Al and H incorporation and Al-diffusion in natural rutile and its high-pressure polymorph TiO2 (II)

Bastian Joachim-Mrosko; Jürgen Konzett; Thomas Ludwig; Thomas Griffiths; Gerlinde Habler; Eugen Libowitzky; Roland Stalder

Al and H incorporation and Al-diffusion in natural rutile and its high-pressure polymorph TiO₂ (II)

Bastian Joachim-Mrosko (Corresponding author), Jürgen Konzett, Thomas Ludwig, Thomas Griffiths, Gerlinde Habler, Eugen Libowitzky, Roland Stalder

Publications: Contribution to book › Chapter › Peer Reviewed

Abstract

Rutile is an important accessory mineral in metamorphic rocks and is used as a geothermobarometer or geochronometer. This study aims to bridge the gap between diffusion studies in simplified and complex natural systems by investigating the incorporation and mobility of Al in natural rutile and its high-pressure polymorph TiO₂ (II).
Experiments were performed at 0.1 MPa to 7 GPa, 1223–1373 K, at buffered μ(Al₂O₃) and with fO₂ constrained to ≤CCO, which is the equilibrium between graphite and a CO-CO₂ gas phase. Based on electron probe microanalysis, secondary ion mass spectrometry and Fourier transform infrared analyses, we suggest a complex combination of mechanisms to explain the incorporation of Al and H in natural rutile and TiO₂ (II). This includes: (1) the incorporation of Al³⁺ on octahedral Ti-sites charge balanced by the formation of oxygen
vacancies; and (2) the incorporation of oxygen in interstitial positions charge balanced by hydrogen interstitials.
Determined Al-diffusivities in natural TiO₂ are approximately eight to nine orders of magnitude faster compared to previously published data. A possible explanation includes a significantly enhanced rate of ionic diffusion through the combined effect of hydrolytic weakening, enhanced Al-diffusion through extended defects and to a minor extent oxygen fugacity variations. Consequently, results of this study question that the inferred
high closure temperatures for the Al-in-rutile geothermobarometer can be applied to all natural systems.

Original language	English
Title of host publication	Minor Minerals, Major Implications
Subtitle of host publication	Using Key Mineral Phases to Unravel the Formation and Evolution of Earth's Crust
Editors	V. van Schijndel, K. Cutts, I. Pereira, M. Guitreau, S. Volante, M. Tedeschi
Place of Publication	Bath
Publisher	The Geological Society of London
Pages	123-147
ISBN (Print)	978-1-78620-594-0
Publication status	Published - 18 Oct 2023

Publication series

Series	Geological Society Special Publications
Volume	537
ISSN	0305-8719

Austrian Fields of Science 2012

105116 Mineralogy
105113 Crystallography

Keywords

DIFFUSION
Trace element
Rutile
experimental petrology
Aluminium

Access to Document

https://doi.org/10.6084/m9.figshare.c.6829367.v1

Cite this

Joachim-Mrosko, B., Konzett, J., Ludwig, T., Griffiths, T., Habler, G., Libowitzky, E., & Stalder, R. (2023). Al and H incorporation and Al-diffusion in natural rutile and its high-pressure polymorph TiO₂ (II). In V. V. Schijndel, K. Cutts, I. Pereira, M. Guitreau, S. Volante, & M. Tedeschi (Eds.), Minor Minerals, Major Implications: Using Key Mineral Phases to Unravel the Formation and Evolution of Earth's Crust (pp. 123-147). The Geological Society of London. https://doi.org/10.6084/m9.figshare.c.6829367.v1

Joachim-Mrosko, Bastian ; Konzett, Jürgen ; Ludwig, Thomas et al. / Al and H incorporation and Al-diffusion in natural rutile and its high-pressure polymorph TiO₂ (II). Minor Minerals, Major Implications: Using Key Mineral Phases to Unravel the Formation and Evolution of Earth's Crust. editor / V. van Schijndel ; K. Cutts ; I. Pereira ; M. Guitreau ; S. Volante ; M. Tedeschi. Bath : The Geological Society of London, 2023. pp. 123-147 (Geological Society Special Publications, Vol. 537).

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abstract = "Rutile is an important accessory mineral in metamorphic rocks and is used as a geothermobarometer or geochronometer. This study aims to bridge the gap between diffusion studies in simplified and complex natural systems by investigating the incorporation and mobility of Al in natural rutile and its high-pressure polymorph TiO2 (II).Experiments were performed at 0.1 MPa to 7 GPa, 1223–1373 K, at buffered μ(Al2O3) and with fO2 constrained to ≤CCO, which is the equilibrium between graphite and a CO-CO2 gas phase. Based on electron probe microanalysis, secondary ion mass spectrometry and Fourier transform infrared analyses, we suggest a complex combination of mechanisms to explain the incorporation of Al and H in natural rutile and TiO2 (II). This includes: (1) the incorporation of Al3+ on octahedral Ti-sites charge balanced by the formation of oxygenvacancies; and (2) the incorporation of oxygen in interstitial positions charge balanced by hydrogen interstitials.Determined Al-diffusivities in natural TiO2 are approximately eight to nine orders of magnitude faster compared to previously published data. A possible explanation includes a significantly enhanced rate of ionic diffusion through the combined effect of hydrolytic weakening, enhanced Al-diffusion through extended defects and to a minor extent oxygen fugacity variations. Consequently, results of this study question that the inferredhigh closure temperatures for the Al-in-rutile geothermobarometer can be applied to all natural systems.",

