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Licensed Unlicensed Requires Authentication Published by De Gruyter March 28, 2022

Ferro-tschermakite with polysomatic chain-width disorder identified in silician magnetite from Wirrda Well, South Australia: A HAADF STEM study

  • Cristiana L. Ciobanu , Max R. Verdugo-Ihl ORCID logo , Nigel J. Cook ORCID logo , Kathy Ehrig ORCID logo , Ashley Slattery and Liam Courtney-Davies
From the journal American Mineralogist

Abstract

Silician magnetite within ~1.85 Ga lithologies hosting the ~1.6 Ga Wirrda Well iron oxide copper gold (IOCG) prospect, South Australia, was examined at the nanoscale. The magnetite is oscillatory-zoned with respect to the density and orientation of nanometer-scale inclusions, among which Si-Fe-nanorods and Al-rich amphibole (as much as hundreds of nanometers long and tens of nanometers wide) form swarms along <111> directions in magnetite. The amphibole is identified as ferro-tschermakite (Ftsk) with the crystal-chemical formula: A K 0.06 N a 0.01 0.07 B C a 1.65 N a 0.35 2 C F e 2.07 2 A l 1.64 M g 1.15 T i 0.06 F e 0.04 33 M n 0.04 5 T S i 6.48 A l 1.52 8 O 22 W ( O H ) 2 . This contains single and double rows of a triple-chain silicate attributed to clinojimthompsonite (Cjt) as coherently intergrown (010) zippers along the entire length of the grains. High-angle annular dark-field scanning transmission electron microscopy (HAADF STEM) imaging and simulation of Ftsk and Cjt on the [001] zone axis provide direct visualization of crystal structures. These are defined by the 7- and 10-atom octahedron strips (B+C sites) and flanked by double- and triple-pairs of Si atoms (T sites). Remarkably, the sites for light cations and/or vacancies are clearly imaged as single and double, darkest, diamond-shaped motifs separating the octahedron strips showing that A cavities known in amphibole are readily depicted in the wider-chain silicate. I-beam models show that nanoscale intergrowths among the two silicates are coherent along zigzag chains of cations at the edges of the octahedron strips, with single and double rows of the triple-chain silicate corresponding to 1 and 1.5 unit cells of Cjt (27 and 41 Å intervals along the b axis). This type of polysomatic chain-width disorder is widely reported in Mg-rich pyriboles but is shown here in an Al-Fe-rich amphibole. The lack of planar deffects and/or reaction fronts at mutual contacts between three-chain zippers and host amphibole indicates primary co-crystallization growth, promoted by the formation of the Si-Fe-nanorods. Co-crystallizing plagioclase is also preserved in close vicinity to the amphibole hosted by magnetite (from a few nanometers to micrometers apart). In contrast, the replacement of amphibole by phyllosilicates is recognizable as irregular swells along the (010) zippers and results in extensive chloritization of the amphibole during an overprinting event. Pressures of ~11.5 kbar are estimated using Al-in-hornblende nano-geobarometry and calculated Al content in Ftsk (3.16 apfu). Assuming the amphibole-plagioclase association buffered by host magnetite fulfills the textural equilibration criteria required for application of this barometer, we interpret the Ftsk nanoinclusions in magnetite as preserved evidence for amphibolite facies metamorphism afecting host lithologies at Wirrda Well with subsequent retrograde alteration during the ~1.6 Ga IOCG mineralizing event. Magnetite records petrogenetic processes by accommodating variable ranges of nanomineral inclusions and preserving them over geological time scales. HAADF STEM imaging is ideally suited to the depiction of crystal-structural modularity and also provides insights into the evolution of geological terranes with protracted histories.

Acknowledgments

This is a contribution to the “FOX” project (trace elements in iron oxides: deportment, distribution and application in ore genesis, geochronology, exploration and mineral processing), supported by BHP Olympic Dam and the South Australian Government Mining and Petroleum Services Centre of Excellence. We acknowledge reviews by Fernando Cámara, David M. Jenkins, and an anonymous reviewer, and manuscript handling by Associate Editor Simon Redfern.

