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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: [email protected]
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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

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