Abiotic Hydrocarbons Research Articles

Reaction path model of the formation of abiotic immiscible hydrocarbon fluids in subducted carbonated serpentinites, Lanzo Massif (Western Italian Alps)

Fluids generated from subducted slabs participate in the cycling of deep carbon in the crust and upper mantle. In these fluids, aqueous carbon species vary in oxidation state between +IV and -IV depending on whether the fluids are oxidizing or reducing, respectively. Most studies of subduction-zone fluids have focused on oxidized carbon species. However, recent studies of natural samples have demonstrated the occurrence of deep, reducing fluids, generated in both subducted oceanic upper mantle and crustal rocks. CH4-H2-rich fluid inclusions in subducted carbonated serpentinites have demonstrated the existence of abiotic, immiscible, hydrocarbon fluids at upper mantle conditions. To investigate the formation of such immiscible hydrocarbon fluids during the evolution of subducted carbonated serpentinites, we used equilibrium constants from the Deep Earth Water model to carry out predictive chemical mass transfer modeling to simulate the alteration reactions. A novel feature of the models was the inclusion of an immiscible hydrocarbon fluid containing six components (CH4,f,C2H6,f,C3H8,f,isoC4H10,f,CO2,f,H2,f). This feature enabled prediction of the formation of a separate immiscible fluid in equilibrium with aqueous species and minerals.We developed a predictive reaction path model of invasive H2,f reacting with carbonated serpentinites and interstitial aqueous fluids for comparison with the natural samples from the Lanzo Massif, western Italian Alps. Over a range of temperatures and pressures, immiscible hydrocarbon fluids formed in association with altered mineral assemblages. Reaction progress caused the transformation of carbonated serpentinites and the formation of clinopyroxene, brucite, graphite, and hydrocarbon fluids, along with changes of pH, logfO2, and aqueous species. CH4,f was the most abundant hydrocarbon species in all the models. The overall results at 2.0 GPa and 400 to 450 °C were consistent with the natural samples from the Lanzo Massif. Interestingly, large amounts of H2O formed due to oxidation of H2. More hydrocarbons and H2O formed in models with lower fluid/rock mass ratios or with more reactant H2. Models at different pressure and temperature conditions showed similar results with some variation in the relative stabilities of aragonite, graphite and olivine solid solution, and associated differences in mineral sequences, hydrocarbon fluids, values of aqueous species, and the final logfO2 and pH. Our models strongly support the laboratory and field evidence that reduction of carbonated serpentinites by infiltrating H2 fluids can cause the formation of immiscible, abiotic hydrocarbon fluids in subduction zones.

Unusual 13C depletion in the central carbon of propane in the gases of Longmaxi shale in the Sichuan Basin

Abiotically synthesized hydrocarbons are significant in the fields of astrobiology, biosphere, energy, environment, and geology. Abiotic hydrocarbons have never been unambiguously proven to occur in common sediments partly because identifying these components in crustal settings is challenging as they share similar characteristics with hydrocarbons of biotic origin. In this study, we measured intramolecular carbon isotopes of 10 propane samples from Longmaxi shale in the Sichuan Basin, China, and found distinct 13C-depletion in the central position carbon with its δ13C decreased by −8.0 to −7.0‰ (Vienna Pee Dee Belemnite) with respect to terminal carbons. The δ13C value of central carbon (H3C–#CH2-CH3) in propane is equal to the second methyl (H3C–#CH3) in ethane possibly resulting from surface catalytic polymerization reactions of methane. Our novel findings indicate that the abiotic synthesis of C2+ hydrocarbons by the surface catalyzed polymerization of methane occurs in commercial gas reservoirs and suggest that this process may be more common than previously thought in methane-rich scenarios on Earth and other planets.

