department of Industrial Sciences BME–CTL, High School Ghent, Schoonmeersstraat 52, B-9000 Gent, Belgium 119 Abstracts Book Abstracts 120 3rd Mid-European Clay Conference – MECC 06 1 Ti ( basisthe of 4(PO on analyses 21 from calculated formula crystal-chemical composition chemical ItsmicroprobeAverage electronanalyses.by determined was 1). (Fig. matrix clayey in ing spheres of radiating (ca crystals 200 well-developed forms Mantienneite gypsum. fissure-filling secondary in enriched also arehorizons tienneite-bearing horizons exceptionallyisand ranges high Man 9.41%. tofrom 4.97 these in content TOC subordinateamounts.The by represented dominating are smectite and kaolinite, while illite is present in minerals clay where horizons some in only mineral accessory an as found was pyrite.Mantienneite and siderite (nontronite), chlorite, smectite plagioclase, quartz, illite, kaolinite, of consists matrix rock The analyses. (TOC) carbon organic total and technique XRD capacity), traps nutrients and insoil many others. protectscrops and trees against drought (water absorption It facilities. specific its of because agriculture in useful rial mate raw a is Alginite (Pontian). activity volcanic basalt UpperMiocene the during formed was which lake maar a in organicin Itmatterdeposited rich clayalgal minerals.wasand rock sedimentary the is alginite lage (Slovakia). The the in mineral world. It was found this at the alginite deposit near Pincin of occurrence second the is deposit LET etal., 1984). intercalated inblack shales of origin (FRANSO lacustrine layerssandy of matrixmantienneite layer),constitutes the mixed chlorite–montmorillonite (kaolinite, minerals clay of Anluoa, Cameroon. Associated with quartz, siderite and vivianitedepositfrom described was mineral this ofrence cal formula KMg Mantienneite is a phosphate mineral with idealized chemi 3 2 □ ENVIGEO, a.s., Kynceľovská 2,97411Banská Bystrica, Slovak Republic Geological Institute, Slovak Academy ofSciences, Severná Geological ofSlovak Survey Republic, Kynceľovská 4+ 0.53 1.00 The drill- The Pincinmantienneitefrom the knowledge, best our In K (PO 0.45 Na 4 ) 4.00 0.02 (OH) ) Mantienneite from Pinciná alginite deposit(Slovakia) Σ hole =1 2.65 (Mg 2 . 15H Al 4 sampleswereusingalginiteexaminedof 1.99 ) is: Jana VAVROV 2 Ti(PO 2 Ca O. 0.08 Fe 4 2+ ) 4 0.04 (OH) Mn 0.01 3 . Á 15H µ ) Σ m in diameter) grow =2.12 1 , Adri 2 (Al .Tefis occur first O. The 10,974 11Bansk 1.38 á Fe n BIRO 5, 97411Bansk 3+ 0.32 Ti 0.27 á á Bystrica, Slovak Republic([email protected]) ) Ň Σ vil =1.97 2 á , IgorGALKO ------

á Bystrica, Slovak Republic of basalt pyroclastics. Direct precipitationDirect mantienneitepyroclastics.of basalt of alteration during released probably were Ti) and Fe Mg, matter organic algal (Al, elements evolu P,other of while source as served have of may maar decomposition of gradual stage The tion. post-volcanic during ﬂuids hot by mobilized been have may crystallization mantienneitefor required components probablyfromdirectly solution. The cate habit of suggestscrystals that this mineral precipitated containingDeli sequencealginite. sedimentary within ity fore its excess over 1apfu is attributed to M M The M in dominant is Al 1984). al., et FRANSOLET apfu; (1.43 Anluoa from mantienneite in then higher much is which member. Its Mg content ranges between 1.91 and 2.2 pancy,mantienneitePincin from with only negligible Na content. Considering M Fig. 1Mantienneite from Pinciná deposit. F. PILLARD, & F. FONTAIN, P., OUSTRIÉRE, M., A. FRANSOLET, gypsum. secondary with association close by supported also is solution from 3+ Origin Origin of mantienneite is probably related activ to ﬂuid M The e iint dAlu, aeon– ultn e iéaoi, 107, 737–744. Minéralogie, de Bulletin Cameroun.– d’Anloua, vivianite de gisement du minérale espèce nouvelle mantiennéite,une La (1984): site and its content is ranging from 1.06 to 1.8 to 1.06 from ranging is contentits and site 4+ structural structural position is fully occupied with Ti, there 1+ 3 and Michal MAJD andMichal oiin s cuid y (0.12 K by occupied is position Reference á Á is almost pure Mg end- Mg purealmost is N 3 3+ site. – 2+ .2 apfu) 0.92 site occu 7 7 apfu. apfu, - - - - - Abstracts Book

