Composition of barian mica in multiphase solid inclusions from orogenic garnet peridotites as evidence of mantle metasomatism in a subduction zone setting

  • Renata ČopjakováEmail author
  • Jana Kotková
Original Paper


Multiphase solid inclusions in minerals formed at ultra-high-pressure (UHP) provide evidence for the presence of fluids during deep subduction. This study focuses on barian mica, which is a common phase in multiphase solid inclusions enclosed in garnet from mantle-derived UHP garnet peridotites in the Saxothuringian basement of the northern Bohemian Massif. The documented compositional variability and substitution trends provide constraints on crystallization medium of the barian mica and allow making inferences on its source. Barian mica in the multiphase solid inclusions belongs to trioctahedral micas and represents a solid solution of phlogopite KMg3(Si3Al)O10(OH)2, kinoshitalite BaMg3(Al2Si2)O10(OH)2 and ferrokinoshitalite BaFe3(Al2Si2)O10(OH)2. In addition to Ba (0.24–0.67 apfu), mica is significantly enriched in Mg (XMg ~ 0.85 to 0.95), Cr (0.03–0.43 apfu) and Cl (0.04–0.34 apfu). The substitution vector involving Ba in the I-site which describes the observed chemical variability can be expressed as BaFeIVAlClK−1Mg−1Si−1(OH)−1. A minor amount of Cr and VIAl enters octahedral sites following a substitution vector VI(Cr,Al)2VI(Mg,Fe)−3 towards chromphyllite and muscovite. As demonstrated by variable Ba and Cl contents positively correlating with Fe, barian mica composition is partly controlled by its crystal structure. Textural evidence shows that barian mica, together with other minerals in multiphase solid inclusions, crystallized from fluids trapped during garnet growth. The unusual chemical composition of mica reflects the mixing of two distinct sources: (1) an internal source, i.e. the host peridotite and its garnet, providing Mg, Fe, Al, Cr, and (2) an external source, represented by crustal-derived subduction-zone fluids supplying Ba, K and Cl. At UHP–UHT conditions recorded by the associated diamond-bearing metasediments (c. 1100 °C and 4.5 GPa) located above the second critical point in the pelitic system, the produced subduction-zone fluids transporting the elements into the overlying mantle wedge had a solute-rich composition with properties of a hydrous melt. The occurrence of barian mica with a specific chemistry in barium-poor mantle rocks demonstrates the importance of its thorough chemical characterization.


Ba-rich phlogopite Kinoshitalite Multiphase solid inclusions Orogenic garnet peridotite Metasomatism Bohemian Massif 



This research was financially supported by Czech Science Foundation Project 18-27454S. We wish to acknowledge the constructive comments and suggestions of J. Majka and of an anonymous reviewer, which significantly contributed to the final version of this paper. The authors thank Daniela Rubatto for editorial handling.


