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Kinetics of hydrogen extraction and deuteration in grossular

Published online by Cambridge University Press:  05 July 2018

A. Kurka
Affiliation:
LMTG, CNRS, UMR 5563, Minéralogie, 14 Av. Edouard Belin, 31400 Toulouse, France
M. Blanchard
Affiliation:
LMTG, CNRS, UMR 5563, Minéralogie, 14 Av. Edouard Belin, 31400 Toulouse, France
J. Ingrin*
Affiliation:
LMTG, CNRS, UMR 5563, Minéralogie, 14 Av. Edouard Belin, 31400 Toulouse, France
*

Abstract

The kinetics of hydrogen mobility in grossular with a chemically homogeneous composition of Gr83.2 And14.3 Py2.2 were studied by sequential annealing experiments monitored by Fourier transform infrared spectroscopy. Slices of single crystals <0.5 mm thick were annealed at temperatures in the range 1073–1323 K at ambient pressure in air and in gas mixtures of Ar(90%)/D2(10%) and Ar(90%)/H2(10%). The change of total infrared (IR) absorbance in the OH-stretching region (3700–3500 cm–1) and the OD-stretching region (2750–2580 cm–1) was used to calculate the diffusion coefficients. The law for diffusion of deuterium is given by D = D0 exp[–102±45 kJ mol–1/ RT] with log D0 (m2/s) = –7.6. For hydrogen extraction in air the diffusion law is expressed by D = D0 exp[–323±46 kJ mol–1/RT] with log D0 (m2/s) = 1.0. This activation energy agrees with the values found for Dora Maira pyrope and for other pyropes from mantle xenoliths, but the diffusivity is slower for the grossular. A detailed investigation of the decrease in individual OH bands during hydrogen extraction in air revealed two different kinds of kinetics behaviour, suggesting that at least two different types of OH defects are present in this grossular.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2005

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Footnotes

Present address: The Royal Institution of Great Britain, 21 Albemarle Street, London W1S 4BS, UK

