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High-Resolution Transmission Electron Microscopy (HRTEM) Study of Stacking Irregularity in Fe-Rich Chlorite From Selected Hydrothermal Ore Deposits

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Clays and Clay Minerals

Abstract

The structures of Fe-rich chlorite and berthierine and the formation mechanisms of 7 Å–14 Å interstratified minerals were not previously fully understood owing to the difficulties in analyzing them by X-ray diffraction (XRD). The present study characterizes Fe-rich chlorites in quartz veins of epithermal to xenothermal vein-type ore deposits without later structural modifications, based on high-resolution transmission electron microscopy (HRTEM) along with XRD examination and chemical analysis. Samples have a wide range of Fe/(Fe+Mg) ratios from 0.38 to 0.98 and tetrahedral Al substitution for Si from 0.94 to 1.44 atoms per formula unit (apfu). The variation in Fe content nearly parallels the tetrahedral Al content. The formation temperatures estimated by chlorite geothermometry range from 190°C to 320°C. In HRTEM, most of the samples showed interstratification between 7 Å, 14 Å, and/or (in some samples) smectite layers. Chlorites with relatively low Fe contents (Fe/(Fe+Mg) ≈ 0.4) were characterized by mostly 14 Å periodicity with the polytype IIbb. In contrast, interstratification of 7 Å and 14 Å layers predominated with increasing Fe content and the proportion of 7 Å layers exceeds 80% in Fe-rich samples with Fe/(Fe+Mg) > 0.9. The 7 Å component layer approximated Fe-rich berthierine based on the chemical composition. Layer stacking structures in the Fe-rich samples were complex, and characterized by disorder of 7 Å and 14 Å layers, differences in the polarity of the tetrahedral sheets, variations of the slant of the octahedral sheets, and positional disorder between octahedral and tetrahedral sheets involving the hydrogen bonding, as indicated from HRTEM observations along the Yi directions of the phyllosilicates. The complex stacking structures observed in Fe-rich samples suggest that irregularity was controlled by neither the Fe/(Fe+Mg) ratio nor the formation temperature; stacking was controlled by kinetic factors in the process of mineral precipitation under disequilibrium conditions.

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References

  • Bailey, S.W. and Brown, G. (1962) Chlorite polytypism: I. Regular and semirandom one-layer structures. American Mineralogist, 47, 819–850.

    Google Scholar 

  • Bailey, S.W. (1969) Polytypism of trioctahedral 1:1 layer silicates. Clays and Clay Minerals, 17, 355–371.

    Article  Google Scholar 

  • Bailey, S.W. (1988a) Chlorites: Structures and crystal chemistry. Pp. 347–403 in: Hydrous Phyllosilcates (Exclusive of Micas) (S.W. Bailey, editor). Reviews in Mineralogy, 19, Mineralogical Society of America, Chantilly, Virginia, USA.

    Chapter  Google Scholar 

  • Bailey, S.W. (1988b) Structures and compositions of other trioctahedral 1: 1 phyllosilicates. Pp. 169–188 in: Hydrous Phyllosilcates (Exclusive of Micas) (S.W. Bailey, editor). Reviews in Mineralogy, 19, Mineralogical Society of America, Chantilly, Virginia, USA.

    Chapter  Google Scholar 

  • Banfield, J.F. and Bailey, S.W. (1996) Formation of regularly interstratified serpentine-chlorite minerals by tetrahedral inversion in long-period serpentine polytypes. American Mineralogist, 81, 79–91.

    Article  Google Scholar 

  • Baronnet, A. (1992) Polytypism and stacking disorder. Pp. 231–288 in: Minerals and Reactions at the Atomic Scale: Transmission Electron Microscopy (P.R. Buseck, editor). Reviews in Mineralogy, 27, Mineralogical Society of America, Chantilly, Virginia, USA.

    Chapter  Google Scholar 

  • Beaufort, D., Baronnet, A., Lanson, B., and Meunier, A. (1997) Corrensite: A single phase or a mixed-layer phyllosilicate in the saponite-to-chlorite conversion series? A case study of Sancerre-Couy deep drill hole (France). American Mineralogist, 82, 109–124.

    Article  Google Scholar 

  • Billault, V., Beaufort, D., Baronnet, A., and Lacharpagne, J. C. (2003) A nanopetrographic and textural study of graincoating chlorites in sandstone reservoirs. Clay Minerals, 38, 315–328.

    Article  Google Scholar 

  • Blanc, P., Gailhanou, H., Rogez, J., Mikaelian, G., Kawaji, H., Warmont, F., Gaboreau, S., Grangeon, S., Grenèche, J. M., Vieillard, P., Fialips, C., Giffaut, E., Gaucher, E., and Claret, F. (2014) Thermodynamic properties of chlorite and berthierine derived from calorimetric measurements. Physics and Chemistry of Minerals, 41, 603–615.