  1. Behn MD, Kelemen PB, Hirth G, Hacker BR, Massonne H-J (2011) Diapirs as the source of the sediment signature in arc lavas. Nat Geosci 4:641–646. CrossRefGoogle Scholar
  2. Bocchio R (2007) Barium-rich phengite in eclogites from the Voltri Group (northwestern Italy). Per Mineral 76:155–167. CrossRefGoogle Scholar
  3. Bol LCGM, Bos A, Sauter PCC, Jansen JBH (1989) Barium-titanium-rich phlogopites in marbles from Rogaland, southwest Norway. Am Mineral 74:439–447Google Scholar
  4. Carswell DA, van Roermund HLM (2005) On multi-phase mineral inclusions associated with microdiamond formation in mantle-derived peridotite lens at Bardane on Fiørtoft, west Norway. Eur J Mineral 17:31–42. CrossRefGoogle Scholar
  5. Dasgupta S, Chakraborti S, Sengupta P, Bhattacharya PK, Banerjee H, Fukuoka M (1989) Compositional characteristics of kinoshitalite from the Sausar Group, India. Am Mineral 74:200–202Google Scholar
  6. Doležalová H, Houzar S, Losos Z, Škoda R (2006) Kinoshitalite with a high magnesium content in sulphide-rich marbles from the Rožná uranium deposit, Western Moravia, Czech Republic. N Jb Miner Abh 182:165–171. CrossRefGoogle Scholar
  7. Edgar AD (1992) Barium-rich phlogopite and biotite from some Quaternary alkali mafic lavas, West Eifel, Germany. Eur J Mineral 4:321–330CrossRefGoogle Scholar
  8. Faryad SW, Jedlička R, Ettinger K (2013) Subduction of lithospheric upper mantle recorded by solid phase inclusions and compositional zoning in garnet: example from the Bohemian Massif. Gondwana Res 23:944–955. CrossRefGoogle Scholar
  9. Frezzotti ML, Ferrando S (2015) The chemical behavior of fluids released during deep subduction based on fluid inclusions. Am Mineral 100:352–377. CrossRefGoogle Scholar
  10. Frimmel HE, Hoffmann D, Watkins RT, Moore JM (1995) An Fe analogue of kinoshitalite from the Broken Hill Massie sulfide deposit in the Namaqualand Metamorphic Complex, South Africa. Am Mineral 80:833–840. CrossRefGoogle Scholar
  11. Gaspar JC, Wyllie PJ (1982) Barium phlogopite from the Jacupiranga carbonatite, Brazil. Am Mineral 67:997–1000Google Scholar
  12. Gnos E, Armbruster T (2000) Kinoshitalite, Ba(Mg)3(Al2Si2)O10(OH,F)2, a brittle mica from a manganese deposit in Oman: paragenesis and crystals chemistry. Am Mineral 85:242–250. CrossRefGoogle Scholar
  13. Greenwood JC (1998) Barian–titanian micas from Ilha da Trindade, South Atlantic. Mineral Mag 62:687–695. CrossRefGoogle Scholar
  14. Guggenheim S, Frimmel HE (1999) Ferrokinoshitalite, a new species of brittle mica from the Broken Hill mine, South Africa: structural and mineralogical characterization. Can Mineral 37:1445–1452Google Scholar
  15. Haifler J, Kotková J (2016) UHP–UHT peak conditions and near-adiabatic exhumation path of diamond-bearing garnet-clinopyroxene rocks from the Eger Crystalline Complex, North Bohemian Massif. Lithos 248–251:366–381. CrossRefGoogle Scholar
  16. Halter WE, Pettke T, Heinrich CHA, Rothen-Rutishauser B (2002) Major to trace element analysis of melt inclusions by laser-ablation ICP–MS: methods of quantification. Chem Geol 183:63–86. CrossRefGoogle Scholar
  17. Harlow GE (1995) Crystal chemistry of barian enrichment in micas from metasomatized inclusions in serpentinite, Motagua Fault Zone, Guatemala. Eur J Mineral 7:775–790. CrossRefGoogle Scholar
  18. Hermann J, Rubatto D (2009) Accessory phase control on the trace element signature of sediment melts in subduction zones. Chem Geol 265:512–526. CrossRefGoogle Scholar