References cited

Abdu, Y.A., and Hawthorne, F.C. (2009) Crystal structure and Mössbauer spectroscopy of tschermakite from the Ruby locality at Fiskenaesset, Greenland. Canadian Mineralogist, 47, 917–926.10.3749/canmin.47.4.917Search in Google Scholar

Ams, B.E., and Jenkins, D.M. (2011) Formation conditions for triple-chain silicates. American Mineralogist, 96, 814–819.10.2138/am.2011.3568Search in Google Scholar

Bosi, F., Biagioni, C., and Pasero, M. (2019) Nomenclature and classification of the spinel supergroup. European Journal of Mineralogy, 31, 183–192.10.1127/ejm/2019/0031-2788Search in Google Scholar

Bozhilov, K.N. (2013) Structures and microstructures of non-classical pyriboles. EMU Notes in Mineralogy, 14, 109–152.10.1180/EMU-notes.14.4Search in Google Scholar

Champness, P.E. (2002) Applications of transmission electron microscopy. In P.W. Hawkes, B. Kazantor, T. Mulvey, Eds., Advances in Imaging and Electron Physics, vol. 121, p. 53–90. Academic Press.10.1016/S1076-5670(02)80025-8Search in Google Scholar

Chen, T., Jin, Z., Zhang, J., and Wang, L. (2019) Calcium amphibole exsolution lamellae in chromite from the Semail ophiolite: Evidence for a high-pressure origin. Lithos, 334-335, 273–280.10.1016/j.lithos.2019.03.020Search in Google Scholar

Ciobanu, C.L., Cook, N.J., Utsunomiya, S., Pring, A., and Green, L. (2011) Focused ion beam–transmission electron microscopy applications in ore mineralogy: Bridging micro- and nanoscale observations. Ore Geology Reviews, 42, 6–31.10.1016/j.oregeorev.2011.06.012Search in Google Scholar

Ciobanu, C.L., Cook, N. J., Maunders, C., Wade, B.P., and Ehrig, K. (2016) Focused ion beam and advanced electron microscopy for minerals: Insights and outlook from bismuth sulphosalts. Minerals, 6, 112.10.3390/min6040112Search in Google Scholar

Ciobanu, C.L., Kontonikas-Charos, A., Slattery, A., Cook, N.J., Ehrig, K., and Wade, B.P. (2017) Short-range stacking disorder in mixed-layer compounds: a HAADF STEM study of bastnäsite-parisite intergrowths. Minerals, 7, 227.10.3390/min7110227Search in Google Scholar

Ciobanu, C.L., Utsunomiya, S., Reich, M., Plümper, O., and Cook, N.J. (2019a) Editorial for Special Issue “Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes”. Minerals, 9, 692.10.3390/min9110692Search in Google Scholar

Ciobanu, C.L., Verdugo-Ihl, M.R., Slattery, A., Cook, N.J., Ehrig, K., Courtney-Davies, L., and Wade, B.P. (2019b) Silician magnetite: Si–Fe-nanoprecipitates and other mineral inclusions in magnetite from the Olympic Dam Deposit, South Australia. Minerals, 9, 311.10.3390/min9050311Search in Google Scholar

Cook, N.J., Ciobanu, C.L., Liu, W.Y., Slattery, A., Wade, B.P., Mills, S., and Stanley, C.J. (2019) Polytypism and polysomatism in mixed-layer chalcogenides: Characterization of PbBi4Te4S3 and inferences for ordered phases in the aleksite series. Minerals, 9, 628.10.3390/min9100628Search in Google Scholar

Courtney-Davies, L., Ciobanu, C.L., Verdugo-Ihl, M.R., Dmitrijeva, M., Cook, N.J., Ehrig, K., and Wade, B.P. (2019) Hematite geochemistry and geochronology resolve genetic and temporal links among iron-oxide copper gold systems, Olympic Dam district, South Australia. Precambrian Research, 335, 105480.10.1016/j.precamres.2019.105480Search in Google Scholar

