Mineralogy and Petrology

, 95:291 | Cite as

Lithium, boron and chlorine as tracers for metasomatism in high-pressure metamorphic rocks: a case study from Syros (Greece)

  • Horst R. Marschall
  • Rainer Altherr
  • Katalin Gméling
  • Zsolt Kasztovszky
Original Paper


High-pressure metamorphic (HPM) rocks (derived from igneous protoliths) and their metasomatised rinds from the island of Syros (Greece) were analysed for their B and Cl whole-rock abundances and their H2O content by prompt-gamma neutron-activation analysis (PGNAA) and for their Li and Be whole-rock abundances by ICP-OES. In the HPM rocks, B /Be and Cl /Be ratios correlate with H2O contents and appear to be controlled by extraction of B and Cl during dehydration and prograde metamorphism. In contrast, samples of the metasomatised rinds show no such correlation. B /Be ratios in the rinds are solely governed by the presence or absence of tourmaline, and Cl /Be ratios vary significantly, possibly related to fluid inclusions. Li/Be ratios do not correlate with H2O contents in the HPM rocks, which may in part be explained by a conservative behaviour of Li during dehydration. However, Li abundances exceed the vast majority of published values for Li abundances in fresh, altered, or differentiated oceanic igneous rocks and presumably result from metasomatic enrichment of Li. High Li concentrations and highly elevated Li/Be ratios in most metasomatised samples demonstrate an enrichment of Li in the Syros HP mélange during fluid infiltration. This study suggests that B and Cl abundances of HPM meta-igneous rocks can be used to trace prograde dehydration, while Li concentrations seem to be more sensitive for retrograde metasomatic processes in such lithologies.


Fluid Inclusion Tourmaline Hydrous Mineral Hydrous Fluid Prograde Metamorphism 



This paper benefited from discussions with Stefan Prowatke, Jens Paquin, and Thomas Zack. Chung Choi is thanked for performing ICP-OES analyses. Helpful and constructive comments by Marco Scambelluri and an anonymous reviewer helped to clarify the presentation of this study. Financial support by the Deutsche Forschungsgemeinschaft (DFG, grants KA 1023/8-1 and AL 166/15-3) and by a European Union Marie-Curie Fellowship awarded to HRM (ID 025844: “Isotopes in subduction zones – the metamorphic perspective”) is greatly acknowledged. PGNAA and ICP-OES work was financed by the European Community Access to Research Infrastructure framework, Contract HPRI-1999-CT-00099, awarded to G.L. Molnár, and Contract HPRI-1999-CT-00008, awarded to B.J. Wood.


