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Hypogene and supergene alteration of the Late Palaeozoic Ratburi Limestone during the Mesozoic and Cenozoic (Thailand, Surat Thani Province). Implications for the concentration of mineral commodities and hydrocarbons

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Abstract

An interdisciplinary study of the Upper Carboniferous to Middle Permian Ratburi Group, Peninsular Thailand, is presented. The investigation involved sedimentary petrography, inorganic geochemistry, Sr, C, O isotope analyses, micropalaeontology as well as radio-carbon age dating. Emphasis was placed on the post-depositional evolution of the Ratburi Limestone in the Surat Thani Province. The Holocene chemical residues and the various calcite and dolomite minerals which have formed since the Late Palaeozoic in the Ratburi Limestone are the product of a complex, multistage alteration which is called supergene and hypogene karstifications, respectively. Sedimentation took place in a shelf environment with some reefs evolving during the late Murgabian at the shelf margin. There was no pre-concentration of elements, except for Ca and F during sedimentation. Diagenetic neomorphism and cementation under marine and freshwater conditions caused the Ratburi Limestone to convert into a marble-like rock. Fabric-selective dolomitization is of local scale and has impacted only on part of the Ratburi Limestone during the Lower to Upper Permian. A significant enhancement of pore space and better conduits were generated during the Late Cretaceous epithermal alteration. The most favorable conditions for the accumulation of metals were provided during the high-temperature stage of epithermal alteration when a low-metal concentration with As, Zn, Sb, U, Co and Pb existed. Unlike the other elements, Sb was subject to a multiphase concentration, giving rise to a considerable Sb deposit in the region. The most recent stage of karstification produced numerous caves, dripstones, tufa terraces and encrustations around brine pools in the study area. This alteration originated from per descensum and per ascensum processes which may be traced back to 15,000 years before present. The alteration of the Ratburi Limestone may be subdivided into two parts. The prograde post-depositional alteration, beginning with diagenesis, reached its temperature climax during epithermal subsurface alteration I. The retrograde branch of alteration lasted until the most recent times. The initial stages deposition and diagenesis took place under more or less closed-system conditions relative to the succeeding stages of the prograde alteration which saw the strongest influx of metal-bearing brine during the epithermal stage I. The retrograde branch of alteration is “element-conservative”.

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References

  • Abimbola AF, Akande SO (1997) Fluid inclusions in fluorite from the F-Pb-Zn deposits of Middle Benue Trough Nigeria. Miner Wealth 102:39–44

    CAS  Google Scholar 

  • Amadi UMP, Shaffer NR (1986) Low sulphate groundwater and its relationship to the gypsum-fluorite replacement in the karst terrains of the Southern Indiana, USA, vol 161. Karst water resources IAHS publication, pp 449–466

  • Anand RR, Phang C, Wildman JE, Lintern MJ (1997) Genesis of some calcretes in the southern Yilgarn Craton, Western Australia; implications for mineral exploration. Aust J Sci 44:87–103

    CAS  Google Scholar 

  • Andrew CJ (1991) Irish zinc deposits—style and process in an orefield context. Miner Industry Int 1001:16

    Google Scholar 

  • Aoki M, Comsti EC, Lazo FB (1993) Advanced argillic alteration and geochemistry of alunite in an evolving hydrothermal system at Baguio, Northern Luzon, Philippines. Resour Geol 43:155–164

    CAS  Google Scholar 

  • Arribas A Jr, Cunningham CG, Rytuba JJ, Rye RO, Kelly WC, Podwysocki MH, McKee EH, Tosdal RM (1995) Geology, Geochronology, Fluid inclusions, and Isotope Geochemistry of Rodalquilar Gold Alunite Deposit. Spain Econ Geol 90:795–822

    CAS  Google Scholar 

  • Baird AM (1992) The sedimentological and diagenetic evolution of the Ratburi Limestone, northern Peninsular Thailand. PhD Thesis, University of London, p 318

  • Booler J, Tucker ME (2002) Distribution and geometry of facies and early diagenesis: the key to accommodation space variation and sequence stratigraphy: upper cretaceous congost carbonate platform, Spanish Pyrenees. Sediment Geol 146:225–247

    Google Scholar 

  • Bruno H (2000) Die Flotation von Cerussit-Bleierzen in Thailand. Bergbau 51:56–64

    Google Scholar 

  • Burchette TP, Wrigth VP (1992) Carbonate ramp depositional systems. Sediment Geol 79:3–57

