Clay mineralogy, chemistry, and diagenesis of Late Devonian K-bentonite occurrences in northwestern Turkey

Thin beds of tephra (K-bentonites) formed by the diagenesis of volcanic ash are exposed within the limestone-dolomitic limestone successions of the Yılanlı formation at Zonguldak and Bartın in northwestern Turkey. They were deposited on the Middle Devonian-Lower Carboniferous shallow carbonate platform of the Zonguldak terrane. In this study, K-bentonite samples collected from Gavurpınarı and Yılanlı Burnu limestone quarries are investigated in order to reveal their mineralogical and geochemical characteristics and diagenetic evolution. Illite is the major clay mineral in the studied K-bentonites. Additionally, kaolinite and mixed-layer illite-smectite are identified in some samples. The nonclay minerals calcite, dolomite, quartz, gypsum, feldspar, pyrite, and zircon are also found. Crystal-chemical characteristics (Kübler index, d060 values, and polytypes of illites) from two different sampling locations do not show significant variations. Kübler index values for the Yılanlı Burnu and Gavurpınarı sampling locations, 0.47-0.93 (average: 0.71 $\Delta$°2$\theta$) and 0.69-0.77 (average: 0.72 $\Delta$°2$\theta$), respectively, indicate that illites were affected by high-grade diagenetic conditions. The swelling (or smectite) component (~5%), crystallite size (N = 10-20 nm), and polytype (2M1 > 1Md) data of illites support the same conditions. Illite d060 values of 1.491-1.503 Ã correspond to a range of octahedral Mg+Fe values of 0.27-0.51 atoms per formula, indicating a composition between end-member muscovite and phengite unit. Trace and rare earth element-based chemical classification of the K-bentonite samples revealed that composition of original volcanic ash is basaltic. Illitization took place by fixation of K from volcanic minerals and ash, and diffusion of elements (Mg+Fe) into and out of the beds during diagenesis. Mineralogical-chemical data point out that these K-bentonites evolved in high-grade diagenetic conditions (approximately 100-150 °C) from the products of volcanic eruptions of disputed sources and distances during the Late Devonian time.

Clay mineralogy, chemistry, and diagenesis of Late Devonian K-bentonite occurrences in northwestern Turkey

Thin beds of tephra (K-bentonites) formed by the diagenesis of volcanic ash are exposed within the limestone-dolomitic limestone successions of the Yılanlı formation at Zonguldak and Bartın in northwestern Turkey. They were deposited on the Middle Devonian-Lower Carboniferous shallow carbonate platform of the Zonguldak terrane. In this study, K-bentonite samples collected from Gavurpınarı and Yılanlı Burnu limestone quarries are investigated in order to reveal their mineralogical and geochemical characteristics and diagenetic evolution. Illite is the major clay mineral in the studied K-bentonites. Additionally, kaolinite and mixed-layer illite-smectite are identified in some samples. The nonclay minerals calcite, dolomite, quartz, gypsum, feldspar, pyrite, and zircon are also found. Crystal-chemical characteristics (Kübler index, d060 values, and polytypes of illites) from two different sampling locations do not show significant variations. Kübler index values for the Yılanlı Burnu and Gavurpınarı sampling locations, 0.47-0.93 (average: 0.71 $\Delta$°2$\theta$) and 0.69-0.77 (average: 0.72 $\Delta$°2$\theta$), respectively, indicate that illites were affected by high-grade diagenetic conditions. The swelling (or smectite) component (~5%), crystallite size (N = 10-20 nm), and polytype (2M1 > 1Md) data of illites support the same conditions. Illite d060 values of 1.491-1.503 Ã correspond to a range of octahedral Mg+Fe values of 0.27-0.51 atoms per formula, indicating a composition between end-member muscovite and phengite unit. Trace and rare earth element-based chemical classification of the K-bentonite samples revealed that composition of original volcanic ash is basaltic. Illitization took place by fixation of K from volcanic minerals and ash, and diffusion of elements (Mg+Fe) into and out of the beds during diagenesis. Mineralogical-chemical data point out that these K-bentonites evolved in high-grade diagenetic conditions (approximately 100-150 °C) from the products of volcanic eruptions of disputed sources and distances during the Late Devonian time.

___

  • Akbaş B, Altun IE, Aksay A (2002). 1/100.000 Ölçekli Türkiye Jeoloji Haritaları. Zonguldak-E28 Paftası. Ankara, Turkey: MTA Jeoloji Etütleri Dairesi (in Turkish).
