Skip to main content
SpringerLink
Log in

Formation of ferrian chromite in podiform chromitites from the Golyamo Kamenyane serpentinite, Eastern Rhodopes, SE Bulgaria: a two-stage process

  • Original Paper
  • Published:
Contributions to Mineralogy and Petrology Aims and scope Submit manuscript

Abstract

The Golyamo Kamenyane serpentinite is a portion of a metaophiolite, located in the Upper High-Grade Unit of the metamorphic basement of the Eastern Rhodope Metamorphic Complex, SE Bulgaria. It consists of metaharzburgite and metadunite hosting layers of metagabbro and some chromitite bodies. All these lithologies were affected by ultrahigh-pressure (UHP) metamorphism and subsequent retrograde evolution during exhumation. Chromite from chromitites can be classified into four textural groups: (1) partly altered chromite, (2) porous chromite, (3) homogeneous chromite and (4) zoned chromite. Partly altered chromite shows unaltered, Al-rich cores with unit cell size of 8.255 Å and Cr# [Cr/(Cr + Al) atomic ratio] = 0.52–0.60, Mg# [Mg/(Mg + Fe2+) atomic ratio] = 0.65–0.70 and Fe3+/(Fe3+ + Fe2+) = 0.20–0.30, surrounded by porous chromite, with a cell size of 8.325 Å, Fe3+/(Fe3+ + Fe2+) < 0.20 and values of Cr# and Mg# evolving from 0.60 to 0.91 and 0.65–0.44, respectively, from core to rim. The chemical composition of porous chromite varies within the following ranges: Cr# = 0.93–0.96, Mg# = 0.48–0.35 and Fe3+/(Fe3+ + Fe2+) = 0.22–0.53. Its unit cell size is very constant (8.350 Å). Most pores in porous and partly altered chromite are filled with chlorite, which also occurs between chromite grains. Homogeneous chromite has Fe3+/(Fe3+ + Fe2+) = 0.55–0.66, Cr# = 0.96–0.99, Mg# = 0.32–0.19 and a cell size of 8.385 Å. The cores of zoned chromite are similar to those of partially altered chromite, but the rims are identical to homogeneous chromite. Although chlorite predominates in the silicate matrix of homogeneous and zoned chromite, it coexists with some antigorite, talc and magnesiohornblende. Mineral data and thermodynamic modeling allow interpretation of the alteration patterns of chromite as the consequence of a two-stage process developed during retrograde metamorphic evolution coeval with fluid infiltration. During the first stage, chromite reacts in the presence of fluid with olivine to produce chlorite and Cr- and Fe2+-rich residual chromite (ferrous chromite) at ~700 to ~450 °C. This dissolution–precipitation reaction involves continuous chromite mass loss resulting in the development of a porous texture. This stage takes place progressively on cooling under water-saturated and reducing conditions. The second stage mainly consists of the formation of homogeneous chromite with ferrian chromite composition by the addition of magnetite to the porous ferrous chromite during a late oxidizing hydrothermal event.

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

  • Abzalov MZ (1998) Chromite-spinel in gabbro-wehrlite intrusions of the Pechenga area, Kola Peninsula, Russia: emphasis on alteration features. Lithos 43:109–134

    Article  Google Scholar 

  • Allan JF, Sack RO, Batiza R (1988) Cr-rich spinels as petrogenetic indicators: MORB-type lavas from the Lamont seamount chain, Eastern Pacific. Am Miner 73:741–753

    Google Scholar 

  • Arai S (1992) Chemistry of chromian spinel in volcanic rocks as a potential guide to magma chemistry. Mineral Mag 56:173–184

    Article  Google Scholar 

  • Arai S (1994) Compositional variations of olivine-chromian spinel in Mg-rich magmas a guide to their residual spinel peridotites. J Vocanol Geotherm Res 59:273–293

    Google Scholar 

  • Barnes SJ (2000) Chromite in komatiites, II. Modification during greenschist to mid-amphibolite facies metamorphism. J Petrol 41:387–409

    Article  Google Scholar 

  • Barnes SJ, Roeder PL (2001) The range of spinel compositions in terrestrial mafic and ultramafic rocks. J Petrol 42:2279–2302

