A microscopic approach to the pedogenic formation of palygorskite associated with Quaternary calcretes of the Adana area, southern Turkey

Quaternary calcretes in the Adana area (southern Turkey) are widespread and occur in a variety of forms such as nodular, columnar/tubular, fracture-infill, laminated hardpan, and conglomeratic crusts. Palygorskite associated with calcrete nodules, tubes, and fracture-infills in the columnar horizon and adjacent host-rock mudstones suggests a cogenetic formation. The Beta-fabric (biogenic) constituents and stable isotope values of calcretes support a pedogenic origin for calcretes and also palygorskite. Extensions of palygorskite fibre and fibre bundles from euhedral to subhedral calcite crystals in calcretes and from smectite flakes in adjacent host-rock mudstone suggest an authigenic origin related to calcretisation in which precipitation and dissolution/precipitation are the main processes for palygorskite formation, respectively. The presence of palygorskite in subspherical aggregates containing calcite crystals, and with smectitic clay coatings around the palygorskite aggregate, similarly suggests a relationship of pedogenic evolution between the 2 clays. Palygorskite precipitated in a vadose zone from strongly evaporated alkaline water, rich in Si and Mg and low in Al and Fe, at elevated temperatures and at an advanced stage of calcrete formation. Development of palygorskite mainly on relict calcite crystals indicates its formation during or shortly following calcite formation in calcretes. Palygorskite precipitation on relative large crystal surfaces has resulted in encrusted and platy fan-like crystal morphologies, whereas its nucleation on the crystal edge relief triggers fibre-like morphologies from crystal edges.

A microscopic approach to the pedogenic formation of palygorskite associated with Quaternary calcretes of the Adana area, southern Turkey

Quaternary calcretes in the Adana area (southern Turkey) are widespread and occur in a variety of forms such as nodular, columnar/tubular, fracture-infill, laminated hardpan, and conglomeratic crusts. Palygorskite associated with calcrete nodules, tubes, and fracture-infills in the columnar horizon and adjacent host-rock mudstones suggests a cogenetic formation. The Beta-fabric (biogenic) constituents and stable isotope values of calcretes support a pedogenic origin for calcretes and also palygorskite. Extensions of palygorskite fibre and fibre bundles from euhedral to subhedral calcite crystals in calcretes and from smectite flakes in adjacent host-rock mudstone suggest an authigenic origin related to calcretisation in which precipitation and dissolution/precipitation are the main processes for palygorskite formation, respectively. The presence of palygorskite in subspherical aggregates containing calcite crystals, and with smectitic clay coatings around the palygorskite aggregate, similarly suggests a relationship of pedogenic evolution between the 2 clays. Palygorskite precipitated in a vadose zone from strongly evaporated alkaline water, rich in Si and Mg and low in Al and Fe, at elevated temperatures and at an advanced stage of calcrete formation. Development of palygorskite mainly on relict calcite crystals indicates its formation during or shortly following calcite formation in calcretes. Palygorskite precipitation on relative large crystal surfaces has resulted in encrusted and platy fan-like crystal morphologies, whereas its nucleation on the crystal edge relief triggers fibre-like morphologies from crystal edges.

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  • Akbulut A, Kadir S (2003). The geology and origin of sepiolite, palygorskite and saponite in Neogene lacustrine sediments of the Serinhisar-Acpayam basin, Denizli, SW Turkey. Clays Clay Miner 51: 279–292.
  • Allen BL, Hajek BF (1989). Mineral occurrence in soil environment. In: Dixon JB, Weed SB, editors. Minerals in Soil Environments. Soil Science Society of America Book Series 1. Madison, WI, USA: Soil Science Society of America, pp. 199–278.
  • Alonso-Zarza AM (1999). Initial stages of laminar calcrete formation by roots: examples from the Neogene of central Spain. Sediment Geol 126: 177–191.