Late Mesozoic and Cenozoic Geodynamics of the Arctic Region: Implications for Abiogenic Generation of Hydrocarbons

Late Mesozoic and Cenozoic geodynamics of the Arctic region is discussed in the context of possible mechanisms which provide multistage cyclic transformations and transport of carbon through crust and mantle. Geodynamic processes control the abiogenic generation of hydrocarbons and the patterns of their localization. Possible mechanisms of abiotic hydrocarbon generation are explained in the context of carbon transport from subduction zones to rifts and serpentinization of ultramafic rocks in the rifts in the case of the Laptev Sea and Gakkel Ridge areas. The carbon of shallow crust origin migrates with encapsulated fragments of marine sediments which are consumed in the Pacific subduction zone where they become destroyed and transformed by different chemical and physical processes. The resulting C-species are involved in mantle convection flows and reach the continental rifts of the Laptev Sea and the Gakkel mid-ocean ridge. Thus, the hydrocarbons formed in the crust and in the mantle acquire signatures of abiotic origin. According to the authors, the scale of manifestation of abiogenic methanogenesis in the lower parts of the lithosphere and in the upper mantle is not so wide. Numerous small (mm and fractions of the mm) particles of exogenous matter and dispersed carbon pulled into the mantle can only form a stable crustal geochemical plume that propagates in the plane of movement of convective flows. Indirectly, the scale of manifestation of this process can be judged by the volumes of degassing of hydrocarbon and carbon dioxide gases, as well as hydrogen and its compounds in the rift systems of the earth’s crust, which are extremely insignificant. However, in the cold seas of the Eastern Arctic, massive emissions of bubble methane of mixed genesis were found. As shown in the literature, the range of variability of stable isotopes of carbon and 14C of methane in certain areas of discharge associated with rifting demonstrates values (anomalously heavy 13C, and young 14C) that can be considered as examples of presumably abiogenic origin. Our work is mostly theoretical and suggests further discussion and improvement of the mechanism of formation of abiogenic hydrocarbons and the processes of their transformation.

Low 13C-13C abundances in abiotic ethane

Distinguishing biotic compounds from abiotic ones is important in resource geology, biogeochemistry, and the search for life in the universe. Stable isotopes have traditionally been used to discriminate the origins of organic materials, with particular focus on hydrocarbons. However, despite extensive efforts, unequivocal distinction of abiotic hydrocarbons remains challenging. Recent development of clumped-isotope analysis provides more robust information because it is independent of the stable isotopic composition of the starting material. Here, we report data from a 13C-13C clumped-isotope analysis of ethane and demonstrate that the abiotically-synthesized ethane shows distinctively low 13C-13C abundances compared to thermogenic ethane. A collision frequency model predicts the observed low 13C-13C abundances (anti-clumping) in ethane produced from methyl radical recombination. In contrast, thermogenic ethane presumably exhibits near stochastic 13C-13C distribution inherited from the biological precursor, which undergoes C-C bond cleavage/recombination during metabolism. Further, we find an exceptionally high 13C-13C signature in ethane remaining after microbial oxidation. In summary, the approach distinguishes between thermogenic, microbially altered, and abiotic hydrocarbons. The 13C-13C signature can provide an important step forward for discrimination of the origin of organic molecules on Earth and in extra-terrestrial environments.

Abiotic Hydrocarbons Generation Simulated by Fischer‐Tropsch Synthesis under Hydrothermal Conditions in Ultra‐deep Basins

