Stability of kaolin sand from the Vyšný Petrovec deposit (south Slovakia) in an acid environment

Open access


Comprehensive characterization of kaolin sand from the Vyšný Petrovec (VP) deposit in Slovakia by a variety of experimental methods was performed. The quantitative XRD analysis (RockJock software) revealed that the acid-untreated sample contained mainly kaolinite (~60 wt. %), a considerable amount of dioctahedral micas (~32 wt. %) and quartz (~ 7 wt. %). The Hinckley index (HI) and Aparicio-Galán-Ferrel index (AGFI) calculated from the 02l and 11l reflections showed medium-defect kaolinite to be present in the VP kaolin. The influence of the mineral composition of VP kaolin on its stability in 6 mol · dm-3 HCl at 95 °C was investigated. The solid reaction products were examined by chemical analysis; XRD and infrared spectroscopy in both middle (MIR) and near (NIR) regions. Considerably higher dissolution rate of Fe compared to Al indicated that Fe was bounded in a readily soluble phase rather than in kaolinite. While the MIR spectra confirmed the gradual release of the central atoms from the clay minerals layers and creation of amorphous silica upon acid treatment, the NIR spectra revealed the formation of Si-OH groups in the solid reaction product. Relatively high dissolution rate of VP kaolin resulted from the presence of small-grains of mediumdefect kaolinite and clay admixtures in VP kaolin sand.

Aparicio P. & Galán E. 1999: Mineralogical interference on kaolinite crystallinity index measurements. Clays and Clay Miner. 47, 12-27.

Aparicio P., Galán E. & Ferrell R.E. 2006: A new kaolinite order index based on XRD profile fitting. Clay Miner. 41, 811-817.

Bahranowski K., Serwicka E.M., Stoch L. & Strychalski P. 1993: On the possibility of removal of non-structural iron from kao-linite-group minerals. Clay Miner. 28, 379-391.

Baláž P. & Kúšik D. (Eds.) 2010: Slovak Minerals Yearbook. Statistical data to 2009. State Geological Institute of Dionýz Stúr, 1-158.

Bish D.L. & Duffy C.J. 1990: Thermogravimetric analysis of minerals. In: Stucki J.W. & Bish D.L. (Eds.): Thermal analysis in clay science. CMS Workshop Lectures. Clay Minerals Society, Boulder, Colorado, USA, 124-129.

Bookin A.S., Drits V.A., Plancon A. & Tchoubar C. 1989: Stacking faults in kaolin-group minerals in the light of real structural features. Clays and Clay Miner. 37, 297-307.

Breen C., Zahoor F.D., Madejová J. & Komadel P. 1997: Characterization and catalytic activity of acid-treated, size-fractionated smectites. J. Physical Chemistry B 101, 5324-5331.

Brindley G.W. & Nakahira M. 1959: The kaolinite-mullite reactions series. I. A survey of outstanding problems. II. Metakaolin. III. The high temperature phases. J. Amer. Ceramic Soc. 42, 311-324.

Bruker AXS 2000, TOPAS V2.0: General profile and structure analysis software for powder diffraction data. User Manual,

Bruker AXS, Karlsruhe, Germany. Bulens M. & Delmon B. 1977: The exothermic reaction of metakaolinite in the presence of mineralizers. Influence of crystallinity.

Clays and Clay Miner. 25, 271-277. Chipera S.J. & Bish D.L. 2001: Baseline studies of the Clay Minerals Society Source Clays: Powder X-ray diffraction analyses.

Clays and Clay Miner. 49, 398-409. Číčel B. & Novák I. 1976: Dissolution of smectites in hydrochloric acid. I. Half-time of dissolution as a measure of reaction rate. 7-th Conference on Clay Mineralogy and Petrology, Karlovy Vary.

Drits V.A., Eberl D.D. & Šrodoň J. 1998: XRD measurement of mean thickness, thickness distribution and strain for illite and illite-smectite crystallites by the Bertaut-Warren-Averbach technique. Clays and Clay Miner. 46, 38-50.

