Skip to main content
SpringerLink
Log in

Controls on the distribution of hydrous defects in forsterite from a thermodynamic model

  • Original Paper
  • Published:
Physics and Chemistry of Minerals Aims and scope Submit manuscript

Abstract

The distribution of hydrogen across different crystallographic sites and point defects in forsterite determines how many properties, such as rheology, conductivity and diffusion are affected by water. In this study, we use lattice dynamics and Density Functional Theory (DFT) to build a thermodynamic model of H-bearing defects in Al,Ti bearing forsterite. From this, the distribution of hydrogen in forsterite as a function of pressure (P), temperature (T), water, Al and Ti concentration is determined. Primarily, hydrogen distribution in forsterite is complex and highly varied in different P, T and composition regimes. Therefore, extrapolation of properties that depend upon water between these different regimes is non-trivial. This extrapolation has often been done by determining exponents which describe how defect-specific defect concentrations or properties dependent upon them vary with water concentration/fugacity. We show here that these exponents can vary radically across common experimental and geophysical P, T and [H2O]bulk ranges as the favoured hydrogen-bearing defects change. In general, at low pressures hydrogen favours Mg vacancies (high temperatures) or complexes with titanium (low temperatures) whilst at high pressures, hydrogen favours Si vacancies regardless of all other conditions. Higher values of [H2O]bulk also favours hydrated Si vacancies. We evaluate these distributions along geotherms and find that hydrogen distribution and thus its effect on forsterite properties is highly varied across the expected conditions of the upper mantle and thus cannot be simply represented. No such distribution of hydrogen has been previously constructed and it is essential to consider this hydrogen distribution when considering the properties of a wet mantle.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  • Berry AJ, Hermann J, O’Neill HSC, Foran GJ (2005) Fingerprinting the water site in mantle olivine. Geology 33:869–872

    Article  Google Scholar 

  • Berry AJ, O’Neill HSC, Hermann J, Scott DR (2007a) The infrared signature of water associated with trivalent cations in olivine. Earth Planet Sci Lett 261:134–142

    Article  Google Scholar 

  • Berry AJ, Walker AM, Hermann J, O’Neill HS, Foran GJ, Gale JD (2007b) Titanium substitution mechanisms in forsterite. Chem Geol 242:176–186

    Article  Google Scholar 

  • Blanchard M, Ingrin J, Balan E, Kovacs I, Withers AC (2017) Effect of iron and trivalent cations on OH defects in olivine. Am Miner 102:302–311

    Article  Google Scholar 

  • Bromiley GD, Keppler H (2004) An experimental investigation of hydroxyl solubility in jadeite and Na-rich clinopyroxenes. Contrib Miner Petrol 147:189–200

    Article  Google Scholar 

  • Costa F, Chakraborty S (2008) The effect of water on Si and O diffusion rates in olivine and implications for transport properties and processes in the upper mantle. Phys Earth Planet Inter 166:11–29

    Article  Google Scholar 

  • Crepisson C, Blanchard M, Bureau H, Sanloup C, Withers AC, Khodja H, Surble S, Raepsaet C, Beneut K, Leroy C, Giura P, Balan E (2014) Clumped fluoride-hydroxyl defects in forsterite: implications for the upper-mantle. Earth Planet Sci Lett 390:287–295

    Article  Google Scholar 

  • de Hoog JCM, Gall L, Cornell DH (2010) Trace-element geochemistry of mantle olivine and application to mantle petrogenesis and geothermobarometry. Chem Geol 270:196–215

    Article  Google Scholar 

  • Demouchy S, Bolfan-Casanova N (2016) Distribution and transport of hydrogen in the lithospheric mantle: a review. Lithos 240:402–425

    Article  Google Scholar 

  • Demouchy S, Tommasi A, Barou F, Mainprice D, Cordier P (2012) Deformation of olivine in torsion under hydrous conditions. Phys Earth Planet Inter 202:56–70

    Article  Google Scholar 

  • Fei HZ, Katsura T (2016) Si and O self-diffusion in hydrous forsterite and iron-bearing olivine from the perspective of defect chemistry. Phys Chem Miner 43:119–126