Mineralogy of ﬁne-grained sediments related to karst phenomena in Villány Mts., SE Transdanubia, Hungary

István VICZIÁN1, József DEZSŐ2 and Béla RAUCSIK3

In the Villány Mts. various clay and silt sized sediments have cite is occasionally present. Normally both TiO2 minerals, been accumulated in connection with karstified Mesozoic anatase and rutile are present. Iron is mostly represented limestones. Samples were collected from red clays filling by hematite, goethite is less frequent. The clay samples are fissures in limestone, fine clays deposited in the bottom of of typical red colour. caves, partly produced by the ascent of thermal karst water, The second type is a moderately weathered assemblage palaeosols and loess covering the surface of the limestone consisting of mainly well crystallized clay minerals. The and lacustrine sediments of Upper Pannonian age depos- dominant clay minerals are illite and chlorite, accompa- ited on the top of the limestone. The samples were collected nied by mixed-layer illite/smectite, discrete smectite, kao- from the limestone quarries at Beremend and Nagyharsány, linite and occasionally vermiculite. The quartz contents are as well as from various caves of the Villány Mts. high, calcite is variable. Ti-minerals are much less frequent The grain size analysis has shown bimodal distribution, than in the first type. Iron is represented mainly by goethite with maxima in the phi ranges 5–6 and 8–9, respectively. while hematite is much less abundant.

The proportion of the two maxima varies from sample to The results indicate two main periods of clay forma- 3r sample. tion. The first one may go back to the Upper Cretaceous d Mid-European Clay Conference – MECC 06 X-ray diffraction analysis was carried out on the bulk tropical climate, the second one represent redeposited clas- samples and on the <2 µm fraction. Essentially two types of tic sediments of the Upper Pliocene and Quaternary. The mineral composition could be distinguished. results are compared with data obtained earlier from the The first type is characterized by deeply weathered min- Beremend quarry and the surrounding, from the study of eral assemblage consisting of mainly disordered clay min- Upper Pannonian sequences of bore holes in neighbour- erals. The dominant components are disordered kaolinite, ing areas, as well as with data obtained from other red clay partly forming mixed layers with smectite, discrete smec- occurrences in south-eastern Transdanubia and the north tite. Basal reflections are relatively week. There is a few per- Hungarian karst region. cent of gibbsite in most cases. Quartz is low or absent, cal-