References

Blanchard, M. and Ingrin, J. (2004a) Kinetics of deuteration in pyrope. European Journal of Mineralogy. 16, 567576.CrossRefGoogle Scholar
Blanchard, M. and Ingrin, J. (2004b) Hydrogen diffusion in Dora Maira pyrope. Physics and Chemistry of Minerals, 31, 593605.CrossRefGoogle Scholar
Carslaw, H.S. and Jaeger, J.C. (1959) Conduction of Heat in Solids. Clarendon Press, Oxford, UK, 510 pp.Google Scholar
Clowe, C.A., Popp, R.K. and Fritz, S.J. (1988) Experimental investigation of the effect of oxygen fugacity on ferric ferrous ratios and unit cell parameters of four natural clinoamphiboles. American Mineralogist, 73, 487499.Google Scholar
Cohen-Addad, C., Ducros, P. and Bertaut, E.F. (1967) Etude de la substitution du groupement SiO4 par (OH)4 dans les composés Al2Ca3(OH)12 et Al2Ca3(SiO4)2.16(OH) 3.36 de type grenat. Acta Crystallographica, 23, 220230.CrossRefGoogle Scholar
Dyar, M.D., Mackwell, S.J., McGuire, A.V., Cross, L.R. and Robertson, J.D. (1993) Crystal chemistry of Fe3+and H+ in mantle kaersutite: Implications for mantle metasomatism. American Mineralogist, 78, 968979.Google Scholar
Geiger, C.A., Langer, K., Bell, D.R., Rossman, G.R. and Winkler, B. (1991) The hydroxide component in synthetic pyrope. American Mineralogist, 76, 4959.Google Scholar
Hercule, S. and Ingrin, J. (1999) Hydrogen in diopside: Diffusion, kinetics of extraction-incorporation and solubility. American Mineralogist, 84, 15771587.CrossRefGoogle Scholar
Ingrin, J. and Skogby, H. (2000) Hydrogen in nominally anhydrous upper mantle minerals: concentration levels and implications. European Journal of Mineralogy, 12, 543570.CrossRefGoogle Scholar
Ingrin, J., Hercule, S. and Charton, T. (1995) Diffusion of hydrogen in diopside: results of dehydrogenation experiments. Journal of Geophysical Research, 100, 1548915499.CrossRefGoogle Scholar
Kohlstedt, D.L. and Mackwell S.J. (1998) Diffusion of hydrogen and intrinsic point defects in olivine. Zeitschrift für Physikalische Chemie, 207, 147162.CrossRefGoogle Scholar
Lacroix, A. (1922) Minéralogie de Madagascar. Ed. Callamel, Paris, tome, I, 641 pp.Google Scholar
Lager, G.A., Armbruster, T. and Faber, J. (1987) Neutron and X-ray diffraction study of hydrogarnet Ca3Al2(O4H4). American Mineralogist, 72, 756765.Google Scholar
Lager, G.A., Armbruster, T., Rotella, F.J. and Rossman, G.R. (1989) The OH substitution in garnets: X-ray and neutron diffraction, infrared and geometric-modelling studies. American Mineralogist, 74, 840851.Google Scholar
Langer, K., Robarick, E., Sobolev, N.V., Shatsky, V.S. and Wang, W. (1993) Single-crystal spectra of garnets from diamondiferous high-pressure meta-morphic rocks from Kazakhstan: implications for OH, H2O, and FeTi charge transfer. European Journal of Mineralogy, 5, 10911100.CrossRefGoogle Scholar
Lemaire, C, Kohn, S.C. and Brooker, R.A. (2004) The effect of silica activity on the incorporation mechanism of water in synthetic forsterite: a polarised infrared spectroscopic study. Contributions to Mineralogy and Petrology, 147, 4857.Google Scholar
Mackwell, S.D. and Kohlstedt, D.L. (1990) Diffusion of hydrogen in olivine: Implications for water in the mantle. Journal of Geophysical Research, 95, 50795088.CrossRefGoogle Scholar
Maldener, J., Hösch, A., Langer, K. and Rauch, F. (2003) Hydrogen in some natural garnets studied by nuclear reaction analysis and vibrational spectroscopy. Physics and Chemistry of Minerals, 30, 337344.CrossRefGoogle Scholar
Matveev, S., O'Neill, H.ST.C., Ballhaus, C., Taylor, W.R. and Green, D.H. (2001) Effect of silica activity on OH IR spectra of olivine: implications for low-aSiO2 mantle metasomatism. Journal of Petrology, 42, 721729.CrossRefGoogle Scholar
Mikenda, W. (1986) Stretching frequency versus bond distance correlation of O-D(H)…Y (Y = N, O, S, Se, Cl, Br, I) hydrogen bonds in solid hydrates. Journal of Molecular Structure, 147, 115.CrossRefGoogle Scholar
Rossman, G.R and Aines, R.D. (1991) The hydrous components in garnets: grossular-hydrogrossular.American Mineralogist, 76, 11531164.Google Scholar
Sacerdoti, M. and Passaglia, E. (1985) The crystal structure of katoite and implications within the hydrogrossular group of minerals.. Bulletin de Minéralogie, 108, 18.CrossRefGoogle Scholar
Skogby, H. and Rossman, G.R. (1989) OH– in pyroxene: an experimental study of incorporation mechanism and stability. American Mineralogist, 74, 10591069.Google Scholar
Wang, L., Zhang, Y. and Essene, E. (1996) Diffusion of the hydrous component in pyrope.. American Mineralalogist, 81, 706718.CrossRefGoogle Scholar
Zabinski, W. (1966) Hydrogarnets. Polska Akademia Nauk, Komisja Nauk Mineralogicznych. Prace Mineralogiczne, 3, 161.Google Scholar
Zheng, Y.F., Fu, B., Gong, B. and Li, L. (2003) Stable isotope geochemistry of ultrahigh pressure metamorphic rocks from the Dabie-Sulu orogen in China: implications for geodynamics and fluid regime. Earth Science Reviews, 62, 105161.CrossRefGoogle Scholar