«IZVESTIYA IRKUTSKOGO GOSUDARSTVENNOGO UNIVERSITETA». SERIYA «NAUKI O ZEMLE»
«THE BULLETIN OF IRKUTSK STATE UNIVERSITY». SERIES «EARTH SCIENCES»
ISSN 2073-3402 (Print)

List of issues > Series «Earth Sciences». 2021. Vol 38

To the Issue of the Presence of the Occurrence of Rare Earth Elements in the Structure of Chromium Pyrope Garnet

Author(s)
V. V. Lin, A. I. Turkin, A. A. Chepurov
Abstract

Rare earth elements (REE) in garnet are of interest in various fields of modern geology. The geochemistry of REEs in magmatic minerals is widely used in determining the distribution coefficients of crystal/melt and crystal/fluid, modeling the processes of melting and crystallization of magmatic rocks, studying deep mantle processes, age estimates and other issues of petrogenesis. The aim of the present work was a synthesis of a peridotite mineral association including the garnet containing REE at high pressure and high temperature. The initial sample consisted mainly of natural serpentine collected from ophiolites of the Eastern Sayan (Russia). As is known, the extreme stage of the regressive metamorphism of peridotites is serpentinization. It is depleted in calcium, but can recrystallize at high PT conditions into a harzburgite paragenesis, and at the initial stage of the experiment the chemical composition of the sample was a model harzburgite depleted in calcium and chromium, as well as a fluid of predominantly aqueous composition. As a source of chromium, chromite grains of 1–2 mm in size from peridotite xenoliths of the Udachnaya kimberlite pipe (Yakutia) were used. REE were added to the initial charge in the form of water-soluble salts. The experiment at a pressure of 5 GPa and temperature 1300 was performed on a multi-anvil high-pressure apparatus of the “split sphere” type (BARS) designed and developed at the V.S. Sobolev Institute of Geology and Mineralogy SB RAS. A container based on refractory oxide ZrO2 was used as a highpressure medium. The pressure in the cell before sample heating was estimated using the reference substances Bi and PbSe. The temperature was measured by a platinum-platinum-rhodium thermocouple PtRh30-PtRh6. The quenched was performed by switching off the voltage in the heater circuit. The experiment products contain an association of olivine + garnet + orthopyroxene + newly formed spinel. The predominant phase was olivine of a forsterite composition. A low-Fe orthopyroxene (1.49 – 1.68 wt% FeO) was found in elongated grains uniformly distributed throughout the sample. The newly formed spinel shows the faceted grains. The chromium content in the spinel significantly exceeds that of the initially added to the initial charge, 61.63 and 54.04 wt% Cr2O3, respectively. The garnet is characterized by a purple color, and was identified in the sample volume between olivine grains in the form of individual faceted crystals or their clusters. The largest garnets reached 0.5 mm in size. The synthesized garnet was determined as a high-Cr low-Ca pyrope variety. The contents of Cr2O3 and CaO are 10.15-11.21 and 0.06-0.11 wt%, respectively. The total content of REE in the garnet identified by the microprobe analysis is relatively high reaching 5-7 wt%. As a result of the work a mineral association corresponding to the peridotite paragenesis was obtained, including the subcalcic Crrich pyrope containing rare earth elements in significant amounts. It was estimated that their content in garnet mainly depends on the size of the ionic radius and, accordingly, on the atomic weight. This is consistent with the known facts about the preferable position of heavy REEs into the garnet structure compared to the light REEs.

About the Authors

Lin Vladimir Valer’evich, Senior Technologist, V. S. Sobolev Institute of Geology and Mineralogy SB RAS, 3/1, Akademik Koptyug ave., Novosibirsk, 630090, Russian Federation, e-mail: lumenex@mail.ru

Turkin Alexander Ivanovich, Doctor of Sciences (Geology and Mineralogy), Senior Researcher, V. S. Sobolev Institute of Geology and Mineralogy SB RAS, 3/1, Akademik Koptyug аve., Novosibirsk, 630090, Russian Federation, e-mail:turkin@igm.nsc.ru

Chepurov Aleksei Anatol’evich, Doctor of Sciences (Geology and Mineralogy), Senior Researcher, V. S. Sobolev Institute of Geology and Mineralogy SB RAS, 3/1, Akademik Koptyug аve., Novosibirsk, 630090, Russian Federation, e-mail: achepurov@igm.nsc.ru