  1. Ague JJ (2007) Models of permeability contrasts in subduction zone mélange: implications for gradients in fluid fluxes, Syros and Tinos Islands, Greece. Chem Geol 239:217–227CrossRefGoogle Scholar
  2. Bach W, Alt JC, Niu Y, Humphris SE, Erzinger J, Dick HJB (2001) The geochemical consequences of late-stage low-grade alteration of lower ocean crust at the SW Indian Ridge: results from ODP Hole 735B (Leg 176). Geochim Cosmochim Acta 65:3267–3287CrossRefGoogle Scholar
  3. Barr H (1990) Preliminary fluid inclusion studies in high-grade blueschist terrain, Syros, Greece. Mineral Mag 54:159–168CrossRefGoogle Scholar
  4. Bebout GE (2007) Metamorphic chemical geodynamics of subduction zones. Earth Planet Sci Lett 260:373–393CrossRefGoogle Scholar
  5. Bebout GE, Ryan JG, Leeman WP (1993) B-Be systematics in subduction-related metamorphic rocks: characterization of the subducted component. Geochim Cosmochim Acta 57:2227–2237CrossRefGoogle Scholar
  6. Bebout GE, Ryan JG, Leeman WP, Bebout AE (1999) Fractionation of trace elements by subduction-zone metamorphism—effect of convergent-margin thermal evolution. Earth Planet Sci Lett 171:63–81CrossRefGoogle Scholar
  7. Bonifacie M, Busigny V, Mével C, Philippot P, Agrinier P, Jendrzejewski N, Scambelluri M, Javoy M (2008) Chlorine isotopic composition in seafloor serpentinites and high-pressure metaperidotites. Insights into oceanic serpentinization and subduction processes. Geochim Cosmochim Acta 72:126–139CrossRefGoogle Scholar
  8. Breeding CM, Ague JJ, Bröcker M (2004) Fluid-metasedimentary rock interactions in subduction-zone mélange: implications for the chemical composition of arc magmas. Geology 32:1041–1044CrossRefGoogle Scholar
  9. Brenan JM (1993) Partitioning of fluorine and chlorine between apatite and aqueous fluids at high pressure and temperature: implications for the F and Cl content of highP-T fluids. Earth Planet Sci Lett 117:251–263CrossRefGoogle Scholar
  10. Brenan JM, Ryerson FJ, Shaw HF (1998) The role of aqueous fluids in the slab-to-mantle transfer of boron, beryllium, and lithium during subduction: experiments and models. Geochim Cosmochim Acta 62:3337–3347CrossRefGoogle Scholar
  11. Bröcker M, Enders M (2001) Unusual bulk-rock compositions in eclogite-facies rocks from Syros and Tinos (Cyclades, Greece): implications for U-Pb zircon geochronology. Chem Geol 175:581–603CrossRefGoogle Scholar
  12. Chan LH, Alt JC, Teagle DAH (2002) Lithium and lithium isotope profiles through the upper oceanic crust: a study of seawater–basalt exchange at ODP Sites 504B and 896A. Earth Planet Sci Lett 201:187–201CrossRefGoogle Scholar
  13. Chaussidon M, Jambon A (1994) Boron content and isotopic composition of oceanic basalts: geochemical and cosmochemical implications. Earth Planet Sci Lett 121:277–291CrossRefGoogle Scholar
  14. Danyushevsky LV, Eggins SM, Falloon TJ, Christie DM (2000) H2O abundance in depleted to moderately enriched mid-ocean ridge magmas; part I: incompatible behaviour, implications for mantle storage, and origin of regional variations. J Petrol 41:1329–1364CrossRefGoogle Scholar
  15. Dixon JE (1968) The metamorphic rocks of Syros, Greece. Ph.D. thesis, St. John’s College, CambridgeGoogle Scholar
  16. Dixon JE, Ridley J (1987) Syros. In: Helgeson HC (ed) Chemical transport in metasomatic processes. NATO ASI Series C, Math Phys Sci, vol 218. Reidel, Dordrecht, pp 489–501Google Scholar
  17. Dürr S, Altherr R, Keller J, Okrusch M, Seidel E (1978) The median Aegean crystalline belt: stratigraphy, structure, metamorphism, magmatism. In: Closs H, Roeder DH, Schmidt K (eds) Alps, Apennines, Hellenides. Inter-Union Commission on Geodynamics, Scientific Report, vol 38. Schweizerbart, Stuttgart, pp 455–477Google Scholar
  18. Gméling K, Szabolcs H, Kasztovszky Zs (2005) Boron and chlorine concentration of volcanic rocks: an application of prompt gamma activation analysis. J Radioanal Nucl Chem 265:201–214CrossRefGoogle Scholar