Courtney-Davies, L., Ciobanu, C.L., Tapster, S.R., Cook, N.J., Ehrig, K., Crowley, J.L., Verdugo-Ihl, M.R., Wade, B.P., and Condon, D.J. (2020a) Opening the magmatic-hydrothermal window: High-precision U-Pb geochronology of the Mesoproterozoic Olympic Dam Cu-U-Au-Ag Deposit, South Australia. Economic Geology, 115, 1855–1870.10.5382/econgeo.4772Search in Google Scholar

Courtney-Davies, L., Ciobanu, C.L., Verdugo-Ihl, M.R., Cook, N.J., Ehrig, K., Wade, B.P., Zhu, Z.-Y., and Kamenetsky, V.S. (2020b) ~1760 Ma magnetite-bearing protoliths in the Olympic Dam deposit, South Australia: Implications for ore genesis and regional metallogeny. Ore Geology Reviews, 118, 103337.10.1016/j.oregeorev.2020.103337Search in Google Scholar

Cressey, B.A., Whittaker, E. J.W., and Hutchison, J.L. (1982) Morphology and alteration of asbestiform grunerite and anthophyllite. Mineralogical Magazine, 46, 77–87.10.1180/minmag.1982.046.338.13Search in Google Scholar

Deditius, A.P., Reich, M., Simon, A.C., Suvorova, A., Knipping, J., Roberts, M.P., Rubanov, S., Dodd, A., and Saunders, M. (2018) Nanogeochemistry of hydrothermal magnetite. Contributions to Mineralogy and Petrology, 173, 46.10.1007/s00410-018-1474-1Search in Google Scholar

Deer, W.A., Howie, R.A., and Zussman, J. (2013) An Introduction to the Rock-Forming Minerals, 3rd edition. Mineralogical Society of Great Britain and Ireland.10.1180/DHZSearch in Google Scholar

Drits, V.A., Guggenheim, S., Zviagina, B.B., and Kogure, T. (2012) Structures of the 2:1 layers of pyrophyllite and talc. Clays and Clay Minerals, 60, 574–587.10.1346/CCMN.2012.0600603Search in Google Scholar

Fleet, M.E., Bilcox, G.A., and Barnett, R.L. (1980) Oriented magnetite inclusions in pyroxenes from the Grenville Province. Canadian Mineralogist, 18, 89–99.Search in Google Scholar

Gao, W., Ciobanu, C.L., Cook, N.J., Slattery, A., Huang, F., and Wang, D. (2019a) Nanoscale study of lamellar exsolutions in clinopyroxene from olivine gabbro: Recording crystallization sequences in iron-rich layered intrusions. American Mineralogist, 104, 244–261.Search in Google Scholar

Gao, W., Ciobanu, C.L., Cook, N.J., Slattery, A., Huang, F., and Song, D. (2019b) Nanoscale study of titanomagnetite from the Panzhihua Layered Intrusion, Southwest China: Multistage exsolutions record ore formation. Minerals, 9, 513.10.3390/min9090513Search in Google Scholar

Grobety, B.H. (1996) New short-range biopyribole polysomes from the Lepontine Alps, Switzerland. American Mineralogist, 81, 404–417.10.2138/am-1996-3-415Search in Google Scholar

Grobéty, B.H. (1997) The replacement of anthophyllite by jimthompsonite: a model for hydration reactions in biopyriboles. Contributions to Mineralogy and Petrology, 127, 237–247.10.1007/s004100050277Search in Google Scholar

Hammarstrom, J.M., and Zen, E-A. (1986) Aluminum in hornblende: An empirical igneous geobarometer. American Mineralogist, 71, 1297–1313.Search in Google Scholar

Hawthorne, F., and Grundy, H. (1973) The crystal chemistry of the amphiboles. I: Refinement of the Crystal structure of ferrotschermakite. Mineralogical Magazine, 39, 36–48.10.1515/9781501508523-002Search in Google Scholar

