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Coexisting nanoscale phases of K-illite, NH4,K-illite and NH4-illite-smectite: an organic nitrogen contribution in the hydrothermal system of Harghita Bãi, East Carpathians, Romania

Published online by Cambridge University Press:  29 March 2019

Iuliu Bobos
Iuliu Bobos*
Affiliation:
Institute of Earth Sciences – Porto, Faculty of Science, University of Porto, Rua do Campo Alegre 687, 4168-007 Porto, Portugal
*
*E-mail: [email protected]
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Abstract

Nitrogen influx was identified in the Harghita Bãi area, where the mechanism of NH4+-fixation in illitic clays is relevant for the N-input budget estimation. The nanotextural features of K-illite (K-I), NH4,K-I and NH4-illite-smectite (NH4-I-S) mixed layers observed in argillic-altered andesitic rocks from the hydrothermal area of Harghita Bãi (East Carpathians) were studied by X-ray diffraction, infrared spectroscopy and transmission and analytical electron microscopy (TEM-AEM). The texture of undisturbed argillic-altered andesite rocks exhibits chaotic intergrowths of randomly oriented and curved illitic packets with abundant pore spaces and high porosity between packets. The TEM images of K-I and NH4,K-I intergrowths show subparallel packets with clear contacts, exhibiting a diffuse contrast across layers. The thicknesses of K-I and NH4,K-I packets range from 150 to 500 Å, and 1Md and 1M polytypes were identified by selected area electron diffraction patterns. Crystal chemistry of K-I, NH4,K-I and NH4-I-S was carried out by AEM. A third interlayer cation Na+ beside K+ was detected in several NH4,K-I packets. The NH4,Na,K-I packets interleaved with NH4,K-I or NH4-I-S (12% smectite layers) packets were also identified by TEM. The thicknesses of NH4,Na,K-I packets range from 300 to 1200 Å, with abundant lenses and lenticular layer separation along the boundaries between them. The 1Md polytype dominates the NH4,Na,K-I packets. Straight and parallel packets, continuous 00l layers and collapsed swelling layers at the boundary of individual NH4-I (5% smectite layers) packets with thicknesses ranging from 20 to 95 Å were observed. The nanotextural observations indicate direct crystallization of NH4-I crystals within a NH4-I-S series from a pore fluid, where NH4-I packets occupy void spaces previously occupied by fluids.

Keywords

ammonium-illiteone- and two-layer polytypetransmission and analytic electron microscopyHarghita BãiEast Carpathians
Type
Article
Information
Clay Minerals , Volume 54 , Issue 1 , March 2019 , pp. 27 - 40
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2019 

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Footnotes

Guest Associate Editor: S. Potel

This paper was originally presented during the session: ‘GG01 – Clays in faults and fractures + MI-03 Clay mineral reaction progress in very low-grade temperature petrologic studies’ of the International Clay Conference 2017.

