Abstract
Polytypism is a typical feature of layered minerals with differences only in stacking sequences. There is no obvious “phase” boundary among different polytypes, although the frequency of polytypes occurrence is related to its crystallization environment. In the past decades, X‑ray studies of molybdenite specimens from a variety of geological environments have revealed that most molybdenite crystals contain both 2H1 (hexagonal) and 3R (rhombohedral) polytypes. However, the stacking sequences of these molybdenite polytypic intergrowths and their formation mechanism are not well understood. Here, we report stacking faults and domains of long-period polytypes identified by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) in a molybdenite sample from a carbonatite vein in the Huanglongpu Mo-Pb ore deposit in Qinling orogenic belt, Northern China. Several layers of disordered domains intergrown with ordered 2H1 domain were recognized based on the contrast in HAADF image with one-dimensional lattice fringes. In addition, a 30-layer long-period polytype was unambiguously identified by a STEM image. The stacking sequences of 4-, 6-, and 8-layer disordered domains and the 30-layer long-period polytype were further examined using HRSTEM images at the atomic resolution. A 2H3 polytype with three repetitions was also discovered in the sample. We propose that non-equilibrium conditions related to the fluctuation of fluid composition during crystallization resulted in the oscillation of 2H1 and 3R polytypes and intergrowth of various disordered domains. More broadly, our study demonstrates that HAADF-STEM imaging method may be applicable for studying other disordered layered crystals and twinned minerals.
Acknowledgments and Funding
The authors thank Daniel Hummer for handling this paper, and two anonymous reviewer for reviewing the manuscript and providing constructive comments and suggestions. This study was financially supported by the National Key R&D Program of China (2018YFA0702600), China National Funds for Distinguished Young Scientists (Grant No. 41825003), National Natural Science Foundation of China (Grant Nos. 41772039 and 41921003), Youth Innovation Promotion Association CAS (Grant No. 2021353), CAS Key Research Program of Frontier Sciences (Grant No. QYZDJ-SSW-DQC023), Tuguangchi Award for Excellent Young Scholar GIG, CAS, and Science and Technology Planning of Guangdong Province, China (2020B1212060055). This is Contribution No. IS-3170 from GIG-CAS.
References cited
Aoki, M., Miyazaki, M., Nishiguchi, T., Kinoshita, H., and Yoshimoto, M. (2008) TEM observation of the polytype transformation of bulk SiC ingot. Materials Science Forum. https://doi.org/10.4028/www.scientific.net/msf.600-603.36510.4028/www.scientific.net/MSF.600-603.365Search in Google Scholar
Ayres, D. (1974) Distribution and occurrence of some naturally-occurring polytypes of molybdenite in Australia and Papua New Guinea. Journal of the Geological Society of Australia, 21, 273–278.10.1080/00167617408728850Search in Google Scholar
Baronnet, A. (1992) Polytypism and stacking disorder. In P.R. Buseck, Ed., Minerals and Reactions at the Atomic Scale: Transmission Electron Microscopy, vol. 27, p. 231–288. Reviews in Mineralogy, Mineral Society of America, Chantilly, Virginia.10.1515/9781501509735-011Search in Google Scholar
Bell, R.E., and Herfert, R.E. (1957) Preparation and characterization of a new crystalline form of molybdenum disulfide. Journal of the American Chemical Society, 79, 3351–3354.10.1021/ja01570a012Search in Google Scholar
Ciobanu, C.L., Cook, N.J., Kelson, C.R., Guerin, R., Kalleske, N., and Danyushevsky, L. (2013) Trace element heterogeneity in molybdenite fingerprints stages of mineralization. Chemical Geology, 347, 175–189.10.1016/j.chemgeo.2013.03.011Search in Google Scholar
Drábek, M., and Rieder, M.B. (2010) The Re-Mo-S system: new data on phase relations between 400 and 1200°C. European Journal of Mineralogy, 22, 479–484.10.1127/0935-1221/2010/0022-2044Search in Google Scholar