  19. Hecht J (1984) Geological map of Greece 1:50 000, Syros island. Institute of Geology and Mineral Exploration, AthensGoogle Scholar
  20. Hofmann AW (1988) Chemical differentiation of the Earth: the relationship between mantle, continental crust, and oceanic crust. Earth Planet Sci Lett 90:297–314CrossRefGoogle Scholar
  21. Ishikawa T, Nakamura E (1994) Origin of the slab component in arc lavas from across-arc variation of B and Pb isotopes. Nature 370:205–208CrossRefGoogle Scholar
  22. Jambon A, Déruelle B, Dreibus G, Pineau F (1995) Chlorine and bromine abundance in MORB: the contrasting behaviour of the Mid-Atlantic Ridge and East Pacific Rise and implications for chlorine geodynamic cycle. Chem Geol 126:101–117CrossRefGoogle Scholar
  23. John T, Schenk V (2003) Partial eclogitisation of gabbroic rocks in a late Precambrian subduction zone (Zambia): prograde metamorphism triggered by fluid infiltration. Contrib Mineral Petrol 146:174–191CrossRefGoogle Scholar
  24. Kamenetsky VS, Everard JL, Crawford AJ, Varne R, Eggins SM, Lanyon R (2000) Enriched end-member of primitive MORB melts: petrology and geochemistry of glasses from Macquarie Island (SW Pacific). J Petrol 41:411–430CrossRefGoogle Scholar
  25. Keiter M, Piepjohn K, Ballhaus C, Bode M, Lagos M (2004) Structural development of high-pressure metamorphic rocks on Syros island (Cyclades, Greece). J Struct Geol 26:1433–1445CrossRefGoogle Scholar
  26. Leeman WP, Sisson VB (2002) Geochemistry of boron and its implications for crustal and mantle processes. In: Grew ES, Anovitz LM (eds) Boron: mineralogy, petrology and geochemistry, vol 33. Mineral Soc Am, 2nd edn. Mineralogical Society of America, Washington, DC, pp 645–708Google Scholar
  27. Magenheim AJ, Spivack AJ, Michael PJ, Gieskes JM (1995) Chlorine stable isotope composition of the oceanic crust: implications for Earth’s distribution of chlorine. Earth Planet Sci Lett 131:427–432CrossRefGoogle Scholar
  28. Marschall HR (2005) Lithium, beryllium, and boron in high-pressure metamorphic rocks from Syros (Greece). Dr rer nat thesis, Univ Heidelberg, GermanyGoogle Scholar
  29. Marschall HR, Kasztovszky Zs, Gméling K, Altherr R (2005) Chemical analysis of high-pressure metamorphic rocks by PGNAA—comparison with results from XRF and solution-ICP-MS. J Radioanal Nucl Chem 265:339–348CrossRefGoogle Scholar
  30. Marschall HR, Altherr R, Ludwig T, Kalt A, Gméling K, Kasztovszky Zs (2006a) Partitioning and budget of Li, Be and B in high-pressure metamorphic rocks. Geochim Cosmochim Acta 70:4750–4769CrossRefGoogle Scholar
  31. Marschall HR, Ludwig T, Altherr R, Kalt A, Tonarini S (2006b) Syros metasomatic tourmaline: evidence for very high-δ 11B fluids in subduction zones. J Petrol 47:1915–1942CrossRefGoogle Scholar
  32. Marschall HR, Altherr R, Rüpke L (2007a) Squeezing out the slab—modelling the release of Li, Be and B during progressive high-pressure metamorphism. Chem Geol 239:323–335CrossRefGoogle Scholar
  33. Marschall HR, Pogge von Strandmann PAE, Seitz H-M, Elliott T, Niu Y (2007b) The lithium isotopic composition of orogenic eclogites and deep subducted slabs. Earth Planet Sci Lett 262:563–580CrossRefGoogle Scholar
  34. Marschall HR, Altherr R, Kalt A, Ludwig T (2008a) Detrital, metamorphic and metasomatic tourmaline in high-pressure metasediments from Syros (Greece): intra-grain boron isotope patterns determined by secondary-ion mass spectrometry. Contrib Mineral Petrol 155:703–717CrossRefGoogle Scholar
  35. Marschall HR, Korsakov AV, Luvizotto GL, Nasdala L, Ludwig T (2008b) On the occurence and boron isotopic composition of tourmaline in (ultra)high-pressure metamorphic rocks. J Geol Soc (Lond.) (in press)Google Scholar
  36. McDonough WF, Sun S-S (1995) The composition of the Earth. Chem Geol 120:223–253CrossRefGoogle Scholar
