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Trace-element remobilisation from W–Sn–U–Pb zoned hematite: Nanoscale insights into a mineral geochronometer behaviour during interaction with fluids

Published online by Cambridge University Press:  16 June 2020

Max R. Verdugo-Ihl Open the ORCID record for Max R. Verdugo-Ihl [Opens in a new window] ,
Cristiana L. Ciobanu ,
Nigel J. Cook Open the ORCID record for Nigel J. Cook [Opens in a new window] ,
Kathy Ehrig Open the ORCID record for Kathy Ehrig [Opens in a new window] ,
Ashley Slattery Open the ORCID record for Ashley Slattery [Opens in a new window]  and
Liam Courtney-Davies Open the ORCID record for Liam Courtney-Davies [Opens in a new window]
Max R. Verdugo-Ihl*
Affiliation:
School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA5005, Australia
Cristiana L. Ciobanu
Affiliation:
School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA5005, Australia
Nigel J. Cook
Affiliation:
School of Civil, Environmental and Mining Engineering, The University of Adelaide, Adelaide, SA5005, Australia
Kathy Ehrig
Affiliation:
BHP Olympic Dam, 10 Franklin St, AdelaideSA, 5000, Australia
Ashley Slattery
Affiliation:
Adelaide Microscopy, The University of Adelaide, Adelaide, SA, 5005, Australia
Liam Courtney-Davies
Affiliation:
School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA5005, Australia
*
*Author for correspondence: Max R. Verdugo-Ihl, Email: max.verdugoihl@adelaide.edu.au
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Abstract

Preferential removal of W relative to other trace elements from zoned, W–Sn–U–Pb-bearing hematite coupled with disturbance of U–Pb isotope systematics is attributed to pseudomorphic replacement via coupled dissolution reprecipitation reaction (CDRR). This hematite has been studied down to the nanoscale to understand the mechanisms leading to compositional and U/Pb isotope heterogeneity at the grain scale. High-Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF STEM) imaging of foils extracted in situ from three locations across the W-rich to W-depleted domains show lattice-scale defects and crystal structure modifications adjacent to twin planes. Secondary sets of twins and associated splays are common, but wider (up to ~100 nm) inclusion trails occur only at the boundary between the W-rich and W-depleted domains. STEM energy-dispersive X-ray mapping reveals W- and Pb-enrichment along 2–3 nm-wide features defining the twin planes; W-bearing nanoparticles occur along the splays. Tungsten and Pb are both present, albeit at low concentrations, within Na–K–Cl-bearing inclusions along the trails. HAADF STEM imaging of hematite reveals modifications relative to ideal crystal structure. A two-fold hematite superstructure (a = b = c = 10.85 Å; α = β = γ = 55.28°) involving oxygen vacancies was constructed and assessed by STEM simulations with a good match to data. This model can account for significant W release during interaction with fluids percolating through twin planes and secondary structures as CDRR progresses from the zoned domain, otherwise apparently undisturbed at the micrometre scale. Lead remobilisation is confirmed here at the nanoscale and is responsible for a disturbance of U/Pb ratios in hematite affected by CDRR. Twin planes can provide pathways for fluid percolation and metal entrapment during post-crystallisation overprinting. The presence of complex twinning can therefore predict potential disturbances of isotope systems in hematite that will affect its performance as a robust geochronometer.

Keywords

HAADF STEMW–Sn–U–Pb-bearing hematitemetal (re)mobilisationnanoparticlestwinningopen systemgeochronology
Type
Article
Information
Mineralogical Magazine , Volume 84 , Issue 4 , August 2020 , pp. 502 - 516
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2020

