Hostname: page-component-cd9895bd7-mkpzs Total loading time: 0 Render date: 2024-12-25T13:43:16.329Z Has data issue: false hasContentIssue false

K-Ar, δ18O and REE constraints on the genesis of ammonium illite from the Harghita Bãi hydrothermal system, Romania

Published online by Cambridge University Press:  09 July 2018

N. Clauer*
Affiliation:
Laboratoire d'Hydrologie et de Géochimie de Strasbourg (CNRS-UdS), 1 rue Blessig, 67084 Strasbourg, France
N. Liewig
Affiliation:
Institut Pluridisciplinaire Hubert Curien, UMR 7178, 23 rue Becquerel, 67087 Strasbourg, France
I. Bobos
Affiliation:
GIMEF- Departamento de Geologia, Universidade do Porto, 4099-002 Porto, Portugal
*

Abstract

Ammonium illite and ammonium illite-smectite mixed layers, together with potassium illite, smectite and minute amounts of kaolinite were identified in hydrothermally altered andesite rocks from the Harghita Bãi area of the Eastern Carpathians, Romania. K-Ar dating and oxygen isotope tracing, as well as rare-earth elemental analyses were made to provide new information on the timing and crystal-chemical processes characterizing the crystallization and further evolution of these illite-type mineral phases.

The combined results suggest the occurrence of hydrothermal activity in two distinct episodes with nucleation of two generations of illite-type particles of different chemistry and morphology. About 9.5 Ma ago, potassium illite crystallized in alteration halos of the porphyry Cu system, probably at a temperature of ~270ºC from fluids having a δ18O of ~2.9% (V-SMOW). Associated smectite seems to have precipitated slightly later in external alteration halos at a similar temperature, but from fluids depleted in alkalis and with a different δ18O. Alternately, ammonium-rich illite-smectite mixed layers formed very recently, less than ~1 million years ago at a temperature of ~90ºC from fluids of probable meteoric origin that altered the previously crystallized potassium illite, resulting in the crystallization of a new generation of ammonium illite-smectite mixed layers. Evidence of this dissolution-precipitation process is provided by a significant increase in the δ18O of the mixed-layer structures and by a significant change in their REE contents and distribution patterns. Occurrence of potassium in the ammonium-rich mixed layers probably relates to the progressive alteration of the first-generation potassium illite and a discrete concomitant take up of released K by the new NH4-rich interlayers of the ammonium mixed layered sequence.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2010