Dubíková M., Cambier P., Šucha V. & Čaplovičová M. 2002: Experimental soil acidification. App. Geochem. 17, 245-257.

Eberl D.D. 2003: User's guide to RockJock - a program for determining quantitative mineralogy from powder X-ray diffraction data. U.S. Geol. Surv., Open-File Report, 3-78.

Egiebor N.O. & Oni B. 2007: Acid rock drainage formation and treatment: a review. Asia-Pacific J. Chem. Engineering 2, 47-62.

Evans B.W. & Guggenheim S. 1988: Talc, pyrophyllite and related minerals. In: Bailey S.W. (Ed.): Hydrous phyllosilicates (exclusive of micas). Rev. in Mineralogy, 19, Mineral. Soc. Amer., Washington, D.C., 225-294.

Farmer V.C. 1974: Layer silicates. In: Farmer V.C. (Ed.): Infrared spectra of minerals. Monograph. Mineral. Soc., London 4, 331-363.

Fijal J., Klapyta Z., Zietkiewicz J. & Žyla M. 1975: On the mechanism of the montmorillonite acid activation. I. Degradation of Ca-montmorillonite structure. Mineral. Pol. 6, 29-43.

Galán E., Aparicio P., La Iglesia A. & González I. 2006: The effect of pressure on order/disorder in kaolinite under wet and dry conditions. Clays and Clay Miner. 54, 232-241.

Ganor J., Mogollon J.L. & Lasaga A.C. 1995: The effect of pH on kaolinite dissolution rates and on activation energy. Geochim. Cosmochim. Acta 59, 1037-1052.

Giese R.F. 1988: Kaolin minerals: Structures and stabilities. In: Bailey S.W. (Ed.): Hydrous phyllosilicates (exclusive of micas). Rev. in Mineralogy, 19, Mineral. Soc. Amer., Washington, D.C., 29-66.

Guggenheim S. & Koster van Groos A.F. 2001: Baseline studies of the Clay Minerals Society Source Clays: Thermal analysis. Clays and Clay Miner. 49, 433-443.

Hano V. 1973: Vyšný Petrovec, preliminary exploration - kaolin sands. Report, Geofond, Bratislava, 1-74 (in Slovak).

Harvey C.C. & Lagaly G. 2006: Conventional applications. In: Bergaya F., Theng B.K.G. & Lagaly G. (Eds.): Handbook of clay science. Developments in clay science. Vol. 1. Elsevier Ltd., The Netherlands, 501-540.

He M.C., Zhao J., Fang Z.J. & Zhang P. 2011: First-principles study of isomorphic ('dual-defect'). Clays and Clay Miner. 59, 501-506.

Hinckley D.N. 1963: Variability in "crystallinity" values among the kaolin deposits of the coastal plain of Georgia and South Carolina. In: Swineford A. (Ed.): Clays and Clay Miner., Proc. 11th Natl. Conf., Ottawa, Ontario, 1962. Pergamon, New York, 229-235.

Hradil D., Hostomský J. & Soukupová J. 2002: Aluminium release rates from acidified clay structures: comparative kinetic study. Geol. Carphathica 53, 2, 117-121.

Janotka I., Puertas F., Palacios M., Kuliffayová M. & Varga C.I. 2010: Metakaolin sand-blended-cement pastes: Rheology, hydration process and mechanical properties. Construction and Building Materials 24, 791-802.

Jozefaciuk G. & Bowanko G. 2002: Effect of acid and alkali treatments on surface areas and adsorption energies of selected minerals. Clays and Clay Miner. 50, 771-783.

Kadir S., Erman H. & Erkoyun H. 2011: Mineralogical and geochemical characteristics and genesis of hydrothermal kaolinite deposits within neogene volcanites, Kütahya (Western Anatolia), Turkey. Clays and Clay Miner. 59, 250-276.

Kalinowski B.E. & Schweda P. 1996: Kinetics of muscovite, phlo-gopite and biotite dissolution and alteration at pH 1-4, room temperature. Geochim. Cosmochim. Acta 60, 367-385.