    Article  Google Scholar 

  • Bliss NW, MacLean WH (1975) The paragenesis of zoned chromite from central Manitoba. Geochim Cosmochim Acta 39:973–990

    Article  Google Scholar 

  • Bonev N (2006) Cenozoic tectonic evolution of the eastern Rhodope massif (Bulgaria): basement structure and kinematics of syn- to postcollisional extensional deformation. In: Dilek Y, Pavlides S (eds) Post-collisional tectonics and magmatism in the Mediterranean region and Asia. Geol Soc Am Special Pap 49:211–235

  • Burg J-P, Ricou L-E, Ivanov Z, Godfriaux I, Dimov D, Klain L (1996) Syn-metamorphic nape complex in the Rhodope Massif: structure and kinematics. Terra Nova 8:6–15

    Article  Google Scholar 

  • Burkhard DJM (1993) Accessory chromium spinels: their coexistence and alteration in serpentinites. Geochim Cosmochim Acta 57:1297–1306

    Article  Google Scholar 

  • Candia MAF, Gaspar JC (1997) Chromian spinels in metamorphosed ultramafic rocks from Mangabal I and II complexes, Goiás, Brazil. Mineral Petrol 60:27–40

    Article  Google Scholar 

  • Connolly JAD (2009) The geodynamic equation of state: what and how. Geochem Geophys Geosyst 10:Q10014. doi:10.1029/2009GC002540

  • Dick HJB, Bullen T (1984) Chromian spinel as petrogenetic indicator in abyssal and alpine-type peridotites and spatially associated lavas. Contrib Mineral Petrol 86:54–76

    Article  Google Scholar 

  • Evans BW, Frost BR (1975) Chrome-spinel in progressive metamorphism—a preliminary analysis. Geochim Cosmochim Acta 39:959–972

    Article  Google Scholar 

  • Fisher JK (2011) The effect of chromium on chlorite stability—a HP-HT experimental study with the introduction of two new minerals. PhD Thesis. Università degli studi di Milano

  • Fleet ME, Angeli N, Pan Y (1993) Oriented chlorite lamellae in chromite from the Pedra Branca mafic-ultramafic complex, Ceará, Brazil. Am Miner 78:68–74

    Google Scholar 

  • Frost BR (1991) Stability of oxide minerals in metamorphic rocks. In: Lindsley RH (ed) Oxide minerals: petrologic and magnetic significance. Mineral Soc Am Rev Mineral 25:469–487

  • Frost BR, Beard JS (2007) On silica activity and serpentinization. J Petrol 48:1351–1368

    Article  Google Scholar 

  • Girnis AV, Brey GP, Doroshev AM, Turkin AI, Simon N (2003) The system MgO–Al2O3–Cr2O3 revisited: reanalysis of Doroshev et al.’s (1997) experiments and new experiments. Eur J Mineral 15:953–964

    Article  Google Scholar 

  • González-Jiménez JM, Kerestedjian T, Proenza JA, Gervilla F (2009) Metamorphism on chromite ores from the Dobromirtsi Ultramafic Massif, Rhodope Mountains (SE Bulgaria). Geol Acta 7:413–429

    Google Scholar 

  • Haslam HW, Harding RR, Tresham AE (1976) Chromite-chlorite intergrowths in peridotite at Chimwadzulu Hill, Malawi. Mineral Mag J Mineral Soc 40:695–701

    Article  Google Scholar 

  • Haydoutov I, Kolcheva K, Dieva LA, Savov I, Carrigan C (2004) Island arc origin of the variegated formations from the east Rhodope, Bulgaria—implications for the evolution of the Rhodope Massif. Ofioliti 29(2):145–157

    Google Scholar 

  • Hill R, Roeder P (1974) The crystallization of spinel from basaltic liquid as function of oxygen fugacity. J Geol 82:709–729

    Article  Google Scholar 

  • Holland TJB, Powell R (1998) An internally consistent thermodynamic data set for phases of petrological interest. J Metamor Geol 16:309–343

