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Super-reducing conditions in ancient and modern volcanic systems: sources and behaviour of carbon-rich fluids in the lithospheric mantle

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Abstract

Oxygen fugacity (ƒO2) is a key parameter of Earth’s mantle, because it controls the speciation of the fluids migrating at depth; a major question is whether the sublithospheric mantle is metal-saturated, keeping ƒO2 near the Iron-Wustite (IW) buffer reaction. Cretaceous basaltic pyroclastic rocks on Mt. Carmel, Israel erupted in an intraplate environment with a thin, hot lithosphere. They contain abundant aggregates of hopper-shaped crystals of Ti-rich corundum, which have trapped melts with phenocryst assemblages (Ti2O3, SiC, TiC, silicides, native V) requiring extremely low ƒO2. These assemblages are interpreted to reflect interaction between basaltic melts and mantle-derived fluids dominated by CH4 + H2. Similar highly reduced assemblages are found associated with volcanism in a range of tectonic situations including subduction zones, major continental collisions, intraplate settings, craton margins and the cratons sampled by kimberlites. This distribution, and the worldwide similarity of δ13C in mantle-derived SiC and associated diamonds, suggest a widespread process, involving similar sources and independent of tectonic setting. We suggest that the common factor is the ascent of abiotic (CH4 + H2) fluids from the sublithospheric mantle; this would imply that much of the mantle is metal-saturated, consistent with observations of metallic inclusions in sublithospheric diamonds (e.g. Smith et al. 2016). Such fluids, perhaps carried in rapidly ascending deep-seated magmas, could penetrate high up into a depleted cratonic root, establishing the observed trend of decreasing ƒO2 with depth (e.g. Yaxley et al. in Lithos 140:142–151, 2012). However, repeated metasomatism (associated with the intrusion of silicate melts) will raise the FeO content near the base of the craton over time, developing a carapace of oxidizing material that would prevent the rise of CH4-rich fluids into higher levels of the subcontinental lithospheric mantle (SCLM). Oxidation of these fluids would release CO2 and H2O to drive metasomatism and low-degree melting both in the carapace and higher in the SCLM. This model can explain the genesis of cratonic diamonds from both reduced and oxidized fluids, the existence of SiC as inclusions in diamonds, and the abundance of SiC in some kimberlites. It should encourage further study of the fine fractions of heavy-mineral concentrates from all types of explosive volcanism.

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Acknowledgements

We thank Paul Asimov, Dorrit Jacob, Oded Navon and Zsanett Pinter for helpful discussions. Constructive comments from two anonymous reviewers and handling editor Graham Pearson helped to improve the manuscript. This study used instrumentation funded by Australian Research Council Large Infrastructure and Equipment Fund and Department of Education Science and Technology Systemic Infrastructure Grants, Macquarie University and industry. This is contribution 1160 from the ARC–CCFS (www.ccfs.mq.edu.au) and 1224 from the GEMOC Key Centre (www.gemoc.mq.edu.au).

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Authors and Affiliations

  1. Australian Research Council Centre of Excellence for Core to Crust Fluid Systems (ARC–CCFS) and ARC National Key Centre for Geochemical Evolution and Metallogeny of Continents (GEMOC), Department of Earth and Planetary Sciences, Macquarie University, Sydney, NSW, 2109, Australia

    William L. Griffin, Jin-Xiang Huang, Sarah E. M. Gain & Suzanne Y. O’Reilly

  2. Centre de Recherches Pétrographiques et Géochimiques-CNRS, Université de Lorraine, 54501 Vandoeuvre-Lès-, Nancy, France

    Emilie Thomassot

  3. Institut de Physique du Globe de Paris, 1 Rue Jussieu, 75 005, Paris, France

    Emilie Thomassot

  4. Shefa Yamim (A.T.M.) Ltd., 4210602, Netanya, Israel

    Vered Toledo

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  1. William L. Griffin
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  2. Jin-Xiang Huang
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  3. Emilie Thomassot
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  4. Sarah E. M. Gain
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  5. Vered Toledo
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  6. Suzanne Y. O’Reilly
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Correspondence to William L. Griffin.

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Editorial handling: G. Pearson

Appendix: Sampling procedures

Appendix: Sampling procedures

The Shefa Yamim exploration project (www.shefayamim.com) has sampled the Cretaceous pyroclastic centers on Mt. Carmel and adjacent areas, and minor and major drainages within the drainage basin of the Kishon River. Samples range in size from several kg to >1000 t. All samples were put through a static grizzly screen to remove pieces larger than 100 mm in diameter. Rock samples (black pyroclastics, consolidated) from the vents were coarsely crushed and then treated in the same way as alluvial samples. The material that passed the grizzly was washed in a scrubber that breaks up any clods. The <0.5 mm component is suspended in the wash water and pumped to settling ponds; fractions larger than 25 mm are used to backfill exploration pits. Samples in the +8–16 mm and + 16–24 mm size fractions are sorted by hand on a picking belt. The +0.5–8 mm component of the sample is washed and classified into 5 fractions: 0.5–0.7 mm, 0.7–1 mm, 1–2 mm, 2–4 mm, 4–6 mm, 6–8 mm. These fractions are transferred to a pulsating jig plant for gravity separation. Samples in the 2 mm–8 mm size fractions are visually inspected after the jigging process and then sorted in the recovery laboratory. The three smallest size fractions are jigged separately. The heavy concentrate in the center of the jig pan is collected and dried; material on the outer part of the jig pan is discarded. The sorters in the laboratory have demonstrated their efficiency in identifying and recovering a wide range of mineral species, including garnet (pyrope), ilmenite, spinel, chrome-diopside, diamond, moissanite, sapphire, ruby, Carmel Sapphire and hibonite, as well as rutile and zircon.

Several samples of unprocessed heavy mineral concentrates provided by Shefa Yamim were hand-picked under a binocular microscope; a few rock samples also have been processed by selFrag (electrostatic disaggregation) techniques, sieved and hand-picked after magnetic and heavy-liquid separation. Some larger xenocrysts, and mantle-derived xenoliths, were collected by hand from natural and artificial exposures in the vents and layered pyroclastics.

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Griffin, W.L., Huang, JX., Thomassot, E. et al. Super-reducing conditions in ancient and modern volcanic systems: sources and behaviour of carbon-rich fluids in the lithospheric mantle. Miner Petrol 112 (Suppl 1), 101–114 (2018). https://doi.org/10.1007/s00710-018-0575-x

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