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

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Abstract

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.

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Acknowledgments

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.

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Author notes

  1. Qun-Ke Xia

    Present address: School of Earth Sciences, Zhejiang University, Hangzhou, 310027, China

Authors and Affiliations

  1. Geological and Geophysical Institute of Hungary, Stefánia Street 14., Budapest, 1143, Hungary

    István Kovács, Edit Király, Kálmán Török, Ábel Szabó, György Falus, Tamás Fancsik & Beatrix Udvardi

  2. Research Centre for Astronomy and Earth Sciences, Institute for Geological and Geochemical Research, Hungarian Academy of Sciences, Budaörsi Street 45., Budapest, 1112, Hungary

    Attila Demény & György Czuppon

  3. Laboratoire de Géologie de Lyon, CNRS UMR 5276, University of Lyon, Lyon, France

    Christophe Lécuyer & Francois Fourel

  4. School of Earth and Space Sciences, University of Science and Technology of China, Jinhzai Road 95, Hefei, China

    Qun-Ke Xia & Jia Liu

  5. Lithosphere Fluid Research Lab, Eötvös University, Pázmány Péter sétány 1/C, Budapest, 1117, Hungary

    Zsanett Pintér & Ábel Szabó

  6. Bayerisches Geoinstitut, University of Bayreuth, 95440, Bayreuth, Germany

    Zsanett Pintér

  7. Centre de Recherche Pétrographiques et Géochimiques, CNRS UMR-5873, Univ. de Lorraine, BP 20, 54501, Vandoeuvre-lès-Nancy, France

    Etienne Deloule

  8. Department of Earth Sciences, University of Toronto, 22 Russell St., Toronto, Canada

    Zoltán Zajacz

  9. Hungarian Institute for Forensic Sciences, Mosonyi u. 9, Budapest, 1087, Hungary

    Judit Sándorné Kovács

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  1. István Kovács
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Corresponding author

Correspondence to István Kovács.

Additional information

Communicated by Jochen Hoefs.

Electronic supplementary material

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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)

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)

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)

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)

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)

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)

STable 2

Minor element compositions of clinopyroxenes determined by LA-ICP-MS (given in ppm wt.%) (XLSX 26 kb)

Supplementary material 8 (XLSX 39 kb)

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Kovács, I., Demény, A., Czuppon, G. et al. Water concentrations and hydrogen isotope compositions of alkaline basalt-hosted clinopyroxene megacrysts and amphibole clinopyroxenites: the role of structural hydroxyl groups and molecular water. Contrib Mineral Petrol 171, 38 (2016). https://doi.org/10.1007/s00410-016-1241-0

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