References

Ahn, J.H., Peacor, D.R. & Essene, E.J. (1985) Coexisting paragonite-phengite in blueschist eclogite: a TEM study. American Mineralogist, 70, 1193–1204.Google Scholar
Ahn, J.H., Peacor, D.R. & Essene, E.J. (1986) Cation-diffusion-induced characteristic beam damage in transmission electron microscope images of micas. Ultramicroscopy, 19, 375–382.Google Scholar
Árkai, P., Livi, K.J.T., Frey, M., Brukner-Wein, A. & Sajgo, C. (2004) White micas with mixed interlayer occupancy: a possible cause of pitfalls in applying illite Kübler index (‘crystallinity’) for the determination of metamorphic grade. European Journal of Mineralogy, 16, 469–482.Google Scholar
Bannister, F.A. (1942) Brammallite (sodium-illite), a new mineral from Llandebie, South Wales. Mineralogical Magazine, 26, 304–307.Google Scholar
Bauluz, B. (2013) Clays in low-temperature environments. Pp. 181–216 in: Minerals at the Nanoscale (Nieto, F. & Livi, K.J., editors), EMU Notes in Mineralogy, 14. European Mineralogical Union, Mineralogical Society of Great Britain & Ireland, London, UK.Google Scholar
Bauluz, B. & Subías, I. (2010) Coexistence of pyrophyllite, I/S, R1 and NH4+-rich illite in Silurian black shales (Sierra de Albarracín, NE Spain): metamorphic vs. hydrothermal origin. Clay Minerals, 45, 383–392.Google Scholar
Baxter-Grubb, S.M., Peacor, D.R. & Jiang, W.-T. (1991) Transmission electron microscope observations of illite polytypism. Clays and Clay Minerals, 39, 540–550.Google Scholar
Bobos, I. (2012) Characterization of smectite to NH4-illite conversion series in the fossil hydrothermal system of Harghita Bãi, East Carpathians, Romania. American Mineralogist, 97, 962–982.Google Scholar
Bobos, I. & Ghergari, L. (1999) Conversion of smectite to ammonium illite in the hydrothermal system of Harghita Bãi, Romania: SEM and TEM investigations. Geologica Carpathica, 50, 379–387.Google Scholar
Bobos, I. & Eberl, D.D. (2013) Thickness distributions and evolution of growth mechanisms of NH4-illite from the fossil hydrothermal system of Harghita Bãi, eastern Carpathians, Romania. Clays and Clay Minerals, 61, 375–391.Google Scholar
Bobos, I. & Williams, L.B. (2017) Boron, lithium and nitrogen isotope geochemistry of NH4-illite clays in the fossil hydrothermal system of Harghita Bãi, East Carpathians, Romania. Chemical Geology, 473, 22–39.Google Scholar
Boles, J.R. & Franks, S.G. (1979) Clay diagenesis in Wilcox sandstones of southwest Texas: implications of smectite diagenesis on sandstone cementation. Journal of Sedimentary Petrology, 49, 55–70.Google Scholar
Buseck, P.R. (1992) Principles of transmission electron microscopy. Pp. 1–35 in: Minerals and Reactions at the Atomic Scale: Transmission Electron Microscopy (Buseck, P.R., editor), Reviews in Mineralogy, 27. Mineralogical Society of America, Washington, DC, USA.Google Scholar
Buseck, P.R., Cowley, J.M. & Eyring, L. (1988) High-Resolution Transmission Electron Microscopy and Associated Techniques. Oxford University Press, Oxford, UK.Google Scholar
Capitani, G.C., Schingaro, E., Lacalamita, M., Mesto, E. & Scordari, F. (2016) Structural anomalies in tobelite-2M 2 explained by high resolution and analytical electron microscopy. Mineralogical Magazine, 80, 143–156.Google Scholar
Chen, T. & Wang, H.J. (2007) Determination of layer stacking microstructures and interlayer transition of illite polytypes by high-resolution transmission electron microscopy (HRTEM). American Mineralogist, 92, 926–932.Google Scholar
Chourabi, B. & Fripiat, J.J. (1981) Determinations of tetrahedral substitutions and interlayer surface heterogeneity from vibrational spectra of ammonium in smectites. Clays and Clay Minerals, 29, 260–268.Google Scholar
Clauer, N., Liewig, N. & Bobos, I. (2010) K-Ar, δ18O and REE constraints to the genesis of ammonium-illite from Harghita Bãi hydrothermal system, Romania. Clay Minerals, 45, 393–411.Google Scholar
Cliff, G. & Lorimer, G.W. (1975) The quantitative analysis of thin specimens. Journal Microscopy, 103, 203–207.Google Scholar
