Startseite Inclusions in calcite phantom crystals suggest role of clay minerals in dolomite formation
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Inclusions in calcite phantom crystals suggest role of clay minerals in dolomite formation

  • Stefan Farsang ORCID logo , Péter Pekker , Giulio I. Lampronti , Zsombor Molnár , Rastislav Milovský , Mihály Pósfai , Daniel Ozdín , Timothy D. Raub und Simon A.T. Redfern ORCID logo
Veröffentlicht/Copyright: 2. Juli 2022
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 107 Heft 7

Abstract

Micro- and nano-inclusions embedded in calcite phantom crystals from Gemerská Ves, Slovak Republic, have been characterized by a combination of Raman spectroscopy, scanning and transmission electron microscopy, X‑ray powder difraction, and C and O isotope analysis. Whereas the outer, colorless part of the phantom crystal is relatively homogeneous and cavity and inclusion-free, the inner terracotta-colored part contains abundant cavities, dolomite, hematite, goethite, titanite, phyllosilicates (mainly kaolinite and illite), and apatite inclusions and nanostructures that have formed on the walls of cavities. The nanostructures comprise hematite and goethite particles sandwiched between either two phyllosilicate crystals or a phyllosilicate and a carbonate (calcite or dolomite) crystal. Our observations suggest that all inclusions in the terracotta calcite originate from the terra rossa (a common soil type in karstic areas) and limestone outcropping adjacent to the calcite crystals. While the micrometer-sized phyllosilicate and hematite particles were likely transported from the terra rossa and attached to the surface of growing calcite, the presence of phyllosilicates that are only a few atomic layers thick and of euhedral hematite, goethite, and dolomite crystals suggests that these particles precipitated along with the phantom calcite in situ, from an aqueous solution carrying terra rossa-derived and limestone-derived solutes. The compositional differences between the terra rossa (e.g., smectite as the only major Mg-rich phase) and terracotta calcite inclusions (e.g., dolomite as the only major Mg-rich phase and the presence of only Mg-free clays) hint that a smectite-illite conversion provides the Mg necessary for the precipitation of dolomite and possibly the Fe associated with the iron oxyhydroxide nanostructures. Phyllosilicate nucleation on calcite and dolomite nucleation on phyllosilicates, as inferred from nanoscale mineralogical associations, suggest that carbonates and phyllosilicates may mutually enhance nucleation and growth. This enhancement may result in the formation of large-scale clay-carbonate successions in aqueous settings, including the enigmatic, pink-colored cap dolostones succeeding late Neoproterozoic “Snowball Earth” deposits. The distribution of inclusions in the terracotta calcite and the preferred nucleation of hematite and goethite on phyllosilicate, rather than on carbonate surfaces, indicates that phyllosilicates have a potential to not only disrupt crystal growth and trigger the formation of cavities in the structure of the calcite host, but also to provide surfaces for the precipitation of different phases in the cavities and to uniformly distribute otherwise incompatible materials in a calcite host crystal. This calls for further exploration of the potential application of phyllosilicates in composite structure development.

Keywords: Calcite; cap carbonate; clay; dolomite; hematite; goethite; illite; kaolinite; nanoparticle; nucleation; phantom crystal; phyllosilicate; Raman spectroscopy; SEM; Snowball Earth; TEM; XRD

Funding statement: This work was supported by the Natural Environment Research Council (grant number NE/L002507/1) and the Slovak Research and Development Agency (grant number APVV- 19-0065). TEM studies were performed at the electron microscopy laboratory of the University of Pannonia, established using grant number GINOP-2.3.3-15-2016-0009 from the European Structural and Investments Funds and the Hungarian Government.

Acknowledgments

We thank Stefan Farsang Sr. for his help with sample collection. The Sedgwick Museum of Earth Sciences, University of Cambridge, is acknowledged for the hematite sample. We thank Tamás G. Weiszburg for a constructive discussion as well as the anonymous reviewers and the associate editor Adam Wallace for their helpful comments and suggestions.