AbstractFTT experiments with water as a hydrogen source and three types of possible carbon sources in the subsurface (diiron nonacarbonyl, siderite and formic acid, representing CO, CO2 and a simple organic acid, respectively) were carried out in this study. Our experimental results showed that n‐alkanes with the highest carbon number of C33 were produced when CO was used as a carbon source (series A); a variety of polycyclic aromatic hydrocarbons (PAHs) were detected in series B with CO2 as a carbon source; gaseous hydrocarbons were also detected with formic acid added (series C). The different products in the three series showed that there were different hydrocarbon generation mechanisms and reaction processes with different carbon sources. The generation of long‐chain n‐alkanes in series A provided experimental support for the formation of abiogenic petroleum underground, which was of significance to early membranes on the Earth. PAHs in series B provide experimental support for the possibility of an abiotic source of reduced carbon on other planets. The carbon isotopes of gaseous hydrocarbons produced by CO exhibited a partial reversed order (δ13C1 < δ13C2 > δ13C3 > δ13C4 > δ13C5), while the gaseous hydrocarbons produced by CO2 and HCOOH showed a positive order (δ13C1 < δ13C2 < δ13C3 < δ13C4 < δ13C5). Based on these, the alkylene mechanism and the carbonyl insertion mechanism were used to reasonably explain these characteristics.

Validity of geochemical signatures of abiotic hydrocarbon gases on Earth

Abiotic synthesis has been hypothesized as a mechanism for occurrences of hydrocarbon gases with atypical molecular and isotopic compositions. This paper provides biotic interpretations of these atypical compositions, as follows: (1) microbial CH 4 oxidation and CO 2 -sourced methanogenesis may enrich 13 C in hydrothermal CH 4 ; (2) microbial hydrocarbon generation using serpentinization-derived H 2 may deplete deuterium in hydrocarbons; (3) three processes may cause isotopic reversal with the carbon number in biotic hydrocarbons (the decrease of kinetic isotope effect (KIE) with the increase of carbon number during alkane biodegradation, inverse KIE during the thermal decomposition of higher alkanes and isotopic fractionation during gas diffusion in rock samples); (4) random scission of long alkyl chains may form the exponential distribution of alkane abundance with respect to carbon number (the ‘Schulz–Flory distribution’); (5) isotopic compositions are often not equilibrated; even if they are, the equilibrium temperatures are not necessarily the same as the temperature of hydrocarbon generation. Case studies demonstrate that previously proposed abiotic hydrocarbon gases in continental serpentinite-hosted seepages, continental or oceanic hydrothermal vents, volcanic emissions, gas fields in volcanic reservoirs and fluid inclusions in alkaline or granitic rocks were formed by various biotic processes. The occurrence of abiotic hydrocarbon gas with decisive evidence is limited to fluid inclusions in some mantle minerals. Supplementary material: Expressions for isotopic fractionation of CH 4 and model details of the Xujiaweizi gas are available at https://doi.org/10.6084/m9.figshare.c.5660278

In-situ abiogenic methane synthesis from diamond and graphite under geologically relevant conditions

Diamond and graphite are fundamental sources of carbon in the upper mantle, and their reactivity with H2-rich fluids present at these depths may represent the key to unravelling deep abiotic hydrocarbon formation. We demonstrate an unexpected high reactivity between carbons’ most common allotropes, diamond and graphite, with hydrogen at conditions comparable with those in the Earth’s upper mantle along subduction zone thermal gradients. Between 0.5-3 GPa and at temperatures as low as 300 °C, carbon reacts readily with H2 yielding methane (CH4), whilst at higher temperatures (500 °C and above), additional light hydrocarbons such as ethane (C2H6) emerge. These results suggest that the interaction between deep H2-rich fluids and reduced carbon minerals may be an efficient mechanism for producing abiotic hydrocarbons at the upper mantle.

Carbon and hydrogen isotope fractionation during aerobic oxidation of short-chain alkanes in experimental incubations of vent fluids