1 Hungarian Institute of Geology, Stefánia út 14, H-1143 Budapest, Hungary (viczian@mafi.hu) 2 University of Pécs, Institute of Geography, Ifjúság útja 6, H-7624 ,Pécs Hungary 3 University of Veszprém, Department of Earth and Environmental Sciences, P.O.B. 158, H-8200Veszprém, Hungary 121 Abstracts Book Abstracts 122 3rd Mid-European Clay Conference – MECC 06 rlmccospae.Tevldae)dt eeplotted were data valid(ated) The phases. micaceous dral dioctahe iron-rich for database the in entries 310 about tering process Fe outlawed more than half of the data, leaving measured of presence/absence Fe the on filtered were data Chemical entries. 700 than more contains database second thatmoment, the Attoo. counterparts, aluminous containingiron their on outlook some literature,with the in available CGGM on data chemical all on database ond sec a up building by started we CGGM, on collected we origin may havetary overlapping chemical composition. literature the suggestthat of mineralsmagmatic andsedimen in accumulating data However, origin. sedimentary glauconite while magmatic, have to supposed was donite cela environment:formation on on, century 19th the of identification (d methods formal used routinely The basis. lochemical crystal a on distinguish to thatmineralsare these difficult forecasts already nomenclatures based chemistry crystal of charge multitude The tetrahedral BAILEY, 1980). nomenclature, (AIPEA and 1986) BAILEY, nomenclature, (AIPEA charge octahedral 1998), al., et RIEDER clature, crystal possible their chemical positions, of namely interlayer charge all (IMA nomen upon differentiated and defined cela the phases, donite mica-related iron-rich dioctahedral The 2 1 Museum ofMineralogy, Babe ofMineralogy,Department Eötvös Loránd University, Pázmány Péter sétány 1/C, H-1117Budapest,Hungary 3+ Continuous space chemical crystal for iron-rich thedioctahedral For comparison the chemical data set (>350 analysis) (>350 set data chemical the comparison For half separated,second from the been have CGGM also rto n oecytlceia osrit.Tefil The constraints. chemical crystal some and ratios – glauconite group minerals (CGGM), have been been have (CGGM), minerals group glauconite micas andrelatedmicas phases(celadonite, glauconite, Fe-illite) 060 and FTIR)do have strong limits. ş– Bolyai University, 1Kog Tam á s G. WEISZBURG ă lniceanu St., RO-400084 Cluj lniceanu St.,RO-400084 1 , Erzs 2+ ------/ é bet T tion in the octahedral layer.tion octahedral inthe decrease andofoccupancy octahedral by Al–Fe charge consequence of the K uptake is compensated by the Fe an into turning gradually is material smectitic Al–Mg-rich an glauconitisation: of illite. of ing IMA definition the interlayer charge regions, pointing out the need for enlarg low the in continuous is regions Al-rich interlayer the towards tion lower at transi The side. Al-rich the onpopulated more chargesis field glauconite the while side, rich Fe the the towards populated more of is nomenclature field IMA celadonite The continuous. is minerals these chemical range ofcrystal minerals. these the check to systems representation graphical into different IDR M, AAZN, . DYKNV YS, FRANK-KA Y.S., D’YAKONOV, G., CAVAZZINI, M., RIEDER, BAILEY, S.W. of (1986): Report AIPEA Nomenclature Committee.– Sup BAILEY,S.W.Nomenrecommendations AIPEA ofof Summary (1980): hs nig ge elwt h rdce trend predicted the with well agree findings These by occupied space chemical crystal the thatWe found 905–912. 36, Mineralogist, Canadian (1998): Nomenclature of D.R. the Micas.– The WONES, & Z. WEISS, F.P., H., TAKEDA, SASSI, J.-L.,ERT, E.W.,ROB RADOSLOVICH, NEIVA,A.M.R., P.V.,G., MÜLLER, KOVAL, S., GUGGENHEIM, G., V.A., GOTTARDI, MENETSKII, plement to AIPEA Newsletter, 22. clature Committee.– Clays and Clay Minerals, 28,73–78. – Ó Napoca, Romania TH 1 andDanaPOP References ([email protected]) 3+ 2 –Mg-rich mica, where the the where mica, –Mg-rich 2+ substitu 3+ ------Abstracts Book

Triassic red clays in Poland and their importance for ceramic industry

Piotr WYSZOMIRSKI

In the last years, the intense development of the Triassic tion loss is also low (below 8 wt.%) which – with reference red clays exploitation has been observed in Poland. It to non-calcareous clays – indicates the lack of organic mat- mainly takes place in central part of the country in the ter (STEIN et al., 1980). area of Świętokrzyskie voivodeship. Apart from Baranów The clays studied show a good ability for sintering, deposit – that has been exploited since 1880 – the output of most often at the temperature range 1100–1150°C. It is the red clays out of Chełsty (1993), Szkucin (1999), Pałęgi confirmed, among others, by the character of their firing (2001) and Kozów (2004) has been undertaken. Moreover, curves (WYSZOMIRSKI, 2003; WYSZOMIRSKI et al., the Gościniec open pit will begin its activity this year. So, the current share of Triassic red clays in domestic output of 2004), especially by very low (even <0.1wt.%) water absorp- clayey raw materials for heavy clay industry is high (more tion. Phase composition of sintered clays can be revealed than 11%) at hardly 2% share in reserves. These raw mate- by the presence of quartz, hematite, the small amount of rials are utilized in the Polish ceramic industry for the pro- mullite and also by the amorphous phase. Such a composi- duction not only heavy clay products (building bricks, roof- tion is characteristic for the fired non-calcareous clays. 3r