  19. Hermann J, Rubatto D (2014) Subduction of continental crust to mantle depth: geochemistry of ultrahigh-pressure rocks. In: Holland HD, Turekian KK (eds) Treatise on geochemistry, 2nd edn. Elsevier, New York, pp 309–340. CrossRefGoogle Scholar
  20. Hermann J, Spandler C, Hack A, Korsakov AV (2006) Aqueous fluids and hydrous melts in high-pressure and ultra-high pressure rocks: implications for element transfer in subduction zones. Lithos 92:399–417. CrossRefGoogle Scholar
  21. Houzar S, Cícha J (2016) Chondrodite- and clinohumite-bearing marbles of the Podolsko Complex in Písek area and related F-rich Mg–Si–Ti–Ba–Zr mineral assemblage (Moldanubian Zone, Bohemian Massif). Bull mineral-petrolog Odd Nár. Muz (Praha) 24 1:33–45 (in Czech) Google Scholar
  22. Ionov DA, Hofmann AW (1995) Nb–Ta-rich mantle amphiboles and micas: implications for subduction-related metasomatic trace element fractionations. Earth Planet Sci Lett 131:341–356. CrossRefGoogle Scholar
  23. Keppler H (2017) Fluids and trace element transport in subduction zones. Am Mineral 102:5–20. CrossRefGoogle Scholar
  24. Kogarko LA, Uvarova YA, Sokolova E, Hawthorne FC, Ottolini L, Grice JD (2005) Oxykinoshitalite, a new species of mica from Fernando de Noronha island, Pernambuco, Brazil: occurrence and crystal structure. Can Mineral 43:1501–1510. CrossRefGoogle Scholar
  25. Kopecký L, Sattran V (1966) Buried occurrences of pyrope-peridotite and the structure of the crystalline basement in the extreme SW of the České středohoří Mts. Krystalinikum 4:65–86Google Scholar
  26. Kopecký L, Paděra K (1974) Bänderung der ultramafi tischen Gesteine in der Bohrung T-7 Staré bei Trebenice (Nordböhmen), in Alexiev J et al. eds. Minerogenesis Bulgar Acad Sci Geol Inst Sofia 1974:161–169Google Scholar
  27. Kotková J (1993) Tectonometamorphic history of lower crust in the Bohemian Massif-example of north Bohemian granulites. Czech Geol Surv Spec Pap 2:1–42Google Scholar
  28. Kotková J, Janák M (2015) UHP kyanite eclogite associated with garnet peridotite and diamond-bearing granulite, northern Bohemian Massif. Lithos 226:255–264. CrossRefGoogle Scholar
  29. Kotková J, Kröner A, Todt W, Fiala J (1996) Zircon dating of North Bohemian granulites, Czech Republic: further evidence for the Lower Carboniferous high-pressure event in the Bohemian Massif. Geol Rundsch 85:154–161. CrossRefGoogle Scholar
  30. Kotková J, O’Brien PJ, Ziemann MA (2011) Diamond and coesite discovered in Saxony-type granulite: solution to the Variscan garnet peridotite enigma. Geology 39:667–670. CrossRefGoogle Scholar
  31. Kotková J, Whitehouse M, Schaltegger U, D’Abzac F-X (2016) The fate of zircon during UHT-UHP metamorphism: isotopic (U/Pb, δ18O, Hf) and trace element constraints. J Met Geol 34:719–739. CrossRefGoogle Scholar
  32. Kullerud K (1995) Chlorine, titanium and barium-rich biotites: factors controlling biotite composition and the implications for garnet-biotite geothermometry. Contrib Mineral Petrol 120:42–59. CrossRefGoogle Scholar
  33. Liou JG, Ernst WG, Zhang RY, Tsujimori T, Jahn BM (2009) Ultrahigh-pressure minerals and metamorphic terranes—the view from China. J Asian Earth Sci 35:199–231. CrossRefGoogle Scholar
  34. Majka J, Kruszewski Ł, Rosén Å, Klonowska I (2015) Ba-and Ti-enriched dark mica from the UHP metasediments of the Seve Nappe Complex, Swedish Caledonides. Mineralogia 46:41–50. CrossRefGoogle Scholar