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Joachim-Mrosko, B, Konzett, J, Ludwig, T, Griffiths, T , Habler, G , Libowitzky, E & Stalder, R 2023, Al and H incorporation and Al-diffusion in natural rutile and its high-pressure polymorph TiO₂ (II). in VV Schijndel, K Cutts, I Pereira, M Guitreau, S Volante & M Tedeschi (eds), Minor Minerals, Major Implications: Using Key Mineral Phases to Unravel the Formation and Evolution of Earth's Crust. The Geological Society of London, Bath, Geological Society Special Publications, vol. 537, pp. 123-147. <https://doi.org/10.6084/m9.figshare.c.6829367.v1>

Al and H incorporation and Al-diffusion in natural rutile and its high-pressure polymorph TiO₂ (II). / Joachim-Mrosko, Bastian (Corresponding author); Konzett, Jürgen; Ludwig, Thomas et al.
Minor Minerals, Major Implications: Using Key Mineral Phases to Unravel the Formation and Evolution of Earth's Crust. ed. / V. van Schijndel; K. Cutts; I. Pereira; M. Guitreau; S. Volante; M. Tedeschi. Bath: The Geological Society of London, 2023. p. 123-147 (Geological Society Special Publications, Vol. 537).

Publications: Contribution to book › Chapter › Peer Reviewed

TY - CHAP

T1 - Al and H incorporation and Al-diffusion in natural rutile and its high-pressure polymorph TiO2 (II)

AU - Joachim-Mrosko, Bastian

AU - Konzett, Jürgen

AU - Ludwig, Thomas

AU - Griffiths, Thomas

AU - Habler, Gerlinde

AU - Libowitzky, Eugen

AU - Stalder, Roland

PY - 2023/10/18

Y1 - 2023/10/18

N2 - Rutile is an important accessory mineral in metamorphic rocks and is used as a geothermobarometer or geochronometer. This study aims to bridge the gap between diffusion studies in simplified and complex natural systems by investigating the incorporation and mobility of Al in natural rutile and its high-pressure polymorph TiO2 (II).Experiments were performed at 0.1 MPa to 7 GPa, 1223–1373 K, at buffered μ(Al2O3) and with fO2 constrained to ≤CCO, which is the equilibrium between graphite and a CO-CO2 gas phase. Based on electron probe microanalysis, secondary ion mass spectrometry and Fourier transform infrared analyses, we suggest a complex combination of mechanisms to explain the incorporation of Al and H in natural rutile and TiO2 (II). This includes: (1) the incorporation of Al3+ on octahedral Ti-sites charge balanced by the formation of oxygenvacancies; and (2) the incorporation of oxygen in interstitial positions charge balanced by hydrogen interstitials.Determined Al-diffusivities in natural TiO2 are approximately eight to nine orders of magnitude faster compared to previously published data. A possible explanation includes a significantly enhanced rate of ionic diffusion through the combined effect of hydrolytic weakening, enhanced Al-diffusion through extended defects and to a minor extent oxygen fugacity variations. Consequently, results of this study question that the inferredhigh closure temperatures for the Al-in-rutile geothermobarometer can be applied to all natural systems.

AB - Rutile is an important accessory mineral in metamorphic rocks and is used as a geothermobarometer or geochronometer. This study aims to bridge the gap between diffusion studies in simplified and complex natural systems by investigating the incorporation and mobility of Al in natural rutile and its high-pressure polymorph TiO2 (II).Experiments were performed at 0.1 MPa to 7 GPa, 1223–1373 K, at buffered μ(Al2O3) and with fO2 constrained to ≤CCO, which is the equilibrium between graphite and a CO-CO2 gas phase. Based on electron probe microanalysis, secondary ion mass spectrometry and Fourier transform infrared analyses, we suggest a complex combination of mechanisms to explain the incorporation of Al and H in natural rutile and TiO2 (II). This includes: (1) the incorporation of Al3+ on octahedral Ti-sites charge balanced by the formation of oxygenvacancies; and (2) the incorporation of oxygen in interstitial positions charge balanced by hydrogen interstitials.Determined Al-diffusivities in natural TiO2 are approximately eight to nine orders of magnitude faster compared to previously published data. A possible explanation includes a significantly enhanced rate of ionic diffusion through the combined effect of hydrolytic weakening, enhanced Al-diffusion through extended defects and to a minor extent oxygen fugacity variations. Consequently, results of this study question that the inferredhigh closure temperatures for the Al-in-rutile geothermobarometer can be applied to all natural systems.

KW - DIFFUSION

KW - Trace element

KW - Rutile

KW - experimental petrology

KW - Aluminium

M3 - Chapter

SN - 978-1-78620-594-0

T3 - Geological Society Special Publications

SP - 123

EP - 147

BT - Minor Minerals, Major Implications

A2 - Schijndel, V. van

A2 - Cutts, K.

A2 - Pereira, I.

A2 - Guitreau, M.

A2 - Volante, S.

A2 - Tedeschi, M.

PB - The Geological Society of London

CY - Bath

ER -

Joachim-Mrosko B, Konzett J, Ludwig T, Griffiths T , Habler G , Libowitzky E et al. Al and H incorporation and Al-diffusion in natural rutile and its high-pressure polymorph TiO₂ (II). In Schijndel VV, Cutts K, Pereira I, Guitreau M, Volante S, Tedeschi M, editors, Minor Minerals, Major Implications: Using Key Mineral Phases to Unravel the Formation and Evolution of Earth's Crust. Bath: The Geological Society of London. 2023. p. 123-147. (Geological Society Special Publications, Vol. 537). Epub 2023 Sept 11.