Aerobic oxidation of short-chain alkanes was observed in gas samples from the Lutao intertidal hydrothermal vents in Taiwan, during storage at 20 °C for up to 29 months without adding bacterial strains and replenishing substrates. The carbon isotope fractionation factors (εC) of methane (C1), ethane (C2), and propane (C3), were calculated using the Rayleigh fractionation equation to be −37.1 ± 7.5‰, −14.8 ± 4.8‰, and −4.7 ± 5.2‰, respectively. The hydrogen isotope fractionation factor (εH) of methane was determined to be −281 ± 187‰. DNA sequencing of the 16S rRNA gene in the vent fluids suggests that aerobic oxidation is dominated by methanotrophs of the genera Methylomicrobium and Methylophaga, which use the ribulose monophosphate pathway (RuMP). The degrees of isotope fractionation (εC and εH values) herein are larger than previously reported values, possibly due to the limited O2 supply and low abundance of aerobic methane-oxidizing bacteria in the experiments. Since the fractionation factor of methane is higher than those of ethane and propane, the aerobic oxidation of thermogenic or microbial alkanes could produce a carbon isotope reversal, which is frequently noted as a trait of abiotic hydrocarbons. This work demonstrates that in addition to anaerobic microbial oxidation, aerobic oxidation with a low cell density can also produce significant isotope fractionation of alkanes in geological closed/semi-closed environments and open flow reaction systems that are characterized by moderate temperatures and a limited supply of substrates and O2; these environments include cold seeps, mud volcanoes, and low-temperature hydrothermal plumes/aquifers/reservoirs.

High-pressure serpentinization and abiotic methane formation in metaperidotite from the Appalachian subduction, northern Vermont

Serpentinization is the process of hydroxylation of olivine-rich ultramafic rocks to produce minerals such as serpentine, brucite and magnetite. This process is commonly accompanied by Fe oxidation and release of H2, which can be involved in abiotic reaction pathways leading to the genesis of abiotic light hydrocarbons such as methane (CH4). Examples of this phenomenon exist at the seafloor, such as at the serpentinite-hosted Lost City hydrothermal field, and on land in ophiolites at relatively shallow depths. However, the possibility for serpentinization to occur at greater depths, especially in subduction zones, raises new questions on the genesis of abiotic hydrocarbons at convergent margin and its impact on the deep carbon cycle. High-pressure ultramafic bodies exhumed in metamorphic belts can provide insights on the mechanisms of high-pressure serpentinization in subduction zones and on the chemistry of the resulting fluids. This study focuses on the ultramafic Belvidere Mountain complex belonging to the Appalachian belt of northern Vermont, USA. Microstructures show overgrowth of both primary (Mg# 0.91) and metamorphic (Mg# 0.95) olivine by delicate antigorite crystals, pointing to at least one stage of serpentinization at high-temperature conditions and consistent with the high-pressure subduction evolution of the Belvidere Mountain complex. Formation of ubiquitous magnetite and local Fe–Ni alloys testifies to the partial oxidation of Fe2+ into Fe3+ and generation of reduced conditions. Fluid inclusion trails cross-cutting the primary olivine relicts suggest their formation during the antigorite serpentinization event. MicroRaman spectroscopy on the fluid inclusions reveals a CH4-rich gaseous composition, as well as N2, NH3 and H2S. Moreover, the precipitation of daughter minerals such as lizardite and brucite in the fluid inclusions indicate the initial presence of H2O in the fluid. High-pressure serpentinization driven by the infiltration of metasediment-derived aqueous fluids is proposed at the origin of CH4 and other reduced fluid species preserved in the fluid inclusions. This suggests the Belvidere Mountain complex as an example of deep abiotic hydrocarbon genesis related to high-pressure serpentinization in an early Paleozoic subduction zone.

Abiotic Methane Generation via CO2 Hydrogenation With Natural Chromitite Under Hydrothermal Conditions