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Footnotes

Associate Editor: Jason Harvey

References

Abakumov, A.M., Hadermann, J., Bals, S., Nikolaev, I.V., Antipov, E.V. and Van Tendeloo, G. (2006) Crystallographic shear structures as a route to anion-deficient perovskites. Angewandte Chemie International Edition, 45, 6697–6700. https://dx.doi.or/10.1002/anie.200602480CrossRefGoogle ScholarPubMed
Abakumov, A.M., Batuk, D., Hadermann, J., Rozova, M.G., Sheptyakov, D.V., Tsirlin, A.A., Niermann, D., Waschkowski, F., Hemberger, J., Van Tendeloo, G. and Antipov, E.V. (2011) Antiferroelectric (Pb,Bi)1−x Fe1+xO3−y perovskites modulated by crystallographic shear planes. Chemistry of Materials, 23, 255–265. https://dx.doi.org/10.1021/cm102907hCrossRefGoogle Scholar
Brugger, J., Liu, W., Etschmann, B., Mei, Y., Sherman, D.M. and Testemale, D. (2016) A review of the coordination chemistry of hydrothermal systems, or do coordination changes make ore deposits? Chemical Geology, 447, 219–253. https://dx.doi.org/10.1016/j.chemgeo.2016.10.021CrossRefGoogle Scholar
Bykova, E., Dubrovinsky, L., Dubrovinskaia, N., Bykov, M., McCammon, C., Ovsyannikov, S.V., Liermann, H.-P., Kupenko, I., Chumakov, A.I., Rüffer, R., Hanfland, M. and Prakapenka, V. (2016) Structural complexity of simple Fe2O3 at high pressures and temperatures. Nature Communications, 7, 10661. https://dx.doi.org/10.1038/ncomms10661CrossRefGoogle ScholarPubMed
Chen, Z., Cvelbar, U., Mozetič, M., He, J. and Sunkara, M.K. (2008) Long-range ordering of oxygen-vacancy planes in α-Fe2O3 nanowires and nanobelts. Chemistry of Materials, 20, 3224–3228. https://dx.doi.org/10.1021/cm800288yCrossRefGoogle Scholar
Ciobanu, C.L., Cook, N.J., Utsunomiya, S., Pring, A. and Green, L. (2011) Focussed ion beam-transmission electron microscopy applications in ore mineralogy: Bridging micro- and nanoscale observations. Ore Geology Reviews, 42, 6–31. https://dx.doi.org/10.1016/j.oregeorev.2011.06.012CrossRefGoogle Scholar
Ciobanu, C.L., Wade, B.P., Cook, N.J., Schmidt Mumm, A. and Giles, D. (2013) Uranium-bearing hematite from the Olympic Dam Cu–U–Au deposit, South Australia: A geochemical tracer and reconnaissance Pb–Pb geochronometer. Precambrian Research, 238, 129–147. https://dx.doi.org/10.1016/j.precamres.2013.10.007CrossRefGoogle Scholar
Ciobanu, C., Cook, N., Maunders, C., Wade, B. and Ehrig, K. (2016) Focused ion beam and advanced electron microscopy for minerals: Insights and outlook from bismuth sulphosalts. Minerals, 6, 112. https://dx.doi.org/10.3390/min6040112CrossRefGoogle Scholar
Cook, N., Ciobanu, C., Ehrig, K., Slattery, A., Verdugo-Ihl, M., Courtney-Davies, L. and Gao, W. (2017) Advances and opportunities in ore mineralogy. Minerals, 7, 233. https://dx.doi.org/10.3390/min7120233CrossRefGoogle Scholar
Courtney-Davies, L., Tapster, S.R., Ciobanu, C.L., Cook, N.J., Verdugo-Ihl, M.R., Ehrig, K.J., Kennedy, A.K., Gilbert, S.E., Condon, D.J. and Wade, B.P. (2019) A multi-technique evaluation of hydrothermal hematite U Pb isotope systematics: Implications for ore deposit geochronology. Chemical Geology, 513, 54–72. https://dx.doi.org/10.1016/j.chemgeo.2019.03.005CrossRefGoogle 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. (2020) Opening the magmatic-hydrothermal window: High-precision U-Pb geochronology of the Mesoproterozoic Olympic Dam Cu-U-Au-Ag deposit, South Australia. Economic Geology (in press).CrossRefGoogle Scholar
Fougerouse, D., Kirkland, C., Saxey, D., Seydoux-Guillaume, A.-M., Rowles, M.R., Rickard, W.D. and Reddy, S.M. (2020) Nanoscale Isotopic Dating of Monazite. Geostandards and Geoanalytical Research, in press. https://dx.doi.org/10.1111/ggr.12340CrossRefGoogle Scholar