Klug H.P. & Alexander L.E. 1974: X-ray diffraction procedures for polycrystalline and amorphous materials. 2nd edition. Wiley,

New York, USA, 1-992.

Komadel P., Stucki J.W. & Číčel B. 1993: Readily HCl-soluble iron in the fine fractions of some Czech bentonites. Geol. Carpathica - Clays 44, 11-16.

Komadel P., Madejová J., Janek M., Gates W.P., Kirkpatrick R.J. & Stucki J.W. 1996: Dissolution of hectorite in inorganic acids. Clays and Clay Miner. 44, 228-236.

Komadel P. 2003: Chemically modified smectites. Clay Miner. 38, 127-138.

Kováč M., Baráth I., Fordinál K., Grigorovich A.S., Halásová E., Hudáčková N., Joniak P., Sabol M., Slamková M., Sliva II. & Vojtko R. 2006: Late Miocene to Early Pliocene sedimentary environments and climatic changes in the Alpine-Carpathian-Pannonian junction area: A case study from the Danube Basin northern margin (Slovakia). Palaeogeogr. Palaeoclimatol. Palaeoecol. 238, 32-52.

Kováčová M., Doláková N. & Kováč M. 2011: Miocene vegetation pattern and climate change in the northwestern Central Para-tethys domain (Czech and Slovak Republic). Geol. Carphathica 62, 3, 251-266.

Krajči II., Janotka I., Kraus I. & Jamnický P. 2007: Burnt kaolin sand as pozzolanic material for cement hydration. Ceramics-Silikáty 51, 217-224.

Kraus I. 1989: Kaolins and kaolinite clays of the Western Carpathians. Western Carpathians, mineralogy petrography geochemistry metalogensis series. Geological Institute of Dionýz Štúr, Bratislava 13, 1-287.

Kraus I. & Hano V. 1976: Genetic classification and age of kaolinite group minerals from the Western Carpathians deposits. Miner. Slovaca 8, 431-436 (in Slovak).

Kraus I. & Horváth I. 1978: Mineralogy and age of Slovakian kaolins. Schrift. Geol. Wissenschaft. 11, 125-136.

Lagaly G. 1999: Introduction: from clay mineral-polymer interaction to clay mineral-polymer nanocomposites. Applied Clay Sci. 15, 1-9.

Lintnerová O., Šucha V. & Streško V. 1999: Mineralogy and geochemistry of acid mine Fe-precipitates from the main Slovak mining regions. Geol. Carpathica 50, 395-404.

Ma M. 2011: The dispersive effect of sodium silicate on kaolinite particles in process water: Implications for iron-ore processing. Clays and Clay Miner. 59, 233-239.

Madejová J. & Komadel P. 2001: Baseline studies of The Clay Minerals Society Source Clays: Infrared methods. Clays and Clay Miner. 49, 410-432.

Madejová J., Kraus I., Tunega D. & Šamajová E. 1997: Fourier transform infrared spectroscopic characterisation of kaolinite group minerals from the main Slovak deposits. Geol. Carpathica - Clays 6, 3-10.

Madejová J., Bujdák J., Janek M. & Komadel P. 1998: Comparative FT-IR study of structural modifications during acid treatment of dioctahedral smectites and hectorite. Spectrochim. Acta, Part A 54, 1397-1406.

Madejová J., Kečkéš J., Pálková H. & Komadel P. 2002: Identification of components in smectite/kaolinite mixtures. Clay Miner. 37, 377-388.

Madejová J., Pentrák M., Pálková H. & Komadel P. 2009: Near-infrared spectroscopy: A powerful tool in studies of acid-treated clay minerals. Vibrational Spectroscopy 49, 211-218.

Matusik J., Gawel A., Bielaňska E., Osuch W. & Bahranowski K. 2009: The effect of structural order on nanotubes derived from kaolin-group minerals. Clays and Clay Miner. 57, 452-464.

Matusik J., Gawel A., Bielaňska E. & Bahranowski K. 2011: Surface area and porosity of nanotubes obtained from kaolin minerals of different structural order. Clays and Clay Miner. 59, 116-135.