    Article  Google Scholar 

  • Chuenbunchon S, Heward AP, Mäkel G (1997) The reservoir geology of the pre-tertiary sequences of the Nang Nuan A and B structures, and the B 6/27 concession, offshore, Gulf of Thailand. In: The international conference on stratigraphy and tectonic evolution of Southeast Asia and the South Pacific (GEOTHAI 97), 19–24 August 1997, Bangkok, pp 1–16

  • Chuenbunchom S, Heward AP, Mäkel G (2000) The reservoir geology of the “pre-tertiary” sequences of palaeokarst structures, gulf of Thailand. J Geol Soc Thai 1:8–18

    Google Scholar 

  • Craig H (1965) The measurement of oxygen isotope palaeotemperatures. In: Tongiorgi E (ed) Stable isotopes in oceanographic studies and palaeotemperatures: Pisa, Consiglio Nazionale delle Ricerche Laboratorio di Geologia Nucleare, pp 161–182

  • Department of Mineral Resources (1975) Copper-lead-zinc.—1:2,500,00. Geological Survey Division, DMR, Bangkok

  • Department of Mineral Resources (1997a) Thailand’s minerals. Industrial Miner 363:62–69

    Google Scholar 

  • Department of Mineral Resources (1997b) Mineral potential map of Thailand. 1:2,500,00. Geological Survey Division, DMR, Bangkok

  • Department of Mineral Resources (1999) Geological Map of Thailand 1:2,500,00.- Geological Survey Division, DMR, Bangkok

    Google Scholar 

  • Dill HG (2001) The geology of aluminium phosphates and sulphates of the alunite supergoup: a review. Earth Sci Rev 53:25–93

    Article  Google Scholar 

  • Dill HG, Pöllmann H, Bosecker K, Hahn L, Mwiya S (2002) Supergene mineralization in mining residues of the Matchless cupreous pyrite deposit (Namibia)—a clue to the origin of modern and fossil duricrusts in semiarid climates. J Geochem Explor 75:43–70

    Article  CAS  Google Scholar 

  • Dunham RJ (1962) Classification of carbonate rocks according to depositional texture. In: Ham WE (ed) Classification of carbonate rocks. Am Assoc Petrol Geol Mem 1:108–121

    Google Scholar 

  • Dzulynski S, Sass-Gustkiewicz M (1989) Pb-Zn ores. In: Bosak P, Ford D, Glazek J, Horacek I (eds) Palaeokarst—a systematic and regional review. Amsterdam, Elsevier, pp 377–397

    Google Scholar 

  • Ebert SW, Rye RO (1997) Secondary precious metal enrichment by steam-heated fluids in the Crofoot-Lewis Hot Spring Gold-Silver deposit and relation to palaeoclimate. Econ Geol 92:578–600

    CAS  Google Scholar 

  • Emrich K, Ehhalt DH, Vogel JC (1970) Carbon isotope fractionation during the precipitation of calcium carbonate. Earth Planet Sci Lett 8:363–371

    Article  CAS  Google Scholar 

  • Esteban M, Klappa CF (1983) Subaerial exposure environment. In: Scholle PA, Bebout D, Moore CH (eds) Carbonate depositional environment. AAPG Memoir 33:1–95

    Google Scholar 

  • Flügel E (1978) Mikrofazielle Untersuchungsmethoden von Kalken. Springer, Berlin Heidelberg New York

    Google Scholar 

  • Fohrer B (1997) Ostracoden aus dem Oberkarbon und Unterperm der Karnischen Alpen (Österreich): Systematik, Biostratigraphie und Palökologie. Jahrbuch Geologische Bundesanstalt 140:99–191

    Google Scholar 

  • Folk RL (1959) Practical petrographic classification of limestones. Am Assoc Petrol Geol 19:730–781

    Google Scholar 

  • Fontaine H (1986) The Permian of Southeast Asia. CCOP Technical Bulletin, Tokyo 18:171

  • Friedman GM (1965) Terminology of crystallization textures and fabrics in sedimentary rocks. J Sediment Petrol 35:643–655

    CAS  Google Scholar 

  • Friedman G, Sanders JE, Kopaska-Merkel DC (1992) Principles of sedimentary deposits. Stratigraphy and sedimentology. Macmillan, New York, p 717

    Google Scholar 

  • Gardner LS (1967) Antimony deposits of Thailand. US Geol Surv Rep 13:1–45

    Google Scholar 

  • Gillieson D (1996) Caves—processes, development, management. Blackwell, Oxford, p 324