  • Alexandre P, Chalot-Prat F, Saintot A, Wijbrans J, Stephenson R, Wilson M, Kitchka A, Stovba, S (2004). The 40Ar/39Ar dating of magmatic activity in the Donbas Fold Belt and the Scythian Platform (Eastern European Craton). Tectonics 23: 1–15.
  • Alişan C, Derman AS (1995). The first palynological age, sedimentological and stratigraphic data for the Çakraz Group (Triassic), western Black Sea. In: Erler A, editor. Geology of the Black Sea Region: Proceedings of the International Symposium on the Geology of Black Sea Region. Ankara, Turkey: General Directorate of Mineral Research and Exploration, pp. 93–98.
  • Allen VT (1932). Ordovician altered volcanic material in Iowa, Wisconsin, and Missouri. J Geol 40: 259–269.
  • Altaner SP, Ylagan RF (1997). Comparison of models of mixed-layer illite/smectite and reaction mechanism of smectite illitization. Clay Clay Miner 45: 517–533.
  • Aydın M, Serdar HS, Şahintürk O, Yazman M, Çokuğraş R, Demir O, Özçelik Y (1987). Çamdağ (Sakarya) - Sünnicedağ (Bolu) yöresinin jeolojisi. Bull Geol Soc Turkey 30/1: 1–4 (in Turkish).
  • Bailey SW (1988). X-ray diffraction identification of the polytypes of mica, serpentine, and chlorite. Clay Clay Min 36: 193–213.
  • Bethke CM, Vergo N, Altaner SP (1986). Pathways of smectite illitization. Clay Clay Miner 34: 125–135.
  • Bozkaya Ö, Yalçın H, Göncüoğlu MC (2012). Mineralogic evidences of a mid-Paleozoic tectono-thermal event in the Zonguldak terrane, NW Turkey: implications for the dynamics of some Gondwana-derived terranes during the closure of the Rheic Ocean. Can J Earth Sci 49: 559–575.
  • Bozkaya Ö, Yalçın H, Kozlu H (2011). Clay mineralogy of the Paleozoic-Lower Mesozoic sedimentary sequence from the northern part of the Arabian Platform, Hazro (Diyarbakır), Southeast Anatolia. Geol Carpath 62: 489–500.
  • Calarge L, Meunier A, Lanson B, Formoso M (2006). Chemical signature of two Permian volcanic ash deposits within a bentonite bed from Melo, Uruguay. Anais da Academica Brasileira de Ciencias 78: 525–541.
  • Chalot-Prat F, Tikhomirov P, Saintot A (2007). Late Devonian and Triassic basalts from the southern continental margin of the East European Platform, tracer of a single heterogeneous lithospheric mantle source. J Earth Syst Sci 116: 469–495.
  • Christidis GE (1998). Comparative study of the mobility of major and trace elements during alteration of an andesite and a rhyolite to bentonite in Island of Milos and Kimolos, Aegean, Greece, Clay Clay Miner 46: 379–399.
  • Dean WT, Martin F, Monod O, Demir O, Richards RB, Bultynck P, Bozdoğan N (1997). Lower Paleozoic stratigraphy, Karadere- Zirze area, Central Pontides, N Turkey. In: Göncüoğlu MC, Derman AS, editors. Early Paleozoic Evolution in NW Gondwana. Ankara, Turkey: Turkish Association of Petroleum Geologists Special Publication 3, pp. 32–38.
  • Derman AS (1997). Sedimentary characteristics of Early Paleozoic rocks in the western Black Sea region, Turkey. In: Göncüoğlu MC, Derman AS, editors. Early Paleozoic Evolution in NW Gondwana. Ankara, Turkey: Turkish Association of Petroleum Geologists Special Publication 3, pp. 24–31.
  • Dil N (1976). Assemblages caracteristiques de foraminiferes du Devonien superieur et du Dinantien de Turquie (Bassin Carbonifere de Zonguldak). Annales de la Societe Geologique de Belgique 99: 373–400 (in French).
  • Eberl DD, Velde B (1989). Beyond the Kübler index. Clay Miner 24: 571–577.
  • Floyd PA, Winchester JA (1978). Identification and discrimination of altered and metamorphosed volcanic rocks using immobile elements. Chem Geol 21: 291–306.