    Article  Google Scholar 

  • Irvine TN (1965) Chromian spinel as a petrogenetic indicator. Part I: theory. Canad J Earth Sci 2:648–672

    Article  Google Scholar 

  • Irvine TN (1967) Chromian spinel as a petrogenetic indicator: part II, petrologic applications. Canad J Earth Sci 4:71–103

    Article  Google Scholar 

  • Jackson ED (1969) Chemical variations in co-existing chromite and olivine in chromite zones of the Still water complex. In: Wilson HDB (ed) Magmatic ore deposits. Econ Geol Monograr 4:41–71

  • Kamenetsky VS, Crawford AJ, Meffre S (2001) Factors controlling chemistry of magmatic spinel: an empirical study of associated olivine, Cr-spinel and melt inclusions from primitive rocks. J Petrol 42:665–671

    Article  Google Scholar 

  • Klemme S, Ivanic TJ, Connolly JAD, Harte B (2009) Thermodynamic modelling of Cr-bearing garnets with implications for diamond inclusions and peridotite xenoliths. Lithos 112:986–991

    Article  Google Scholar 

  • Kolcheva K, Eskenazy G (1988) Geochemistry of metaeclogites from the Central and Eastern Rhodope Mountains. Gologica Balcanica 18:61–78

    Google Scholar 

  • Kolcheva K, Haydoutov I, Daieva L (2000) Dismembered ultramafic ophiolites from the Avren synform, Eastern Rhodopes. Geochem Mineral Petrol 37:25–38

    Google Scholar 

  • Kozhoukharov D, Kozhoukharova E, Papanikolaou D (1988) Precambrian in the Rhodope Massif. In: Zoubek V (ed) Precambrian in younger fold belts. Wiley, Chichester, pp 723– 778

  • Kozhoukharova E (1984) Origin and structural position of the serpentinized ultrabasic rocks of the Precambrian ophiolitic association in the Rhodope Massif: I. Geologic position and composition of ophiolite association. Geologica Balcanica 14:9–36 (in Russian)

    Google Scholar 

  • Kozhoukharova E (1998) Eclogitization of serpentinites into narrow shear zones from the Avren syncline, Eastern Rhodopes. Geochem Mineral Petrol 35:29–46 (in Bulgarian)

    Google Scholar 

  • Krohe A, Mposkos E (2002) Multiple generations of extensional detachments in the Rhodope Mountains (northern Greece): evidences of episodic exhumation of high-pressure rocks. In: Blundell DJ et al (eds) The timing and location of major ore deposits in an evolving orogen. Geol Soc Lond Special Publ 204:151–178

  • Lindsley DH (1976) The crystal chemistry and structure of oxide minerals as exemplified by the Fe-Ti oxides. In: Rumble D (ed) Oxide minerals. Reviews in mineralogy. Mineral Soc Am 3:L1–L60

  • Macheva LA (1998) 3T-phengites in the rocks of Biala reka metamorphic group: an indicator for high pressure metamorphism. Geochem Mineral Petrol 35:17–28

    Google Scholar 

  • Maurel C, Maurel P (1982) Étude expérimentale de la distribution de l′aluminium entre bain silicaté basique et spinelle chromifère. Implications pétrogénétiques: teneur en chrome des spinelles. Bull Mineral 105:197–202

    Google Scholar 

  • Mellini M, Trommsdorff V, Compagnoni R (1987) Antigorite polysomatism: behaviour during progressive metamorphism. Contrib Miner Petrol 97:147–155

    Article  Google Scholar 

  • Mellini M, Rumori C, Viti C (2005) Hydrothermally reset magmatic spinels in retrograde serpentinites: formation of “ferritchromit” rims and chlorite aureoles. Contrib Mineral Petrol 149:266–275

    Article  Google Scholar 

  • Merlini A, Grieco G, Diella V (2009) Ferritchromite and chromian-chlorite formation in mélange-hosted Kalkan chromitite (Southern Urals, Russia). Am Mineral 94:1459–1467

    Article  Google Scholar 

  • Mogessie A, Scheipl G, Bauer C, Krenn K, Georgieva M (2008) Petrology and geochemistry of the Avren Complex, Rhodope Massif, Bulgaria. Abstract, International Geological Congress, Oslo