AbstractIn modern continental serpentinization systems and ultramafic rock‐hosted sub‐seafloor hydrothermal systems, it is believed that chromitite plays an important role in abiotic hydrocarbon generation. Previous experiments have suggested that chromite acts as a catalyst of CH4 generation, but the composition of chromite used in the previous experiment is unrealistic on Earth. On the other hand, other studies have suggested that natural chromite including Mg and Al cannot function as a catalyst for CH4 generation. Consequently, it still remains uncertain whether naturally occurring Cr‐rich minerals promote CH4 generation. We monitored the reaction between naturally occurring chromitite and CO2‐rich fluid at 300°C, 500 bars. We performed two experiments in different initial CO2/H2 ratios. In both experiments, CH4 was generated immediately after the beginning of experiments. When CO2 was more abundant than H2, the CH4 concentration in the fluid decreased below the detection limit value. On the other hand, when H2 was more abundant than CO2, the CH4 concentration in the fluid was maintained above 0.01 mmol/kg. This is the first report to demonstrate that naturally occurring Cr‐rich minerals act as a promotor of CH4 generation. Cr‐rich minerals such as Cr spinel are common accessory mineral in ultramafic rock. Therefore, on the early Earth, a certain level (on the order of 0.01 mmol/kg) of CH4 was likely produced through reactions between ultramafic rock and CO2‐bearing fluid. To produce more abundant CH4, more favorable conditions featuring greater quantities of Cr spinel and much higher H2 concentration (H2/CO2 ratio) must be necessary.

Hydrogen and Abiotic Hydrocarbons: Molecules that Change the World

Molecular hydrogen (H2), methane, and hydrocarbons with an apparent abiotic origin have been observed in a variety of geologic settings, including serpentinized ultramafic rocks, hydrothermal fluids, and deep fractures within ancient cratons. Molecular hydrogen is also observed in vapor plumes emanating from the icy crust of Saturn’s moon Enceladus, and methane has been detected in the atmosphere of Mars. Geologic production of these compounds has been the subject of increasing scientific attention due to their use by chemosynthetic biological communities. These compounds are also of interest as possible energy resources. This issue summarizes the geological sources of abiotic H2 and hydrocarbons on Earth and elsewhere and examines their impact on microbial life and energy resources.

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 CH4-rich secondary inclusions in olivine, with less abundant inclusions in plagioclase and clinopyroxene. Olivine-hosted secondary inclusions are chiefly composed of CH4 and minor H2, in addition to secondary minerals including serpentine, brucite, magnetite and carbonates. Secondary inclusions in plagioclase are dominated by CH4 with variable amounts of H2 and H2O, while those in clinopyroxene contain only CH4. 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 CH4 and C2H6 in samples from Cayman (4-313 nmol g-1 CH4 and 0.02-0.99 nmol g-1 C2H6), with lesser amounts in samples from Zambales (2-37 nmol g-1 CH4 and 0.004-0.082 nmol g-1 C2H6). Mafic and ultramafic rocks at Cayman exhibit δ13CCH4 values of -16.7‰ to -4.4‰ and δ13CC2H6 values of -20.3‰ to +0.7‰. Ultramafic rocks from Zambales exhibit δ13CCH4 values of -12.4‰ to -2.8‰ and δ13CC2H6 values of -1.2‰ to -0.9‰. Similarities in the carbon isotopic compositions of CH4 and C2H6 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 CH4 and C2H6 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'.

Sublacustrine hydrothermal seeps and silicification of microbial bioherms in the Ediacaran Oued Dar'a caldera, Anti‐Atlas, Morocco