  35. Malaspina N, Hermann J, Scambelluri M, Compagnoni R (2006) Polyphase inclusions in garnet-orthopyroxenite (Dabie Shan, China) as monitors for metasomatism and fluid-related trace element transfer in subduction zone peridotite. Earth Planet Sci Lett 249:173–187. CrossRefGoogle Scholar
  36. Malaspina N, Hermann J, Scambelluri M (2009) Fluid/mineral interaction in UHP garnet peridotite. Lithos 107:38–52. CrossRefGoogle Scholar
  37. Malaspina N, Alvaro M, Campione M, Wilhelm H, Nestola F (2015) Dynamics of mineral crystallization from precipitated slab-derived fluid phase: first in situ synchrotron X-ray measurements. Contrib Mineral Petrol 169:1–12. CrossRefGoogle Scholar
  38. Mandler BE, Grove TL (2016) Controls on the stability and composition of amphibole in the Earth’s mantle. Contrib Mineral Petrol 171:68. CrossRefGoogle Scholar
  39. Manning CE (2004) The chemistry of subduction-zone fluids. Earth Planet Sci Lett 223:1–16. CrossRefGoogle Scholar
  40. Mansker WL, Ewing RC, Keil K (1979) Barian-titanian biotites in nephelinites from Oahu, Hawaii. Am Mineral 64:156–159Google Scholar
  41. Manuella FC, Carbone S, Ottolini L, Gibilisco S (2012) Micro-Raman spectroscopy and SIMS characterization of oxykinoshitalite in an olivine nephelinite from the Hyblean Plateau (Sicily, Italy). Eur J Mineral 24:527–533. CrossRefGoogle Scholar
  42. Massonne H-J (2003) A comparison of the evolution of diamondiferous quartz-rich rocks from the Saxonian Erzgebirge and the Kokchetav Massif: are so-called diamondiferous gneisses magmatic rocks? Earth Planet Sci Lett 216:347–364. CrossRefGoogle Scholar
  43. Massonne HJ, Burchard M (2000) Exotic minerals in eclogites from the Central Erzgebirge—evidence for fluid-rock interaction at UH metamorphic pressures. In: “Berichte der Deutschen Mineralogischen Gesellschaft”. Beih z Eur J Mineral 12:122Google Scholar
  44. Massonne H-J, Opitz J, Theye T, Nasir S (2013) Evolution of a very deeply subducted metasediment from As Sifah, northeastern coast of Oman. Lithos 156–159:171–185. CrossRefGoogle Scholar
  45. Medaris LG Jr, Wang H, Jelínek E, Mihaljevič M, Jakeš P (2005) Characteristics and origins of diverse Variscan peridotites in the Gföhl Nappe, Bohemian Massif, Czech Republic. Lithos 82:1–23. CrossRefGoogle Scholar
  46. Medaris G, Ackerman L, Jelínek E, Michels Z, Erban V, Kotková J (2015) Depletion, cryptic metasomatism, and modal mesatomatism (refertilization) of Variscan lithospheric mantle: evidence from major elements, trace elements, and Sr–Nd–Os isotopes in a Saxothuringian garnet peridotite. Lithos 226:81–97. CrossRefGoogle Scholar
  47. Merlet C (1994) An accurate computer correction program for quantitative electron probe microanalysis. Microchim Acta 114–115:363–376. CrossRefGoogle Scholar
  48. Mlčoch B, Konopásek J (2010) Pre-Late Carboniferous geology along the contact of the Saxothuringian and Teplá-Barrandian zones in the area covered by younger sediments and volcanics (western Bohemian Massif, Czech Republic). J Geosci 55:137–150. CrossRefGoogle Scholar
  49. Munoz JL, Swenson A (1981) Chloride-hydroxyl exchange in biotite and estimation of relative HCl/HF activities in hydrothermal fluids. Econ Geol 76:2212–2221. CrossRefGoogle Scholar
  50. Naemura K, Yokoyama K, Hirajima T, Svojtka M (2008) Age determination of thorianite in phlogopite-bearing spinel-garnet peridotite in the Gföhl Unit, Moldanubian zone of the Bohemian Massif. J Mineral Petrol Sci 103:285–290. CrossRefGoogle Scholar
