skip to main content


Title: Chemical and isotopic analyses of hydrocarbon-bearing fluid inclusions in olivine-rich rocks
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’.  more » « less
Award ID(s):
1634032
NSF-PAR ID:
10129931
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences
Volume:
378
Issue:
2165
ISSN:
1364-503X
Page Range / eLocation ID:
20180431
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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. 
    more » « less
  2. Abstract

    In hyperalkaline () fluids that have participated in low‐temperature (<150) serpentinization reactions, the dominant form of C is often methane (), but the origin of thisis uncertain. To assessorigin in serpentinite aquifers within the Samail Ophiolite, Oman, we determined fluid chemical compositions, analyzed taxonomic profiles of fluid‐hosted microbial communities, and measured isotopic compositions of hydrocarbon gases. We found that 16S rRNA gene sequences affiliated with methanogens were widespread in the aquifer. We measured clumped isotopologue (D and) relative abundances less than equilibrium, consistent with substantial microbialproduction. Furthermore, we observed an inverse relationship between dissolved inorganic C concentrations andacross fluids bearing microbiological evidence of methanogenic activity, suggesting that the apparent C isotope effect of microbial methanogenesis is modulated by C availability. An additional source ofis evidenced by the presence of‐bearing fluid inclusions in the Samail Ophiolite and our measurement of highvalues of ethane and propane, which are similar to those reported in studies of‐rich inclusions in rocks from the oceanic lithosphere. In addition, we observed 16S rRNA gene sequences affiliated with aerobic methanotrophs and, in lower abundance, anaerobic methanotrophs, indicating that microbial consumption ofin the ophiolite may further enrichin13C. We conclude that substantial microbialis produced under varying degrees of C limitation and mixes with abioticreleased from fluid inclusions. This study lends insight into the functioning of microbial ecosystems supported by water/rock reactions.

     
    more » « less
  3. Abstract

    Carbonate‐brucite chimneys are a characteristic of low‐ to moderate‐temperature, ultramafic‐hosted alkaline hydrothermal systems, such as the Lost City hydrothermal field located on the Atlantis Massif at 30°N near the Mid‐Atlantic Ridge. These chimneys form as a result of mixing between warm, serpentinization‐derived vent fluids and cold seawater. Previous work has documented the evolution in mineralogy and geochemistry associated with the aging of the chimneys as hydrothermal activity wanes. However, little is known about spatial heterogeneities within and among actively venting chimneys. New mineralogical and geochemical data (87Sr/86Sr and stable C, O, and clumped isotopes) indicate that the brucite and calcite precipitate at elevated temperatures in vent fluid‐dominated domains in the interior of chimneys. Exterior zones dominated by seawater are brucite‐poor and aragonite is the main carbonate mineral. Carbonates record mostly out of equilibrium oxygen and clumped isotope signatures due to rapid precipitation upon vent fluid‐seawater mixing. On the other hand, the carbonates precipitate closer to carbon isotope equilibrium, with dissolved inorganic carbon in seawater as the dominant carbon source and have δ13C values within the range of marine carbonates. Our data suggest that calcite is a primary mineral in the active hydrothermal chimneys and does not exclusively form as a replacement of aragonite during later alteration with seawater. Elevated formation temperatures and lower87Sr/86Sr relative to aragonite in the same sample suggest that calcite may be the first carbonate mineral to precipitate.

     
    more » « less
  4. Abstract

    Single‐celled microbial eukaryotes inhabit deep‐sea hydrothermal vent environments and play critical ecological roles in the vent‐associated microbial food web. 18S rRNA amplicon sequencing of diffuse venting fluids from four geographically‐ and geochemically‐distinct hydrothermal vent fields was applied to investigate community diversity patterns among protistan assemblages. The four vent fields include Axial Seamount at the Juan de Fuca Ridge, Sea Cliff and Apollo at the Gorda Ridge, all in the NE Pacific Ocean, and Piccard and Von Damm at the Mid‐Cayman Rise in the Caribbean Sea. We describe species diversity patterns with respect to hydrothermal vent field and sample type, identify putative vent endemic microbial eukaryotes, and test how vent fluid geochemistry may influence microbial community diversity. At a semi‐global scale, microbial eukaryotic communities at deep‐sea vents were composed of similar proportions of dinoflagellates, ciliates, Rhizaria, and stramenopiles. Individual vent fields supported distinct and highly diverse assemblages of protists that included potentially endemic or novel vent‐associated strains. These findings represent a census of deep‐sea hydrothermal vent protistan communities. Protistan diversity, which is shaped by the hydrothermal vent environment at a local scale, ultimately influences the vent‐associated microbial food web and the broader deep‐sea carbon cycle.

     
    more » « less
  5. Abstract

    Deep-sea hydrothermal vent geochemistry shapes the foundation of the microbial food web by fueling chemolithoautotrophic microbial activity. Microbial eukaryotes (or protists) play a critical role in hydrothermal vent food webs as consumers and hosts of symbiotic bacteria, and as a nutritional source to higher trophic levels. We measured microbial eukaryotic cell abundance and predation pressure in low-temperature diffuse hydrothermal fluids at the Von Damm and Piccard vent fields along the Mid-Cayman Rise in the Western Caribbean Sea. We present findings from experiments performed under in situ pressure that show cell abundances and grazing rates higher than those done at 1 atmosphere (shipboard ambient pressure); this trend was attributed to the impact of depressurization on cell integrity. A relationship between the protistan grazing rate, prey cell abundance, and temperature of end-member hydrothermal vent fluid was observed at both vent fields, regardless of experimental approach. Our results show substantial protistan biomass at hydrothermally fueled microbial food webs, and when coupled with improved grazing estimates, suggest an important contribution of grazers to the local carbon export and supply of nutrient resources to the deep ocean.

     
    more » « less