  • Fortey NJ, Merriman RJ, Huff WD (1996). Silurian and Late- Ordovician K-bentonites as a record of late Caledonian volcanism in the British Isles. T RSE Earth 86: 167–180.
  • Frey M (1987). Very low-grade metamorphism of clastic sedimentary rocks. In: Frey M, editor. Low Temperature Metamorphism. Glasgow, UK: Blackie, pp. 9–58.
  • Gedik İ, Pehlivan S, Duru M, Timur E (2005). 1:50.000 Scaled Geological Maps and Explanations: Sheets Bursa G22a and Istanbul F22d. Ankara, Turkey: General Directorate of Mineral Research Exploration.
  • Göncüoğlu MC, Dirik K, Kozlu H (1997). General characteristics of pre-Alpine and Alpine terranes in Turkey: explanatory notes to the terrane map of Turkey. Annal Géologique Pays Héllenique 37: 515–536.
  • Göncüoğlu, MC, Kozlu H (2000). Early Paleozoic evolution of the NW Gondwanaland: data from southern Turkey and surrounding regions. Gondwana Res 3: 315–324.
  • Göncüoğlu MC, Kozur HW (1998). Facial development and thermal alteration of Silurian rocks in Turkey. In: Gutierrez-Marco JC, Rabano I, editors.. Proceedings of the 1998 Silurian Field- Meeting. Madrid, Spain: Temas Geologico-Mineros ITGE 23, pp. 87–90.
  • Göncüoğlu MC, Kozur HW (1999). Remarks on the pre-Variscan development in Turkey. In: Linnemann U, Heuse T, Fatka O, Kraft P, Brocke R, Erdtmann BT, editors. Prevariscan Terrane Analyses of Gondwanean Europa. Dreseden, Germany: Schriften des Staatlichen Museums, Mineralogie, Geologie, pp. 137–138.
  • Göncüoğlu MC, Okuyucu C, Dimitrova T (2011). Late Permian (Tatarian) deposits in NW Anatolia: palaeogeographical implications. Geoecomarina 17: 79–82.
  • Göncüoğlu MC, Sachanski V, Gutiérrez-Marco JC, Okuyucu C (2014). Ordovician graptolites from the basal part of the Palaeozoic transgressive sequence in the Karadere area, Zonguldak Terrane, NW Turkey. Estonian J Earth Sci 63: 227– 232.
  • Göncüoğlu MC, Saydam DG, Gedik İ, Okuyucu C, Özgül N, Timur E, Yanev S, Boncheva İ, Lakova İ, Sachanski V et al (2004). Correlation of the Paleozoic Units in Bulgaria and Turkey. Ankara, Turkey: MTA-BAS-TÜBİTAK 2004–16B4 Project Report.
  • Grathoff GH, Moore DM (1996). Illite polytype quantification using Wildfire© calculated X-ray diffraction patterns. Clay Clay Miner 44: 835–842.
  • Guggenheim S, Bain DC, Bergaya F, Brigatti MF, Drits V, Eberl DD, Formoso M, Galan E, Merriman RJ, Peacor DR et al (2002). Report of the Association Internationale pour L’etude des Argiles (AIPEA) Nomenclature Committee for 2001: order, disorder, and crystallinity in phyllosilicates and the use of the “crystallinity” index. Clay Clay Miner 50: 406–409.
  • Harries PJ (2009). Epeiric seas: a continental extension of shelf biotas. In: Cilek V, Smith RH, editors. Earth System: History and Natural Variability, Vol. IV. Oxford, UK: EOLSS Publishers, pp.
  • Histon K, Klein P, Schonlaub HP, Huff WD (2007). Lower Palaeozoic K-bentonites from the Carnic Alps, Austria. Austrian J Earth Sci 100: 26–42.
  • Hoffman J, Hower J (1979). Clay mineral assemblages as low grade metamorphic geothermometers: application to the thrust- faulted disturbed belt of Montana, U.S.A. In: Scholle PA, Schluger R, editors. Aspects of Diagenesis. Tulsa, OK, USA: SEPM Special Publication 26, pp. 55–80.
  • Huff WD, Bergstrom SM, Kolata DR (1992). Gigantic Ordovician volcanic ash fall in North America and Europe: biological, tectonomagmatic and event-stratigraphic significance. Geology 20: 875–878.
  • Huff WD, Türkmenoğlu AG (1981). Chemical characteristics and origin of Ordovician K-bentonites along the Cincinnati Arch. Clay Clay Miner 29: 113–123.