Meads R.E. & Malden P.S. 1975: Electron-spin resonance in natural kaolinites containing Fe3+ and other transition metal ions. Clay Miner. 10, 313-345.

Mestdagh M.M., Vielvoye L. & Herbillon A.J. 1980: Iron in kaolin-ites. II. The relationship between kaolinite crystallinity and iron content. Clay Miner. 15, 1-13.

Moussi B., Medhioub M., Hatira N., Yans J., Hajjaji W., Rocha F., Labrincha J.A. & Jamoussi F. 2011: Identification and use of white clayey deposits from the area of Tamra (northern Tunisia) as ceramic raw materials. Clay Miner. 46, 165-175.

Murray H.H., Bundy W.M. & Harvey C.C. 1993: Kaolin genesis and utilization. Spec. Publ. No. 1. Clay Miner. Soc., Boulder, CO, 1-341.

Murray H.H. 2007: Applied clay mineralogy. Occurrences, processing and application of kaolins, bentonites, palygorskite-sepio-lite, and common clays. Elsevier, Developments in Clay Sci. 2, 1-180.

Nguetnkam J.P., Kamga R., Villiéras F., Ekodeck G.E., Razafitian-amaharavo A. & Yvon J. 2011: Alteration of cameroonian clays under acid treatment. Comparison with industrial adsorbents. Applied Clay Sci. 52, 122-132.

Novák I. & Číčel B. 1978: Dissolution of smectites in hydrochloric acid: II. Dissolution rate as a function of crystallochemical composition. Clays and Clay Miner. 26, 341-344.

Novembre D., Di Sabatino B., Gimeno D. & Pace C. 2011: Synthesis and characterization of Na-X, Na-A and Na-P zeolites and hydroxysodalite from metakaolinite. Clay Miner. 46, 339-354.

Novotná M., Kraus I. & Horváth I. 1993: Expression of kaolinite ordering in selected kaolin deposits. Miner. Slovaca 25, 55-59 (in Slovak).

Pentrák M., Madejová J. & Komadel P. 2009: Acid and alkali treatment of kaolins. Clay Miner. 44, 511-523.

Pentrák M., Madejová J. & Komadel P. 2010: Effect of chemical composition and swelling on acid dissolution of 2: 1 clay minerals. Philosophical Mag. 90, 2387-2397.

Pentrák M., Czímerová A., Madejová J. & Komadel P. 2012: Changes in layer charge of clay minerals upon acid treatment as obtained from their interactions with methylene blue. Applied Clay Sci. 55, 100-107.

Petit S., Madejová J., Decarreau A. & Martin F. 1999: Characterization of octahedral substitutions in kaolinites using near infrared spectroscopy. Clays and Clay Miner. 47, 103-108.

Plancon A. & Tchoubar C. 1977a: Determination of structural defects in phyllosilicates by X-ray powder difraction. I. Principle of calculation of the diffraction phenomenon. Clays and Clay Miner. 25, 430-435.

Plancon A. & Tchoubar C. 1977b: Determination of structural defects in phyllosilicates by X-ray powder difraction. II. Nature and proportion of defects in natural kaolinites. Clays and Clay Miner. 25, 436-450.

Plancon A., Giese R.F. & Snyder R. 1988: The Hinckley index for kaolinites. Clay Miner. 23, 249-260.

Plancon A., Giese R.F., Snyder R., Drits V.A. & Bookin A.S. 1989: Stacking faults in the kaolin-group minerals: defect structures of kaolinite. Clays and Clay Miner. 37, 203-210.

Plancon A. & Zacharie C. 1990: An expert system for the structural characterization of kaolinite. Clay Miner. 25, 249-260.

Premovič P.I., Ciesielczuk J., Bzovska G. & Dordevič M.G. 2012: Geochemistry and electron spin resonance of hydrothermal dickite (Nowa Ruda, Lower Silesia, Poland): vanadium and chromium. Geol. Carphathica 63, 3, 241-252.