Compton, J.S., Williams, L.B. & Ferrell, R.E. Jr (1992) Mineralisation of organogenic ammonium in the Monterey Formation, Santa Maria and San Joaquin basins, California, U.S.A. Geochimica et Cosmochimica Acta, 56, 1979–1991.Google Scholar
Cooper, J.E. & Evans, W.S. (1983) Ammonium-nitrogen in Green River Formation oil shale. Science, 219, 492–493.Google Scholar
Daniels, E.J. & Altaner, S.P. (1990) Clay mineral authigenesis in coal and shale from the Anthracite region, Pennsylvania. American Mineralogist, 75, 103–111.Google Scholar
Drits, V.A. (2003) Structural and chemical heterogeneity of clay minerals. Clay Minerals, 38, 403–432.Google Scholar
Drits, V.A., Lindgreen, H. & Salyn, A. (1997a) 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, 79–87.Google Scholar
Drits, V.A., Sakharov, B.A., Lindgreen, H. & Salyn, A. (1997b) Sequential structural transformation of illite-smectite-vermiculite during diagenesis of Upper Jurassic shales from North Sea and Denmark. Clay Minerals, 32, 351–372.Google Scholar
Drits, V.A., Lindgreen, H., Sakharov, B.A., Jakobsen, H.J., Salyn, A. & Dainyak, L.G. (2002) Tobelitization of smectite during oil generation in oil source shales. Application to North Sea illite-tobelite-smectite-vermiculite. Clays and Clay Minerals, 50, 82–98.Google Scholar
Drits, V.A., Sakharov, B., Salyn, A.L. & Lindgreen, H. (2005) Determination of the content and distribution of fixed ammonium in illite-smectite using a modified X-ray diffraction technique: application to oil source rocks of western Greenland. American Mineralogist, 90, 71–84.Google Scholar
Drits, V.A. & Zvyagina, B.B. (2009) Trans-vacant and cis-vacant 2:1 layer silicates: structural feature, identification, and occurrence. Clays and Clay Minerals, 57, 405–415.Google Scholar
Eberl, D.D. (2002) Determination of illite crystallite thickness distributions using X-ray diffraction, and the relation of the thickness to crystal growth mechanisms using MUDMASTER, GALOPER, and associated computer programs. Pp. 131–142 in: Teaching Clay Science (Rule, A. & Guggenheim, S., editors). CMS Workshop Lectures, 11, The Clay Minerals Society, Aurora, CO, USA.Google Scholar
Elkins, L., Fischer, T., Hilton, D., Sharp, Z., McKnight, S. & Walker, J. (2006) Tracing nitrogen in volcanic and geothermal volatiles from the Nicaragua volcanic front. Geochimica et Cosmochimica Acta, 70, 5213–5235.Google Scholar
Giorgetti, G., Tropper, P., Essene, E.J. & Peacor, D.R. (2000) Characterization of non-equilibrium and equilibrium occurrences of paragonite/muscovite intergrowths in an eclogite from the Sesia–Lanzo Zone (Western Alps, Italy) Contribution to Mineralogy and Petrology, 138, 326–336.Google Scholar
Guthrie, G.D. & Veblen, D.R. (1989) High-resolution transmission electron microscopy of mixed-layer illite-smectite: computer simulation. Clays and Clay Minerals, 37, 1–11.Google Scholar
Guthrie, G.D. & Veblen, D.R. (1990) Interpreting one-dimensional high-resolution transmission electron microscopy of sheet silicates by computer simulation. American Mineralogist, 75, 276–288.Google Scholar
Hall, A. (1999) Ammonium in granites and its petrogenetic significance. Earth Science Review, 45, 145–165.Google Scholar
Harlov, D.E., Andrut, M. & Poter, B. (2001) Characterization of tobelite (NH4)Al2(AlSi3O10)OH2 and ND4-tobelite (ND4)Al2(Al3Si3O10)OH2 using IR spectroscopy and Rietvield refinement of XRD spectra. Physics Chemistry Minerals, 28, 268–276.Google Scholar
Higashi, S. (1978) Dioctahedral mica minerals with ammonium ions. Mineralogical Journal, 9, 16–27.Google Scholar
Higashi, S. (1982) Tobelite, a new ammonium dioctahedral mica. Mineralogical Journal, 11, 138–146.Google Scholar
Higashi, S. (2000) Ammonium-bearing mica and mica/smectite of several pottery stone and pyrophyllite deposits in Japan: their mineralogical properties and utilization. Applied Clay Science, 16, 171–184.Google Scholar
Jackson, M.L. (1975) Soil Chemical Analysis – Advanced Course. Published by author, Madison, WI, USA.Google Scholar
Jiang, W.T., Essene, E.J. & Peacor, D.R. (1990a) Transmission electron microscopic study of coexisting pyrophyllite and muscovite: direct evidence for the metastability of illite. Clays and Clay Minerals, 38, 225–240.Google Scholar