    Google Scholar 

  • Goudie AS, Pye K (1983) Chemical sediments and geomorphology—precipitates and residua in the near-surface environment. Academic, London, p 439

    Google Scholar 

  • Harrison DJ, Chaodumrong P, Charusribandhu M (1997) Assessment of limestone resources from Surat Thani Province, Thailand. In: The international conference on stratigraphy and tectonic evolution of Southeast Asia and the South Pacific (GEOTHAI 97), 19–24 August 1997, Bangkok, pp 640–649

  • Hedenquist JW, Matsuhisa Y, Izawa E, White NC, Giggenbach WF, Aoki M (1994) Geology, geochemistry, and origin of high sulphidation Cu-Au mineralization in the Nansatsu District, Japan. Econ Geol 89:1–30

    CAS  Google Scholar 

  • Herrmann W, Blake M, Doyle M, Huston D, Kamprad J, Merry N, Pontual S (2001) Short wavelength infrared (SWIR) spectral analysis of hydrothermal alteration zones associated with base metal sulphide deposits at Rosebery and Western Tharsis, Tasmania, and Highway-Reward, Queensland. Econ Geol 96:939–955

    CAS  Google Scholar 

  • Heydaria E, Hassandzadehb J, Wadec WJ (2000) Geochemistry of central Tethyan Upper Permian and Lower Triassic strata, Abadeh region. Iran Sediment Geol 137:85–99

    Article  Google Scholar 

  • Holterhoff PF (1997) Filtration models, guilds, and biofacies: Crinoid paleoecology of the Stanton Formation (Upper Pennsylvanian), midcontinent, North America. Palaeogeogr Palaeoclimatol Palaeoecol 130:177–208

    Article  Google Scholar 

  • Hovorka S, Nance HS, Kerans C (1993) Parasequence geometry as a control on permeability evolution: examples from the San Andres and Greyburg formation in the Gualalupe Mountains, New Mexico. In: Loucks RG, Sarg JF (eds) Carbonate sequence stratigraphy. Mem Am Assoc Petrol Geol 57:493–514

    Google Scholar 

  • Howart RJ, McArthur JM (1997) Statistics for strontium isotope stratigraphy with a look-up table version. J Geol 105:441–456

    Google Scholar 

  • Irwin H, Curtis C, Coleman M (1977) Isotopic evidence for source of diagenetic carbonates formed during burial of organic rich sediments. Nature 269:209–213

    CAS  Google Scholar 

  • James NP, Choquette PW (1988) Palaeokarst. Springer, Berlin Heidelberg New York, p 416

    Google Scholar 

  • James NP, Choquette PW (1990a) Limestones—the sea-floor diagenetic environment. In: McIlreath IA, Morrow DW (eds) Diagenesis. Geoscience Canada Reprint Series 4:13–34

    Google Scholar 

  • James NP, Choquette PW (1990b) Limestones—the meteoric diagenetic environment. In: McIlreath IA, Morrow DW (eds) Diagenesis. Geoscience Canada Reprint Series 4:35–73

    Google Scholar 

  • Jones GV (1995) The Duddar Fe-Zn-Pb-Ba deposit, Baluchistan, Pakistan. Annual Review-Irish Assoc Econ Geol 1995:101–111

    Google Scholar 

  • Kaufman J (1994) Numerical models of fluid flowing carbonate platforms-implications for dolomitization. J Sediment Res Sect A 64:128–139

    Google Scholar 

  • Keeling CD (1958) The concentration and isotopic abundance of carbon dioxide in rural areas. Geochim Cosmochim Acta 13:322–334

    Article  CAS  Google Scholar 

  • Khadkikar AS, Merh SS, Malik JN, Chamyal LS (1998) Calcretes in semi-arid alluvial systems; formative pathways and sinks. Sediment Geol 116:251–260

    Article  CAS  Google Scholar 

  • Land LS (1980) The isotopic and trace element geochemistry of dolomite: the state of the art. In: Zenger DH, Dunham JB, Ethington RL (eds) Concepts and models of dolomitization. Spec Publ Soc Econ Palaeont Miner (SEPM) Tulsa 28:87–110

    Google Scholar 

  • Loucks RG, Handford CR (1992) Origin and recognition of fractures, breccias, and sediment fills in palaeocave-reservoir networks. SEPM Publ 92(33):31–44

    Google Scholar 

  • Love DA, Clark AH, Hodgon CJ, Mortensen JK, Archibald DA, Farrar E (1998) The timing of adularia-sericite-type mineralization and alunite-kaolinite-type alteration, Mount Skukum epithermal gold deposit, Yuikon Territory, Canada,40Ar/39Ar and U–Pb geochronology. Econ Geol 93:437–462