  37. Michael PJ, Cornell WC (1998) Influeance of spreading rate and magma supply on crystallization and assimilation beneath mid-ocean ridges: evidence from chlorine and major element chemistry of mid-ocean ridge basalts. J Geophys Res 103:18325–18356CrossRefGoogle Scholar
  38. Miller DP, Marschall HR, Schumacher JC (2008) Metasomatic formation and petrology of blueschist-facies hybrid rocks from Syros (Greece): implications for reactions at the slab-mantle interface. Lithos. doi:10.1016/j.lithos.2008.07.015
  39. Molnár GL (2004) Handbook of prompt gamma activation analysis with neutron beams. Kluwer, DordrechtGoogle Scholar
  40. Moran AE, Sisson VB, Leeman WP (1992) Boron depletion during progressive metamorphism: implications for subduction processes. Earth Planet Sci Lett 111:331–349CrossRefGoogle Scholar
  41. Morgan GB IV, London D (1989) Experimental reactions of amphibolite with boron-bearing aqueous fluids at 200MPa: implications for tourmaline stability and partial melting in mafic rocks. Contrib Mineral Petrol 102:281–297CrossRefGoogle Scholar
  42. Nakano T, Nakamura E (2001) Boron isotope geochemistry of metasedimentary rocks and tourmalines in a subduction zone metamorphic suite. Phys Earth Planet Inter 127:233–252CrossRefGoogle Scholar
  43. Niu Y, Batiza R (1997) Trace element evidence from seamounts for recycled oceanic crust in the Eastern Pacific mantle. Earth Planet Sci Lett 148:471–483CrossRefGoogle Scholar
  44. Okrusch M, Bröcker M (1990) Eclogites associated with high-grade blueschists in the Cyclades archipelago, Greece: a review. Eur J Mineral 2:451–478Google Scholar
  45. Palmer MR, Swihart GH (2002) Boron isotope geochemistry: an overview. In: Grew ES, Anovitz LM (eds) Boron: mineralogy, petrology and geochemistry. Rev Mineral, vol 33. Mineral Soc Am, chap 13, 2nd edn. Mineralogical Society of America, Washington, DC, pp 709–744Google Scholar
  46. Perfit MR, Ridley WI, Jonasson IR (1999) Geologic, petrologic, and geochemical relationships between magmatism and massive sulfide mineralization along the eastern Galapagos spreading center. In: Barrie CT, Hannington MD (eds) Volcanic-associated massive sulfide deposits; processes and examples in modern and ancient settings. Rev Econom Geol, vol 8. Society of Economic Geologists, Socorro, pp 75–100Google Scholar
  47. Philippot P, Agrinier P, Scambelluri M (1998) Chlorine cycling during subduction of altered oceanic crust. Earth Planet Sci Lett 161:33–44CrossRefGoogle Scholar
  48. Regelous M, Niu Y, Wendt JI, Batiza R, Greig A, Collerson KD (1999) Variations in the geochemistry of magmatism on the East Pacific Rise at 10°30’ N since 800ka. Earth Planet Sci Lett 168:45–63CrossRefGoogle Scholar
  49. Révay Zs, Belgya T, Ember PP, Molnár GL (2001) Recent developments in HYPERMET PC. J Radioanal Nucl Chem 248:401–405CrossRefGoogle Scholar
  50. Révay Zs, Belgya T, Kasztovszky Zs, Weil JL, Molnár GL (2004) Cold neutron PGAA facility at Budapest. Nucl Instr Meth Phys Res B 213:385–388CrossRefGoogle Scholar
  51. Ridley J (1984) Evidence for temperature-dependent ‘blueschist’ to ‘eclogite’ transformation in high-pressure metamorphism of metabasic rocks. J Petrol 25:852–870Google Scholar
  52. Rosenbaum G, Avigad D, Sánchez-Gómez M (2002) Coaxial flattening at deep levels of orogenic belts: evidence from blueschists and eclogites on Syros and Sifnos (Cyclades, Greece). J Struct Geol 24:1451–1462CrossRefGoogle Scholar
  53. le Roux PJ, Shirey SB, Hauri EH, Perfit MR, Bender JF (2006) The effects of variable sources, processes and contaminants on the composition of northern EPR MORB (8-10°N and 12-14°N): evidence from volatiles (H2O, CO2, S) and halogens (F, Cl). Earth Planet Sci Lett 251:209–231CrossRefGoogle Scholar
  54. Ryan JG (2002) Trace-elements systematics of beryllium in terrestrial materials. In: Grew ES (ed) Beryllium: mineralogy, petrology and geochemistry. Rev Mineral, vol 50. Mineralogical Society of America, Washington, DC, pp 121–145Google Scholar