ing tiles) but also for making engineering bricks, among d Mid-European Clay Conference – MECC 06 them wall and floor tiles. The latter are being produced by Acknowledgement: This study has been supported by the Polish fast firing which needs great requirements concerning – KBN grant No. 1063/T08/2004/27 as a research project of the AGH among others – their mineral and chemical composition. University of Science and Technology. The mineral composition of studied Triassic red clays References is similar. The clay minerals are represented by illite which is accompanied in varying amounts by kaolinite, smectite, STEIN, V., ECKHARDT, F.-J., HILKER, E., IRRLITZ, W., KOSMAHL, W., chlorite and mixed layered minerals (mainly illite/smectite MATTIAT, B., PILTZ, G., RASCHKA, H. & RÖSCH, H. (1980): Un- tersuchung von Tonen und Tonsteinen auf ihre ziegeltechnische Eig- I/S). Non-clay minerals are quartz, hematite and some- nung.– In: BENDER, W. & HÄNDLE, F. (eds.): Brick and tile making. times – feldspars. Generally, the raw materials are free Bauverlag GmbH, Wiesbaden und Berlin, 832 p. from undesirable phases, such as: carbonate minerals (cal- de la TORRE, J., LORES, M.T., BASTIDA, J. & MONTÓN, J.B. (1996): cite, dolomite), pyrite and water soluble sulphates. Oxidation of organic matter in powdered clays at temperature lower In clayey raw materials for the production of ceramic than dehydroxylation temperature of clay minerals.– British Ceramic Transactions, 95/5, 194–198. tiles the special importance has the presence of organic matter. Its elevated share is the reason of undesirable black WYSZOMIRSKI, P. (2003): Red Triassic clays and their current importance in Polish ceramic industry.– Ceramika/Ceramics, 81, 66–77 (in core in products. It is assumed that the organic matter con- Polish with English abstract). tent of green bodies for wall and floor tiles produced in WYSZOMIRSKI, P., STOBIERSKA, E., POMADOWSKI, H. & WIŚKOW- single fast firing, expressed as elemental carbon, should be SKA, A. (2004): Clayey raw material of Pałęgi deposit for the produc- lower than 0.3 wt.% (de la TORRE et al., 1996). This con- tion of ceramic tiles.– Ceramika/Ceramics, 84, 559–566 (in Polish tent in Triassic red clays studied is distinctly lower (e.g. in with English abstract). the Chełsty clay the TOC amounts to 0.08 wt.%). The igni-