  51. Naemura K, Hirajima T, Svojtka M (2009) The pressure-temperature path and the origin of phlogopite in spinel-garnet peridotites from the Blanský Les Massif of the Moldanubian Zone, Czech Republic. J Petrol 50:1795–1827. CrossRefGoogle Scholar
  52. Palme H, O’Neill H (2014) Cosmochemical estimates of mantle composition. In: Carlson RW (ed) Treatise on geochemistry, 2nd edn, vol 3. Elsevier, Oxford, pp 1–39Google Scholar
  53. Pan Y, Fleet ME (1991) Barian feldspar and barian-chromian muscovite from the Hemlo area, Ontario. Can Mineral 29:481–498Google Scholar
  54. Pattiaratch DB, Saari E, Sahama TG (1967) Anandite, a new barium iron silicate from Wilagedera, North Western Province, Ceylon. Mineral Mag 36:1–4. CrossRefGoogle Scholar
  55. Pettke T, Halter WE, Webster JD, Aigner-Torres M, Heinrich ChA (2004) Accurate quantification of melt inclusion chemistry by LA-ICPMS: a comparison with EMP and SIMS and advantages and possible limitations of these methods. Lithos 78:333–361. CrossRefGoogle Scholar
  56. Philippot P, Chevallier P, Chopin Ch, Dubessy J (1995) Fluid composition and evolution in coesite-bearing rocks (Dora-Maira massif, Western Alps): implications for element recycling during subduction. Contrib Mineral Petrol 121:29–44. CrossRefGoogle Scholar
  57. Rollinson H, Mameri L, Barry T (2018) Polymineralic inclusions in mantle chromitites from the Oman ophiolite indicate a highly magnesian parental melt. Lithos 310–311:381–391. CrossRefGoogle Scholar
  58. Scambelluri M, van Roermund H, Pettke T (2010) Mantle wedge peridotites: fossil reservoirs of deep subduction zone processes. Inferences from high and ultrahigh-pressure rocks from Bardane (Western Norway) and Ulten (Italian Alps). Lithos 120:186–201. CrossRefGoogle Scholar
  59. Schmädicke E, Evans BW (1997) Garnet-bearing ultramafic rocks from the Erzgebirge, and their relation to other settings in the Bohemian Massif. Contrib Mineral Petrol 127:57–74. CrossRefGoogle Scholar
  60. Schmädicke E, Okrusch M, Schmidt W (1992) Eclogite-facies rocks in the Saxonian Erzgebirge, Germany: high pressure metamorphism under contrasting P–T conditions. Contrib Mineral Petrol 110:226–241. CrossRefGoogle Scholar
  61. Seifert W, Kampf H (1994) Ba-enrichment in phlogopite of a nephelinite from Bohemia. Eur J Mineral 6:497–502CrossRefGoogle Scholar
  62. Shaw CS, Penczak RS (1996) Barium and titanium-rich biotite and phlogopite from the western and eastern gabbro, Coldwell alkaline complex, northwestern Ontario. Can Mineral 34:967–975Google Scholar
  63. Solie DN, Su SC (1987) An occurrence of Ba-rich micas from the Alaska Range. Am Mineral 72:995–999Google Scholar
  64. Solovova IP, Girnis AV, Ryabchikov ID, Kononkova NN (2009) Mechanisms of formation of barium-rich phlogopite and strontium-rich apatite during the final stages of alkaline magma evolution. Geochem Int 47:578–591. CrossRefGoogle Scholar
  65. Sorensen SS, Grossman JN, Perfit MR (1997) Phengite-hosted LILE enrichment in eclogite and related rocks: implications for fluid-mediated mass transfer in subduction zones and arc magma genesis. J Petrol 38:3–34. CrossRefGoogle Scholar
  66. Spandler C, Pirard C (2013) Element recycling from subducting slabs to arc crust: a review. Lithos 170–171:208–223. CrossRefGoogle Scholar
  67. Taylor SR, McLennan SM (1985) The continental crust: its composition and evolution. Blackwell, LondonGoogle Scholar
  68. Tracy RJ (1991) Ba-rich micas from the Franklin marble, Lime Crest and Sterling Hill, New Jersey. Am Mineral 76:1683–1693Google Scholar