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bau, M. (1991) Rare earth element mobility during hydrothermal and metamorphic fluid-rock interaction and the significance of the oxidation state of europium. Chemical Geology, 93, 219230.Google Scholar
Bechtel, A., Elliott, W.C. & Oszczepalski, S. (1996) Indirect age determination of Kuperfschiefer-type mineralization in the Polish Basin by K/Ar dating of illite; preliminary results. Economic Geology, 91, 13101319.Google Scholar
Bechtel, A., Elliott, W.C., Wampler, J.M. & Oszczepalski, S. (1999) Clay Mineralogy, crystallinity, and K-Ar ages of illites within the Polish Zechstein Basin: implications for the age of Kupferschiefer mineralization. Economic Geology, 94, 261272.CrossRefGoogle Scholar
Bobos, I. (1995) Hydrothermal ammonium-bearing illite from Harghita Bai area; XRD, FR-spectroscopy, DTA and chemical analysis. Romanian Journal of Mineralogy, 77, Suppl., 1011.Google Scholar
Bobos, I. & Ghergari, L. (1999) Conversion of smectite to ammonium illite in the hydrothermal system of Harghita Bai, Romania; SEM and TEM investigations. Geologica Carpathica (Bratislava), 50, 379387.Google Scholar
Bonhomme, M., Thuizat, R., Pinault, Y., Clauer, N., Wendling, R. & Winkler, R. (1975) Méthode de datation Potassium-Argon. Appareillage et technique. Institut de Géologie, Université Louis Pasteur, Strasbourg, Note Technique, no. 3, 53 pp.Google Scholar
Brockamp, O., Zuther, M. & Clauer, N. (1987) Epigenetic-hydrothermal origin of the sedimenthosted Muellenbach uranium deposit, Baden- Baden, W-Germany. Monograph Series on Mineral Deposits, 27, 8798.Google Scholar
Čičel, B. & Machajdik, D. (1981) Potassium- and ammonium-treated montmorillonites; I, Interstratified structures with ethylene glycol and water. Clays and Clay Minerals, 29, 4046.CrossRefGoogle Scholar
Clauer, N. & Chaudhuri, S. (1995) Clays in Crustal Environments — Isotope Dating and Tracing. Springer Verlag, Heidelberg, Germany, 359 pp.Google Scholar
Clauer, N., Ey, F. & Gauthier-Lafaye, F. (1985) K-Ar dating of different rock types from the Cluff Lake uranium ore deposits (Saskatchewan-Canada). Pp. 4753 in. The Carswell Structure Uranium Deposits, Saskatchewan (Laine, R., Alonso, D. & Svab, M., editors) Special Paper, Geological Association of Canada, 29. Google Scholar
Clayton, R.N. & Mayeda, T.K. (1963) The use of bromine pentafluoride in the extraction of oxygen from oxides and silicates for isotopic analysis. Geochimica et Cosmochimica Ada, 27, 4352.Google Scholar
Compton, J.S., Williams, L.B. & Ferrell, R.E. Jr. (1992) Mineralization of organogenic ammonium in the Monterey Formation, Santa Maria and San Joaquin basins, California, USA. Geochimica et Cosmochimica Acta, 56, 19791991.Google Scholar
Cooper, I.E. & Abedin, K.Z. (1981) The relationship between fixed ammonium-nitrogen and potassium in clays from a seep well on the Texas Gulf Coast. Texas Journal of Science, 33, 103111.Google Scholar
Cooper, J.E. & Evans, W.S. (1983) Ammonium-nitrogen in Green River Formation oil shale. Science, 219, 492493.Google Scholar
Daniels, E.J. & Altaner, S.P. (1990) Clay mineral authigenesis in coal and shale from the anthracite region, Pennsylvania. American Mineralogist, 75, 825839.Google Scholar
Daniels, E.J., Aronson, J.L., Altaner, S.P. & Clauer, N. (1994) Late Permian age of NH4-bearmg illite in anthracite from eastern Pennsylvania; temporal limits on coalification in the Central Appalachians. Geological Society of America Bulletin, 106, 760766.Google Scholar
Drits, V.A., Lindgreen, H. & Salyn, A.L. (1997) Determination of the content and distribution of fixed ammonium in illite-smectite by X-ray diffraction: application to North Sea illite-smectite. American Mineralogist, 82, 7987.Google Scholar
Drits, V.A., Lindgreen, H., Sakharov, B.A., Jakobsen, H.J., Salyn, A.L. & Dalnyak, L.G. (2002) Tobelitization of smectite during oil generation in oil-source shales. Application to North Sea illite-tobelite-smectitevermiculite. Clays and Clay Minerals, 50, 8298.Google Scholar
Eberl, D.D., Srodon, J. & Northrop, H.R. (1986) Potassium fixation in smectite by wetting and drying. ACS Symposium Series, 323, 296326.Google Scholar
Eberl, D.D., Srodon, J., Lee, M.C., Nadeau, P.H. & Northrop, H.R. (1987) Sericite from the Silverton Caldera, Colorado; correlation among structure, composition, origin, and particle thickness. American Mineralogist, 72, 914934.Google Scholar
Higashi, S. (1979) X-ray basal reflections of mica clay minerals, with special reference to characteristic features of ammonium-bearing mica minerals. Journal of the Mineralogical Society of Japan, 14, Special issue, 197-204.Google Scholar