Fang, Y., and Xu, H. (2019) A new approach to quantify the ordering state of protodolomite using XRD, TEM, and Z-contrast imaging. Journal of Sedimentary Research, 89, 537–551.10.2110/jsr.2019.29Search in Google Scholar
Fregola, R.A., and Scandale, E. (2011) A 94-layer long-period mica polytype: A TEM study. American Mineralogist, 96, 172–178.10.2138/am.2011.3624Search in Google Scholar
Frondel, J.W., and Wickman, F.E. (1970) Molybdenite polytypes in theory and occurrence. II. Some naturally-occurring polytypes of molybdenite. American Mineralogist, 55, 1857–1875.Search in Google Scholar
Han, J., Ohnishi, I., and Keller, L.P. (2019) Complex intergrowths of non-stoichiometric defect-structured hibonite and Al-rich spinel in an Allende Ca-Al-rich inclusion. 82nd Annual Meeting of the Meteoritical Society, no. 6487.Search in Google Scholar
Iijama, S., and Buseck, P.R. (1978) Experimental study of disordered mica structures by high-resolution electron microscopy. Acta Crystallographica Section A, 34, 709–719.10.1107/S0567739478001473Search in Google Scholar
Katzke, H., Tolédano, P., and Depmeier, W. (2004) Phase transitions between polytypes and intralayer superstructures in transition metal dichalcogenides. Physical Review B, 69, 134111.10.1103/PhysRevB.69.134111Search in Google Scholar
Keller, L.P., Yasuhara, A., Han, J., and Keller, E.L. (2018) The crystal chemistry of defect-structured meteoritic hibonite: Atomic resolution imaging and x-ray mapping. 49th Lunar and Planetary Science Conference, #2392.Search in Google Scholar
Kogure, T., and Nespolo, M. (1999) A TEM study of long-period mica polytypes: determination of the stacking sequence of oxybiotite by means of atomic resolution images and Periodic Intensity Distribution (PID). Acta Crystallographica. Section B, Structural Science, 55, 507–516.10.1107/S0108768199003845Search in Google Scholar
Lee, J.-U., Kim, K., Han, S., Ryu, G.H., Lee, Z., and Cheong, H. (2016a) Raman signatures of polytypism in molybdenum disulfide. ACS Nano, 10, 1948–1953.10.1021/acsnano.5b05831Search in Google Scholar
Lee, S., Shen, Z., and Xu, H. (2016b) Study on nanophase iron oxyhydroxides in freshwater ferromanganese nodules from Green Bay, Lake Michigan. American Mineralogist, 101, 1986–1995.10.2138/am-2016-5729Search in Google Scholar
Lin, Y.-C., Dumcenco, D.O., Huang, Y.-S., and Suenaga, K. (2014) Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2. Nature Nanotechnology, 9, 391–396.10.1038/nnano.2014.64Search in Google Scholar
McCandless, T.E., Ruiz, J., and Campbell, A.R. (1993) Rhenium behavior in molybdenite in hypogene and near-surface environments: Implications for Re-Os geochronometry. Geochimica et Cosmochimica Acta, 57, 889–905.10.1016/0016-7037(93)90176-WSearch in Google Scholar
McFall, K., Roberts, S., McDonald, I., Boyce, A.J., Naden, J., and Teagle, D. (2019) Rhenium enrichment in the muratdere Cu-Mo (Au-Re) porphyry deposit, Turkey: Evidence from stable isotope analyses (δ34S, δ18O, δD) and laser ablation-inductively coupled plasma-mass spectrometry analysis of sulfides. Economic Geology, 114, 1443–1466.10.5382/econgeo.4638Search in Google Scholar
Newberry, R.J.J. (1979a) Polytypism in molybdenite (I): a non-equilibrium impurity-induced phenomenon. American Mineralogist, 64, 758–769.Search in Google Scholar
Newberry, R.J.J. (1979b) Polytypism molybdenite (II): relationships between polytypism, ore deposition/alteration stages and rhenium contents. American Mineralogist, 64, 768–775.Search in Google Scholar
Pennycook, S.J. (2002) Structure determination through Z-contrast microscopy. Advances in Imaging Electron Physics, 123, 173–206.10.1016/S1076-5670(02)80063-5Search in Google Scholar
Pignatelli, I., Faure, F., and Mosser-Ruck, R. (2016) Self-mixing magma in the Ruiz Peak rhyodacite (New Mexico, USA): A mechanism explaining the formation of long period polytypes of mica. Lithos, 266-267, 332–347.10.1016/j.lithos.2016.10.024Search in Google Scholar