Kusiak, M.A., Whitehouse, M.J., Wilde, S.A., Wilde, S.A., Nemchin, A.A. and Clark, C. (2013) Mobilization of radiogenic Pb in zircon revealed by ion imaging: Implications for early Earth geochronology. Geology, 41, 291–294. https://dx.doi.org/10.1130/G33920.1CrossRefGoogle Scholar
Kusiak, M.A., Dunkley, D.J., Wirth, R., Whitehouse, M.J., Wilde, S. and Marquardt, K. (2015) Metallic lead nanospheres discovered in ancient zircons. Proceedings of the National Academy of Science, 112, 4958–4963. https://dx.doi.org/10.1073/pnas.1415264112CrossRefGoogle ScholarPubMed
Kusiak, M.A., Kovaleva, E., Wirth, R., Klötzli, U., Dunkley, D.J., Yi, K. and Lee, S. (2019) Lead oxide nanospheres in seismically deformed zircon grains. Geochimica et Cosmochimica Acta, 262, 20–30. https://dx.doi.org/10.1016/j.gca.2019.07.026CrossRefGoogle Scholar
Lee, S. and Xu, H. (2016) Size-dependent phase map and phase transformation kinetics for nanometric iron(III) oxides (γ → ɛ → α pathway). The Journal of Physical Chemistry C, 120, 13316–13322. https://dx.doi.org/10.1021/acs.jpcc.6b05287CrossRefGoogle Scholar
Lyon, I.C., Kusiak, M.A., Wirth, R., Whitehouse, M.J., Dunkley, D.J., Wilde, S.A., Schaumlöffel, D., Malherbe, J. and Moore, K.L. (2019) Pb nanospheres in ancient zircon yield model ages for zircon formation and Pb mobilization. Scientific Reports, 9, 13702. https://dx.doi.org/10.1038/s41598-019-49882-8CrossRefGoogle ScholarPubMed
Macmillan, E., Ciobanu, C.L., Ehrig, K., Cook, N.J. and Pring, A. (2016 a) Replacement of uraninite by bornite via coupled dissolution-reprecipitation: Evidence from texture and microstructure. The Canadian Mineralogist, 54, 1369–1383. https://dx.doi.org/10.3749/canmin.1600031CrossRefGoogle Scholar
Macmillan, E., Ciobanu, C.L., Ehrig, K., Cook, N.J. and Pring, A. (2016 b) Chemical zoning and lattice distortion in uraninite from Olympic Dam, South Australia. American Mineralogist, 101, 2351–2354. https://dx.doi.org/10.2138/am-2016-5753CrossRefGoogle Scholar
Maslen, E.N., Streltsov, V.A., Streltsova, N.R. and Ishizawa, N. (1994) Synchrotron X-ray study of the electron density in alpha-Fe2O3. Acta Crystallographica B, 50, 435–441. https://dx.doi.org/10.1107/S0108768194002284CrossRefGoogle Scholar
McBriarty, M.E., Kerisit, S., Bylaska, E.J., Shaw, S., Morris, K. and Ilton, E.S. (2018) Iron vacancies accommodate uranyl incorporation into hematite. Environmental Science & Technology, 52, 6282–6290. https://dx.doi.org/10.1021/acs.est.8b00297CrossRefGoogle ScholarPubMed
Putnis, A. (2009) Mineral replacement reactions. Pp. 87–124 in: Thermodynamics and Kinetics of Water–Rock Interactions (Oelkers, E.H. and Schott, J., editors). Reviews in Mineralogy and Geochemistry, 70, Mineralogical Society of America, Chantilly, Virginia, USA. https://dx.doi.org/10.2138/rmg.2009.70.3CrossRefGoogle Scholar
Putnis, C.V., Tsukamoto, K. and Nishimura, Y. (2005) Direct observations of pseudomorphism: compositional and textural evolution at a fluid-solid interface. American Mineralogist, 90, 1909–1912. https://dx.doi.org/10.2138/am.2005.1990CrossRefGoogle Scholar
Rollog, M., Cook, N.J., Guagliardo, P., Ehrig, K., Ciobanu, C.L. and Kilburn, M. (2019 a) Detection of trace elements/isotopes in Olympic Dam copper concentrates by nanoSIMS. Minerals, 9, 336. https://dx.doi.org/10.3390/min9060336CrossRefGoogle Scholar
Rollog, M., Cook, N.J., Guagliardo, P., Ehrig, K. and Kilburn, M. (2019 b) In situ spatial distribution mapping of radionuclides in minerals by nanoSIMS. Geochemistry: Exploration, Environment, Analysis, 19(3), 245–254. https://dx.doi.org/10.1144/geochem2018-038Google Scholar