Higashi, S. (1982) Tobelite, a new ammonium dioctahedral mica. Mineralogical Journal, 11, 138146.Google Scholar
Jackson, M.L. (1975) Soil Chemical Analysis — Advanced Course. Madison, Wisconsin, USA, 386 pp.Google Scholar
Juster, T.C., Brown, P.E. & Bailey, S.W. (1987) NH4- bearing illite in very low-grade metamorphic rocks associated with coal, northeastern Pennsylvania. American Mineralogist, 72, 555565.Google Scholar
Juvigne, E., Gewelt, M., Gilot, E., Hurtgen, C., Zeghedi, I., Szakacs, A., Gabris, G., Hadnagy, A. & Horvath, E. (1994) Une eruption vieille d'environ 10700 ans (14C) dans les Carpates orientales (Roumanie). An eruption at about 10,700 BP (14C) in the Eastern Carpathians, Romania. Comptes Rendus de l'Académie des Sciences, Série II. Sciences de la Terre et des Planètes, 318, 12331238.Google Scholar
Kawano, M. & Tomita, K. (1988) Ammonium-bearing dioctahedral 2M1 mica from Aira District, Kagoshima Prefecture. Clay Science, 7, 161169.Google Scholar
Kikawada, Y., Ossaka, T., Oi, T. & Honda, T. (2001) Experimental studies on the mobility of lanthanides accompanying alteration of andesite by acidic hot spring water. Chemical Geology, 176, 137149.Google Scholar
Kozak, J., Ocenas, D. & Derco, J. (1977) Amonna hydrosFuda vo Vihorlate. The discovery of ammonium hydromica in the Vihorlat Mountains, eastern Slovakia. Mineralia Slovaca, 9, 479494.Google Scholar
Lagaly, G. (1984) Clay-organic interactions. Pp. 315332 in: Clay minerals; their structure, behaviour and use (Fowden, L., Barrer, R.M. & Tinker, P.B., editors). Philosophical Transactions of the Royal Society of London, Series A: Mathematical and Physical Sciences, 311. Google Scholar
Laverret, E., Clauer, N., Fallick, A., Patrier, P., Beaufort, D., Quirt, D., Kister, P. & Bruneton, P. (2010) K-Ar, 518O and 5D tracing of illitization within and outside the Shea Creek uranium prospect, Athabasca Basin, Canada. Applied Geochemistry, 25, 856871.CrossRefGoogle Scholar
Lewis, A.J., Komninou, A., Yardley, B.W.D. & Palmer, M.R. (1998) Rare earth element speciation in geothermal fluids from Yellowstone National Park, Wyoming, USA. Geochimica et Cosmochimica Ada, 62, 657663.Google Scholar
Lindgreen, H. (1994) Ammonium fixation during illitesmectite diagenesis in Upper Jurassic shale, North Sea. Clay Minerals, 29, 527537.Google Scholar
Lindgreen, H. & Hansen, P.L. (1991) Ordering of illitesmectite in Upper Jurassic claystones from the North Sea. Clay Minerals, 26, 105125.Google Scholar
Lipman, P.W., Fisher, F.S., Mehnert, H.H., Naeser, C.W., Luedke, R.G. & Steven, T.A. (1976) Multiple ages of mid-Tertiary mineralization and alteration in the western San Juan Mountains, Colorado. Economic Geology, 71, 571588.Google Scholar
Marumo, K. & Hattori, K. (1993) Thermal effects of dacite intrusion on alteration mineralogy and K-Ar ages in the Ezuri Kuroko deposits, Japan. Pp. 186196 in: Mineral Resources Symposia; Volume C, Selected papers from the symposium Ferromanganese Deposits, Anoxic Sediments and Massive Sulfide Deposits (Ishihara, S., Urabe, T. & Ohmoto, H., editors). Shigen Chishitsu, Special issue 17.Google Scholar
Marumo, K. & Sawai, O. (1986) K-Ar ages of some veintype and Kuroko-type deposits in southwestern Hokkaido, Japan. Mining Geology, 36, 2126.Google Scholar
Michard, A. (1989) Rare-earth element systematics in hydrothermal fluids. Geochimica et Cosmochimica Ada, 53, 745750.Google Scholar
Moore, D.M. & Reynolds, R.C. (1989) Identification of mixed layered minerals. Pp. 241269 in: X-ray Diffraction and the Identification and Analysis of Clay Minerals (Moore, D.M. and Reynolds, R.C., editors). Oxford University Press, U.K. Google Scholar
Pecskay, Z., Edelstein, O., Seghedi, I., Szakacs, A., Kovacs, M., Crihan, M. & Bernad, A. (1995) K-Ar datings of Neogene-Quaternary calc-alkaline volcanic rocks in Romania. Ada Vulcanologica, 7, 5361.Google Scholar
Peltz, S., Vajdea, E., Balogh, K. Pecskay, Z. (1985) Contributions to the chronological study of the volcanic processes in the Cãlimani and Harghita Mountains (East Carpathians, Romania). Dari de Seama ale Sedintelor - Institutul de Geologie si Geofizica. 1. Mineralogie-Petrologie-Geochimie, 72-73, 323338.Google Scholar
Rãdulescu, D.P. (1973) Considerations on the origin of magmas of the Neozoic subsequent volcanism in the East Carpathians. Anuarul Comitetului de Stat al Geologiei, 41, 6976.Google Scholar
Rãdulescu, D.P. & Sandulescu, M. (1973) The platetectonics concept and the geological structure of the Carpathians. Tectonophysics, 16, 155161.Google Scholar
Rãdulescu, D.P., Peltz, S. & Popescu, A. (1973) Lower compartment of the structure of the Calimani, Gurghiu and Harghita Mountains; the volcanosedimentary formation. Anuarul Comitetului de Stat al Geologiei, 41, 1526.Google Scholar