  • Mposkos E (1998) Cretaceous and tertiary tectonometamorphic events in Rhodope zone (Greece): petrological and geochronological evidences. Bull Geol Soc Greece 32:59–67

    Google Scholar 

  • Mposkos E (2002) Petrology of the ultrahigh pressure metamorphic Kimi complex in Rhodope (NE Greece): a new insight into the Alpine geodynamic evolution of the Rhodope. Bull Geol Soc Greece 34:2126–2188

    Google Scholar 

  • Mposkos E, Kostopoulos DK (2001) Diamond, former coesite and supersilicic garnet in metasedimentary rocks from the Greek Rhodope: a new ultrahigh-pressure metamorphic province established. Earth Planet Sci Lett 192:497–506

    Article  Google Scholar 

  • Mposkos E, Krohe A (2000) Petrological and structural evolution of continental high pressure (HP) metamorphic rocks in the alpine Rhodope domain (N. Greece). In: Panaydes I, Xenopontos C, Malpas J (eds) Proceedings of the 3rd international conference on the geology of the eastern mediterranean (Nicosia, Cyprus). The Geological Survey of Cyprus, Nicosia, pp 221–232

  • Mposkos E, Krohe A (2006) Pressure-temperature-deformation paths of closely associated ultra-high-pressure (diamond-bearing) crustal and mantle rocks of the Kimi complex: implications for the tectonic history of the Rhodope Mountains, northern Greece. Canad J Earth Sci 43:1755–1776

    Article  Google Scholar 

  • Mposkos E, Liati A (1993) Metamorphic evolution of metapelites in the high-pressure terrane of the Rhodope zone, northern Greece. Can Mineral 31:401–424

    Google Scholar 

  • Mukasa S, Haydoutov I, Carrigan C, Kolcheva K (2003) Thermobarometry and 40Ar/39Ar ages of eclogitic and gneissic rocks in the Sredna Gora and Rhodope terranes of Bulgaria. J Czech Geol Soc 48:94–95

    Google Scholar 

  • Mukherjee R, Mondal SK, Rosing MT, Frei R (2010) Compositional variations in the Mesoarchean chromitites of the Nuggihalli schist belt, Western Dharwar Craton (India): potential parental melts and implications for tectonic setting. Contrib Miner Petrol 160:865–885

    Article  Google Scholar 

  • Oka Y, Steinke P, Chatterjee N (1984) Thermodynamic mixing properties of Mg(Al, Cr)2O4t; spinel crystalline solution at high temperatures and pressures. Contrib Mineral Petrol 87:196–204

    Article  Google Scholar 

  • Proenza JA, Gervilla F, Melgarejo JC, Bodinier JL (1999) Al-rich and Cr-rich chromitites from the Mayarí-Baracoa ophiolitic belt (eastern Cuba): consequence of interaction between volatile-rich melts and peridotites in suprasubduction mantle. Econ Geol 94:547–566

    Article  Google Scholar 

  • Proenza JA, Ortega-Gutiérrez F, Camprubí A, Tritlla J, Elías-Herrera M, Reyes-Salas M (2004) Paleozoic serpentinite-enclosed chromitites from Tehuitzingo (Acatlán Complex, southern Mexico): a petrological and mineralogical study. J South Am Earth Sci 16:649–666

    Article  Google Scholar 

  • Ricou L-E, Burg J-P, Godfriaux I, Ivanov Z (1998) Rhodope and Vardar: the metamorphic and the olistostromic paired belts related to the Cretaceous subduction under Europe. Geodinamica Acta 11:1–25

    Google Scholar 

  • Roeder PL (1994) Chromite: from the fiery rain of chondrules to the Kilauea Iki lava lake. Can Miner 32:729–746

    Google Scholar 

  • Sack RO (1982) Spinels as petrogenetic indicators: activity-composition relations at low pressures. Contrib Miner Petrol 79:169–182

    Article  Google Scholar 

  • Sack RO, Ghiorso MS (1991) Chromian spinels as petrogenetic indicators: thermodynamic and petrological applications. Am Miner 76:827–847