For citation
Lin V.V., Turkin A.I., Chepurov A.A. To the Issue of the Presence of the Occurrence of Rare Earth Elements in the Structure of Chromium Pyrope Garnet. The Bulletin of Irkutsk State University. Series Earth Sciences, 2021, vol. 38, pp. 71-87. https://doi.org/10.26516/2073-3402.2021.38.71 (in Russian)
Keywords
chromium pyrope garnet, rare earth elements, isomorphous substitution, highpressure experiment.
UDC
549.621.95
DOI
https://doi.org/10.26516/2073-3402.2021.38.71
References

Chepurov A.I., Tomilenko A.A., Zhimulev E.I., Sonin V.M., Chepurov A.A., Kovjazin S.V., Timina T.Ju., Surkov N.V. Konservacija vodnogo fljuida v mineralah i mezhzernovom prostranstve pri vysokih P-T parametrah v processe razlozhenija antigorita [Preservation of water fluid in minerals and intergranular space at high P-T parameters during the decomposition of antigorite]. Geologija i Geofizika [Geology and Geophysics], 2012, vol. 53, no. 3, pp. 305-320. https://doi.org/10.24411/ 0869-7175-2018-10024 (in Russian)

Ackerson M.R., Tailby N.D., Watson E.B XAFS spectroscopic study of Ti coordination in garnet. American Mineralogist, 2017, vol. 102, no. 1, pp. 173-183. https://doi.org/ 10.2138/am-2017-5633

Akella J., Kennedy G.C. Melting of gold, silver, and cooper-proposal for a new highpressure calibration scale. Journal of Geophysical Research, 1971, vol. 26, no. 20, pp. 4969-4977. https://doi.org/10.1029/JB076I020P04969

Bea F., Montero P., Garuti G., Zacharini F. Pressure-Dependence of Rare Earth Element Distribution in Amphibolite- and Granulite- Grade Garnets. A LA-ICP-MS Study. The Journal of Geostardarts and Geoanalysis, 1997, vol. 21, no. 2, pp. 253-270. https://doi.org/10.1111/j.1751-908X.1997.tb00674.x

Burgess S., Harte B. Tracing Lithosphere Evolution through the Analysis of Heterogeneous G9-G10 Garnets in Peridotite Xenoliths, II: REE Chemistry. Journal of Petrology, 2004, vol. 45, no. 3, pp. 609-634. https://doi:10.1093/petrology/egg095

Caporuscio F.A., Oberti R., Smyth J.R. X-site control on rare earth elements in eclogitic garnets – an XRD study. European Journal of Mineralogy, 2019, vol. 31, no. 3, pp. 453-463. https://doi.org/10.1127/ejm/2019/0031-2828

Carlson W.D. Multicomponent diffusion in aluminosilicate garnet: coupling effects due to charge compensation. International Geology Reviev, 2017, vol. 59, no. 5-6, pp. 526-540. https://doi.org/10.1080/00206814.2016.1189855

Carlson W.D. Rates and mechanism of Y, REE, and Cr diffusion in garnet. American Mineralogist, 2012, vol. 97, no. 10, pp. 1598-1618. https://doi.org/10.2138/am.2012.4108

Carlson W.D., Gale J.D., Wright K. Incorporation of Y and REEs in aluminosilicate garnet: Energetics from atomistic simulation. American Mineralogist, 2014, vol. 99, no. 5-6, pp. 1022-1034. https://doi.org/10.2138/am.2014.4720

Chepurov A.A., Faryad S.W., Agashev A.M., Strnad L., Jedlicka R., Turkin A.I., Mihaljevic M., Lin V.V. Experimental crystallization of a subcalcic Cr-rich pyrope in the presence of REE-bearing carbonatite. Chemical Geology, 2019, vol. 509, pp. 103-114. https://doi.org/10.1016/j.chemgeo.2019.01.011

Chepurov A.A., Turkin A.I., Dereppe J.M. Interaction of serpentine and chromite as a possible formation mechanism of subcalcic chromium garnet in the upper mantle: an experimental study. European Journal of Mineralogy, 2016, vol. 28, no. 2, pp. 329-336. https://doi.org/10.1127/ ejm/2016/0028-2517