  • Hunziker JC, Frey M, Clauer N, Dallmeyer RD, Frıedrichsen A, Flehmig W, Hochstrasser K, Roggwiler P, Schwander H (1986). The evolution of illite to muscovite: mineralogical and isotopic data from the Glarus Alps, Switzerland. Contrib Mineral Petr 92: 157–180.
  • Inoue A, Watanabe T, Kohyama A, Brusewitz AM (1990). Characterization of illitization of smectite in bentonite beds at Kinnekulle, Sweden. Clay Clay Miner 38: 241–249.
  • Kabanov PB, Betekhtin AN, Chikina NN, Fedorcov VV, Devyatka NP, Konstantinova MA, Khorosheva ON (2010). Automicrites, buildups, and reservoir shaping in Late Devonian basins of the East European Craton. In: GeoConvention 2010, Calgary, AB, Canada, 2010, p. 1–4.
  • Kalvoda J (2001). Upper Devonian-Upper Carboniferous foraminiferal paleobiogeography and Perigondwana terranes at the Baltica-Gondwana interface. Geol Carpath 52: 205–215.
  • Kay GM (1944a). Middle Ordovician of central Pennsylvania; Part 1, Chazyan and earlier Mohawkian (Black River) formations. J Geol 52: l–23.
  • Kay GM (1944b). Middle Ordovician of central Pennsylvania; Part 2, Later Mohawkian (Trenton) formations. J Geol 52: 97–116.
  • Keller WD, Reynolds RC, Inoue A (1986). Morphology of clay minerals in the smectite-to-illite conversion series by scanning electron microscopy. Clay Clay Miner 34: 187–197.
  • Kerey IE (1984). Facies and tectonic setting of the upper Carboniferous rocks of NW Turkey. In: Robertson AHF, Dixon J, editors. The Geological Evolution of the Eastern Mediterranean. Oxford, UK: Blackwell Scientific, pp. 123–128.
  • Kisch HJ (1991). Illite crystallinity: recommendations on sample preparation X-ray diffraction settings and inter-laboratory samples. J Metamorph Geol 9: 665–670.
  • Kolata DR, Huff WD, Bergstrom (1996). Ordovician K-bentonites of eastern North America. Geol Soc Am Spec Paper 313: 1–84.
  • Krumm S (1996). WINFIT 1.2: Version of November 1996 (The Erlangen Geological and Mineralogical Software Collection) of WINFIT 1.0: a public domain program for interactive profile analysis under WINDOWS. Acta Universitatis Carolinae Geologica 38: 253–261.
  • Kübler B (1968). Evaluation quantitative du metamorphisme par la cristallinite de l’illite. Bull Centre Rech Pau-SNPA 2: 385–397 (in French).
  • Lanson B, Velde B, Meunier A (1998). Late stage diagenesis of illitic clay minerals as seen by decomposition of X-ray diffraction patterns: contrasted behaviors of sedimentary basins with different burial histories. Clay Clay Miner 46: 69–78.
  • Lindgreen H, Hansen PL (1991). Ordering of illite-smectite in Upper Jurassic claystones from the North Sea. Clay Miner 26: 105– 125.
  • Merriman RJ, Frey M (1999). Patterns of very low-grade metamorphism in metapelitic rocks. In: Frey M, Robinson D, editors. Low Grade Metamorphism. Oxford, UK: Blackwell, pp. 61–107.
  • Merriman RJ, Peacor DR (1999). Very low-grade metapelites: mineralogy, microfabrics and measuring reaction progress. In: Frey M, Robinson D, editors. Low Grade Metamorphism. Oxford, UK: Blackwell, pp. 10–60.
  • Merriman RJ, Roberts B (1990). Metabentonites in the Moffat Shale Group, Southern Uplands of Scotland: geochemical evidence of ensialic marginal basin volcanism. Geol Mag 127: 259–271.
  • Mizens GA (2004). Devonian palaeogeography of the Southern Urals. Geol Quart 48: 205–216.
  • Moore DM, Reynolds RC Jr (1997). X-Ray Diffraction and the Identification and Analysis of Clay Minerals. 2nd ed. Oxford, UK: Oxford University Press.
  • Nadeau PH, Wilson MJ, McHardy WJ, Tait JM (1985). The conversion of smectite to illite during diagenesis: evidence from some illitic clays from bentonites and sandstones. Mineral Mag 49: 393-400.