AbstractThis paper presents a case study of the sublacustrine precipitation of hydrothermal silica ± TiO2 in the Ediacaran Mançour Group of the Saghro inlier, Anti‐Atlas, Morocco. Lacustrine carbonates containing stromatolitic mats and bioherms occur in ephemeral ponds developed within the Oued Da'ra caldera. Its syn‐eruptive infill consists of pyroclastites, ashflow tuffs, and subsidiary lava flows and sills, whereas inter‐eruptive deposition is mainly represented by slope‐related debris‐flow breccias and landslides, alluvial fans and fluvial channels. Carbonate production took place in a mosaic of differentially subsiding, fault‐bounded intra‐caldera blocks controlled by episodic collapse‐induced drowning, pyroclastic blanketing and migration of alluvial/fluvial environments. After microbial carbonate production, the carbonates recorded several early‐diagenetic processes, punctuated by polyphase fissuring (controlling secondary permeability) locally linked to hydrothermal influx. Three generations of carbonate cements are recognisable: (i) fibrous, botryoidal and blocky/drusy mosaics of calcite; (ii) idiotopic mosaics of dolomite caused by flushing of hypersaline Mg‐rich brines; and (iii) euhedral to drusy calcite via dedolomitization. The δ13C and δ18O values from carbonate cements broadly become successively isotopically lighter, as a result of meteoric and hydrothermal influence, and were probably overprinted by the Panafrican‐3 phase that affected the top of the Mançour Group. Two mechanisms of silicification are involved: (i) early‐diagenetic occlusion of interparticle pores at the sediment/water interface of pyroclastic substrates and reefal core and flanks; and (ii) hydrothermal precipitation of silica ± TiO2 lining fissures and vuggy porosity encased in the host rock. Silica conduits cross‐cutting lacustrine mats and bioherms exhibit high potential of preservation in collapsed volcanic calderas. Primary fluid inclusions of hydrothermal silica contain brine relics with NaCl/CaCl2 ratios of 2·1 to 4·4, representing minimum entrapment temperatures of about 142 to 204°C, and abiotic hydrocarbons (heavy alkanes) related to serpentinization of the volcanic and volcanosedimentary basement of the Oued Dar'a caldera.

Water adsorption on olivine(010) surfaces: Effect of alkali and transition metal cation doping.

Dopants have the potential to locally modify water-olivine interactions, which can impact geological processes, such as weathering, CO2 sequestration, and abiotic hydrocarbon generation. As a first step in understanding the role of dopants on the water structure and chemistry at water-olivine interfaces, water monomer adsorption on alkaline earth (AE) and transition metal (TM) doped forsterite(010) [Mg2SiO4(010)] surfaces was studied using density functional theory (DFT). Dopants that occur in olivine minerals were considered and consisted of Ca, Sr, and Ba for the AE dopants and Cr, Mn, Fe, Co, and Ni for the TM dopants. The water molecule adsorbs on the olivine surface through a metal-water bond (Me-Ow) and a hydrogen bond with an adjacent surface lattice oxygen (Ox-Hw). A frontier orbital analysis reveals that the 1b2, 3a1, and 1b1 (HOMO) of the water molecule are involved in the bonding. All of the TM dopants show strong net Me-Ow covalent bonding between 3a1 and 1b1 water orbitals and TM d states, while the AE dopants except for Mg2SiO4(010) show negligible Me-Ow covalent bonding. Both the AE and TM dopants show similar hydrogen bonding features involving both the 1b2 and 3a1 orbitals. While the AE cations show an overall lower Me-Ow covalent interaction, the AE dopants have strong electrostatic interactions between the positive metal cation and the negatively charged water dipole. A bonding model incorporating a linear combination of the covalent Me-Ow bond, the Ox-Hw hydrogen bond, the electrostatic interaction between the dopant cation and the H2O molecule, and the surface distortion energy is needed to capture the variation in the DFT adsorption energies on the olivine surfaces. The bonding analysis is able to identify the dominant contributions to water-dopant interactions and can serve as a basis for future studies of more realistic water-olivine interfaces.

Abiotic synthesis of amino acids in the recesses of the oceanic lithosphere

Abiotic hydrocarbons and carboxylic acids are known to be formed on Earth, notably during the hydrothermal alteration of mantle rocks. Although the abiotic formation of amino acids has been predicted both from experimental studies and thermodynamic calculations, its occurrence has not been demonstrated in terrestrial settings. Here, using a multimodal approach that combines high-resolution imaging techniques, we obtain evidence for the occurrence of aromatic amino acids formed abiotically and subsequently preserved at depth beneath the Atlantis Massif (Mid-Atlantic Ridge). These aromatic amino acids may have been formed through Friedel-Crafts reactions catalysed by an iron-rich saponite clay during a late alteration stage of the massif serpentinites. Demonstrating the potential of fluid-rock interactions in the oceanic lithosphere to generate amino acids abiotically gives credence to the hydrothermal theory for the origin of life, and may shed light on ancient metabolisms and the functioning of the present-day deep biosphere.