  69. Tracy RJ, Beard JS (2003) Manganoan kinoshitalite in Mn-rich marble and skarn from Virginia. Am Mineral 88:740–747. CrossRefGoogle Scholar
  70. Tumiati S, Godard G, Martin S, Klötzli U, Monticelli D (2007) Fluid-controlled crustal metasomatism within a high-pressure subducted mélange (Mt. Hochwart, Eastern Italian Alps). Lithos 94:148–167. CrossRefGoogle Scholar
  71. Tumiati S, Fumagalli P, Tinaboschi C, Poli S (2013) An experimental study on COH-bearing peridotite up to 3.2 GPa, and implications for crust-mantle recycling. J Petrol 54:453–479. CrossRefGoogle Scholar
  72. van Roermund HLM, Carswell DA, Drury MR, Heijboer TC (2002) Microdiamond in a megacrystic garnet websterite pod from Bardane on the island of Fjørtoft, western Norway: evidence for diamond formation in mantle rocks during deep continental subduction. Geology 30:959–962.;2 CrossRefGoogle Scholar
  73. Volfinger M, Robert JL, Vielzeuf D, Neiva AMR (1985) Structural control of the chlorine content of OH-bearing silicates (micas and amphiboles). Geochim Cosmochim Acta 49:37–48. CrossRefGoogle Scholar
  74. Vrijmoed JC, Van Roermund HLM, Davies GR (2006) Evidence for diamond-grade ultra-high pressure metamorphism and fluid interaction in the Svartberget Fe–Ti garnet peridotite-websterite body, Western Gneiss Region, Norway. Mineral Petrol 88:381–405. CrossRefGoogle Scholar
  75. Vrijmoed JC, Smith DC, van Roermund HLM (2008) Raman confirmation of microdiamond in the Svartberget Fe^Ti type garnet peridotite, Western Gneiss Region, Western Norway. Terra Nova 20:295–301. CrossRefGoogle Scholar
  76. Yoshii M, Maeda K (1975) Relations between barium content and the physical and optical properties in the manganoan phlogophite-kinoshitalite series. Mineral J 8:58–65. CrossRefGoogle Scholar
  77. Yoshii M, Maeda K, Kato T, Watanabe T, Yui S, Kato A, Nagashima K (1973) Kinoshitalite, a new mineral from the Noda-Tamagawa mine, Iwate Prefecture. Chigaku Kenkyu 24:181–190 (in Japanese) Google Scholar
  78. Zaccarini F, Stumpel EF, Garuti G (2004) Zirconolite and Zr–Th–U minerals in chromitites of the Finero complex, Western Alps, Italy: evidence for carbonatite-type metasomatism in a subcontinental mantle plume. Can Mineral 42:1825–1845. CrossRefGoogle Scholar
  79. Zanetti A, Mazzucchelli M, Rivalenti G, Vannucci R (1999) The Finero phlogopite-peridotite massif: an example of subduction-related metasomatism. Contrib Mineral Petrol 134:107–122. CrossRefGoogle Scholar
  80. Zhang M, Suddaby P, Thompson RN, Dungan MA (1993) Barian–titanian phlogopite from potassic lavas in northwest China: chemistry, substitutions and paragenesis. Am Mineral 78:1056–1065Google Scholar
  81. Zheng YF, Hermann J (2014) Geochemistry of continental subduction-zone fluids. Earth Planets Sp 66:93. CrossRefGoogle Scholar
  82. Zulauf G, Dörr W, Fiala J, Kotková J, Maluski H, Valverde-Vaquero P (2002) Evidence for high-temperature diffusional creep preserved by rapid cooling of lower crust (North Bohemian shear zone, Czech Republic). Terra Nova 14:343–354. CrossRefGoogle Scholar
  83. Zurevinski SE, Mitchell RH (2011) Highly evolved hypabyssal kimberlite sills from Wemindji, Quebec, Canada: insights into the process of flow differentiation in kimberlite magmas. Contrib Mineral Petrol 161:765–776. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Geological SciencesMasaryk UniversityBrnoCzech Republic
  2. 2.Czech Geological SurveyPrague 1Czech Republic

Personalised recommendations