Water concentrations and hydrogen isotope compositions of alkaline basalt-hosted clinopyroxene megacrysts and amphibole clinopyroxenites: the role of structural hydroxyl groups and molecular water

  • István KovácsEmail author
  • Attila Demény
  • György Czuppon
  • Christophe Lécuyer
  • Francois Fourel
  • Qun-Ke Xia
  • Jia Liu
  • Zsanett Pintér
  • Edit Király
  • Kálmán Török
  • Ábel Szabó
  • Etienne Deloule
  • György Falus
  • Tamás Fancsik
  • Zoltán Zajacz
  • Judit Sándorné Kovács
  • Beatrix Udvardi
Original Paper


The aim of this study was to determine both ‘water’ contents (as OH and H2O) and δD values of several clinopyroxene samples from alkaline basalts. These parameters were first obtained from five clinopyroxene samples using both the classical ‘off-line’ vacuum extraction technique and the ‘on-line’ high-temperature pyrolysis technique. Blanks measured with the ‘on-line’ gas extraction techniques were low enough to prevent any contamination by atmospheric water vapour. The comparison of data has revealed that our ‘on-line’ procedure is more effective for the extraction of ‘water’ from clinopyroxenes and, consequently, this ‘on-line’ technique was applied to ten additional clinopyroxene samples. Sample δD values cover a similar range from −95 to −45 ‰ (VSMOW) regardless of the studied locations, whereas the total ‘water’ content varies from ~115 to ~2570 ppm. The structural hydroxyl content of clinopyroxene samples measured by micro-FTIR spectrometry varies from ~0 to 476 ppm expressed in molecular water equivalent. The total ‘water’ concentrations determined by mass spectrometry differ considerably from structural hydroxyl contents constrained by micro-FTIR, thus indicating that considerable proportion of the ‘water’ may be present in (nano)-inclusions. The structural hydroxyl concentration—apart from clinopyroxenes separated from amphibole clinopyroxenite xenoliths—correlates positively with the δD values of clinopyroxene megacrysts for each locality, indicating that structurally bond hydrogen in clinopyroxenes may have δD values higher than molecular water in inclusions. This implies that there may be a significant hydrogen isotope fractionation for structural hydroxyl during crystallization of clinopyroxene, while for molecular water there may be no or only negligible isotope fractionation.


Mass spectrometry Fourier transformation infrared spectrometry Nominally anhydrous minerals Hydrogen isotopes Fractional crystallization 



IK was supported by the Bolyai Postdoctoral Fellowship Program and a Postdoctoral Grant of the Hungarian Scientific Research Fund (PD-101683). The authors acknowledge J. Ingrin and Cs. Szabó for discussions on an earlier version of this manuscript and the assistance of the Lithosphere Fluidum Research Lab, Judith Mihály and Csaba Németh (MTA TTK). The authors kindly acknowledge the careful editoral handling of Jochen Hoefs and the constructive suggestions of three anonymous reviewers.

Supplementary material

410_2016_1241_MOESM1_ESM.eps (1.4 mb)
SFigure 1 Mg# vs. Al atom per formula unit (a.p.f.u.) in clinopyroxenes (a); Mg# vs. Ti atom per formula unit (a.p.f.u.) in clinopyroxenes (b). Legend for the different localities is on Fig. 1a. Data are taken from STable 1 (EPS 1382 kb)
410_2016_1241_MOESM2_ESM.eps (1.8 mb)
SFigure 2 Primitive mantle (McDonough and Sun 1995) normalized trace element patterns of clinopyroxenes (a); Primitive mantle normalized rare earth elements (REE) patterns of clinopyroxenes (b). Data are taken from STable 2 (EPS 1862 kb)
410_2016_1241_MOESM3_ESM.eps (1.9 mb)
SFigure 3 Ba/Nb vs. Th/Nb ratios of clinopyroxenes (a); Sr/Zr vs. Ce/Zr ratios of clinopyroxenes (b). Data are taken from STable 2 (EPS 1970 kb)
410_2016_1241_MOESM4_ESM.eps (1.3 mb)
SFigure 4 H2O (ppm wt.%) in fluids (i.e. calculated as the difference between the ‘on-line’ mass spectrometry (bulk ‘water’) and micro-FTIR (structural hydroxyl)) vs. δD of hydrogen in clinopyroxenes. Data are taken from Table 1 (EPS 1311 kb)
410_2016_1241_MOESM5_ESM.eps (1.1 mb)
SFigure 5 δD values (‰) of structural hydroxyl in clinopyroxene vs. that of melt as a function of fractional crystallization (see text for details) (EPS 1114 kb)
410_2016_1241_MOESM6_ESM.xlsx (24 kb)
STable 1 Major element compositions of clinopyroxenes determined by EMPA for Nushan and Persány xenoliths and by LA-ICP-MS for BBHVF xenoliths (Szigliget, Kapolcs, Szentbékkálla) given in oxide wt.% (XLSX 23 kb)
410_2016_1241_MOESM7_ESM.xlsx (27 kb)
STable 2 Minor element compositions of clinopyroxenes determined by LA-ICP-MS (given in ppm wt.%) (XLSX 26 kb)
410_2016_1241_MOESM8_ESM.xlsx (39 kb)
Supplementary material 8 (XLSX 39 kb)


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Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • István Kovács
    • 1
    Email author
  • Attila Demény
    • 2
  • György Czuppon
    • 2
  • Christophe Lécuyer
    • 3
  • Francois Fourel
    • 3
  • Qun-Ke Xia
    • 4
    • 5
  • Jia Liu
    • 4
  • Zsanett Pintér
    • 6
    • 7
  • Edit Király
    • 1
  • Kálmán Török
    • 1
  • Ábel Szabó
    • 1
    • 6
  • Etienne Deloule
    • 8
  • György Falus
    • 1
  • Tamás Fancsik
    • 1
  • Zoltán Zajacz
    • 9
  • Judit Sándorné Kovács
    • 10
  • Beatrix Udvardi
    • 1
  1. 1.Geological and Geophysical Institute of HungaryBudapestHungary
  2. 2.Research Centre for Astronomy and Earth Sciences, Institute for Geological and Geochemical ResearchHungarian Academy of SciencesBudapestHungary
  3. 3.Laboratoire de Géologie de Lyon, CNRS UMR 5276University of LyonLyonFrance
  4. 4.School of Earth and Space SciencesUniversity of Science and Technology of ChinaHefeiChina
  5. 5.School of Earth SciencesZhejiang UniversityHangzhouChina
  6. 6.Lithosphere Fluid Research LabEötvös UniversityBudapestHungary
  7. 7.Bayerisches GeoinstitutUniversity of BayreuthBayreuthGermany
  8. 8.Centre de Recherche Pétrographiques et Géochimiques, CNRS UMR-5873Univ. de LorraineVandoeuvre-lès-NancyFrance
  9. 9.Department of Earth SciencesUniversity of TorontoTorontoCanada
  10. 10.Hungarian Institute for Forensic SciencesBudapestHungary

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