  • Alonso-Zarza AM, Arenas C (2004). Cenozoic calcretes from the Teruel Graben, Spain: microstructure, stable isotope geochemistry and environmental significance. Sediment Geol 167: 91–108.
  • Altaner SP, Ylagan RF (1997). Comparison of structural models of mixed-layer illite/smectite and reaction mechanisms of smectite illitization. Clays Clay Miner 45: 517–533.
  • Atalay I (1996). Palaeosols as indicators of the climatic changes during Quaternary period in S Anatolia. J Arid Environ 32: 23–35.
  • Bajnoczi B, Horvath Z, Demeny A, Mindszenty A (2006). Stable isotope geochemistry of calcrete nodules and septarian concretions in a Quaternary ‘red clay’ paleovertisol from Hungary. Isot Environ Healt Stud 42: 335–350.
  • Botha GA, Hughes JC (1992). Pedogenic palygorkite and dolomite in a late Neogen sedimentary succession, Northwestern Transvaal, South Africa. Geoderma 53: 139–154.
  • Boutton TW (1991). Stable carbon isotope ratios of natural materials, II. Atmospheric, terrestrial, marine, and freshwater environments. In: Coleman C, Fry B, editors. Carbon Isotope Techniques. New York, NY, USA: Academic Press, pp. 173–186.
  • Bouza PJ, Simón M, Aquilar J, del Valle H, Rostagno M (2007). Fibrous-clay minerals formation and soil evolution in aridisols of NE Patagonia, Argentina. Geoderma 139: 38–50.
  • Brindley GW (1980). Quantitative X-ray analysis of clays. In: Brindley GW, Brown G, editors. Crystal Structures of Clay Minerals and Their X-ray Identification. Mineralogical Society Monograph 5. London, UK: Mineralogical Society, pp. 411–438.
  • Cerling TE (1984). The stable isotopic composition of modern soil carbonate and its relationship to climate. Earth Planet Sci Lett 71: 229–240.
  • Cerling TE (1992). Use of carbon isotopes in paleosols as indicator of the PCO2 the paleoatmosphere. Global Biogeochem Cycles 6: 307–314.
  • Chahi A, Duplay J, Lucas J (1993). Analyses of palygorskite and associated clays from the Jbel Rhassoul (Morocco): chemical characteristics and origin of formation. Clays Clay Miner 41: 401–411.
  • Colson J, Cojan I, Thirty M (1998). A hydrogeological model for palygorskite formation in the Danian continental facies of the Provence Basin (France). Clay Miner 33: 333–347.
  • Dudek T, Cuadros J, Fiore S (2006). Interstratified kaolinite-smectite: Nature of the layers and mechanism of smectite kaolinization. Am Mineral 91: 159–170.
  • Elprince AM, Mashhady AS, Aba-Husayn MM (1979). The occurrence of pedogenic palygorskite (attapulgate) in Saudi Arabia. Soil Sci 128: 211–218.
  • Eren M (2011). Stable isotope geochemistry of Quaternary calcretes in the Mersin area, southern Turkey - a comparison and implications for their origin. Chem Erde 71: 31–37.
  • Eren M, Kadir S, Hatipoğlu Z, Gül M (2004). Caliche Development in Mersin Area. TÜBİTAK Project No. 102Y036. Ankara, Turkey: TÜBİTAK (in Turkish with English abstract).
  • Eren M, Kadir S, Hatipoğlu Z, Gül M (2008). Quaternary calcrete development in the Mersin area, southern Turkey. Turkish J Earth Sci 17: 763–784.
  • Eren M, Kaplan MY, Kadir S (2007). Petrography, geochemistry and origin of Lower Jurassic dolomites in the Aydıncık area, Mersin, southern Turkey. Turkish J Earth Sci 16: 339–362.
  • Farmer VC (1974). Infrared spectra of minerals. In: Farmer VC, editor. Monograph 4. London, UK: Mineralogical Society, pp. 331–363.