References cited

Allmann, R., and Hinek, R. (2007) The introduction of structure types into the Inorganic Crystal Structure Database ICSD. Acta Crystallographica, A63, 412–417.10.1107/S0108767307038081Suche in Google Scholar

Bálintová, T., Ozdín, D., Fejdi, P., Števko, M., Gregor, M., and Stankovič, J. (2006) Mineralogické štúdium fantómových kalcitov z Gemerskej Vsi—Mineralogical study of phantom calcite from village Gemerská Ves, Slovakia. Mineralia Slovaca, 38, 124–130 (in Slovak).Suche in Google Scholar

Beattie, I.R., and Gilson, T.R. (1970) The single-crystal Raman spectra of nearly opaque materials. Iron(III) oxide and chromium(III) oxide. Journal of the Chemical Society A: Inorganic, Physical, Theoretical, 980–986.10.1039/j19700000980Suche in Google Scholar

Bonev, I.K., Garcia-Ruiz, J.M., Atanassova, R., Otalora, F., and Petrussenko, S. (2005) Genesis of filamentary pyrite associated with calcite crystals. European Journal of Mineralogy, 17, 905–913.10.1127/0935-1221/2005/0017-0905Suche in Google Scholar

Bristow, T.F., Bonifacie, M., Derkowski, A., Eiler, J.M., and Grotzinger, J.P. (2011) A hydrothermal origin for isotopically anomalous cap dolostone cements from south China. Nature, 474, 68–71.10.1038/nature10096Suche in Google Scholar

Cai, L., Tong, M., Wang, X., and Kim, H. (2014) Influence of clay particles on the transport and retention of titanium dioxide nanoparticles in quartz sand. Environmental Science & Technology, 48, 7323–7332.10.1021/es5019652Suche in Google Scholar

Cloots, R. (1991) Raman spectrum of carbonates MIICO3 in the 1100–1000 cm−1 region: Observation of the n1 mode of the isotopic (C16O218O)2– ion. Spectro-chimica Acta Part A: Molecular Spectroscopy, 47, 1745–1750.10.1016/0584-8539(91)80012-8Suche in Google Scholar

Coelho, A.A. (2018) TOPAS and TOPAS-Academic: an optimization program integrating computer algebra and crystallographic objects written in C++. Journal of Applied Crystallography, 51, 210–218.10.1107/S1600576718000183Suche in Google Scholar

Couture, L. (1947) Étude des spectres de vibrations de monocristaux ioniques. Annales de Physique, 12, 5–94. EDP Sciences.10.1051/anphys/194711020005Suche in Google Scholar

Cuadros, J., Diaz-Hernandez, J.L., Sanchez-Navas, A., Garcia-Casco, A., and Yepes, J. (2016) Chemical and textural controls on the formation of sepiolite, palygorskite and dolomite in volcanic soils. Geoderma, 271, 99–114.10.1016/j.geoderma.2016.01.042Suche in Google Scholar

De La Pierre, M., Carteret, C., Maschio, L., André, E., Orlando, R., and Dovesi, R. (2014) The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study. The Journal of Chemical Physics, 140, 164509.10.1063/1.4871900Suche in Google Scholar PubMed

Díaz-Hernández, J.L., Sánchez-Navas, A., and Reyes, E. (2013) Isotopic evidence for dolomite formation in soils. Chemical Geology, 347, 20–33.10.1016/j.chemgeo.2013.03.018Suche in Google Scholar

Elečko, M., Gaál, Ľ., Lexa, J., Mello, J., Pristaš, J., Vass, D., and Vozárová, A. (1985) Geologická mapa Rimavskej kotliny a priľahlej časti Slovenského rudohoria 1:50 000—Geological map of the Rimava Basin and the adjacent part of the Slovak Ore Mountains 1:50 000 (in Slovak). Bratislava. GÚDŠ.Suche in Google Scholar

Eslinger, E., Highsmith, P., Albers, D., and De Mayo, B. (1979) Role of iron reduction in the conversion of smectite to illite in bentonites in the disturbed belt, Montana. Clays and Clay Minerals, 27, 327–338.10.1346/CCMN.1979.0270503Suche in Google Scholar