  • Nelson WA (1921). Notes on a volcanic ash bed in the Ordovician of Middle Tennessee. Tennessee Geological Survey Bulletin 25: 46–48.
  • Nelson WA (1922). Volcanic ash bed in the Ordovician of Tennessee. Geol Soc Am Bull 33: 605–616.
  • Nzegge OM, Satır MA, Siebel WA, Taubald HA (2006). Geochemical and isotopic constraints on the genesis of the Late Palaeozoic Deliktaş and Sivrikaya granites from the Kastamonu Granitoid Belt (Central Pontides, Turkey). Neues Jb Miner Abh 183: 27–40.
  • Okay N, Zack T, Okay AI (2010). A missing provenance: sandstone petrography and detrital zircon-rutile geochronology of the Carboniferous flysch of the Istanbul zone. In: Tectonic Crossroads: Evolving Orogens of Eurasia-Africa-Arabia. Ankara, Turkey: Geological Society of America, p. 67.
  • Racki G, Sobon-Podgorska J (1993). Givetian and Frasnian calcareous microbiotas of the Holy Cross Mountains. Acta Palaent Polonica 37: 255–289.
  • Rosenkrans RR (1934). Correlation studies of the central and south- central Pennsylvania bentonite occurrences. Am J Sci 17:
  • Sabirov AA (2004). Pre-Visean foraminifers from Central Asia and Kazakhstan. Paleontol J 38: 238–246.
  • Sachanski V, Göncüoğlu MC, Gedik I (2010). Late Telychian (early Silurian) graptolitic shales and the maximum Silurian highstand in the NW Anatolian Palaeozoic terranes. Palaeogeogr Palaeoecl 291: 419–428.
  • Şengör AMC, Natal’in BA (1996). Paleotectonics of Asia: fragment of a synthesis. In: Yin A, Harrison TM, editors. The Tectonic Evolution of Asia. Cambridge, UK: Cambridge University Press, pp. 486–640.
  • Środoń J (1984). X-ray powder diffraction identification of illitic materials. Clay Clay Miner 32: 337–349.
  • Sun SS, McDonough WF (1989). Chemical and isotopic systematics of oceanic basalts: implications for mantle composition and process. In: Saunders AD, Norry MJ, editors. Magmatism in Ocean Basins. London, UK: Geological Society of London Special Publication 42, pp. 313–345.
  • Türkmenoğlu AG (2001). A Paleozoic K-bentonite occurrence in Turkey. In: Mid-European Clay Conference’01, Stara Leusa, Slovakia, Book of Abstracts, p. 108.
  • Türkmenoğlu AG, Göncüoğlu MC, Bayraktaroğlu Ş (2009). Early Carboniferous K-bentonite formation around Bartın: geological implications. In: 2nd International Symposium on the Geology of the Black Sea Region, İstanbul, Turkey, p. 209.
  • Vachard D (1991). Parathuramminides et Moravamminides (Microproblematica) de l’emsien superieur de la formation Moniello (Cordilleres Cantabriques, Espagne). Revue de Paléobiologie 10: 255–299 (in French).
  • Vachard D (1994). Foraminiferes et Moravamminides du domaine Ligerien (Massif Armoricain, France). Palaeontographica Abt A 231: 1–92 (in French).
  • Warr LN, Rice AHN (1994). Interlaboratory standardisation and calibration of clay mineral crystallinity and crystallite size data. J Metamorph Geol 12: 141–152.
  • Weaver CE (1953). Mineralogy and petrology of some Ordovician K-bentonites and related limestones. Geol Soc Am Bull 64: 921–944.
  • Weaver CE (1961). Clay minerals of the Ouachita structural belt and adjacent foreland. In: Flawn PT, Goldstein A Jr, King PB, Weaver CE, editors. The Ouachita Belt. Austin, TX, USA: University of Texas Geology Publication 6120, pp. 147–162.
  • Wehrmann A, Yılmaz İ, Wilde V, Yalçın MN, Schindler E (2010). The Devonian coastline of northern Gondwana: sedimentary signatures of depositional environments at the land-sea transition (Taurides, Turkey). In: 7th International Symposium on Eastern Mediterranean Geology, Çukurova University, Adana, Turkey, p. 55.
  • Winchester JA, Floyd PA (1977). Geochemical discrimination of different magma series and their differentiation products using immobile elements. Chem Geol 20: 325–344.
  • Yalçın MN, Yılmaz İ (2010). Devonian in Turkey – a review. Geol Carpath 61: 235–253.