  • Foster MD (1953). Geochemical studies of clay minerals. II Relation between ionic substitution and swelling in montmorillonite. Am Mineral 38: 994–1006.
  • Frost RL, Locos OB, Ruan J, Kloprogge JT (2001). Nearinfrared and mid-infrared spectroscopic study of sepiolites and palygorskites. Vib Spectrosc 27: 1–3.
  • Galán E, Pozo M (2011). Palygorskite and sepiolite deposits in continental environments. Description, genetic patterns and sedimentary settings. In: Galán E, Singer E, editors. Developments in Palygorskite-Sepiolite Research. A New Outlook on these Nanomaterials. Developments in Clay Science, Vol. 3. Amsterdam, the Netherlands: Elsevier, pp. 125–173.
  • Garcia-Romero E, Suárez M (2010). On the chemical composition of sepiolite and palygorskite. Clays Clay Miner 58: 1–20.
  • Gong SY, Mii HS, Wei KY, Horng CS, You CF, Huang FW, Chi WR, Yui TZ, Torng PK, Huang ST et al. (2005). Dry climate near the Western Pacific Warm Pool: Pleistocene caliches of the Nansha Islands, South China Sea. Palaeogeogr Palaeoclimatol Palaeoecol 226: 205–213.
  • Goudie AS (1973). Duricrusts in Tropical Landscapes. Oxford, UK: Clarendon Press.
  • Gürbüz K (1999). Regional implications of structural and eustatic controls in the evolution of submarine fans: an example from the Miocene Adana Basin, southern Turkey. Geol Mag 136: 311–319.
  • Hassouba H, Shaw HF (1980). The occurrence of palygorskite in the Quaternary sediments of the coastal plain of North-west Egypt. Clay Miner 15: 77–83.
  • Hillier S, Pharande AL (2008). Contemporary pedogenic formation of palygorskite in irrigation-induced, saline-sodic, shrink-swell soils of Maharashtra India. Clays Clay Miner 56: 531–548.
  • Hower J, Eslinger E, Hower M, Perry E (1976). The mechanism of burial diagenetic reactions in argillaceous sediments: 1. Mineralogical and chemical evidence. Geol Soc Am Bull 87: 725–737.
  • Inglès M, Anadón P (1991). Relationship of clay minerals to depositional environment in the non-marine Eocene Pontils Group, SE Ebro basin (Spain). J Sediment Petrol 61: 926–939.
  • Inoue A, Meunier A, Beaufort D (2004) Illite-smectite mixed- layer minerals in felsic volcaniclastic rocks from drill cores, Kakkonda, Japan. Clays Clay Miner 52: 66–84.
  • James NP, Choquette PW (1984). Diagenesis 9. Limestones - The meteoric diagenetic environment. Geosci Can 11: 161–194.
  • Jimenez De Cisneros C, Molina JM, Nieto LM, Ruiz-Ortiz PA, Vera JA (1993). Calcretes from a palaeosinkhole in Jurassic palaeokarst (Subbetic, southern Spain). Sediment Geol 87: 13–24.
  • Kadir S, Eren M (2008). The occurrence and genesis of clay minerals associated with Quaternary caliches in the Mersin area, southern Turkey. Clays Clay Miner 56: 244–258.
  • Kadir S, Eren M, Atabey E (2010). Dolocretes and associated palygorskite occurrences in siliciclastic red mudstones of the Sariyer formation (Middle Miocene), southeastern side of the Çanakkale strait, Turkey. Clays Clay Miner 58: 205–219.
  • Kadir S, Eren M, Külah T, ÖnalgilN, Cesur M,Gürel A (2014). Genesis of Late Miocene-Pliocene lacustrine palygorskite and calcretes from Kırşehir, central Anatolia, Turkey. Clay Miner 49: 433–454.