    Article  Google Scholar 

  • Bourdelle, F., Benzerara, K., Beyssac, O., Cosmidis, J., Neuville, D. R., Brown, G.E., and Paineau, E. (2013) Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges. Contributions to Mineralogy and Petrology, 166, 423–434.

    Article  Google Scholar 

  • Brindley, G.W. (1982) Chemical-compositions of berthierines — a review. Clays and Clay Minerals, 30, 153–155.

    Article  Google Scholar 

  • Buddington, A.F. (1935) High-temperature mineral associations at shallow to moderate depths. Economic Geology and the Bulletin of the Society of Economic Geologists, 30, 205–222.

    Article  Google Scholar 

  • Cassagnabère, A. (1998) Characterization and interpretation of kaolinite-to-dickite transition in Froy and Rind hydrocarbons reservoirs (North Sea, Norway). PhD Thesis, University of Poitiers, France, 237 pp.

  • Chernosky, J.V., Berman, R.G., and Bryndzia, L.T. (1988) Stability, phase relations, and thermodynamic properties of chlorite and serpentine group minerals. Pp. 295–346 in: Hydrous Phyllosilcates (Exclusive of Micas) (S.W. Bailey, editor). Reviews in Mineralogy, 19, Mineralogical Society of America, Chantilly, Virginia, USA.

    Chapter  Google Scholar 

  • Foster, M.D. (1962) Interpretation of the composition and a classification of the chlorites. U. S. Geological Survey Professional Paper, 414-A, 1–33.

    Google Scholar 

  • Gregory, M.R. and Johnston, K.A. (1987) A nontoxic substitute for hazardous heavy liquids — aqueous sodium polytungstate (3Na2WO4·9WO3·H2O) solution (Note). New Zealand Journal of Geology and Geophysics, 30, 317–320.

    Article  Google Scholar 

  • Hillier, S. (1993) Origin, diagenesis, and mineralogy of chlorite minerals in Devonian lacustrine mudrocks, Orcadian Basin, Scotland. Clays and Clay Minerals, 41, 240–259.

    Article  Google Scholar 

  • Hornibrook, E.R. and Longstaffe, F.J. (1996) Berthierine from the Lower Cretaceous Clearwater Formation, Alberta, Canada. Clays and Clay Minerals, 44, 1–21.

    Article  Google Scholar 

  • Iijima, A. and Matsumoto, R. (1982) Berthierine and chamosite in coal measures of Japan. Clays and Clay Minerals, 30, 264–274.

    Article  Google Scholar 

  • Imai, H., Lee, M.S., Iida, K., Fujiki, Y., and Takenouchi, S. (1975) Geologic structure and mineralization of the xenothermal vein-type deposits in Japan. Economic Geology, 70, 647–676.

    Article  Google Scholar 

  • Inoue, A., Meunier, A., Patrier-Mas, P., Rigault, C., Beaufort, D., and Vieillard, P. (2009) Application of chemical geothermometry to low-temperature trioctahedral chlorites. Clays and Clay Minerals, 57, 371–382.

    Article  Google Scholar 

  • Inoue, A., Kurokawa, K., and Hatta, T. (2010) Application of chlorite geothermometry to hydrothermal alteration in Toyoha geothermal system, southwestern Hokkaido, Japan. Resource Geology, 60, 52–70.

    Article  Google Scholar 

  • Inoue, A., Kurokawa, K., and Nitta, M. (2012) Environment of mineral-fluid interactions in the Toyoha hydrothermal system, southwestern Hokkaido, Japan. Clay Science, 16, 59–81.

    Google Scholar 

  • Jahren, J. and Aagaard, P. (1989) Compositional variations in diagenetic chlorites and illites, and relationships with formation*water chemistry. Clay Minerals, 24, 157–170.

    Article  Google Scholar 

  • Jiang, W.T., Peacor, D.R., and Slack, J.F. (1992) Microstructures, mixed layering, and polymorphism of chlorite and retrograde berthierine in the Kidd Creek massive sulfide deposit, Ontario. Clays and Clay Minerals, 40, 501–514.

    Article  Google Scholar 

  • Kilaas, R. (1998) Optimal and near-optimal filters in highresolution electron microscopy. Journal of Microscopy, 190, 45–51.

    Article  Google Scholar 

  • Kogure, T. and Banfield, J. F. (1998) Direct identification of the six polytypes of chlorite characterized by semi-random stacking. American Mineralogist, 83, 925–930.

    Article  Google Scholar 

  • Kogure, T., Hybler, J., and Durovic, S. (2001) A HRTEM study of cronstedtite: determination of polytypes and layer polarity in trioctahedral 1:1 phyllosilicates. Clays and Clay Minerals, 49, 310–317.

    Article  Google Scholar 

  • Kogure, T., Drits, V.A., and Inoue, S. (2013) Structure of mixed-layer corrensite-chlorite revealed by high-resolution transmission electron microcopy (HRTEM). American Mineralogist, 98, 1253–1260.