Hawthorne, F.C., Della Ventura, G., Oberti, R., Robert, J.-L., and Iezzi, G. (2005) Short-range order in minerals: Amphiboles. Canadian Mineralogist, 43, 1895–1920.10.2113/gscanmin.43.6.1895Search in Google Scholar

Hawthorne, F.C., Oberti, R., Harlow, G.E., Maresch, W.V., Martin, R.F., Schumacher, J.C., and Welch, M.D. (2012) Nomenclature of the amphibole supergroup. American Mineralogist, 97, 2031–2048.10.2138/am.2012.4276Search in Google Scholar

Keyser, W., Ciobanu, C.L., Cook, N.J., Courtney-Davies, L., Kennedy, A., Wade, B.P., Ehrig, K., Dmitrijeva, M., Kontonikas-Charos, A., Feltus, H., and Johnson, G. (2019) Petrographic and geochronological constraints on the granitic basement to the Middleback Ranges, South Australia. Precambrian Research, 324, 170–193.10.1016/j.precamres.2019.01.024Search in Google Scholar

Konishi, H., Akai, J., and Kurokawa, K. (1993) Calcic analog of clinojimthompsonite from the Oeyama ophiolite, southwest Japan. The Journal of the Geological Society of Japan, 99, 679–682.10.5575/geosoc.99.679Search in Google Scholar

Konishi, H., Alviola, R., and Buseck, P.R. (2004) 2111 biopyribole intermediate between pyroxene and amphibole: Artifact or natural product? American Mineralogist, 89, 15–19.10.2138/am-2004-0103Search in Google Scholar

Konishi, H., Xu, H., and Dymek, R.F. (2010) High-resolution TEM study of jimthompsonite, chesterite, and chain-width disorder in Archean ultramafic rocks from Isua, West Greenland. American Mineralogist, 95, 73–80.10.2138/am.2010.3212Search in Google Scholar

Kontonikas-Charos, A., Ciobanu, C.L., Cook, N.J., Ehrig, K., Ismail, R., Krneta, S., and Basak, A. (2018) Feldspar mineralogy and rare earth element (re)mobilization in iron-oxide copper gold systems from South Australia: a nanoscale study. Mineralogical Magazine, 82, S173–S197.10.1180/minmag.2017.081.040Search in Google Scholar

Léger, A., and Ferry, J.M. (1991) Highly aluminous hornblende from low-pressure metacarbonates and a preliminary thermodynamic model for the Al content of calcic amphibole. American Mineralogist, 76, 1002–1017.Search in Google Scholar

Li, W., Ciobanu, C.L., Slattery, A., Cook, N.J., Liu, W., Wade, B.P., and Xie, G.Q. (2019) Chessboard structures: Atom-scale imaging of homologues from the kobellite series. American Mineralogist, 104, 459–462.10.2138/am-2019-6860Search in Google Scholar

Locock, A.J. (2014) An Excel spreadsheet to classify chemical analyses of amphiboles following the IMA2012 recommendations. Computers & Geosciences, 62, 1–11.10.1016/j.cageo.2013.09.011Search in Google Scholar

Medlin, D.L., and Snyder, G.J. (2013) Atomic-scale interfacial structure in rock salt and tetradymite chalcogenide thermoelectric materials. JOM, 65, 390–400.10.1007/s11837-012-0530-ySearch in Google Scholar

Medlin, D.L., Ramasse, Q.M., Spataru, C.D., and Yang, N.Y.C. (2010) Structure of the (0001) basal twin boundary in Bi2Te3. Journal of Applied Physics, 108, 043517.10.1063/1.3457902Search in Google Scholar

Medlin, D., Erickson, K., Limmer, S., Yelton, W., and Siegal, M.P. (2014) Dissociated 1/3 <0111> dislocations in Bi2Te3 and their relationship to seven-layer Bi3Te4 deffects. Journal of Materials Science, 49, 3970–3979.10.1007/s10853-014-8035-4Search in Google Scholar