Farfan, G.A., and Post, J.E. (2019) Quartz from Madagascar with fuchsite phantom inclusions. The Journal of Gemmology, 36, 698–699.10.15506/JoG.2019.36.8.698Suche in Google Scholar

Farsang, S., Facq, S., and Redfern, S.A.T. (2018) Raman modes of carbonate minerals as pressure and temperature gauges up to 6 GPa and 500 °C. American Mineralogist, 103, 1988–1998.Suche in Google Scholar

Fodor, M.A., Ható, Z., Kristóf, T., and Pósfai, M. (2020) The role of clay surfaces in the heterogeneous nucleation of calcite: Molecular dynamics simulations of cluster formation and attachment. Chemical Geology, 538, 119497.10.1016/j.chemgeo.2020.119497Suche in Google Scholar

Gaál, Ľ. (2008) Geodynamika a vývoj jaskýň Slovenského krasu—Geodynamics and development of caves in the Slovak Karst (in Slovak), 168 p. State Nature Conservancy of the Slovak Republic, Slovak Caves Administration, Žilina.Suche in Google Scholar

Galindo-Gonzalez, C., Feinberg, J.M., Kasama, T., Gontard, L.C., Pósfai, M., Kósa, I., Duran, J.D.G., Gil, J.E., Harrison, R. J., and Dunin-Borkowski, R.E. (2009) Magnetic and microscopic characterization of magnetite nanoparticles adhered to clay surfaces. American Mineralogist, 94, 1120–1129.10.2138/am.2009.3167Suche in Google Scholar

Gornitz, V. (1981) Phantom crystals. In Mineralogy. Encyclopedia of Earth Science, p. 368–369, Springer.10.1007/0-387-30720-6_99Suche in Google Scholar

Green, D.C., Ihli, J., Thornton, P.D., Holden, M.A., Marzec, B., Kim, Y.-Y., Kulak, A.N., Levenstein, M.A., Tang, C., Lynch, C., and others (2016) 3D visualization of additive occlusion and tunable full-spectrum fluorescence in calcite. Nature Communications, 7, 13524–13513.10.1038/ncomms13524Suche in Google Scholar

Haas, J., Demény, A., Hips, K., and Vennemann, T.W. (2006) Carbon isotope excursions and microfacies changes in marine Permian-Triassic boundary sections in Hungary. Palaeogeography, Palaeoclimatology, Palaeoecology, 237, 160–181.10.1016/j.palaeo.2005.11.017Suche in Google Scholar

Hyodo, M., Sano, T., Matsumoto, M., Seto, Y., Bradák, B., Suzuki, K., Fukuda, J., Shi, M., and Yang, T. (2020) Nanosized authigenic magnetite and hematite particles in mature-paleosol phyllosilicates: New evidence for a magnetic enhancement mechanism in loess sequences of China. Journal of Geophysical Research: Solid Earth, 125, e2019JB018705.10.1029/2019JB018705Suche in Google Scholar

Johnston, W.D., and Butler, R.D. (1946) Quartz crystal in Brazil. Bulletin of the Geological Society of America, 57, 601–650.10.1130/0016-7606(1946)57[601:QCIB]2.0.CO;2Suche in Google Scholar

Kahle, C.F. (1965) Possible roles of clay minerals in the formation of dolomite. SEPM Journal of Sedimentary Research, 35, 448–453.Suche in Google Scholar

Katz, B., Elmore, R.D., and Engel, M.H. (1998) Authigenesis of magnetite in organic-rich sediment next to a dike: Implications for thermoviscous and chemical remagnetizations. Earth and Planetary Science Letters, 163, 221–234.10.1016/S0012-821X(98)00189-7Suche in Google Scholar

Katz, B., Elmore, R.D., Cogoini, M., Engel, M.H., and Ferry, S. (2000) Associations between burial diagenesis of smectite, chemical remagnetization, and magnetite authigenesis in the Vocontian trough, SE France. Journal of Geophysical Research: Solid Earth, 105, 851–868.10.1029/1999JB900309Suche in Google Scholar