    Google Scholar 

  • Sarov S, Yordanov B, Valkov V, Georgiev S, Kamburov D, Raeva E, Grozdev V, Balkanska E, Moskovska L, Dobrev G, Voynova E, Ovcharova M (2007) Geological map of the republic of Bulgaria 1:50000: scheet K-35-88-V (Krumovgrad) and K-35-100-A (Egrek). Ministry of Environment and Water, Bulgarian geological Survey, project Nr. 425/20.07.2004, Geology and Geophysics JSCo., Apis 50 Ltd. printhouse.Sofia

  • Torres-Roldán RL, García-Casco A, García-Sánchez PA (2000) CSpace: an integrated workplace for the graphical and algebraic analysis of phase assemblages on 32-bit Wintel platforms. Comput Geosci 26:779–793

    Article  Google Scholar 

  • Voigt M, von der Handt A (2011) Influence of subsolidus processes on the chromium number in spinel in ultramafic rocks. Contrib Mineral Petrol 162(4):675–689

    Article  Google Scholar 

  • Whitney DL, Evans BW (2010) Abbreviations for names of rock-forming minerals. Am Miner 95:185–187

    Article  Google Scholar 

  • Wylie AN, Candela PA, Burke TM (1987) Compositional zoning in unusual Zn-rich chromite from the Sykesville district of Maryland and its bearing on the origin of "ferritchromite". Am Miner 72:413-422

    Google Scholar 

Download references

Acknowledgments

The authors greatly acknowledge M. Mellini for his willingness to study some preliminary samples under HRTEM. Angel Caballero is also acknowledged for his help in drawing some of the figures for this paper. We are also indebted to William L. Griffin for his help in editing English language. We wish to thank J. Connolly for his patience and suggestions regarding solid solutions. Two anonymous reviewers are thanked for their constructive criticism and helpful comments. This paper is a contribution to the collaborative project 2007BG0006 between the Spanish IACT (University of Granada-CSIC) and the Geological Institut (Bulgarian Academy of Sciences), and to the projects CGL2010-1517 and CGL2010-14848 funded by the Spanish Ministry of Education and Science. This is contribution 824 from the ARC National Key Centre for Geochemical Evolution and Metallogeny of Continents (www.es.mq.edu.au/GEMOC) and paper 176 from the ARC Centre of Excellence for Core to Crust Fluid Systems.

Author information

Authors and Affiliations

  1. Departamento de Mineralogía y Petrología, Universidad de Granada-CSIC, Avda. Fuentenueva s/n, 18002, Granada, Spain

    F. Gervilla & J. A. Padrón-Navarta

  2. Instituto Andaluz de Ciencias de la Tierra, Facultad de Ciencias, Universidad de Granada-CSIC, Avda. Fuentenueva s/n, 18002, Granada, Spain

    F. Gervilla

  3. Bulgarian Academy of Sciences, Geological Institute, 24 Georgi Bonchev Str., 1113, Sofia, Bulgaria

    T. Kerestedjian & I. Sergeeva

  4. ARC National Key Centre GEMOC and ARC Centre of Excellence for Core to Crust Fluid Systems, Department of Earth and Planetary Science, Macquarie University, Sydney, NSW, 2109, Australia

    J. M. González-Jiménez

  5. Departamento de Ciencias de la Tierra, Cristalografía y Mineralogía, Universidad de Zaragoza, Pedro Cerbuna 12, 50009, Zaragoza, Spain

    I. Fanlo

Authors
  1. F. Gervilla
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. J. A. Padrón-Navarta
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. T. Kerestedjian
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. I. Sergeeva
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. J. M. González-Jiménez
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. I. Fanlo
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to F. Gervilla.

Additional information

Communicated by T. L. Grove.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Gervilla, F., Padrón-Navarta, J.A., Kerestedjian, T. et al. Formation of ferrian chromite in podiform chromitites from the Golyamo Kamenyane serpentinite, Eastern Rhodopes, SE Bulgaria: a two-stage process. Contrib Mineral Petrol 164, 643–657 (2012). https://doi.org/10.1007/s00410-012-0763-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00410-012-0763-3

Keywords

Search

Navigation