AGH University of Mining and Metallurgy, al. Mickiewicza 30, 30–059 Cracow, Poland ([email protected]) 123 Abstracts Book Abstracts 124 3rd Mid-European Clay Conference – MECC 06 on lithogenic the substrate. soil environment soil the of influence direct the with linked be should presence horizons.Their mollic and ochric surface tite type or vermiculite type HIV has been noted in the sub- minerals. the of origin a lithogenic for testifies processes. This pedogenic of influence the arebeyond lying rocks minerals Triassic the from these minerals of features the of to similar very features that shows diffractograms the of analysis Detailed vermiculite. or chlorite of volume studied soils; these minerals are accompanied all by a variable of horizons genetic the of substrate soil the in olinite substrate. soil XRD and SEM were methods applied analysis. inthe the of formation the during pedogenesis and litho- of processes the between relation the termine de to allowing minerals, clay of assemblage the of istics soils. these the of formation the physical on and chemical, wellasexploitationas properties of processes pedogenic of influence the determine specific to the parentcharacterdifficult the ofisit rock, to Due investigations. to subject been have TriassicLower the ofgraphic–faciesunits (Buntsandstein) strati different of deposits clay red from developed Soils Division of Soil Science, Department of Soil Environmental ofSoil Sciences, Warsaw Science, of Soil Department Division Agricultural –SGGW, University Nowoursynowska 159,02–776Warszawa, Poland ([email protected]) A lowA content of mixed-layer mineralsillite–smece.g. ka or illite ofdomination the to pointed studies XRD character mineralogical the on focused was study The Preliminary mineralogicalPreliminary characteristicsofsoilsdeveloped from Lower Triassic clay deposits(Buntsandstein) in theHolyCross Mts. (SPoland) Zbigniew ZAGÓRSKI andSylwia GRELA - - - - - erals and formation of new pedogenic minerals is poorly min is minerals pedogenic of new of formation and transformation erals the to leading whereas influence chemical surface destruction, the physical to in restricted reflected is and horizons is processes pedogenic of fluence In soils. studied the in substrate soil the featuresof genic aggregation. secondary by followed dispersion, towards transformed featuresstronglyare structural horizons the surface the In TriassicLower(BARCZUK,1979). depositsthe clay of cal literatureto represent they datatypistructures diagenetic According units. independent as well as grains, between pores in observed been have illite or kaolinite of packets builtstructuresofintact cm), 50 (belowca. andlower part of the clay substrate within the soil horizons. In the middle ACU, . 17) Ptorpi suy f h Bnsnsen sedi Buntsandstein the of study Petrographic (1979): A. BARCZUK, to pedogenicfactors. of resistance large distinctly the clay soil substrate developed from Lower Triassic the rocks from and profiles) soil of in processes the studied soils may result from their pedogenic ‘young’ age (erosion of development poor The marked. h bandrslsidct h oiac of litho dominance the indicate results obtained The SEManalysis showed variable the properties structural Poland).– Arch. Mineralog., 252,87–160. ments from the north-eastern border of the Holy Cross Mts (Central Reference

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Mineralogy, Mössbauer characteristics and isotope age of Middle Riphean glauconites (the Olenek Uplift, Northern Siberia)

Tatyana S. ZAITSEVA1, Igor M. GOROKHOV1, Tatyana A. IVANOVSKAYA2, Nikolai N. MELNIKOV1 and Oxana V. YAKOVLEVA1