  55. Ryan JG, Langmuir CH (1987) The systematics of lithium abundances in young volcanic rocks. Geochim Cosmochim Acta 51:1727–1741CrossRefGoogle Scholar
  56. Ryan JG, Langmuir CH (1988) Be systematics in young volcanic rocks: implications for 10Be. Geochim Cosmochim Acta 52:237–244CrossRefGoogle Scholar
  57. Ryan JG, Langmuir CH (1993) The systematics of boron abundances in young volcanic rocks. Geochim Cosmochim Acta 57:1489–1498CrossRefGoogle Scholar
  58. Scambelluri M, Müntener O, Ottolini L, Pettke TT, Vanucci R (2004) The fate of B, Cl and Li in subducted oceanic mantle and in the antigorite breakdown fluids. Earth Planet Sci Lett 222:217–234CrossRefGoogle Scholar
  59. Scambelluri M, Hermann J, Morten L, Rampone E (2006) Melt- versus fluid-induced metasomatism in spinel to garnet wedge peridotites (Ulten Zone, Eastern Italian Alps): clues from trace element and Li abundances. Contrib Mineral Petrol 151:372–394CrossRefGoogle Scholar
  60. Seck HA, Kötz J, Okrusch M, Seidel E, Stosch HG (1996) Geochemistry of a meta-ophiolite suite: an association of metagabbros, eclogites and glaucophanites on the island of Syros, Greece. Eur J Mineral 8:607–623Google Scholar
  61. Stewart MA, Spivack AJ (2004) The stable-chlorine isotope compositions of natural and anthropogenic materials. In: Johnson CM, Beard BL, Albarède F (eds) Geochemistry of non-traditional stable isotopes. Rev Mineral, vol 55. Mineral Soc Am, chap 7. Mineralogical Society of America, Washington, DC, pp 231–254Google Scholar
  62. Straub SM, Layne GD (2003) The systematics of chlorine, fluorine, and water in Izu arc volcanic rocks: implications for volatile recycling in subduction zones. Geochim Cosmochim Acta 67:4179–4203CrossRefGoogle Scholar
  63. Szakmány G, Kasztovszky Zs (2004) Prompt Gamma Activation Analysis, a new method in the archeological study of polished stone tools and their raw materials. Eur J Mineral 16:285–295CrossRefGoogle Scholar
  64. Tomascak PB (2004) Developments in the understanding and application of lithium isotopes in the earth and planetary sciences. In: Johnson CM, Beard BL, Albarède F (eds) Geochemistry of non-traditional stable isotopes. Rev Mineral, vol 55. Mineral Soc Am, chap 5. Mineralogical Society of America, Washington, DC, pp 153–195Google Scholar
  65. Trotet F, Vidal O, Jolivet L (2001) Exhumation of Syros and Sifnos metamorphic rocks (Cyclades, Greece). New constraints on the P − T paths. Eur J Mineral 13:901–920CrossRefGoogle Scholar
  66. Vanko DA (1986) High-chlorine amphiboles from oceanic rocks: product of high-saline hydrothermal fluids? Am Mineral 71:51–59Google Scholar
  67. Weisbrod A, Polak C, Roy D (1986) Experimental study of tourmaline solubility in the system Na-Mg-Al-Si-B-O-H. Applications to the boron content of natural hydrothermal fluids and tourmalinization processes. Exp Mineral Geochem Int Symp, Nancy, Abstr 140Google Scholar
  68. Woodland AB, Seitz H-M, Altherr R, Olker B, Marschall H, Ludwig T (2002) Li abundances in eclogite minerals: a clue to a crustal or mantle origin? Contrib Mineral Petrol 143:587–601 (Erratum: Contrib Mineral Petrol 144, 128–129)Google Scholar
  69. Zack T, Tomascak PB, Rudnick RL, Dalpe C, McDonough WF (2003) Extremely light Li in orogenic eclogites: the role of isotope fractionation during dehydration in subducted oceanic crust. Earth Planet Sci Lett 208:279–290CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2008

Authors and Affiliations

  • Horst R. Marschall
    • 1
    • 2
  • Rainer Altherr
    • 2
  • Katalin Gméling
    • 3
  • Zsolt Kasztovszky
    • 3
  1. 1.Department of Earth Sciences, Wills Memorial Building, Queen’s RoadUniversity of BristolBristolUK
  2. 2.Mineralogisches InstitutUniversität HeidelbergHeidelbergGermany
  3. 3.Institute of IsotopesHungarian Academy of SciencesBudapestHungary

Personalised recommendations