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We report the formation of minerals from the tochilinite-valleriite group (TVG) during laboratory serpentinization experiments conducted at 300 and 328 °C. Minerals in the TVG are composed of a mixture of sulfide and hydroxide layers that can contain variable proportions of Fe, Mg, Cu, Ni, and other cations in both layers. Members of this group have been observed as accessory minerals in several serpentinites, and have also been observed in association with serpentine minerals in meteorites. To our knowledge, however, TVG minerals have not previously been identified as reaction products during laboratory simulation of serpentinization. The serpentinization experiments reacted olivine with artificial seawater containing 34S-labeled sulfate, with a small amount of solid FeS also added to the 300 °C experiment. In both experiments, the predominant reaction products were chrysotile serpentine, brucite, and magnetite. At 300 °C, these major products were accompanied by trace amounts of the Ni-bearing TVG member haapalaite, Ni,Fe-sulfide (likely pentlandite), and anhydrite. At 328 °C, valleriite occurs rather than haapalaite and the accompanying Ni,Fe-sulfide is proportionally more enriched in Ni. Reduction of sulfate by H2 produced during serpentinization evidently provided a source of reduced S that contributed to formation of the TVG minerals and Ni,Fe-sulfides. The results provide new constraints on the conditions that allow precipitation of tochilinite-valleriite group minerals in natural serpentinites.

 

Recent geochemical evidence confirms the oxidized nature of arc magmas, but the underlying processes that regulate the redox state of the subarc mantle remain yet to be determined. We established a link between deep subduction-related fluids derived from dehydration of serpentinite ± altered oceanic crust (AOC) using B isotopes and B/Nb as fluid proxies, and the oxidized nature of arc magmas as indicated by Cu enrichment during magma evolution and V/Yb. Our results suggest that arc magmas derived from source regions influenced by a greater serpentinite (±AOC) fluid component record higher oxygen fugacity. The incorporation of this component into the subarc mantle is controlled by the subduction system’s thermodynamic conditions and geometry. Our results suggest that the redox state of the subarc mantle is not homogeneous globally: Primitive arc magmas associated with flat, warm subduction are less oxidized overall than those generated in steep, cold subduction zones. 

Quantifying the concurrent changes in rock volume and fluid composition during serpentinization remains a major challenge in assessing its physicochemical effects during continental rifting, seafloor spreading, and subduction. Here we conducted a series of 11 hydrothermal laboratory experiments where cylindrical cores of natural dunite, harzburgite, and pyroxenite were reacted with an aqueous solution at 300 °C and 35 MPa for up to 18 months. Using three-dimensional microcomputed tomography and thermogravimetry, we show that rock volume systematically increased with time and extent of reaction, leading to a volume increase of 44% (±8%) in altered rock domains after 10–18 months of serpentinization. The volume expansion was accompanied by Mg-Ca exchange between fluid and rock, while Fe and Si were largely conserved. We find that the protolith composition (olivine/orthopyroxene ratio) plays a significant role in controlling the fluid chemistry and the proportions of hydrous secondary minerals during serpentinization. Agreement between alteration mineralogy, composition of reacting fluids, and measured volume changes suggests that serpentinization under static conditions is a volume-increasing process in spite of demonstrable mass transfer. Volume expansion implies an increased water carrying capacity and buoyancy force of serpentinite per unit mass of protolith, while Mg-Ca exchange during serpentinization may affect the Mg/Ca ratio of seawater on Earth and possibly other ocean worlds. 

A series of three laboratory experiments were conducted to investigate how pH affects reaction pathways and rates during serpentinization. Two experiments were conducted under strongly alkaline conditions using olivine as reactant at 200 and 230°C, and the results were compared with previous studies performed using the same reactants and methods at more neutral pH. For both experiments, higher pH resulted in more rapid serpentinization of the olivine and generation of larger amounts of H 2 for comparable reaction times. Proportionally greater amounts of Fe were partitioned into brucite and chrysotile and less into magnetite in the experiments conducted at higher pH. In a third experiment, alkaline fluids were injected into an ongoing experiment containing olivine and orthopyroxene to raise the pH from circumneutral to strongly alkaline conditions. Increasing the pH of the olivine-orthopyroxene experiment resulted in an immediate and steep increase in H 2 production, and led to far more extensive reaction of the primary minerals compared to a similar experiment conducted under more neutral conditions. The results suggest that the development of strongly alkaline conditions in actively serpentinizing systems promotes increased rates of reaction and H 2 production, enhancing the flux of H 2 available to support biological activity in these environments. This article is part of a discussion meeting issue ‘Serpentinite in the Earth System’. 

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’. 

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. 

Abstract Hydrogenation reactions are a major route of electron and proton flow on Earth. Interfacing geology and organic chemistry, hydrogenations occupy pivotal points in the Earth’s global geochemical cycles. Some examples of hydrogenation reactions on Earth today include the production and consumption of methane in both abiotic and biotic reactions, the reduction of protons in hydrothermal settings, and the biological synthesis and degradation of fatty acids. Hydrogenation reactions were likely important for prebiotic chemistry on the early Earth, and today serve as one of the fundamental reaction classes that enable cellular life to construct biomolecules. An understanding and awareness of hydrogenation reactions is helpful for comprehending the larger web of molecular and material inter-conversions on our planet. In this brief review we detail some important hydrogenation and dehydrogenation reactions as they relate to geology, biology, industry, and atmospheric chemistry. Such reactions have implications ranging from the suite of reactions on early Earth to industrial applications like the production of hydrocarbon fuel. 

The lithified lower oceanic crust is one of Earth’s last biological frontiers as it is difficult to access. It is challenging for microbiota that live in marine subsurface sediments or igneous basement to obtain sufficient carbon resources and energy to support growth1–3 or to meet basal power requirements4 during periods of resource scarcity. Here we show how limited and unpredictable sources of carbon and energy dictate survival strategies used by low-biomass microbial communities that live 10– 750 m below the seafloor at Atlantis Bank, Indian Ocean, where Earth’s lower crust is exposed at the seafloor. Assays of enzyme activities, lipid biomarkers, marker genes and microscopy indicate heterogeneously distributed and viable biomass with ultralow cell densities (fewer than 2,000 cells per cm3). Expression of genes involved in unexpected heterotrophic processes includes those with a role in the degradation of polyaromatic hydrocarbons, use of polyhydroxyalkanoates as carbon-storage molecules and recycling of amino acids to produce compounds that can participate in redox reactions and energy production. Our study provides insights into how microorganisms in the plutonic crust are able to survive within fractures or porous substrates by coupling sources of energy to organic and inorganic carbon resources that are probably delivered through the circulation of subseafloor fluids or seawater.