    CAS  Google Scholar 

  • Machel HG, Lonnee J (2002) Hydrothermal dolomite-a product of poor definition and imagination. Sediment Geol 152:163–171

    Article  CAS  Google Scholar 

  • Magaritz M, Anderson RY, Holser WT, Saltzman ES, Garber J (1983) Isotope shifts in the Late Permian of the Delaware Basin, Texas, precisely timed by varved sediments. Earth Planet Sci Lett 66:111–124

    Article  CAS  Google Scholar 

  • Mark H (1991) Karststudien in Thailand. Bochumer Geogr Arbeiten 54:1–154

    Google Scholar 

  • Mateau E, Klappa CF (1983) Subaerial exposure environment. In: Scholle PA, Bebout DG, Moore CH (eds) Carbonate depositional environments. AAPG Mem 33:2–54

    Google Scholar 

  • Mazzullo SJ (1992) Geochemical and neomorphic alteration of dolomite, a review. Carbonates Evaporites 7:21–37

    Google Scholar 

  • McCrea JM (1950) The isotope chemistry of carbonates and a palaeotemperature scale. J Chem Phys 18:849–957

    CAS  Google Scholar 

  • McKenzie JA (1981) Holocene dolomitization of calcium carbonate sediments from the coastal sabkhas of Abu Dhabi UAE: a stable isotope study. J Geol 89:185–198

    CAS  Google Scholar 

  • Molenaar N, Zijlstrab JJP (1997) Differential early diagenetic low-Mg calcite cementation and rhythmic hardground development in Campanian-Maastrichtian chalk. Sediment Geol 109:261–281

    Article  Google Scholar 

  • Nakinbodee V, Wongwanich T, Lumjuan A (1985) Geological map of Changwat Surat Thani, scale 1:250,000. Geological Survey Division, DMR, Bangkok

    Google Scholar 

  • Netterberg F, Caiger JH (1983) A geotechnical classification of calcretes and other pedocretes. In: Wilson RCL (ed) Residual deposits: surface related weathering processes and materials. Geol Soc Spec Publ 11:235–243, Blackwell, London

    Google Scholar 

  • Neumann N, Sandiford M, Foden J (2000) Regional geochemistry and continental heat flow; implications for the origin of the South Australian heat flow anomaly. Earth Planet Sci Lett 183:107–120

    Article  CAS  Google Scholar 

  • O‘Neil JR, Clayton RN, Mayeda TK (1969) Oxygen isotope fractionation in divalent metal carbonates. J Chem Phys 51:5547–5558

    Article  Google Scholar 

  • Polyak VJ, Guven N (1996) Alunite, natroalunite, and hydrated halloysite in Carlsbad Cavern. Clays Clay Miner 44:843–850

    CAS  Google Scholar 

  • Polyak VJ, McIntosh WC, Guven N, Provencio P (1998) Age and origins of Carlsbad Cavern and related caves from 40Ar/39Ar alunite. Science 279:1919–1922

    Article  CAS  PubMed  Google Scholar 

  • Purnachandra RV, Thamban M (1997) Dune associated calcretes, rhizoliths and palaeosols from the western continental shelf of India. J Geol Soc India 49:297–306

    Google Scholar 

  • Qing H, Mountjoy EW (1994a) Formation of coarsely crystalline, hydrothermal dolomite reservoirs in the Presqu‘íle Barrier, Western Canada Sedimentary Basin. AAPG Bull 78:55–77

    CAS  Google Scholar 

  • Qing H, Mountjoy EW (1994b) Rare earth element geochemistry of dolomites in the Middle Devonian Presqu‘íle barrier, Western Canada Sedimentary Basin: implications for fluid-rock ratios during dolomitization. Sedimentology 41:787–804

    CAS  Google Scholar 

  • Radke BH, Mathis RL (1980) On the formation and occurrence of saddle dolomite. J Sediment Petrol 50:1149–1168

    CAS  Google Scholar 

  • Railsback LB, Hood EC (2001) A survey of multi-stage diagenesis and dolomitization of Jurassic limestones along a regional shelf-to-basin transect in the Ziz Valley, Central High Atlas Mountains, Morocco. Sediment Geol 139:285–317

    Article  CAS  Google Scholar 

  • Sangster DF (1986) Classification, distribution and grade-tonnage summaries of Canadian lead-zinc deposits. Geol Surv Can Rep 37:1–68