    Article  Google Scholar 

  • Marks, L.D. (1996) Wiener-filter enhancement of noisy HREM images. Ultramicroscopy, 62, 43–52.

    Article  Google Scholar 

  • Meunier, A. (2005) Clays. Springer, Berlin, 472 pp.

    Google Scholar 

  • Moore, D.M. and Reynolds, R.C. (1989) X-ray Diffraction and the Identification and Analysis of Clay Minerals. Oxford University Press, New York, 332 pp.

    Google Scholar 

  • Mosser-Ruck, R., Cathelineau, M., Guillaume, D., Charpentier, D., Rousset, D., Barres, O., and Michau, N. (2010) Effects of temperature, pH, and iron/clay and liquid/clay ratios on experimental conversion of dioctahedral smectite to berthierine, chlorite, vermiculite, or saponite. Clays and Clay Minerals, 58, 280–291.

    Article  Google Scholar 

  • Murakami, T., Sato, T., and Inoue, A. (1999) HRTEM evidence for the process and mechanism of saponite-to-chlorite conversion through corrensite. American Mineralogist, 84, 1080–1087.

    Article  Google Scholar 

  • Nakamura, T. (1970) Mineral zoning and characteristic minerals in the polymetallic veins of the Ashio copper mine. Pp. 231–246 in: Volcanism and Ore Genesis (T. Tatsumi, editor), University of Tokyo Press, Tokyo.

    Google Scholar 

  • Parra, T., Vidal, O., and Theye, T. (2005) Experimental data on the Tschermak substitution in Fe-chlorite. American Mineralogist, 90, 359–370.

    Article  Google Scholar 

  • Reynolds, R. (1988) Mixed layer chlorite minerals. Pp. 601–629 in: Hydrous Phyllosilcates (Exclusive of Micas) (S.W. Bailey, editor). Reviews in Mineralogy, 19, Mineralogical Society of America, Chantilly, Virginia, USA.

    Chapter  Google Scholar 

  • Reynolds, R.C., Distefano, M.P., and Lahann, R.W. (1992) Randomly interstratified serpentine/chlorite: Its detection and quantification by powder X-ray diffraction methods. Clays and Clay Minerals, 40, 262–267.

    Article  Google Scholar 

  • Shikazono, N. (2003) Geochemical and Tectonic Evolution of Arc-Backarc Hydrothermal Systems: Implication for the Origin of Kuroko and Epithermal Vein-type Mineralizations and the Global Geochemical Cycle. Elsevier, Amsterdam, 463 pp.

    Google Scholar 

  • Shirozu, H. (1978) Chlorite minerals. Pp. 243–264 in: Clays and Clay Minerals of Japan (T. Sudo and S. Shimoda, editors). Developments in Sedimentology, 26. Elsevier Applied Science.

    Chapter  Google Scholar 

  • Shirozu, H. and Bailey, S.W. (1965) Chlorite polytypism: III. Crystal structure of an orthohexagnal iron chlorite. American Mineralogist, 50, 868–885.

    Google Scholar 

  • Slack, J.F. and Coad, P.R. (1989) Multiple hydrothermal and metamorphic events in the Kidd Creek volcanogenic massive sulphide deposit, Timmins, Ontario: Evidence from tourmalines and chlorites. Canadian Journal of Earth Sciences, 26, 694–715.

    Article  Google Scholar 

  • Slack, J.F., Jiang, W.T., Peacor, D.R., and Okita, P.M. (1992) Hydrothermal and metamorphic berthierine from the Kidd Creek volcanogenic massive sulfide deposit, Timmins, Ontario. The Canadian Mineralogist, 30, 1127–1142.

    Google Scholar 

  • Velde, B. (1985) Clay Minerals: A Physico-Chemical Explanation of their Occurrence. Elsevier, Amsterdam, 427 pp.

    Google Scholar 

  • Vidal, O., Parra, T., and Vieillard, P. (2005) Thermodynamic properties of the Tschermak solid solution in Fe-chlorite: Application to natural examples and possible role of oxidation. American Mineralogist, 90, 347–358.

    Article  Google Scholar 

  • Xu, H.F. and Veblen, D.R. (1996) Interstratification and other reaction microstructures in the chlorite-berthierine series. Contributions to Mineralogy and Petrology, 124, 291–301.

    Article  Google Scholar 

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Correspondence to Sayako Inoué.

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Inoué, S., Kogure, T. High-Resolution Transmission Electron Microscopy (HRTEM) Study of Stacking Irregularity in Fe-Rich Chlorite From Selected Hydrothermal Ore Deposits. Clays Clay Miner. 64, 131–144 (2016). https://doi.org/10.1346/CCMN.2016.0640205

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  • DOI: https://doi.org/10.1346/CCMN.2016.0640205

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