    Article  Google Scholar 

  • Fei H, Wiedenbeck M, Yamazaki D, Katsura T (2013) Small effect of water on upper-mantle rheology based on silicon self-diffusion coefficients. Nature 498:213

    Article  Google Scholar 

  • Fei HZ, Koizumi S, Sakamoto N, Hashiguchi M, Yurimoto H, Marquardt K, Miyajima N, Katsura T (2018) Mg lattice diffusion in iron-free olivine and implications to conductivity anomaly in the oceanic asthenosphere. Earth Planet Sci Lett 484:204–212

    Article  Google Scholar 

  • Girard J, Chen J, Raterron P, Holyoke CW III (2013) Hydrolytic weakening of olivine at mantle pressure: evidence of 100 (010) slip system softening from single-crystal deformation experiments. Phys Earth Planet Inter 216:12–20

    Article  Google Scholar 

  • Grant KJ, Kohn SC, Brooker RA (2006) Solubility and partitioning of water in synthetic forsterite and enstatite in the system MgO-SiO(2)-H(2)O +/- Al(2)O(3). Contrib Miner Petrol 151:651–664

    Article  Google Scholar 

  • Green DH, Ringwood AE (1970) Mineralogy of peridotitic compositions under upper mantle conditions. Phys Earth Planet Inter 3:359–371

    Article  Google Scholar 

  • Hermann J, O’Neill HSC, Berry AJ (2005) Titanium solubility in olivine in the system TiO2-MgO-SiO2: no evidence for an ultra-deep origin of Ti-bearing olivine. Contrib Miner Petrol 148:746–760

    Article  Google Scholar 

  • Jacobsen SD, Jiang F, Mao Z, Duffy TS, Smyth JR, Holl CM, Frost DJ (2008) Effects of hydration on the elastic properties of olivine. Geophys Res Lett 35:2

    Article  Google Scholar 

  • Jollands MC, O’Neill HS, Berry AJ, le Losq C, Rivard C, Hermann J (2021) A combined Fourier transform infrared and Cr K-edge X-ray absorption near-edge structure spectroscopy study of the substitution and diffusion of H in Cr-doped forsterite. Eur J Mineral 33:113–138

    Article  Google Scholar 

  • Jung H, Karato S (2001) Water-induced fabric transitions in olivine. Science 293:1460–1463

    Article  Google Scholar 

  • Karato SI, Jung H (2003) Effects of pressure on high-temperature dislocation creep in olivine. Phil Mag 83:401–414

    Article  Google Scholar 

  • Karato SI, Paterson MS, Fitz Gerald JD (1986) Rheology of synthetic olivine aggregates—influence of grain-size and water. J Geophys Res Solid Earth Planets 91:8151–8176

    Article  Google Scholar 

  • Karato S, Jung H, Katayama I, Skemer P (2008) Geodynamic significance of seismic anisotropy of the upper mantle: New insights from laboratory studies. Ann Rev Earth Planet Sci 2:2

    Google Scholar 

  • Kent AJR, Rossman GR (2002) Hydrogen, lithium, and boron in mantle-derived olivine: the role of coupled substitutions. Am Miner 87:1432–1436

    Article  Google Scholar 

  • Kohlstedt DL (2006) The role of water in high-temperature rock deformation. In: Keppler H, Smyth JR (eds) Water in nominally anhydrous minerals. Mineralogical Soc Amer & Geochemical Soc, Chantilly

    Google Scholar 

  • Kohlstedt DL, Keppler H, Rubie DC (1996) Solubility of water in the alpha, beta and gamma phases of (Mg, Fe)(2)SiO4. Contrib Miner Petrol 123:345–357

    Article  Google Scholar 

  • Kudoh Y, Kuribayashi T, Kagi H, Inoue T (2006) Cation vacancy and possible hydrogen positions in hydrous forsterite, Mg1.985Si0.993H0.06O4, synthesized at 13.5 GPa and 1300 degrees C. J Mineral Petrol Sci 101:265–269