    Google Scholar 

  • Saunders CM, Strong DF, Sangster DF (1992) Carbonate-hosted lead-zinc deposits of western Newfoundland. Can Geol Surv Bull 419:1–78

    Google Scholar 

  • Schidlowski M, Eichmann R, Junge ChE (1975) Carbon isotope geochemistry of the Precambrian Lomagundi carbonate province, Rhodesia. Geochim Cosmochim Acta 40:449–455

    Article  Google Scholar 

  • Stoffers P, Botz R (1994) Formation of hydrothermal carbonate in Lake Tanganyika, east-Central Africa. Chem Geol 115:117–122

    Article  CAS  Google Scholar 

  • Subias I, Moritz R, Fernandez-Nieto C (1998) Isotopic composition of strontium in the Valle de Tena (Spanish Central Pyrenees) fluorite deposits-relevance for the source of elements and genetic significance. Miner Dep 33:416–424

    Article  CAS  Google Scholar 

  • Tepsongkroh P (2000) Geoecology of karst topography in southern Thailand. Zeitschr F Geomorph Suppl Bd NF 122:247–272

    Google Scholar 

  • Thompson JFH, Abidin HZ, Both RA, Martosuroyo S, Rafferty WJ, Thompson AJB (1994) Alteration and epithermal mineralization in the Masupa Ria volcanic center, Central Kalimantan, Indonesia. J Geochem Explor 50:429–455

    Article  CAS  Google Scholar 

  • Toriyama R (1992) Summary of the Fusuline Faunas in Thailand and Malaysia. Bull Kitakyushu Mus Nat Hist 12:625–634

    Google Scholar 

  • Tucker ME (1990) Diagenetic processes, products and environments. In: Tucker ME, Wright VP (eds) Carbonate sedimentology. Blackwell, Oxford, pp 314–364

    Google Scholar 

  • Uhlig H (1994) Turmkarst und “Hong” im tropischen Meer Süd-Thailands. Geoökodynamik 15:197–217

    Google Scholar 

  • Verdoya M, Pasquale V, Chiozzi P, Kukkonen IT (1998) Radiogenic heat production in the Variscan crust; new determinations and distribution models in Corsica (north-western Mediterranean). Tectonophysics 291:63–75

    Article  CAS  Google Scholar 

  • Vikre PG (1998) Quartz-alunite alteration in the western part of the Virginia Range, Washoe and Storey counties. Nevada Econ Geol 93:338–346

    CAS  Google Scholar 

  • Warren JK (1999) Evaporites: their evolution and economics. Blackwell, Oxford, p 438

    Google Scholar 

  • Waterhouse JB (1981) Age of the Ratburi Limestone of southern Thailand. Geol Surv Mem 4:1–42

    Google Scholar 

  • Wellman P (1999) Gamma-ray spectrometric data; modelling to map primary lithology. Explor Geophys 30:167–172

    Google Scholar 

  • White DE (1974) Diverse origins of hydrothermal ore fluids. Econ Geol 69:954–973

    CAS  Google Scholar 

  • Wright VP (1992) A revised classification of limestones. Sediment Geol 76:177–185

    Article  Google Scholar 

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Acknowledgements

The senior author is indebted to the staff members of the Thai-German Cooperation Project, in particular to the leader A. Margane, who provided logistical support during the stay in Thailand. We like to extend our thanks also to our colleagues and the technical staff members from the Department of Mineral Resources who made our study in Thailand so effective through their wilfulness and continuous assistance. Chemical analyses have been performed in the chemical labs of the Federal Institute for Geosciences and Natural Resources, Hannover, under the conductance of U. Siewers and H. Wehner. Radiocarbon dating was performed by A. Techmer (Leibnitz Institute for Applied Geosciencesces, Hannover, Germany). Financial support by the Ministry of Development and Technical Cooperation of the Federal Republic of Germany to the Thai-German Cooperation Project is kindly acknowledged. We acknowledge with thanks the helpful comments on a first draft by J. Lonnee and P. Wright who reviewed the paper for the International Journal of Earth Sciences (Geologische Rundschau) and the editorial handling by W.-C. Dullo and H.G. Machel.

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Dill, H.G., Botz, R., Luppold, F.W. et al. Hypogene and supergene alteration of the Late Palaeozoic Ratburi Limestone during the Mesozoic and Cenozoic (Thailand, Surat Thani Province). Implications for the concentration of mineral commodities and hydrocarbons. Int J Earth Sci (Geol Rundsch) 94, 24–46 (2005). https://doi.org/10.1007/s00531-004-0439-y

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