K–Ar and Rb–Sr dates of globular glauconite correspond respectively) correspond to the Middle Riphean age of the in many cases to early diagenesis of sediments and are close Arymas Formation. to their deposition age. Yet secondary chemical and struc- As a result of the modeling, the proportions of local ca- tural alterations of this mineral can be accompanied by tion arrangements of the Fe3+ and Fe2+ ions were calculated 40 87 loss of radiogenic Ar and Sr and result in “rejuvenated” for both unordered and ordered distributions of octahedral dates. Theö M ssbauer spectroscopy may be useful to detect cations. These values were grouped and compared with the such structural alterations. This paper provides the min- integrated intensities for corresponding quadrupole dou- eralogical and structural characteristics together with iso- blets in the Mössbauer spectra. Use of predicted values of topic dates for Middle Riphean glauconites of the Arymas individual quadrupole splitting from each type of cation Formation of the Olenek Uplift. Chemical state and distri- arrangements of the Fe3+ and Fe2+ ions (DAINYAK et al., bution of the iron atoms between non-equivalent crystal- 2004) allows to calculate model values of quadrupole split- lographic positions in glauconite structure are determined ting for each doublet and to compare them to the Möss- 3r by the Mössbauer spectroscopy. The absorption signals of bauer spectroscopy data. The good agreement between d Mid-European Clay Conference – MECC 06 spectra were computer-fitted to six quadrupole doublets. theory and observation suggests that the chosen model of Based on the chemical composition of the glauconites, glauconite formation is a realistic one. Thus, the results ob- their structural formulae were determined. Then the pro- tained by the Mössbauer spectroscopy can be used as an portions of the local cation arrangements of the Fe3+- and evidence of the absence of secondary structural alteration Fe2+-ions were calculated for both non-ordered and or- of ancient glauconites and a criterion of stratigraphical sig- dered distributions of octahedral cations. The structural nificance of their Rb–Sr and K–Ar dates. studies of Fe-rich dioctahedral 2:1 layer silicates show that they are always trans-vacant (MANCEAU et al., 2001). The Acknowledgement: This work was carried out in the framework modeling is founded on the following concept of glauco- of the Russian Academy of Sciences Programs of Basic Research 6 nite formation. It is supposed (GOROKHOV et al., 1995; and 25, and was partially supported by the Russian Foundation for CLAUER et al., 1992), that an unordered (“statistical”) dis- Basic Research (Projects 05–05–65290 and 06–05–64736). tribution of the octahedral cations is typical of the new- References formed glauconite. At this point atoms of the 40Ar and 87Sr inherited from a mineral-precursor do yet not leave glau- CLAUER, N., STILLE, P., KEPPENS, E. & O’NEIL, J.R. (1992): Le méca- nisme de la glauconitisation: Apports de la géochimie isotopique du conite structure. Only in the closing stages of its formation strontium, du néodyme et de l’oxygène de glauconies récentes.– C.R. involving significant increase of potassium content, the cat- Acad. Sci. Paris., 315, Ser. II, 3, 321–327. ion ordering occurs in the octahedral layer, and a domain DAINYAK, L.G., DRITS, V.A. & LINDGREEN, H. (2004): Computer si- structure originates. The ordered distribution appears to mulation of octahedral cation distribution and interpretation of the 2+ result from a layer-by-layer dissolution–precipitation proc- Mössbauer Fe components in dioctahedral trans-vacant micas.– Eur. J. Mineral, 16, 3, 451–468. ess. The redistribution of the cations in all glauconite layers 40 87 GOROKHOV, I.M., YAKOVLEVA, O.V., SEMIKHATOV, M.A. & IVA- should result in expulsion of radiogenic Ar and Sr alien NOVSKAYA, T.A. (1995): Rb–Sr and K–Ar ages and Moessbauer to the mineral structure and in startup of the “radioactive spectra of globular phyllosilicates of the glauconite series: The Middle clock”, based on decay of 40K and 87Rb. If such a glauco- Riphean Debengda Formation of the Olenek Uplift, northern Sibe- nite is free of secondary alteration, its isotope date should ria.– Lithology and Mineral Resources, 30, 556–571. correspond to the timing of early diagenesis, i.e. should MANCEAU, A., LANSON, B., DRITS, V.A., CHATEIGNER, D., GATES, be close to the stratigraphic age. This is best illustrated by W.P., WU, J., HUO, D. & STUCKI, J.W. (2001): Oxidation–reduction mechanism of iron in dioctahedral smectites: 1. Crystal chemistry glauconites of the Arymas Formation of the Olenek Uplift of oxidized reference nontronites.– American Mineralogist, 85, 133– which Rb–Sr and K–Ar dates (1306–1318 and 1261 m.y. 152.