    Article  Google Scholar 

  • Le Losq C, Jollands MC, Tollan PME, Hawkins R, O’neill, H. S. C. (2019) Point defect populations of forsterite revealed by two-stage metastable hydroxylation experiments. Contrib Mineral Petrol 174:2

    Google Scholar 

  • Lemaire C, Kohn SC, Brooker RA (2004) The effect of silica activity on the incorporation mechanisms of water in synthetic forsterite: a polarised infrared spectroscopic study. Contrib Miner Petrol 147:48–57

    Article  Google Scholar 

  • Lu R, Keppler H (1997) Water solubility in pyrope to 100 kbar. Contrib Miner Petrol 129:35–42

    Article  Google Scholar 

  • Mackwell SJ, Kohlstedt DL, Paterson MS (1985) The role of water in the deformation of olivine single-crystals. J Geophys Res Solid Earth Planets 90:1319–1333

    Article  Google Scholar 

  • Mao Z, Jacobsen SD, Jiang F, Smyth JR, Holl CM, Frost DJ, Duffy TS (2010) Velocity crossover between hydrous and anhydrous forsterite at high pressures. Earth Planet Sci Lett 293:250–258

    Article  Google Scholar 

  • Matveev S, O’Neill HS, Ballhaus C, Taylor WR, Green DH (2001) Effect of silica activity on OH-IR spectra of olivine: Implications for low-aSiO(2) mantle metasomatism. J Petrol 42:721–729

    Article  Google Scholar 

  • Mei S, Kohlstedt DL (2000a) Influence of water on plastic deformation of olivine aggregates 1. Diffusion creep regime. J Geophys Res Solid Earth 105:21457–21469

    Article  Google Scholar 

  • Mei S, Kohlstedt DL (2000b) Influence of water on plastic deformation of olivine aggregates 2. Dislocation creep regime. J Geophys Res Solid Earth 105:21471–21481

    Article  Google Scholar 

  • Mierdel K, Keppler H (2004) The temperature dependence of water solubility in enstatite. Contrib Miner Petrol 148:305–311

    Article  Google Scholar 

  • Mosenfelder JL, Deligne NI, Asimow PD, Rossman GR (2006) Hydrogen incorporation in olivine from 2–12 GPa. Am Miner 91:285–294

    Article  Google Scholar 

  • Mosenfelder JL, le Voyer M, Rossman GR, Guan Y, Bell DR, Asimow PD, Eiler JM (2011) Analysis of hydrogen in olivine by SIMS: evaluation of standards and protocol. Am Miner 96:1725–1741

    Article  Google Scholar 

  • Muir JMR, Jollands M, Zhang FW, Walker AM (2020) Explaining the dependence of M-site diffusion in forsterite on silica activity: a density functional theory approach. Phys Chem Miner 47:2

    Article  Google Scholar 

  • Padron-Navarta JA, Hermann J (2017) A subsolidus olivine water solubility equation for the earth’s upper mantle. J Geophys Res-Solid Earth 122:9862–9880

    Article  Google Scholar 

  • Padron-Navarta JA, Hermann J, O’Neill HSC (2014) Site-specific hydrogen diffusion rates in forsterite. Earth Planet Sci Lett 392:100–112

    Article  Google Scholar 

  • Qin T, Wentzcovitch RM, Umemoto K, Hirschmann MM, Kohlstedt DL (2018) Ab initio study of water speciation in forsterite: Importance of the entropic effect. Am Miner 103:692–699

    Article  Google Scholar 

  • Rauch M, Keppler H (2002) Water solubility in orthopyroxene. Contrib Miner Petrol 143:525–536

    Article  Google Scholar 

  • Smyth JR, Frost DJ, Nestola F, Holl CM, Bromiley G (2006) Olivine hydration in the deep upper mantle: effects of temperature and silica activity. Geophys Res Lett 33:2

    Article  Google Scholar 

  • Stocker RL, Smyth DM (1978) Effect of enstatite activity and oxygen partial-pressure on point-defect chemistry of olivine. Phys Earth Planet Inter 16:145–156