  • Kaplan MY, Eren M, Kadir S, Kapur S (2013). Mineralogical, geochemical and isotopic characteristics of Quaternary calcretes in the Adana region, southern Turkey: Implications on their origin. Catena 101: 164–177.
  • Kapur S, Çavuşgil VS, Fitzpatrick EA (1987). Soil-calcrete (caliche) relationship on a Quaternary surface of the Cukurova Region, Adana (Turkey). In: Federoff N, Bresson LM, Courty MA, editors. Soil Micromorphology. Paris, France: Association Française pour L’Etude du sol, pp. 597–603.
  • Kapur S, Çavuşgil VS, Şenol M, Gürel N, Fitzpatrick E A (1990). Geomorphology and pedogenic evolution of Quaternary calcretes in the northern Adana Basin of southern Turkey. Z Geomorphol 34: 49–59.
  • Kapur S, Saydam C, Akça E, Çavuşgil VS, Karaman C, Atalay I, Özsoy T (2000). Carbonate pools in soil of the Mediterranean: A case study from Anatolia. In: Lal R, Kimble JM, Eswaran H, Stewart BA, editors. Global Climate Change and Pedogenic Carbonates. Boca Raton, FL, USA: Lewis Publishers, pp. 187–212.
  • Kapur S, Yaman S, Gokçen SL, Yetiş C (1993). Soil stratigraphy and Quaternary caliche in the Misis area of the Adana Basin, southern Turkey. Catena 20: 431–445.
  • Karakaya N, Karakaya MÇ, Temel A (2011). Mineralogical and geochemical characteristics and genesis of the sepiolite deposits at Polatlı Basin (Ankara, Turkey). Clays Clay Miner 59: 286–314.
  • Karakaya N, Karakaya MÇ, Temel A, Küpeli Ş, Tunoğlu C (2004). Mineralogical and chemical characterization of the sepiolite occurrences at Karapınar (Konya Basin, Turkey). Clays Clay Miner 52: 495–510.
  • Krekeler MPS, Hammerly E, Rakovan J, Guggenheim S (2005). Microscopy studies of the palygorskite-to-smectite transformation. Clays Clay Miner 53: 92–99.
  • Küçükuysal C, Kapur S (2014). Mineralogical, geochemical and micromorphological evaluation of the Plio-Quaternary paleosols and calcretes from Karahamzalı, Ankara (Central Turkey). Geol Carpath 65: 241–253.
  • Millot G (1970). Geology of Clays. New York, NY, USA: Springer- Verlag.
  • Moore DM, Reynolds RC (1989). X-ray diffraction and the identification and analysis of clay minerals. Oxford, UK: Oxford University Press.
  • Nash DJ, McLaren SJ (2003). Kalahari valley calcretes: their nature, origins, and environmental significance. Quatern Int 111: 3–22.
  • Özer AM, Wieser A, Göksu HY, Müller P, Regulla DF, Erol O (1989). ESR and TL age determination of caliche nodules. Int J Radiat Appl Instrum A 40: 1159–1162.
  • Pimentel NLV (2002). Pedogenic and early diagenetic processes in Palaeogene alluvial fan and lacustrine deposits from the Sado Basin (S Portual). Sediment Geol 148: 123–138.
  • Purvis K, Wright VP (1991). Calcretes related to phreatophytic vegetation from the Middle Triassic Otter Sandstone of South West England. Sedimentology 38: 539–551.
  • Rodas M, Luque FJ, Mas R, Garzon MG (1994) Calcretes, palycretes and silcretes in the Paleogene detrital sediments of the Dueo and Tajo Basins, central Spain. Clay Miner 29: 273–285.
  • Rogers LER, Martin AE, Norrish K (1954). The occurrence of palygorskite near Ipswich, Queensland. Mineral Mag 30: 534– 540.
  • Sánchez C, Galán E (1995) An approach to the genesis of palygorskite in a Neogene-Quaternary continental basin using principal factor analysis. Clay Miner 30: 225–238.