Jiang, W.T., Peacor, D.R., Merriman, R.J. & Roberts, B. (1990b) Transmission and analytical electron microscopic study of mixed-layer illite/smectite formed as an apparent replacement product of diagenetic illite. Clays and Clay Minerals, 38, 449–468.Google Scholar
Jiang, W.T. & Peacor, D.R. (1993) Transmission and analytic electron microscopic study of mixed-layer illite/smectite formed as an apparent replacement product of diagenetic illite. Clays and Clay Minerals, 38, 449–468.Google Scholar
Juster, T.C., Browne, P.E. & Bailey, S.W. (1987) NH4-bearing illite in very low grade metamorphic rocks associated with coal, northeastern Pennsylvania. American Mineralogist, 72, 555–565.Google Scholar
Li, G., Peacor, D.R., Merriman, R.J. & Roberts, B. (1994) The diagenetic to low-grade metamorphic evolution of matrix white micas in the system muscovite-paragonite in a mudrock from Central Wales, United Kingdom. Clays and Clay Minerals, 42, 369–381.Google Scholar
Lindgreen, H. (1994) Ammonium fixation during illite-smectite diagenesis in upper Jurassic shale North-Sea. Clay Minerals, 29, 527–537.Google Scholar
Lindgreen, H., Drits, V.A., Sakharov, B.A., Salyn, A. L., Wrang, P. & Dainyak, L.G. (2000) Illite-smectite structural changes during metamorphism in black Cambrian Alum shales from the Baltic area. American Mineralogist, 85, 1223–1238.Google Scholar
Livi, K.J.T., Veblen, D.R., Ferry, J.M. & Frey, M. (1997) Evolution of 2:1 layered silicates in low-grade metamorphosed Liassic shales of central Switzerland. Journal of Metamorphic Geology, 15, 323–344.Google Scholar
Livi, K.J.T., Christidis, G.E., Árkai, P. & Veblen, D. (2008) White mica domain formation: a model for paragonite, margarite, and muscovite formation during prograde metamorphism. American Mineralogist, 93, 520–527.Google Scholar
Marty, B. (1995) Nitrogen content of the mantle inferred from N2–Ar correlation in oceanic basalts. Nature, 377, 326–329.Google Scholar
McHardy, W.J. & Birnie, A.C. (1987) Scanning electron microscopy. Pp. 74–208 in: A Handbook of Determinative Methods in Clay Mineralogy (Wilson, M.J., editor). Blackie, London, UK.Google Scholar
Mason, P.R.D., Downes, H., Thirlwall, M.F., Seghedi, I., Szakacs, A., Lowry, D. & Mattey, D. (1996) Crustal assimilation as a major petrogenetic process in the East Carpathian Neogene and Quaternary margin arc, Romania. Journal of Petrology, 37, 927–959.Google Scholar
Mason, P.R.D., Seghedi, I., Szakacs, A. & Downes, H. (1998) Magmatic constraints on geodynamic models of subduction in the East Carpathians. Tectonophysics, 297, 157–176.Google Scholar
Moore, D.M. & Reynolds, R.C. (1997) X-Ray Diffraction and the Identification and Analysis of Clay Minerals. Oxford University Press, New York, NY, USA.Google Scholar
Nadeau, P.H. & Bain, D.C. (1986) Composition of some smectites and diagenetic illitic clays and implications for their origin. Clays and Clay Minerals, 34, 455–463.Google Scholar
Nieto, F. (2002) Tobelite in low-grade metamorphic organic-rich shales from Douro-Beira, Portugal. American Mineralogist, 87, 205–216.Google Scholar
Nieto, F., Ortega-Huertas, M., Peacor, D.R. & Arostegui, J. (1996) Evolution of illite/smectite from early diagenesis through incipient metamorphism in sediments of the Basque-Cantabrian basin. Clays and Clay Minerals, 44, 304–323.Google Scholar
Nieto, F., Mellini, M. & Abad, I. (2010) The role of H3O+ in the crystal structure of illite. Clays and Clay Minerals, 58, 238–246.Google Scholar
Peltz, S., Vâjdea, E., Balogh, K. & Pécskay, Z. (1987) Contributions to the chronological study of the volcanic processes in the Cãlimani and Harghita Mountains (East Carpathians, Romania). Compte Rendu de Institute de Geologie e Geofisique, 72–73, 323–338.Google Scholar
Petit, S., Righi, D. & Madejová, J. (2006) Infrared spectroscopy of NH4+-bearing and saturated clay minerals: a review of the study of layer charge. Applied Clay Science, 34, 22–30.Google Scholar