Pruett R.J. & Webb H.L. 1993: Sampling and analysis of KGa-1B well-crystallized kaolin source clay. Clays and Clay Miner. 41, 514-519.

Rožič L., Novakovič T. & Petrovič S. 2010: Modeling and optimization process parameters of acid activation of bentonite by response surface methodology. Applied Clay Sci. 48, 154-158.

Rožič L., Grbič B., Radič N., Petrovič S., Novakovič T., Vukovič Z. & Nedič Z. 2011: Mesoporous 12-tungstophosphoric acid/activated bentonite catalysts for oxidation of 2-propanol. Applied Clay Sci. 53, 151-156.

Sciascia L., Turco Liveri M.L. & Merli M. 2011: Kinetic and equilibrium studies for the adsorption of acid nucleic bases onto K10 montmorillonite. Applied Clay Sci. 53, 657-668.

Siddique R. & Klaus J. 2009: Influence of metakaolin on the properties of mortar and concrete: A review. Applied Clay Sci. 43, 392-400.

Sillitoe R.H. 2010: Porphyry copper systems. Econ. Geol. 105, 3-41.

Slaughter M. & Keller W.D. 1959: High temperature phases from impure Kaolin clays. Bull. Amer. Ceramic Soc. 38, 703-707.

Soták J. 2011: Paleoenvironmental changes across the Eocene-Oli-gocene boundary: insights from the Central-Carpathian Paleo-gene Basin. Geol. Carphathica 61, 5, 393-418.

Stoch L., Bahranowski K., Budek L. & Fijal J. 1977: Bleaching properties of non-bentonitic clay materials and their modification. I. Acid activation of the miocene clays from Machów. Miner. Pol. 8, 31-51.

Šucha V., Kraus I., Šamajová E. & Puškelová II. 1999: Crystallite size distribution of kaolin minerals. Periodico di Mineralogia 68, 81-92.

Tkáč I., Komadel P. & Müller D. 1994: Acid-treated montmorillo-nites - a study by 29Si and 27Al MAS NMR. Clay Miner. 29, 11-19.

Uzarowicz L., Skiba S., Skiba M. & Michalik M. 2011: Clay-mineral formation in soils developed in the weathering zone of pyrite-bearing schists: A case study from the abandoned pyrite mine in Wiešciszowice, Lower Silesia, SW Poland. Clays and Clay Miner. 59, 581-594.

Valášková M., Barabaszová K., Hundáková M., Ritz M. & Plevová E. 2011: Effect of brief milling and acid treatment on two ordered and disordered kaolinite structures. Applied Clay Sci. 54, 70-76.

Van Olphen H. & Fripiat J.J. 1979: Data handbook for clay minerals and other non-metallic materials. Pergamon Press, 1-346.

Vass D., Elečko M., Bezák V., Bodnár J., Konečný V., Lexa J., Molák B., Straka P., Stankovič J., Stolár M., Škvarka L., Vozár J. & Vozárová A. 1992: Geological map of the Lučenská kotlina depression and Cerová vrchovina upland, 1 : 50,000. Geol. Surv. of Slovak Republic, Bratislava.

Worasith N., Goodman B.A., Neampan J., Jeyachoke N. & Thiravetyan P. 2011: Characterization of modified kaolin from the Ranong deposit Thailand by XRD, XRF, SEM, FTIR and EPR techniques. Clay Miner. 46, 539-559.

Yanik G. 2011: Mineralogical, crystallographic and technological characteristics of Yaylayolu kaolin (Kütahya, Turkey). Clay Miner. 46, 397-410.

Geologica Carpathica

The Journal of Geological Institute of Slovak Academy of Sciences

Journal Information

IMPACT FACTOR 2017: 1.169
5-year IMPACT FACTOR: 1.431

CiteScore 2017: 1.26

SCImago Journal Rank (SJR) 2017: 0.551
Source Normalized Impact per Paper (SNIP) 2017: 0.836


All Time Past Year Past 30 Days
Abstract Views 0 0 0
Full Text Views 223 220 19
PDF Downloads 61 60 3