  • Shaaban MN (2004). Diagenesis of the lower Eocene Thebes Formation, Gebel Rewagen area, Eastern Desert, Egypt. Sediment Geol 165: 53–65.
  • Singer A (1979). Palygorskite in sediments: detrital, diagenetic, or neoformed-a critical review. Geol Rundsch 68: 996–1008.
  • Singer A (1989). Palygorskite and sepiolite group minerals. In: Dixon JB, Weed SB, editors. Minerals in Soil Environments. Soil Science Society of America Book Series 1. Madison, WI, USA: Soil Science Society of America, pp. 829–872.
  • Singer A, Norrish K (1974). Pedogenic palygorskite occurrences in Australia. Am Mineral 59: 508–517.
  • Strong GE, Giles JRA, Wright VP (1992). A Holocene calcrete from North Yorkshire, England: implications for interpreting palaeoclimates using calcretes. Sedimentology 39: 333–347.
  • Suárez M, García-Romero E (2006). FTIR spectroscopy study of palygorskite: Influence of the composition of the octahedral sheet. Appl Clay Sci 31: 154–163.
  • Suárez M, Robert M, Elsass F, Martin Pozas JM (1994). Evidence of a precursor in the neoformation of palygorskite- new data by analytical electron microscopy. Clay Miner 29: 255–264.
  • Tucker ME, Wright VP (1990). Carbonate Sedimentology. Oxford, UK: Blackwell Scientific Publications.
  • Verrecchia EP, Le Coustumer MN (1996). Occurrence and genesis of palygorskite and associated clay minerals in a Pleistocene calcrete complex, Sde Bowuer, Negev Desert, Israel. Clay Miner 31: 183–202.
  • Wang MK, Tseng PC, Chang SS, Ray DT, Shau YH, Shen YW, Chen RC, Chiang PN (2009). Origin and mineralogy of sepiolite and palygorskite from the Tuluanshan formation, eastern Taiwan. Clays Clay Miner 57: 521–530.
  • Wang Y, Nahon D, Merino E (1993). Geochemistry and dynamics of calcrete genesis in semi-arid regions. Chem Geol 107: 349–351.
  • Watts NL (1980). Quaternary pedogenic calcretes from the Kalahari (southern Africa): mineralogy, genesis and diagenesis. Sedimentology 27: 661–686.
  • Weaver CE, Pollard LD (1973) The Chemistry of Clay Minerals. New York, NY, USA: Elsevier.
  • Wright VP, Tucker ME (1991). Calcretes. Oxford, UK: Blackwell Scientific Publications.
  • Yalçın H, Bozkaya Ö (2011). Sepiolite-palygorskite occurrences in Turkey. In: Galan E, Singer A, editors. Developments in Clay Science, Vol. 3. Amsterdam, the Netherlands, pp. 175–200.
  • Yalçın MN, Görür N (1983). Sedimentological evolution of the Adana Basin. In: Tekeli O, Göncüoğlu MC, editors. Geology of the Taurus Belt. Proceedings of International Tauride Symposium. Ankara, Turkey: Mineral Research and Exploration Institute of Turkey (MTA), pp. 165–172.
  • Yeniyol M (2012). Geology and mineralogy of a sepiolite-palygorskite occurrence from SW Eskişehir (Turkey). Clay Miner 47: 93– 104.
  • Yetiş C (1988). Reorganization of the Tertiary stratigraphy in the Adana Basin, southern Turkey. Stratigr Newsl 20: 43–58.
  • Yetiş C, Kelling G, Gökçen SL, Baroz F (1995). A revised stratigraphic framework for later Cenozoic sequences in the northeastern Mediterranean region. Geol Rundsch 84: 794–812.
  • Yılmaz K (1999). The genesis of smectite and palygorskite on Harran Plain’s soil series. Tr J Agric For 23: 636–642.