Kim, Y.-Y., Ganesan, K., Yang, P., Kulak, A.N., Borukhin, S., Pechook, S., Ribeiro, L., Kröger, R., Eichhorn, S.J., Armes, S.P., and others (2011) An artificial biomineral formed by incorporation of copolymer micelles in calcite crystals. Nature Materials, 10, 890–896.10.1038/nmat3103Suche in Google Scholar

Krishnamurti, D. (1957) The Raman spectrum of calcite and its interpretation. Proceedings of the Indian Academy of Sciences–Section A, 46, 183–202.10.1007/BF03045968Suche in Google Scholar

Krishnan, R.S. (1945) Raman spectra of the second order in crystals Part I: Calcite. Proceedings of the Indian Academy of Sciences–Section A, 22, 182–192.10.1007/BF03170928Suche in Google Scholar

Kulak, A.N., Semsarilar, M., Kim, Y.-Y., Ihli, J., Fielding, L.A., Cespedes, O.,Armes, S.P., and Meldrum, F.C. (2014) One-pot synthesis of an inorganic heterostructure: uniform occlusion of magnetite nanoparticles within calcite single crystals. Chemical Science, 5, 738–743.10.1039/C3SC52615ASuche in Google Scholar

Liu, D., Xu, Y., Papineau, D., Yu, N., Fan, Q., Qiu, X., and Wang, H. (2019) Experimental evidence for abiotic formation of low-temperature proto-dolomite facilitated by clay minerals. Geochimica et Cosmochimica Acta, 247, 83–95.10.1016/j.gca.2018.12.036Suche in Google Scholar

Massey, M.J., Baier, U., Merlin, R., and Weber, W.H. (1990) Effects of pressure and isotopic substitution on the Raman spectrum of α-Fe2O3: Identification of two-magnon scattering. Physical Review. B, Condensed Matter, 41, 7822–7827.10.1103/PhysRevB.41.7822Suche in Google Scholar

McCarty, K.F., and Boehme, D.R. (1989) A Raman study of the systems Fe3–xCrxO4 and Fe2–xCrxO3. Journal of Solid State Chemistry, 79, 19–27.10.1016/0022-4596(89)90245-4Suche in Google Scholar

McCrea, J.M. (1950) On the isotopic chemistry of carbonates and a paleotemperature scale. The Journal of Chemical Physics, 18, 849–857.10.1063/1.1747785Suche in Google Scholar

McHargue, T.R., and Price, R.C. (1982) Dolomite from clay in argillaceous or shale-associated marine carbonates. Journal of Sedimentary Petrology, 52, 873–886.Suche in Google Scholar

Molnár, Z., Pekker, P., Dódony, I., and Pósfai, M. (2021) Clay minerals affect calcium (magnesium) carbonate precipitation and aging. Earth and Planetary Science Letters, 567, 116971.10.1016/j.epsl.2021.116971Suche in Google Scholar

Montgomery, P., Hailwood, E.A., Gale, A.S., and Burnett, J.A. (1998) The magnetostratigraphy of Coniacian-Late Campanian chalk sequences in southern England. Earth and Planetary Science Letters, 156, 209–224.10.1016/S0012-821X(98)00008-9Suche in Google Scholar

Németh, T., Máthé, Z., Pekker, P., Dódony, I., Kovács-Kis, V., Sipos, P., Cora, I., and Kovács, I. (2016) Clay mineralogy of the Boda Claystone Formation (Mecsek Mts., SW Hungary). Open Geosciences, 8, 259–274.10.1515/geo-2016-0024Suche in Google Scholar

Nyirő-Kósa, I., Rostási, Á., Bereczk-Tompa, É., Cora, I., Koblar, M., Kovács, A., and Pósfai, M. (2018) Nucleation and growth of Mg-bearing calcite in a shallow, calcareous lake. Earth and Planetary Science Letters, 496, 20–28.10.1016/j.epsl.2018.05.029Suche in Google Scholar