Petschick, R. (2000) MacDiff. Available at: http://www.ccp14.ac.uk/ccp/ccp14/ftp-mirror/krumm/Software/macintosh/macdiff/MacDiff.html.Google Scholar
Pöter, B., Gottschalk, M. & Heinrich, W. (2007) Crystal-chemistry of synthetic K-feldspar-buddingtonite and muscovite-tobelite solid solutions. American Mineralogist, 92, 151–165.Google Scholar
Reynolds, R.C. (1985) NEWMOD, a Computer Program for the Calculation of One Dimensional Diffraction Patterns of Mixed Layered Clays. Hanover, NH, USA.Google Scholar
Ruiz-Cruz, M.D. & Sanz de Galdeano, C. (2008) Factors controlling the evolution of mineral assemblages and illite crystallinity in Paleozoic to Triassic sequences from the transition between Maláguide and Alpujáride complexes (Betic Cordillera, Spain): the significance of tobelite. Clays and Clay Minerals, 58, 558–572.Google Scholar
Ruiz-Cruz, M.D. & Sanz de Galdeano, C. (2010) High-temperature ammonium white mica from the Betic Cordillera (Spain). American Mineralogist, 93, 977–987.Google Scholar
Sakharov, B.A., Lindgreen, H., Salyn, A. & Drits, V.A. (1999) Determination of illite-smectite structures using multispecimen X-ray diffraction profile fitting. Clays and Clay Minerals, 47, 555–566.Google Scholar
Schroeder, P.A. & McLain, A.A. (1998) Illite-smectite and the influence of burial diagenesis on the geochemical cycling of nitrogen. Clay Minerals, 33, 539–546.Google Scholar
Szakacs, A. & Seghedi, I. (1995) The Cãlimani–Gurghiu–Harghita volcanic chain, Eastern Carpathians, Romania: volcanological features. Acta Vulcanologica, 7, 145–153.Google Scholar
Seghedi, I. & Downes, H. (2011) Geochemistry and tectonic development of Cenozoic magmatism in the Carpathian–Pannonian region. Gondwana Research, 20, 655–672.Google Scholar
Seghedi, I., Balintoni, I. & Szakacs, A. (1998) Interplay of tectonics and Neogene post-collisional magmatism in the intracarpathian area. Lithos, 45, 483–499.Google Scholar
Seghedi, I., Downes, H., Szakacs, A., Mason, P.R.D., Thirlwall, M.F., Rosu, E., Pécskay, Z., Márton, E. & Panaiotu, C. (2004) Neogene–Quaternary magmatism and geodynamics in the Carpathian–Pannonian region: a synthesis. Lithos, 72, 117–146.Google Scholar
Shau, H.Y., Feather, M.E., Essene, E.J. & Peacor, D.J. (1991) Genesis and solvus relations of submicroscopically intergrown paragonite and phengite in a blueschist from northern California. Contribution to Mineralogy and Petrology, 106, 367–375.Google Scholar
Stanciu, C. (1984) Hypogene alteration of Neogene volcanism of the East Carpathians. Annuare de Institute de Geologique e Geofisique, LXIV, 182–193.Google Scholar
Sterne, E.J., Reynolds, R.C. & Zantop, H. (1982) Natural ammonium illites from black shales hosting a stratiform base metal deposit, Delong Mountains, Northern Alaska. Clays and Clay Minerals, 30, 161–166.Google Scholar
Stevenson, F.J. & Dharival, A.P.S. (1959) Distribution of fixed ammonium in soil. Soil Science of America Proceedings, 23, 121–125.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, 369–377.Google Scholar
Van der Pluijm, B.A., Lee, J.H. & Peacor, D.R. (1988) Analytical electron microscopy and the problem of potassium diffusion. Clays and Clay Minerals, 36, 498–504.Google Scholar
Veblen, D.R., Guthrie, G.D., Livi, K.J.T. & Reynolds, R.C. (1990) High-resolution transmission electron microscopy and electron diffraction of mixed-layer illite/smectite. Clays and Clay Minerals, 38, 1–13.Google Scholar
Watenphul, A., Wunder, B. & Heinrich, W. (2009) High-pressure ammonium-bearing silicates: implications for nitrogen and hydrogen storage in the Earth's mantle. American Mineralogist, 94, 283–292.Google Scholar
Williams, L.B. & Ferrell, R.E. (1991) Ammonium substitution in illite during maturation of organic matter. Clays and Clay Minerals, 39, 400–408.Google Scholar
Yau, Y.C., Peacor, D.R., Beans, R.E., Essene, E.J. & McDowell, S.D. (1988) Microstructures, formation mechanisms, and the depth-zoning of phyllosilicates in geothermally altered shales, Salton Sea, California. Clays and Clay Minerals, 36, 1–10.Google Scholar
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