We examined the mineralogical, chemical and isotopic compositions of secondary fluid inclusions in olivine-rich rocks from two active serpentinization systems: the Von Damm hydrothermal field (Mid-Cayman Rise) and the Zambales ophiolite (Philippines). Peridotite, troctolite and gabbroic rocks in these systems contain abundant CH 4 -rich secondary inclusions in olivine, with less abundant inclusions in plagioclase and clinopyroxene. Olivine-hosted secondary inclusions are chiefly composed of CH 4 and minor H 2 , in addition to secondary minerals including serpentine, brucite, magnetite and carbonates. Secondary inclusions in plagioclase are dominated by CH 4 with variable amounts of H 2 and H 2 O, while those in clinopyroxene contain only CH 4 . We determined hydrocarbon abundances and stable carbon isotope compositions by crushing whole rocks and analysing the released volatiles using isotope ratio monitoring—gas chromatography mass spectrometry. Bulk rock gas analyses yielded appreciable quantities of CH 4 and C 2 H 6 in samples from Cayman (4–313 nmol g −1 CH 4 and 0.02–0.99 nmol g −1 C 2 H 6 ), with lesser amounts in samples from Zambales (2–37 nmol g −1 CH 4 and 0.004–0.082 nmol g −1 C 2 H 6 ). Mafic and ultramafic rocks at Cayman exhibit δ 13 C CH 4 values of −16.7‰ to −4.4‰ and δ 13 C C 2 H 6 values of −20.3‰ to +0.7‰. Ultramafic rocks from Zambales exhibit δ 13 C CH 4 values of −12.4‰ to −2.8‰ and δ 13 C C 2 H 6 values of −1.2‰ to −0.9‰. Similarities in the carbon isotopic compositions of CH 4 and C 2 H 6 in plutonic rocks, Von Damm hydrothermal fluids, and Zambales gas seeps suggest that leaching of fluid inclusions may provide a significant contribution of abiotic hydrocarbons to deep-sea vent fluids and ophiolite-hosted gas seeps. Isotopic compositions of CH 4 and C 2 H 6 from a variety of hydrothermal fields hosted in olivine-rich rocks that are similar to those in Von Damm vent fluids further support the idea that a significant portion of abiotic hydrocarbons in ultramafic-influenced vent fluids is derived from fluid inclusions. This article is part of a discussion meeting issue ‘Serpentinite in the Earth system’.
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Abiotic methane synthesis and serpentinization in olivine-hosted fluid inclusions
The conditions of methane (CH 4 ) formation in olivine-hosted secondary fluid inclusions and their prevalence in peridotite and gabbroic rocks from a wide range of geological settings were assessed using confocal Raman spectroscopy, optical and scanning electron microscopy, electron microprobe analysis, and thermodynamic modeling. Detailed examination of 160 samples from ultraslow- to fast-spreading midocean ridges, subduction zones, and ophiolites revealed that hydrogen (H 2 ) and CH 4 formation linked to serpentinization within olivine-hosted secondary fluid inclusions is a widespread process. Fluid inclusion contents are dominated by serpentine, brucite, and magnetite, as well as CH 4( g ) and H 2( g ) in varying proportions, consistent with serpentinization under strongly reducing, closed-system conditions. Thermodynamic constraints indicate that aqueous fluids entering the upper mantle or lower oceanic crust are trapped in olivine as secondary fluid inclusions at temperatures higher than ∼400 °C. When temperatures decrease below ∼340 °C, serpentinization of olivine lining the walls of the fluid inclusions leads to a near-quantitative consumption of trapped liquid H 2 O. The generation of molecular H 2 through precipitation of Fe(III)-rich daughter minerals results in conditions that are conducive to the reduction of inorganic carbon and the formation of CH 4 . Once formed, CH 4( g ) and H 2( g ) can be stored over geological timescales until extracted by dissolution or fracturing of the olivine host. Fluid inclusions represent a widespread and significant source of abiotic CH 4 and H 2 in submarine and subaerial vent systems on Earth, and possibly elsewhere in the solar system.