Rae Cho, K., Kim, Y.-Y., Yang, P., Cai, W., Pan, H., Kulak, A.N., Lau, J.L., Kulshreshtha, P., Armes, S.P., Meldrum, F.C., and others (2016) Direct observation of mineral-organic composite formation reveals occlusion mechanism. Nature Communications, 7, 10187–10187.10.1038/ncomms10187Suche in Google Scholar PubMed PubMed Central

Ramamurthy, V., and Eaton, D.F. (1994) Perspectives on solid-state host-guest assemblies. Chemistry of Materials, 6, 1128–1136.10.1021/cm00044a011Suche in Google Scholar

Raub, T.D., Evans, D.A.D., and Smirnov, A.V. (2007) Siliciclastic prelude to Elatina-Nuccaleena deglaciation: Lithostratigraphy and rock magnetism of the base of the Ediacaran system. Geological Society Special Publication, 286, 53–76.10.1144/SP286.5Suche in Google Scholar

Rehtijärvi, P., and Kinnunen, K.A. (1979) Fluid and mineral inclusions and inclusion zones of cave calcite from Korsnäs mine, western Finland. Bulletin of the Geological Society of Finland, 51, 75–79.10.17741/bgsf/51.1-2.008Suche in Google Scholar

Saloman, E.B., and Sansonetti, C.J. (2004) Wavelengths, energy level classifications, and energy levels for the spectrum of neutral neon. Journal of Physical and Chemical Reference Data, 33, 1113–1158.10.1063/1.1797771Suche in Google Scholar

Shim, S.-H., and Duffy, T.S. (2002) Raman spectroscopy of Fe2O3 to 62 GPa. American Mineralogist, 87, 318–326.10.2138/am-2002-2-314Suche in Google Scholar

Sinkankas, J. (1966) Mineralogy: A First Course. Van Nostrand Company.Suche in Google Scholar

Tombácz, E., and Szekeres, M. (2006) Surface charge heterogeneity of kaolinite in aqueous suspension in comparison with montmorillonite. Applied Clay Science, 34, 105–124.10.1016/j.clay.2006.05.009Suche in Google Scholar

Wanas, H.A., and Sallam, E. (2016) Abiotically-formed, primary dolomite in the mid-Eocene lacustrine succession at Gebel El-Goza El-Hamra, NE Egypt: An approach to the role of smectitic clays. Sedimentary Geology, 343, 132–140.10.1016/j.sedgeo.2016.08.003Suche in Google Scholar

Weber, J.N. (1964) Carbon isotope ratios in dolostones: some implications concerning the genesis of secondary and “primary” dolostones. Geochimica et Cosmochimica Acta, 28, 1257–1265.10.1016/0016-7037(64)90127-9Suche in Google Scholar

Woods, S.D. (2002) Paleomagnetic dating of the smectite-to-illite conversion: Testing the hypothesis in Jurassic sedimentary rocks, Skye, Scotland. Journal of Geophysical Research, 107.10.1029/2000JB000053Suche in Google Scholar

Zhou, D., Abdel-Fattah, A.I., and Keller, A.A. (2012) Clay Particles destabilize engineered nanoparticles in aqueous environments. Environmental Science & Technology, 26, 7520–7526.10.1021/es3004427Suche in Google Scholar PubMed

Received: 2020-02-20
Accepted: 2021-07-07
Published Online: 2022-07-02
Published in Print: 2022-07-26