High-pressure calibration. A critical review High-pressure calibration. A critical review / D.L. Decker, W.A. Basett, L. Merrill, H.T. Hall, J.D. Barnett. Journal of Physical and Chemical Reference Data, 1972, vol. 1, no. 3, р. 773-836. https://doi.org/10.1063/1.3253105

Dubacq B., Plunder A. Controls on Trace Element Distribution in Oxides and Silicates. Journal of Petrology, 2018, vol. 59, no. 2, pp. 1-23. https://doi:10.1093/petrology/egy027

Gieré R., Rumble D., Günther D., Connolly J., Caddick M.J. Correlation of growth and breakdown of major and accessory minerals in metapelites from Campolungo, central Alps. Journal of Petrology, 2011, vol. 52, no. 12, pp. 2293-2334. https:// doi.org/10.1093/ petrology/egr043

Grew E.S., Marsh J.H., Yates M.G., Lazic B., Armbruster T., Locock A., Bell S.W., Dyar M.D., Bernhardt H., Medenbach O. Menzerite-(y), A new species, {(Y,REE)(Ca,Fe2+)2}[(Mg,Fe2+) (Fe3+,Al)](Si3)O12, From A felsic granulite, parry sound, ontario, and A new garnet end-member, (Y2Ca)[Mg2](Si3)O12. The Canadian Mineralogist, 2010, vol. 48, no. 5, pp. 727-749. https://doi.org/ 10.3749/canmin.48.5.000

Griffin W.L., Smith D., Ryan C.G., O’Reilly S.Y., Win T.T. Trace element zoning in mantle minerals: Metasomatism and thermal events in the upper mantle. The Canadian Mineralogist, 1996, vol. 34, no. 6, pp. 1179-1193.

Hanson G.N. Rare earth elements in petrogenetic studies of igneous systems. Annual Review of Earth and Planetary Science, 1980, vol. 8, pp. 371-406. https://doi.org/10.1146/annurev.ea.08.050180.002103

Hönig S., Čopjakova R., Škoda R., Novak M., Dolejš D., Leichmann J., Galiova M.V. Garnet as a major carrier of the Y and REE in the granitic rocks: An example from the layered anorogenic granite in the Brno Batholith, Czech Republic. American Mineralogist, 2014, vol. 99, no. 10, pp. 1922-1941. https://doi.org/10.2138/am-2014-4728

Iiyama J.T., Volfinger M. A model for trace-element distribution in silicate structures. Mineralogical Magazine, 1976, vol. 40, pp. 555-564.

Jaffe H.W. The role of yttrium and other minor elements in the garnet group. American Mineralogist, 1951, vol. 36, no. 1-2, pp. 133-155.

Kohn M.J. Models of garnet differential geochronology. Geochimica et Cosmochimica Acta, 2009, vol. 73, no. 1, pp. 170-182. https://doi.org/10.1016/ j.gca.2008.10.004

McIntire W.L. Trace element partition coefficients – a review of theory and applications to geology. Geochimica et Cosmochimica Acta, 1963, vol. 27, no. 12, pp. 1209-1264. https://doi.org/10.1016/0016-7037(63)90049-8

Merli M., Callegari A., Cannillo E., Caucia F., Leona M., Oberti R., Ungaretti L. Crystal-chemical complexity in natural garnets: structural constraints on chemical variability. European Journal of Mineralogy, 1995, vol. 7, no. 6, pp. 1239-1249.

Novak G.A., Gibbs G.V. The crystal chemistry of the silicate garnets. American Mineralogist, 1971, vol. 56, no. 5-6, pp. 791-825.

Quartieri S., Antonioli G., Geiger C.A., Artioli G., Lottici P.P. XAFS characterization of the structural site of Yb in synthetic pyrope and grossular garnets. Physics and Chemistry of Minerals, 1999a, vol. 26, no. 3, pp. 251-256. https://doi.org/ 10.1007/s002690050184

Quartieri S., Chaboy J., Antonioli G., Geiger C.A. XAFS characterization of the structural site of Yb in synthetic pyrope and grossular garnets. II. XANES full multiple scattering calculations at the Yb LI- and LIII-edges. Physics and Chemistry of Minerals, 1999b, vol. 27, no. 2, pp. 88-94. https://doi.org/10.1007/s002690050244

Rajendran J., Thampi P.K., Balasubramanian G. Determination of Rare Earth Elements in Garnet Minerals, Geological Materials by Inductively Coupled Plasma-Atomic Emission Spectral and Mass Spectral Analysis. Analytical Letters, 2006, vol. 39. no. 11, pp. 2297-2306. https://doi.org/ 10.1080/00032710600755587