Reynolds, R.C. (1985) Description of Program Newmod for the Calculation of the One-Dimension X-ray diffraction Patterns of Mixed-layered Clays. Department of Earth Sciences, Dartmouth College, Hanover, New Hampshire, 23 pp.Google Scholar
Royden, L.H. (1988) Late Cenozoic tectonics of the Pannonian Basin System. Pp. 2748 in: The Pannonian Basin (Royden, L.H. & Horvath, F., editors). American Association of Petroleum Geologists, Memoir, 45.Google Scholar
Samuel, J., Rouault, R. & Besnus, Y. (1985) Analyse multiélémentaire standardisée des matériaux géologiques en spectrométrie d'émission par plasma inductif. Analusis, 13, 321317.Google Scholar
Savin, S.M. & Lee, M. (1988) Isotopic studies of phyllosilicates. Pp. 189224 in. Hydrous Phyllosilicates (Exclusive of Micas), (Bailey, S.W., editor) Reviews in Mineralogy, 19. Google Scholar
Seghedi, I., Balintoni, I. & Szakacs, A. (1998) Interplay of tectonics and Neogene post-collisional magmatism in the intracarpathian region. Lithos, 45, 483497.Google Scholar
Stanciu, C. (1984) Hydrothermal alteration in the Neogene volcanism zone of the East Carpathians (Romania). International Geological Congress, Abstracts, 27, 313.Google Scholar
Steiger, R.H. & Jäger, E. (1977) Subcommission on Geochronology: Convention on the use of decay constants in geo- and cosmochronology. Earth and Planetary Science Letters, 36, 359362.Google Scholar
Sterne, E.J., Reynolds, R.C. Jr. & Zantop, H. (1982) Natural ammonium illites from black shales hosting a stratiform base metal deposit, DeLong Mountains, northern Alaska. Clays and Clay Minerals, 30, 161166.Google Scholar
Sucha, V. & Siranova, V. (1991) Ammonium and potassium fixation in smectite by wetting and drying. Clays and Clay Minerals, 39, 556559.Google Scholar
Šucha, V., Kraus, I. & Madejova, J. (1994) Ammonium illite from anchimetamorphic shales associated with anthracite in the Zemplinicum of the Western Carpathians. Clay Minerals, 29, 369377.Google Scholar
Szakacs, A. & Seghedi, I. (1995) The Cãlimani-Gurghiu-Harghita volcanic chain, East Carpathians, Romania; volcanological features. Ada Vulcanologica, 7, 145153.Google Scholar
Taylor, S.R. & McLennan, S.M. (1988) The significance of the rare earths in geochemistry and cosmochemistry. Pp. 485578 in. Handbook on the Physics and Chemistry of Rare Earths (Schneider, K.A. Jr. & Eyring, L., editors), 11. Google Scholar
Turpin, L., Clauer, N., Forbes, P. & Pagel, M. (1991) UPb, Sm-Nd and K-Ar systematics of the Akouta uranium deposit, Niger. Chemical Geology, Isotope Geoscience Section, 87, 217230.Google Scholar
Uysal, T.I. & Golding, D.S. (2003) Rare earth element fractionation in authigenic illite-smectite from Late Permian clasic rocks, Bowen Basin, Australia: implications for physico-chemical environments of fluids during illitization. Chemical Geology, 193, 167179.Google Scholar
Weaver, C.E. (1958) The effects and geologic significance of potassium ‘fixation’ by expandable clay minerals derived from muscovite, biotite, chlorite, and volcanic material. American Mineralogist, 43, 839861.Google Scholar
Williams, L.B. & Ferrell, R.E. Jr. (1991) Ammonium substitution in illite during maturation of organic matter. Clays and Clay Minerals, 39, 400408.Google Scholar
Wilson, P.N. & Parry, W.T. (1990) Mesozoic hydrothermal alteration associated with gold mineralization in the Mercur District, Utah. Geology, 18, 866869.Google Scholar
Wilson, P.N. & Parry, W.T. (1995) Characterization and dating of argillic alteration in the Mercur gold district, Utah. Economic Geology, 90, 11971216.Google Scholar
Wilson, P.N., Parry, W.T. & Nash, W.P. (1992) Characterization of hydrothermal tobelitic veins from black shale, Oquirrh Mountains, Utah. Clays and Clay Minerals, 40, 405420.Google Scholar
Yamamoto, T. (1967) Mineralogical studies of sericites associated with Roseki ores in the western part of Japan. Mineralogical Journal, 5, 7797.Google Scholar
Yeh, H.W. & Savin, S.M. (1977) Mechanism of burial metamorphism of argillaceous sediments: O-isotope evidence. Geological Society of America Bulletin, 88, 13211330.Google Scholar
Ylagan, R.F., Kim, C.S., Pevear, D.R. & Vrolijk, P.J. (2002) Illite polytype quantification for accurate KAr age determination. American Mineralogist, 87, 15361545.Google Scholar
Zhao, B., Clauer, N., Robb, L.J., Zwingmann, H., Toulkeridis, T. & Meyer, F.M. (1999) K-Ar dating of white micas from the Ventersdorp contact reef of the Witwatersrand Basin, South Africa; timing of post-depositional alteration. Mineralogy and Petrology, 66, 149170.Google Scholar