Plotinskaya, O.Y., Shilovskikh, V.V., Najorka, J., Kovalchuk, E.V., Seltmann, R., and Spratt, J. (2019) Grain-scale distribution of molybdenite polytypes versus rhenium contents: μXRD and EBSD data. Mineralogical Magazine, 83, 639–644.10.1180/mgm.2019.49Search in Google Scholar
Ross, M., Takeda, H., and Wones, D.R. (1966) Mica polytypes: Systematic description and identification. Science, 151, 191–193.10.1126/science.151.3707.191Search in Google Scholar PubMed
Shen, Z., Konishi, H., Szlufarska, I., Brown, P.E., and Xu, H. (2014) Z-contrast imaging and ab initio study on “d” superstructure in sedimentary dolomite. American Mineralogist, 99, 1413–1889.10.2138/am.2014.4647Search in Google Scholar
Shiojiri, M., Isshiki, T., Enomoto, S., Kobayashi, E., and Takahashi, N. (1991) High-resolution electron microscopy observations of the layer structures and stacking faults in molybdenite crystals. Philosophical Magazine A, 64, 971–980.10.1080/01418619108213959Search in Google Scholar
Smith, J.V., and Yoder, H.S. (1956) Experimental and theoretical studies of the mica polymorphs. Mineralogical Magazine and Journal of the Mineralogical Society, 31, 209–235.10.1180/minmag.1956.031.234.03Search in Google Scholar
Traill, R.J. (1963) A rhombohedral polytype of molybdenite. Canadian Mineralogist, 7, 524–526.Search in Google Scholar
Voudouris, P.C., Melfos, V., Spry, P.G., Bindi, L., Kartal, T., Arikas, K., Moritz, R., and Ortelli, M. (2009) Rhenium-rich molybdenite and rheniite in the Pagoni Rachi Mo-Cu-Te-Ag-Au prospect, Northern Greece: Implications for the Re geochemistry of porphyry-style Cu-Mo and Mo mineralization. Canadian Mineralogist, 47, 1013–1036.10.3749/canmin.47.5.1013Search in Google Scholar
Wang, Y., and Xu, H. (2001) Prediction of trace metal partitioning between minerals and aqueous solutions: A linear free energy correlation approach. Geochimica et Cosmochimica Acta, 65, 1529–1543.10.1016/S0016-7037(01)00551-8Search in Google Scholar
Wickman, F.E., and Smith, D.K. (1970) Molybdenite polytypes in theory and occurrence. I. Theoretical considerations of polytypism in molybdenite. American Mineralogist, 55, 1843–1856.Search in Google Scholar
Wypych, F., and Schöllhorn, R. (1992) 1T-MoS2, a new metallic modification of molybdenum disulfide. Chemical Communications, 1386–1388.10.1039/C39920001386Search in Google Scholar
Xu, H. (2015) Direct observation of Ca-Na ordering and structural polarity in the intermediate plagioclase feldspar with incommensurate modulated structure. American Mineralogist, 100, 510–515.10.2138/am-2015-5022Search in Google Scholar
Xu, H., Jin, S., and Noll, B.C. (2016) Incommensurate density modulation in a Na-rich plagioclase feldspar: Z-contrast imaging and single-crystal X-ray diffraction study. Acta Crystallographica, B72, 904–915.Search in Google Scholar
Xu, H.F., and Veblen, D.R. (1995) Periodic and non-periodic stacking in biotite from the Bingham Canyon porphyry copper deposit, Utah. Clays and Clay Minerals, 43, 159–173.10.1346/CCMN.1995.0430203Search in Google Scholar
Yang, Y.P., He, H.P., Tan, W., Tao, Q., Yao, J.M., Xian, H.Y., Li, S.Y., Xi, J.X., Zhu, J.X., and Xu, H.F. (2022) Incorporation of incompatible trace elements into molybdenite: Layered PbS precipitates within molybdenite. American Mineralogist, 107, 54–64.10.2138/am-2021-7609Search in Google Scholar
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Articles in the same Issue
- Periodic and non-periodic stacking in molybdenite (MoS2) revealed by STEM
- The effect of halogens (F, Cl) on the near-liquidus crystallinity of a hydrous trachyte melt
- Occurrence of tuite and ahrensite in Zagami and their significance for shock-histories recorded in martian meteorites
- Zolenskyite, FeCr2S4, a new sulfide mineral from the Indarch meteorite
- Refined estimation of Li in mica by a machine learning method
- Olivine in picrites from continental flood basalt provinces classified using machine learning