Shannon R.D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica A., 1976, vol. 32, no. 5, pp. 751-767. https://doi.org/10.1107/S0567739476001551

Shimizu N. Rare earth elements in garnets and clinopyroxenes from garnet lherzolite nodules in kimberlites. Earth and Planetary Science Letters, 1975, vol. 25, no. 1, pp. 26-32. https://doi.org /10.1016/0012-821X(75)90206-X

Sobolev A.V. Melt inclusions in minerals as a source of principal petrologic information. Petrology, 1996, vol. 4, no. 3, pp. 209-220.

Stachel T., Viljoen K.S., Brey G., Harris J.W. Metasomatic processes in lherzolitic and harzburgitic domains of diamondiferous lithospheric mantle: REE in garnets from xenoliths and inclusions in diamonds. Earth and Planetary Science Letters, 1998, vol. 159, no. 1-2, pp. 1-12. https://doi.org/10.1016/S0012-821X(98)00064-8

Sun C., Liang Y. The importance of crystal chemistry on REE partitioning betweenmantle minerals (garnet, clinopyroxene, orthopyroxene, and olivine) and basaltic melts. Chemicalal Geology, 2013, vol. 358, no. 1, pp. 23-36. https://doi.org/ 10.1016/j.chemgeo.2013.08.045

Suzuki K. Grain-boundary enrichment of incompatible elements in some mantle peridotites. Chemicalal Geology, 1987, vol. 63, no. 3-4, pp. 319-334. https://doi.org/10.1016/0009-2541(87)90169-0

Tirone M., Ganguly J., Dohmen R., Langenhorst F., R. Hervig, H.-W. Becker Rare earth diffusion kinetics in garnet: Experimental studies and applications. Geochimica et Cosmochimica Acta, 2005, vol. 69, no. 9, pp. 2385-2398. https://doi.org/ 10.1016/j.gca.2004.09.025

Tonkov E.Yu., Ponyatovsky E.G. Phase transformations of elements under high pressure. Fridlyander J.N., Eskin D.G. (eds.). CRC Press, 2004, pp. 392. https://doi.org/10.1201/9781420037609

Turkin A.I. Lead selenide as a continuous internal indicator of pressure in solid-media cells of high-pressure apparatus in the range of 4-6.8 GPa. High Temperatures – High Pressures, 2003/2004, vol. 35/36, pр. 371-376. https://doi.org/ 10.1068/htjr112

Ulmer P., Trommsdorff V. Serpentine stability to mantle depths and subduction-related magmatism. Science, 1995, vol. 268, no. 5212, pp. 858-861. https://doi.org/10.1126/science.268.5212.858

Van Orman J.A., Grove T.L., Shimizu N., Graham L. Rare earth element diffusion in a natural pyrope single crystal at 2.8 Gpa. Contributions to Mineralogy and Petrology, 2002, vol. 142, no. 4, pp. 416-424. https://doi.org/ 10.1007/s004100100304

Van Westrenen W., Allan N.L., Blundy J.D., Purton J.A., Wood B.J. Atomistic simulation of trace element incorporation into garnets-comparison with experimental garnet-melt partitioning data. Geochimica et Cosmochimica Acta, 2000, vol. 64, no. 9, pp. 1629-1639. https://doi.org/ 10.1016/S0016-7037(00)00336-7

Watson E.B. Surface enrichment and trace-element uptake during crystal growth // Geochimica et Cosmochimica Acta, 1996, vol. 60, no. 24, pp. 5013-5020. https://doi.org/10.1016/S0016-7037(96)00299-2

Yoder H.S., Keith M.L. Complete substitution of aluminum for silicon: The system 3MnOꞏAl2O3ꞏ3SiO2–3Y2O3ꞏ5Al2O3. American Mineralogist, 1951, vol. 36, no. 7-8, pp. 519-533.

Zhimulev E.I., Chepurov A.I., Sonin V.M., Litasov K.D., Chepurov, A.A. Experimental modeling of percolation of molten iron through polycrystalline olivine matrix at 2.0-5.5 GPa and 1600oC, High Pressure Research, 2018, vol. 38, pp. 153-164. https://doi.org/10.1080/08957959.2018.1458847


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