© 2022 Mineralogical Society of America

Artikel in diesem Heft

  1. Highlights and Breakthroughs
  2. Mineral evolution heralds a new era for mineralogy
  3. MSA Review
  4. Pauling’s rules for oxide-based minerals: A re-examination based on quantum mechanical constraints and modern applications of bond-valence theory to Earth materials
  5. A cotunnite-type new high-pressure phase of Fe2S
  6. Density determination of liquid iron-nickel-sulfur at high pressure
  7. On the paragenetic modes of minerals: A mineral evolution perspective
  8. Lumping and splitting: Toward a classification of mineral natural kinds
  9. Thermal expansion of minerals in the amphibole supergroup
  10. A multi-faceted experimental study on the dynamic behavior of MgSiO3 glass in the Earth’s deep interior
  11. Origin of β-cristobalite in Libyan Desert Glass: The hottest naturally occurring silica polymorph?
  12. Time-resolved Raman and luminescence spectroscopy of synthetic REE-doped hydroxylapatites and natural apatites
  13. Reexamination of the structure of opal-A: A combined study of synchrotron X-ray diffraction and pair distribution function analysis
  14. A first-principles study of water in wadsleyite and ringwoodite: Implication for the 520 km discontinuity
  15. Inclusions in calcite phantom crystals suggest role of clay minerals in dolomite formation
  16. Crystal-chemical reinvestigation of probertite, CaNa[B5O7(OH)4]·3H2O, a mineral commodity of boron
  17. Crystal structure determination of orthorhombic variscite2O and its derivative AlPO4 structure at high temperature
  18. Transformation of Fe-bearing minerals from Dongsheng sandstone-type uranium deposit, Ordos Basin, north-central China: Implications for ore genesis
  19. Vaterite in a decrepitated diamond-bearing inclusion in zircon from a stromatic migmatite in the Chinese Sulu ultrahigh-pressure metamorphic belt
  20. Oxygen diffusion in garnet: Experimental calibration and implications for timescales of metamorphic processes and retention of primary O isotopic signatures
  21. Oxidation state of iron and Fe-Mg partitioning between olivine and basaltic martian melts
https://doi.org/10.2138/am-2020-7483
Schlagwörter für diesen Artikel
Calcite; cap carbonate; clay; dolomite; hematite; goethite; illite; kaolinite; nanoparticle; nucleation; phantom crystal; phyllosilicate; Raman spectroscopy; SEM; Snowball Earth; TEM; XRD

Artikel in diesem Heft

  1. Highlights and Breakthroughs
  2. Mineral evolution heralds a new era for mineralogy
  3. MSA Review
  4. Pauling’s rules for oxide-based minerals: A re-examination based on quantum mechanical constraints and modern applications of bond-valence theory to Earth materials
  5. A cotunnite-type new high-pressure phase of Fe2S
  6. Density determination of liquid iron-nickel-sulfur at high pressure
  7. On the paragenetic modes of minerals: A mineral evolution perspective
  8. Lumping and splitting: Toward a classification of mineral natural kinds
  9. Thermal expansion of minerals in the amphibole supergroup
  10. A multi-faceted experimental study on the dynamic behavior of MgSiO3 glass in the Earth’s deep interior
  11. Origin of β-cristobalite in Libyan Desert Glass: The hottest naturally occurring silica polymorph?
  12. Time-resolved Raman and luminescence spectroscopy of synthetic REE-doped hydroxylapatites and natural apatites
  13. Reexamination of the structure of opal-A: A combined study of synchrotron X-ray diffraction and pair distribution function analysis
  14. A first-principles study of water in wadsleyite and ringwoodite: Implication for the 520 km discontinuity
  15. Inclusions in calcite phantom crystals suggest role of clay minerals in dolomite formation
  16. Crystal-chemical reinvestigation of probertite, CaNa[B5O7(OH)4]·3H2O, a mineral commodity of boron
  17. Crystal structure determination of orthorhombic variscite2O and its derivative AlPO4 structure at high temperature
  18. Transformation of Fe-bearing minerals from Dongsheng sandstone-type uranium deposit, Ordos Basin, north-central China: Implications for ore genesis
  19. Vaterite in a decrepitated diamond-bearing inclusion in zircon from a stromatic migmatite in the Chinese Sulu ultrahigh-pressure metamorphic belt
  20. Oxygen diffusion in garnet: Experimental calibration and implications for timescales of metamorphic processes and retention of primary O isotopic signatures
  21. Oxidation state of iron and Fe-Mg partitioning between olivine and basaltic martian melts
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