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Depletion, cryptic metasomatism, and modal metasomatism of central European lithospheric mantle: evidence from elemental and Li isotope compositions of spinel peridotite xenoliths, Kozákov volcano, Czech Republic

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Abstract

Spinel peridotite xenoliths in 4.1 Ma basanite lava at Kozákov volcano vary in equilibration temperature from 675 to 1,135 °C and provide a continuous sample of lithospheric mantle from the Moho to a depth of ~82 km. The sub-Kozákov mantle is layered, consisting of an upper equigranular layer (UEL) from 32 to 45 km, an intermediate protogranular layer (PGL) from 45 to 66 km, and a lower equigranular layer (LEL) below 66 km. Relative to primitive mantle, all three layers are depleted in major incompatible elements and heavy rare earth elements, with the UEL being most depleted among the three layers, consisting of harzburgite and having experienced >15 % fractional melting. In contrast, the PGL and LEL experienced <10–15 % melting and consist of lherzolite; the PGL and LEL overlap in major element composition, with the PGL displaying a decreasing degree of depletion with depth. Subsequent metasomatism by silicate melt led to cryptic enrichments in large-ion lithophile elements, light REE, and high field strength elements over all the layers and, locally, modal enrichment in orthopyroxene. Metasomatism is accompanied by elevated whole-rock Li contents (1.2–3.6 ppm) and isotopically light δ7Li (−0.8 to −5.8 ‰). Lithium contents and δ7Li show no strong correlation with rock type or depth, although values of δ7Li are <−3.0 ‰ in the PGL and >−3.5 ‰ in the UEL and LEL. The layered structure and geochemical characteristics of sub-Kozákov lithospheric mantle are the product of Variscan or pre-Variscan melting, Variscan tectonics, and Neogene volcanism and metasomatism.

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Acknowledgments

We are grateful to John Fournelle for his advice and direction in electron probe microanalysis in the Department of Geoscience, University of Wisconsin-Madison, to Jana Ďurišová and Šárka Matoušková for whole-rock trace element ICP-MS analyses and in situ laser ablation analyses at the Institute of Geology, Academy of Sciences CR, and to Jitka Míková and Vladislav Chrastný for maintenance of the clean lab and MC-ICP-MS facility at the Czech Geological Survey. This work has been supported in part by the Czech Science Foundation (GACR), Project P210/12/1990, and by the Institute of Geology, Academy of Sciences CR, Scientific Programme CEZ: RVO67985831.

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  1. Department of Geoscience, University of Wisconsin-Madison, Madison, WI, 53706, USA

    L. Gordon Medaris Jr.

  2. Institute of Geology v.v.i., Academy of Sciences of the Czech Republic, Prague, Czech Republic

    Lukáš Ackerman

  3. Institute of Geochemistry, Mineralogy, and Mineral Resources, Faculty of Science, Charles University, Prague, Czech Republic

    Emil Jelínek

  4. Czech Geological Survey, Prague, Czech Republic

    Tomáš Magna

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Appendix

Appendix

Electron microprobe analysis

Minerals were analyzed by wavelength-dispersion spectrometry (WDS) with a Cameca SX50 instrument at the University of Wisconsin. Operating conditions were as follows: 15 kV accelerating voltage, 20 nA beam current (Faraday cup), and beam diameter of 1 μm. Combinations of natural minerals and synthetic materials were used as standards for each of the mineral species, e.g., natural olivine for Mg, Fe, and Si and Ni metal for Ni in unknown olivine, synthetic spinel for Mg and Al and natural chromite for Fe and Cr in unknown spinel, and comparably appropriate combinations for orthopyroxene and clinopyroxene. Data reduction was performed by Probe for Windows software, utilizing the ϕ(ρz) matrix correction of Armstrong (1988).

Wet chemical technique

Major elements in whole-rock samples were determined by traditional wet-chemistry methods at the Faculty of Science, Charles University. Replicate analyses of reference standard, PCC-1, yield an average precision of ±5 % (1σ).

ICP-MS

Trace element concentrations in whole-rock samples were determined using an Element 2 sector field ICP-MS (Thermo-Finnigan) at the Institute of Geology v.v.i., Academy of Sciences CR, Prague, using the methods outlined in Ackerman et al. [this volume]. Precision of the analyses was typically better than 5 % for all analyzed elements, and the accuracy was monitored by repeated analyses of UB-N peridotite reference material (CNRS, France).

LA-ICP-MS

Trace elements in clinopyroxene were measured at the Institute of Geology v.v.i., Academy of Sciences CR, using an Element 2 ICP-MS coupled with a UP-213 213-nm Nd:YAG laser ablation system (New Wave Research). The analytical protocol followed that described in Ackerman et al. (this volume). In brief, the laser was fired with an output energy of 7–9 J/cm2 and repetition rate of 20 Hz. A 35- to 55-μm beam size was used, and all masses were measured at the low mass resolution mode (m/∆m = 300). Details on precision and accuracy of the analyses can be found in Ackerman et al. [this volume].

Lithium

The analytical procedures for lithium (Li) isolation and purification followed two-stage cation-exchange chromatography outlined in Magna et al. (2004) and Magna et al. (2006). Two olivine separates were washed in distilled 1 M HCl and de-ionized water prior to further chemical procedures in order to avoid contamination from grain-boundary components (cf. Seitz et al. 2004; Magna et al. 2006; Jeffcoate et al. 2007). Lithium abundances in clean Li fractions were determined using a Neptune multiple-collector ICP-MS, housed at the Czech Geological Survey, Prague, Czech Republic, by comparing the ion intensities of unknown samples with those of 1-, 10-, and 20-ppb L-SVEC reference solution (Flesch et al. 1973). Lithium isotopic compositions were measured with a Neptune MC-ICPMS with L4 and H4 Faraday cups for simultaneous collection of 6Li and 7Li, respectively. Bracketing with the L-SVEC reference solution was applied in order to correct for instrumental mass bias (Magna et al. 2004). The international reference rock materials JP-1 (peridotite; GSJ) and BHVO-2 (basalt; USGS) were used to monitor the precision and accuracy of the analytical procedure and their δ7Li of 3.76 ± 0.05 ‰ (n = 4) and 4.62 ± 0.24 ‰ (n = 7), respectively, are consistent with data published by Ackerman et al. (2013), Magna et al. (2006, 2008), and Pogge von Strandmann et al. (2011).

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Medaris, L.G., Ackerman, L., Jelínek, E. et al. Depletion, cryptic metasomatism, and modal metasomatism of central European lithospheric mantle: evidence from elemental and Li isotope compositions of spinel peridotite xenoliths, Kozákov volcano, Czech Republic. Int J Earth Sci (Geol Rundsch) 104, 1925–1956 (2015). https://doi.org/10.1007/s00531-014-1065-y

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