Rollog, M., Cook, N.J., Guagliardo, P., Ehrig, K.J. and Kilburn, M. (2019 c) Radionuclide-bearing minerals in Olympic Dam copper concentrates. Hydrometallurgy, 189, 105153. https://dx.doi.org/10.1016/j.hydromet.2019.105153CrossRefGoogle Scholar
Seydoux-Guillaume, A.-M., Goncalves, P., Wirth, R. and Deutsch, A. (2003) Transmission electron microscope study of polyphase and discordant monazites: Site-specific specimen preparation using the focused ion beam technique. Geology, 31, 973–976. https://dx.doi.org/10.1130/G19582.1CrossRefGoogle Scholar
Seydoux-Guillaume, A.-M., Fougerouse, D., Laurent, A.T., Gardés, E., Reddy, S.M. and Saxey, D.W. (2019) Nanoscale resetting of the Th/Pb system in an isotopically-closed monazite grain: A combined atom probe and transmission electron microscopy study. Geosciences Frontiers, 10, 65–76. https://dx.doi.org/10.1016/j.gsf.2018.09.004CrossRefGoogle Scholar
Šrot, V., Rečnik, A., Scheu, C., Šturm, S. and Mirtič, B. (2003) Stacking faults and twin boundaries in sphalerite crystals from the Trepča mines in Kosovo. American Mineralogist, 88, 1809–1816. https://dx.doi.org/10.2138/am-2003-11-1222CrossRefGoogle Scholar
Valley, J.W., Cavosie, A.J., Ushikubo, T., Reinhard, D.A., Lawrence, D.F., Larson, D.J., Clifton, P.H., Kelly, T.F., Wilde, S.A., Moser, D.E. and Spicuzza, M.J. (2014) Hadean age for a post-magma-ocean zircon confirmed by atom-probe tomography. Nature Geosciences, 7, 219–223. https://dx.doi.org/10.1038/ngeo2075CrossRefGoogle Scholar
van Achterbergh, E., Ryan, C.G., Jackson, S.E. and Griffin, W.L. (2001) Data reduction software for LA-ICP-MS. Pp. 239–243 in: Laser-ablation-ICPMS in the Earth Sciences; Principles and applications (Sylvester, P.J., editor). Short Course Series, 29. Mineralogical Association of Canada.Google Scholar
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. https://dx.doi.org/10.1002/adma.201202107CrossRefGoogle ScholarPubMed
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. https://dx.doi.org/10.1016/j.oregeorev.2017.10.007CrossRefGoogle 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. https://dx.doi.org/10.3390/min9070388CrossRefGoogle Scholar
Verdugo-Ihl, M.R., Ciobanu, C.L., Cook, N.J., Ehrig, K.J. and Courtney-Davies, L. (2020) 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. https://dx.doi.org/10.1007/s00126-019-00896-2CrossRefGoogle Scholar
Wang, X.-S., Timofeev, A., Williams-Jones, A.E., Shang, L.-B. and Bi, X.-W. (2019) An experimental study of the solubility and speciation of tungsten in NaCl-bearing aqueous solutions at 250, 300, and 350°C. Geochimica et Cosmochimica Acta, 265, 313–329. https://dx.doi.org/10.1016/j.gca.2019.09.013CrossRefGoogle Scholar
Weinberg, R.F., Wolfram, L.C., Nebel, O., Hasalová, P., Závada, P., Kylander-Clark, A.R.C. and Becchio, R. (2020) Decoupled U-Pb date and chemical zonation of monazite in migmatites: The case for disturbance of isotopic systematics by coupled dissolution-reprecipitation. Geochimica et Cosmochimica Acta, 269, 398–412. https://dx.doi.org/10.1016/j.gca.2019.10.024CrossRefGoogle Scholar
Whitehouse, M.J., Kusiak, M.A., Wirth, R., and Ravindra Kumar, G.R. (2017) Metallic Pb nanospheres in ultra-high temperature metamorphosed zircon from southern India. Mineralogy and Petrology, 111, 467–474. https://dx.doi.org/10.1007/s00710-017-0523-1CrossRefGoogle Scholar
Xia, F., Brugger, J., Chen, G., Ngothai, Y., O'Neill, B., Putnis, A. and Pring, A. (2009) Mechanism and kinetics of pseudomorphic mineral replacement reactions: A case study of the replacement of pentlandite by violarite. Geochimica et Cosmochimica Acta, 73, 1945–1969. https://dx.doi.org/10.1016/j.gca.2009.01.007CrossRefGoogle Scholar
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