1 Institute of Precambrian Geology and Geochronology, RAS, nab. Makarova 2, St.Petersburg 199034, Russia ([email protected]) 2 Geological Institute, RAS, Pyzhevsky per.7, Moscow, 109017, Russia 125 Abstracts Book Abstracts 126 3rd Mid-European Clay Conference – MECC 06 Fig. 1XRDofCuMnAllayered doublehydroxides. 6, 7, 8 or 9 or 8 pH 7, 6, at out carried was precursors mixed of thesis syn (CAVANI the value 1991), pH intermediateal., an et at occurs frequentlyco-precipitation the that observation reported the of view respectively.In 9, and 6 ca. of values pH completeprecipitationathydroxides is of the solution NaOH the of addition upon that show experiments thesis Cu(NO of M(III) [M(II) formula general the of LDHs of synthesis the for used routinely pH, constant a at method co-precipitation vironment. en of protection the for importance immense of process a (VOCs), compounds organic volatile of combustion for precursorsof as drotalcite-likesolids view of this, our intention was to obtain Cu–Mn-based hy known as active components of total oxidation catalysts. In proper redox ties, their to due Mn, and Cu hand, other the precursorsof mixed oxide catalysts (VACCARI, On1999). possess LDHs of promisingmost the consideredare and properties decomposition unique thermal of products The cations. metal M(III) and M(II) various of number a ers lay the within accommodate can and LDHs is very ﬂexible of structure preparedcoprecipitation.byeasily be The can [M(II) formula general the by characterized are clays, anionic or compounds talcite-like hydroas hydroxidesdoubleLayered also (LDHs),known Institute ofCatalysis Chemistry, andSurface Polish Academy ofSciences, ul. Niezapominajek 8,30–239Cracow, Poland ([email protected]) 1 0 1000 1200 1400 1600 1800 2000 4000 6000 8000 0 0 0 0 0 0 A series of Cu–Mn precursors were synthesized by the the byprecursorsCu–Mnsynthesizedwere of series A especially importantespecially in electron transfer reactions, x Małgorzata ZIMOWSKA, Justyna PLONA, Justyna ZIMOWSKA, Małgorzata AlicjaMICHALIK-ZYM andEwa M.SERWICKA (OH) 2 0 3 ) , by dropwise addition of aqueous solutions of solutions aqueous of addition dropwise by , 2 nuneo h ytei odto nC–nlayered Cu–Mn on condition synthesis the of Inﬂuence · 2 3H ]A 3 0 n- 2 O and Mn(NO and O x/n . Titration curves of aqueous solutionsaqueous of curves Titration . 4 0 HT 2 c- Θ 5 0 Cu Mn 1-x 3 ) Al 2 M(III) · 4H 6 0 mixed oxide systemsoxide mixed HT 2 HT HT HT O used in the syn the in used O c- c- c- c- x Cu (OH) Cu Cu Cu 7 0 Mn Mn Mn Mn double hydroxides HT HT Cu Al Al Al Al -p 2 c- c- -p -p -p (OH) 2 H= Cu Cu ]A H= H= H= 8 0 6 Mn Mn 7 8 9 3 n- (N Al Al x/n O -N -C 3 equal equal ) and O O are 3 3 0 1-x ------

of precipitate the 1). (Fig. ment of pH being the second factor determining the nature adjustappropriate the structure, LDH-like an of mation for the induce to way best the was system Cu–Mn the to acterization of samples. the char physicochemical the for applied been have analyses thermal andchemical as well as methods, XRD,BET XPS, Cu) of half sors some formation structure hydrotalcite the induce attemptto an Inhydrotalcite structure. a formationof the for required cation trivalent Mn(III) provide and oxidize pected that during synthesis carried out in air Mn(II) would 2004; al., GRYGARet ( reports previous Following using carbonate, sodium of Cu(NO VACCARI, A. (1999): Clays and catalysis: a promising future.– Appliedfuture.– promising a catalysis: and Clays (1999): VACCARI,A. KOVANDA, F., GRYGAR, T., DORNICAK, V., ROJKA, T., BEZDICKA, P. TAYLOR,HANSEN,& anaH.C.B.Formationsynthetic of (1991): R.M. KO & VEČERNIKOVÁ, P., E. BEZDIČKA, T., ROJKA, T.,GRYGAR, CAVANI,F., TRIFIRO, F. VACCARI,& Hydrotalcite-type(1991): A. ani 003 T08D 3 project 26 [2004–2006]. research the within Research Scientiﬁc for tee Acknowledgment: procedure leading to active mixed oxide catalysts. porated into solids the increased. incor manganese the of amount the pH co-precipitation observed. was crystallinity material the of increase an Simultaneouslyhydroxide.double ered cipitationresultedformation in ofcarbonate CuMnAllay double hydroxide were observed. Increase of the pH of pre Cu 2 h eut eeldta h nrdcinof aluminium introduction the that revealed results The Clay 14, 161–198. Science oxides.– Applied Clay 28,121–136. Science formed of characterization and hydroxides double layered Mg–Mn Ni– and Cu–Mg–Mn of & JIRATOVA, behaviour K. (2005): Thermal Minerals, Clay 26, 507–525. desautelsite.– of synthesis The II. conditions: pH led control under minerals carbonatemetal–hydroxy double of logues ides.– Journal of State Solid Electrochemistry, 8,252–259. ox Mn Cu, mixed of crystallization thermal the of stages early the of analysis diﬀraction X-ray Voltammetricand VANDA,(2004): F. 11, 173–301. onic clays: preparation, properties and applications.– Catalysis Today synthetic the of optimisation the for allowed work The nitrate copper basic of structure layered a pH=6 At (OH) were 3 ) 2 3 synthesise · (NO 3H , and/or Al and/or , 2 O and Mn(NO 3 ) as well as nitrate form of CuMnAl layered hswr a upre ytePls Commit Polish the by supported was work This d with the addition of Zn of addition the with (replacing half of Mn) of half (replacing