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- Award ID(s):
- 1634032
- NSF-PAR ID:
- 10126515
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 116
- Issue:
- 36
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- 17666 to 17672
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Hydrogen is a rapidly diffusing monovalent cation in nominally anhydrous minerals (NAMs, such as olivine, orthopyroxene, and clinopyroxene), which is potentially re-equilibrated during silicate melt-rock and aqueous fluid-rock interactions in massif and abyssal peridotites. We apply a 3D numerical diffusion modeling technique to provide first-order timescales of complete hydrogen re-equilibration in olivine, clinopyroxene, and orthopyroxene over the temperature range 600-1200°C. Model crystals are 1-3 mm along the c-axis and utilize H+ diffusion coefficients appropriate for Fe-bearing systems. Two sets of models were run with different boundary compositions: 1) “low-H models” are constrained by mineral-melt equilibrium partitioning with a basaltic melt that has 0.75 wt% H2O and 2) “high-H models,” which utilize the upper end of the estimated range of mantle water solubility for each phase. Both sets of models yield re-equilibration timescales that are identical and are fast for all phases at a given temperature. These timescales have strong log-linear trends as a function of temperature (R2 from 0.97 to 0.99) that can be used to calculate expected re-equilibration time at a given temperature and grain size. At the high end of the model temperatures (1000-1200°C), H+ completely re-equilibrates in olivine, orthopyroxene, and clinopyroxene within minutes to hours, consistent with previous studies. These short timescales indicate that xenolith NAM mantle water contents are likely to be overprinted prior to eruption. The models also resolve the decoupled water-trace element relationship in Southwest Indian Ridge peridotites, in which peridotite REE abundances are reproduced by partial melting models whereas the relatively high NAM H2O contents require later re-equilibration with melt. At temperatures of 600-800°C, which correspond to conditions of hydrothermal alteration of pyroxene to amphibole and talc, H+ re-equilibration typically occurs over a range of timescales spanning days to years. These durations are well within existing estimates for the duration of fluid flow in oceanic hydrothermal systems, suggesting that peridotite NAM water contents are susceptible to diffusive overprinting during higher temperature hydrothermal alteration. Thus, diffusion during aqueous fluid-rock interactions may also explain NAM H2O contents that are too high to reflect residues of melting. These relatively short timescales at low temperatures suggest that the origin of water contents measured in peridotite NAMs requires additional constraints on sample petrogenesis, including petrographic and trace element analyses. Our 3D model results also hint that H+ may diffuse appreciably during peridotite serpentinization, but diffusion coefficients at low temperature are unconstrained and additional experimental investigations are needed.more » « less
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Abstract We present phase‐equilibria experiments of a K‐bearing, depleted peridotite (Mg# 92) fluxed with a mixed CO2‐H2O fluid (0.5 wt.% CO2and 0.94 wt.% H2O in the bulk) to gain insight into the stability of volatile‐bearing partial melts versus volatile‐bearing mineral phases in a depleted peridotite system. Experiments were performed at 850–1150 °C and 2–4 GPa using a piston‐cylinder and a multianvil apparatus. Olivine, orthopyroxene, clinopyroxene, and spinel/garnet are present at all experimental conditions. Textural confirmation of partial melt is made at temperatures as low as 1000 °C at 2 GPa, 950 °C at 3 GPa, and 1000 °C at 4 GPa marking the onset of melting at 900–1000 °C at 2 GPa, 850–950 °C at 3 GPa, and 950–1000 °C at 3 GPa. Phlogopite and magnesite breakdown at 900–1000 °C at 2 GPa, 950–1000 °C at 3 GPa, and 1000–1050 °C at 4 GPa. Comparison with previously published experiments in depleted peridotite system with identical CO2‐H2O content introduced via a silicic melt show that introduction of CO2‐H2O as fluid lowers the temperature of phlogopite breakdown by 150–200 °C at 2–4 GPa and stabilizes partial melts at lower temperatures. Our study thus, shows that the volatile‐bearing phase present in the cratonic mantle is controlled by bulk composition and is affected by the process of volatile addition during craton formation in a subduction zone. In addition, volatile introduction via melt versus aqueous fluid, leads to different proportion of anhydrous phases such as olivine and orthopyroxene. Considering the agent of metasomatism is thus critical to evaluate how the bulk composition of depleted peridotite is modified, leading to potential stability of volatile‐bearing phases as the cause of anomalously low shear wave velocity in mantle domains such as mid lithospheric discontinuities beneath continents.
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.1907871116