- The glass transition and the non-Arrhenian viscosity of carbonate melts
- Etching of fission tracks in monazite: Further evidence from optical and focused ion beam scanning electron microscopy
- The low-temperature shift of antigorite dehydration in the presence of sodium chloride: In situ diffraction study up to 3 GPa and 700 °C
- Chemistry-dependent Raman spectral features of glauconite and nontronite: Implications for mineral identification and provenance analysis
- Experimental determination of solubility constants of saponite at elevated temperatures in high ionic strength solutions
- Hydrothermal troctolite alteration at 300 and 400 °C: Insights from flexible Au-reaction cell batch experimental investigations
- Timescales and rates of intrusive and metamorphic processes determined from zircon and garnet in migmatitic granulite, Fiordland, New Zealand
- In situ chemical and isotopic analyses and element mapping of multiple-generation pyrite: Evidence of episodic gold mobilization and deposition for the Qiucun epithermal gold deposit in Southeast China
- Hydrothermal mineralization of celadonite: Hybridized fluid–basalt interaction in Janggi, Korea
- Gungerite, TlAs5Sb4S13, a new thallium sulfosalt with a complex structure containing covalent As-As bonds
- Nitscheite, (NH4)2[(UO2)2(SO4)3(H2O)2]·3H2O, a new mineral with an unusual uranyl-sulfate sheet
- Protocaseyite, a new decavanadate mineral containing a [Al4(OH)6(H2O)12]6+ linear tetramer, a novel isopolycation
- Fission-track etching in apatite: A model and some implications
- Hydrothermal monazite trumps rutile: Applying U-Pb geochronology to evaluate complex mineralization ages of the Katbasu Au-Cu deposit, Western Tianshan, Northwest China
- Erratum
Articles in the same Issue
- Periodic and non-periodic stacking in molybdenite (MoS2) revealed by STEM
- The effect of halogens (F, Cl) on the near-liquidus crystallinity of a hydrous trachyte melt
- Occurrence of tuite and ahrensite in Zagami and their significance for shock-histories recorded in martian meteorites
- Zolenskyite, FeCr2S4, a new sulfide mineral from the Indarch meteorite
- Refined estimation of Li in mica by a machine learning method
- Olivine in picrites from continental flood basalt provinces classified using machine learning
- The glass transition and the non-Arrhenian viscosity of carbonate melts
- Etching of fission tracks in monazite: Further evidence from optical and focused ion beam scanning electron microscopy
- The low-temperature shift of antigorite dehydration in the presence of sodium chloride: In situ diffraction study up to 3 GPa and 700 °C
- Chemistry-dependent Raman spectral features of glauconite and nontronite: Implications for mineral identification and provenance analysis
- Experimental determination of solubility constants of saponite at elevated temperatures in high ionic strength solutions
- Hydrothermal troctolite alteration at 300 and 400 °C: Insights from flexible Au-reaction cell batch experimental investigations
- Timescales and rates of intrusive and metamorphic processes determined from zircon and garnet in migmatitic granulite, Fiordland, New Zealand
- In situ chemical and isotopic analyses and element mapping of multiple-generation pyrite: Evidence of episodic gold mobilization and deposition for the Qiucun epithermal gold deposit in Southeast China
- Hydrothermal mineralization of celadonite: Hybridized fluid–basalt interaction in Janggi, Korea
- Gungerite, TlAs5Sb4S13, a new thallium sulfosalt with a complex structure containing covalent As-As bonds
- Nitscheite, (NH4)2[(UO2)2(SO4)3(H2O)2]·3H2O, a new mineral with an unusual uranyl-sulfate sheet
- Protocaseyite, a new decavanadate mineral containing a [Al4(OH)6(H2O)12]6+ linear tetramer, a novel isopolycation
- Fission-track etching in apatite: A model and some implications
- Hydrothermal monazite trumps rutile: Applying U-Pb geochronology to evaluate complex mineralization ages of the Katbasu Au-Cu deposit, Western Tianshan, Northwest China
- Erratum