KOVANDA et al., 2005) it was ex was it 2005) KOVANDAal., et References

HANSEN 3 M aH o p control. pH for NaOH M 1 ) 2 · 4H 2 O to the basic solution

ih h ices of increase the With & TA & nitrates. YLOR

(replacing precur , 1991; The ------Abstracts Book

Crystal-chemical factors aﬀecting the distribution of octahedral cations over cis- and trans-sites in dioctahedral smectites

Bella B. ZVIAGINA

Dioctahedral 2:1 phyllosilicates may have different pat- view, a cv octahedral sheet is preferable for Mg, Fe2+-rich terns in the octahedral cation distribution over the cis- and montmorillonites having random distribution of isomor- trans-sites. MERING & OBERLIN (1971) were the first phous cations, which implies the presence of R2+–OH–R2+ to report cis-vacant (cv) structure for a sample of Wyo- arrangements. For such an arrangement in a tv sheet two ming montmorillonite. According to experimental data adjacent OH groups are bonded with two R2+ cations; in a (TSIPURSKY & DRITS, 1984) beidellites and nontronites cv sheet, two adjacent OH groups are bonded with three are trans-vacant, whereas montmorillonite and some Al- octahedral cations, which provides more favourable condi- rich smectites, in which the layer negative charge is located tions for local charge compensation. In contrast, Mg-bear- in both octahedral and tetrahedral sheets of the 2:1 layers, ing montmorillonite may be trans-vacant if the distribution are cis-vacant. However, several findings of trans-vacant of isomorphous cations is not random and octahedral Mg (tv) montmorillonites have also been reported (e.g., DRITS cations are dispersed to avoid Mg–OH–Mg arrangements. et al., 2004). Some dioctahedral smectites consist of inter- The formation of cv layers is therefore favoured by stratified cv and tv layers although the information about

relatively high contents of divalent octahedral cations in 3r the existence of such tv–cv smectites is very limited. smectites with random octahedral cation distribution. The d Mid-European Clay Conference – MECC 06 Crystal-chemical analysis of tv and cv dioctahedral presence of only Al and/or Fe3+ in octahedra (nontronite– smectites shows that the formation of tv and cv layers is beidellite series) and dispersion of divalent octahedral cati- related with the octahedral sheet composition and local or- ons in Mg-rich smectites are the factors that beneﬁt the tv der–disorder in the distribution of isomorphous cations. In structure. the nontronite–beidellite series the main negative charge is located in the tetrahedral sheet, and the octahedral cations References are mostly trivalent. Therefore a tv arrangement of these DRITS, V.A., LINDGREEN, H., SAKHAROV, B.A., JAKOBSEN, H.J. & cations can provide local charge compensation for anions ZVIAGINA, B.B. (2004): The detailed structure and origin of clay forming the octahedral sheet. The saturation of hydroxyl minerals at the Cretaceous/Tertiary boundary, Stevns Klint (Den- oxygens by positive charge is achieved by shortening R3+– mark).– Clay Minerals, 39, 367–390. OH bonds due to displacements of adjacent OH groups to- MERING, J. & OBERLIN, A. (1971): Smectites.– In: CARD, J.A. (ed): The * Electron–Optical Investigation of Clays. Mineralogical Society, Lon- wards each other along the c axis. The saturation of oxygen don, 193–229. anions shared by the octahedra and Al-bearing tetrahedra TSIPURSKY, S.I. & DRITS, V.A. (1984): The distribution of octahedral is provided by shortening of the non-bridging Al–O bonds. cations in the 2:1 layers of dioctahedral smectites studied by oblique- In contrast, from the local charge compensation point of texture electron diﬀraction.– Clay Minerals, 19, 177–193.

Geological Institute, Russian Academy of Sciences, 7 Pyzhevsky per., 119017 Moscow, Russia ([email protected]) 127 Abstracts Book Abstracts 128 3rd Mid-European Clay Conference – MECC 06