Medlin, D.L., Yang, N., Spataru, C.D., Hale, L.M., and Mishin, Y. (2019) Unraveling the dislocation core structure at a van der Waals gap in bismuth telluride. Nature Communications, 10, 1820.10.1038/s41467-019-09815-5Search in Google Scholar PubMed PubMed Central

Mutch, E.J.F., Blundy, J.D., Tattitch, B.C., Cooper, F.J., and Brooker, R.A. (2016) An experimental study of amphibole stability in low-pressure granitic magmas and a revised Al-in-hornblende geobarometer. Contributions to Mineralogy and Petrology, 171, 85.10.1007/s00410-016-1298-9Search in Google Scholar

Najorka, J., and Gottschalk, M. (2003) Crystal chemistry of tremolite-tschermakite solid solutions. Physics and Chemistry of Minerals, 30, 108–124.10.1007/s00269-002-0291-1Search in Google Scholar

Oberti, R., Boiocchi, M., Hawthorne, F.C., and Ciriotti, M.E. (2018) Ferro-tschermakite from the Ploumanac’h granitic complex, Brittany, France: Mineral description. European Journal of Mineralogy, 30, 171–176.10.1127/ejm/2018/0030-2700Search in Google Scholar

Papike, J.J., and Ross, M. (1970) Gedrites—Crystal structures and intracrystalline cation distributions. American Mineralogist, 55, 1945–1972.Search in Google Scholar

Reid, A. (2019) The Olympic Cu-Au Province, Gawler Craton: A review of the lithospheric architecture, geodynamic setting, alteration systems, cover successions and prospectivity. Minerals, 9, 371.10.3390/min9060371Search in Google Scholar

Righter, K., Keller, L.P., Rahman, Z., and Christoffersen, R. (2014) Redox-driven exsolution of iron titanium oxides in magnetite in Miller Range (MIL) 03346 nakhlite: Evidence for post crystallization oxidation in the nakhlite cumulate pile? American Mineralogist, 99, 2313–2319.10.2138/am-2014-4926Search in Google Scholar

Schmidt, M.W. (1992) Amphibole composition in tonalite as a function of pressure: an experimental calibration of the Al-in-hornblende barometer. Contributions to Mineralogy and Petrology, 110, 304–310.10.1007/BF00310745Search in Google Scholar

Thompson, J.B. Jr. (1978) Biopyriboles and polysomatic series. American Mineralogist, 63, 239–249.Search in Google Scholar

Utsunomiya, S., and Ewing, R.C. (2003) Application of high-angle annular dark field scanning transmission electron microscopy, scanning transmission electron microscopy-energy dispersive X-ray spectrometry, and the energy-filtered transmission electron microscopy to the characterization of nanoparticles in the environment. Environmental Science & Technology, 37, 786–791.10.1021/es026053tSearch in Google Scholar PubMed

Van Tendeloo, G., Bals, S., Van Aert, S., Verbeeck, J., and Van Dyck, D. (2012) Advanced electron microscopy for advanced materials. Advanced Materials, 24, 5655–5675.10.1002/adma.201202107Search in Google Scholar PubMed

Veblen, D.R. (1981) Non-classical pyriboles and polysomatic reactions in biopyriboles. In D.R. Veblen, Ed., Amphiboles and Other Hydrous Pyriboles—Mineralogy, 9A, p. 189–234. Reviews in Mineralogy, Chantilly, Virginia, Mineralogical Society of America.10.1515/9781501508219-008Search in Google Scholar

Veblen, D.R. (1992) Electron microscopy applied to nonstoichiometry, polysomatism, and replacement reactions in minerals. Reviews in Mineralogy and Geochemistry, 27, 181–229.Search in Google Scholar

Veblen, D.R., and Burnham, C.W. (1978) New biopyriboles from Chester, Vermont: II. The crystal chemistry of jimthompsonite, clinojimthompsonite, and chesterite, and the amphibole-mica reaction. American Mineralogist, 63, 1053–1073.Search in Google Scholar

Veblen, D.R., and Buseck, E.R. (1979) Chain-width order and disorder in biopyriboles. American Mineralogist, 64, 687–700.Search in Google Scholar