    Article  Google Scholar 

  • Sun W, Yoshino T, Kuroda M, Sakamoto N, Yurimoto H (2019) H-D interdiffusion in single-crystal olivine: Implications for electrical conductivity in the upper mantle. J Geophys Res-Solid Earth 124:5696–5707

    Article  Google Scholar 

  • Tollan PME, Smith R, O’Neill HSC, Hermann J (2017) The responses of the four main substitution mechanisms of H in olivine to H2O activity at 1050 degrees C and 3 GPa. Progr Earth Planet Sci 4:2

    Google Scholar 

  • Tollan PME, O’Neill HSC, Hermann J (2018) The role of trace elements in controlling H incorporation in San Carlos olivine. Contrib Mineral Petrol 173:2

    Article  Google Scholar 

  • Ueki K, Kuwatani T, Okamoto A, Akaho S, Iwamori H (2020) Thermodynamic modeling of hydrous-melt-olivine equilibrium using exhaustive variable selection. Phys Earth Planetary Inter 300:2

    Article  Google Scholar 

  • Walker AM, Hermann J, Berry AJ, O’Neill HS (2007) Three water sites in upper mantle olivine and the role of titanium in the water weakening mechanism. J Geophys Res-Solid Earth 112:12

    Article  Google Scholar 

  • Wang D, Mookherjee M, Xu Y, Karato S-I (2006) The effect of water on the electrical conductivity of olivine. Nature 443:977–980

    Article  Google Scholar 

  • Withers AC, Hirschmann MM (2007) H2O storage capacity of MgSiO3 clinoenstatite at 8–13 GPa, 1100–1400 degrees C. Contrib Miner Petrol 154:663–674

    Article  Google Scholar 

  • Withers AC, Hirschmann MM (2008) Influence of temperature, composition, silica activity and oxygen fugacity on the H2O storage capacity of olivine at 8 GPa. Contrib Miner Petrol 156:595–605

    Article  Google Scholar 

  • Withers AC, Hirschmann MM, Tenner TJ (2011) The effect of Fe on olivine H2O storage capacity: consequences for H2O in the martian mantle. Am Miner 96:1039–1053

    Article  Google Scholar 

  • Xue X, Kanzaki M, Turner D, Loroch D (2017) Hydrogen incorporation mechanisms in forsterite: New insights from H-1 and Si-29 NMR spectroscopy and first-principles calculation. Am Miner 102:519–536

    Article  Google Scholar 

  • Zhang B-H, Xia Q-K (2021) Influence of water on the physical properties of olivine, wadsleyite, and ringwoodite. Eur J Mineral 33:39–75

    Article  Google Scholar 

Download references

Acknowledgements

Funding was provided by National Natural Science Foundation of China (41773057, 42050410319), and by the National Environment Research Council as part of the Volatiles, Geodynamics and Solid Earth Controls on the Habitable Planet research programme (NE/M000044/1). JM is highly thankful to Chinese Academy of Sciences (CAS) for PIFI. We would like to thank two anonymous reviewers for very helpful reviews.

Author information

Authors and Affiliations

  1. State Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, 99 West Lincheng Road, Guiyang, 550081, Guizhou, China

    Joshua M. R. Muir & Feiwu Zhang

  2. Department of Earth Sciences, University of Oxford, South Parks Road, Oxford, OX1 3AN, UK

    Andrew M. Walker

  3. Lamont-Doherty Earth Observatory, 61 Rt 9W, Palisades, NY, 10964, USA

    Michael Jollands

  4. Department of Earth Sciences, University of Leeds, Leeds, LS2 9JT, UK

    Joshua M. R. Muir & Andrew M. Walker

Authors
  1. Joshua M. R. Muir
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Michael Jollands
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Feiwu Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Andrew M. Walker
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Joshua M. R. Muir.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 4998 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Muir, J.M.R., Jollands, M., Zhang, F. et al. Controls on the distribution of hydrous defects in forsterite from a thermodynamic model. Phys Chem Minerals 49, 7 (2022). https://doi.org/10.1007/s00269-022-01182-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00269-022-01182-w

Keywords

Search

Navigation