Veblen, D.R., and Buseck, E.R. (1980) Microstructures and reaction mechanisms in biopyriboles. American Mineralogist, 65, 599–623.Search in Google Scholar

Veblen, D.R., Buseck, P.R., and Burnham, C.W. (1977) Asbestiform chain silicates: New minerals and structural groups. Science, 198, 359–365.10.1126/science.198.4315.359Search in Google Scholar PubMed

Veblen, D.R., Banfield, J.F., Guthrie, G.D., Heaney, P.J., Ilton, E.S., Livi, K.J.T., and Smelik, E.A. (1993) High-resolution and analytical transmission electron microscopy of mineral disorder and reactions. Science, 260, 1465–1472.10.1126/science.260.5113.1465Search in Google Scholar PubMed

Verdugo-Ihl, M.R., Ciobanu, C.L., Cook, N.J., Ehrig, K.J., Courtney-Davies, L., and Gilbert, S. (2017) Textures and U-W-Sn-Mo signatures in hematite from the Olympic Dam Cu-U-Au-Ag deposit, South Australia: Defining the archetype for IOCG deposits. Ore Geology Reviews, 91, 173–195.10.1016/j.oregeorev.2017.10.007Search in Google Scholar

Verdugo-Ihl, M.R., Ciobanu, C.L., Cook, N.J., Ehrig, K.J., and Courtney-Davies, L. (2020a) Defining early stages of IOCG systems: evidence from iron oxides in the outer shell of the Olympic Dam deposit, South Australia. Mineralium Deposita, 55, 429–452.10.1007/s00126-019-00896-2Search in Google Scholar

Verdugo-Ihl, M., Ciobanu, C.L., Cook, N.J., Ehrig, K., Slattery, A., and Courtney-Davies, L. (2020b) Trace-element remobilisation from W- Sn-U-Pb zoned hematite: Nanoscale insights into a mineral geochronometer behaviour during interaction with fluids. Mineralogical Magazine, 84, 502–516.10.1180/mgm.2020.49Search in Google Scholar

Verdugo-Ihl, M.R., Ciobanu, C.L., Slattery, A., Cook, N.J., Ehrig, K., and Courtney-Davies, L. (2019) Copper-arsenic nanoparticles in hematite: fingerprinting fluid-mineral interaction. Minerals, 9, 388.10.3390/min9070388Search in Google Scholar

Verdugo-Ihl, M.R., Ciobanu, C.L., Cook, N.J., Ehrig, K.J., Slattery, A., Courtney-Davies, L., and Dmitrijeva, M. (2021) Nanomineralogy of hydrothermal magnetite from Acropolis, South Australia: Genetic implications for iron-oxide copper gold mineralization. American Mineralogist, 106(8), 1273–1293.10.2138/am-2021-7557Search in Google Scholar

Whitney, D.L., and Evans, B.W. (2010) Abbreviations for names of rock-forming minerals. American Mineralogist, 95, 185–187.10.2138/am.2010.3371Search in Google Scholar

Xu, H., Shen, Z., and Konishi, H. (2014) Si-magnetite nano-precipitates in silician magnetite from banded iron formation: Z-contrast imaging and ab initio study. American Mineralogist, 99, 2196–2202.10.2138/am-2014-4964Search in Google Scholar

Yin, S., Wirth, R., Ma, C.Q., and Xu, J.N. (2019) The role of mineral nanoparticles at a fluid-magnetite interface: Implications for trace-element uptake in hydrothermal systems. American Mineralogist, 104, 1180–1188.10.2138/am-2019-6996Search in Google Scholar

Zanazzi, P.F., Montagnoli, M., Nazzareni, S., and Comodi, P. (2007) Structural effects of pressure on monoclinic chlorite: A single-crystal study. American Mineralogist, 92, 655–661.10.2138/am.2007.2341Search in Google Scholar

Received: 2021-01-14
Accepted: 2021-04-21
Published Online: 2022-03-28
Published in Print: 2022-04-26

© 2022 Mineralogical Society of America

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