Characterisation and possible hazard of an atypical asbestiform sepiolite associated with aliphatic hydrocarbons from Sassello, Ligurian Apennines, Italy

AbstractAn unusual occurrence of asbestiform sepiolite, filling veins in the antigorite serpentinites of the Voltri Unit exposed in a borrow pit (now reclaimed) in the Deiva forest, near Sassello, NW Italy, was investigated with an in-depth analytical approach aimed at studying its crystal-chemistry and structure and evaluating its possible hazards for human health. Optical microscopy and scanning electron microscopy (energy-dispersive spectroscopy mode) proved that these sepiolite fibres, apparently up to several cm long, are made up of bundles of thinner fibrils (or laths: average length > 100 µm; thickness ≈ 80 nm), with a composition consistent to that reported in the literature. The dehydration process was monitored through thermo-gravimetric analyses and Fourier-transform infrared spectroscopy, performed at increasingT; the latter, in particular, showed the presence of moderate amounts of aliphatic hydrocarbons – not yet identified thoroughly – associated with the sample. The crystal structure refinement with the Rietveld method showed no relevant difference from the literature models, although a peculiar distribution of zeolitic H2O molecules was observed. The geological context suggests that the Sassello sepiolite precipitated from hydrothermal fluids, which were saturated in Mg and silica by the interaction of the host serpentinites. The same setting favoured formation of abiotic hydrocarbons, by means of the Fischer–Tropsch reaction. The extremely long and flexible fibrils (length/width aspect ratio >> 3) of this sepiolite specimen could represent a serious hazard for human health if air dispersed and inhaled; also, its atypical association with hydrocarbons (only reported once previously) might even favour further fragmentation in thinner units.

Formation of abiotic hydrocarbon from reduction of carbonate in subduction zones: Constraints from petrological observation and experimental simulation

Subduction is a key process for linking the carbon cycle between the Earth’s surface and its interior. Knowing the carbonation and decarbonation processes in the subduction zone is essential for understanding the global deep carbon cycle. In particular, the potential role of hydrocarbon fluids in subduction zones is not well understood and has long been debated. Here we report graphite and light hydrocarbon-bearing inclusions in the carbonated eclogite from the Southwest (S.W.) Tianshan subduction zone, which is estimated to have originated at a depth of at least 80 kilometers. The formation of graphite and light hydrocarbon likely results from the reduction of carbonate under low oxygen fugacity (∼FMQ - 2.5 log units). To better understand the origin of light hydrocarbons, we also investigated the reaction between iron-bearing carbonate and water under conditions relevant to subduction zone environments using large-volume high-pressure apparatus. Our high-pressure experiments provide additional constraints on the formation of abiotic hydrocarbons and graphite/diamond from carbonate-water reduction. In the experimental products, the speciation and concentration of the light hydrocarbons including methane (CH4), ethane (C2H6), and propane (C3H8) were unambiguously determined using gas chromatograph techniques. The formation of these hydrocarbons is accompanied by the formation of graphite and oxidized iron in the form of magnetite (Fe3O4). We observed the identical mineral assemblage (iron-bearing dolomite, magnetite, and graphite) associated with the formation of the hydrocarbons in both naturally carbonated eclogite and the experimental run products, pointing toward the same formation mechanism. The reduction of the carbonates under low oxygen fugacity is, thus, an important mechanism in forming abiotic hydrocarbons and graphite/diamond in the subduction zone settings.

Linking serpentinization, hyperalkaline mineral waters and abiotic methane production in continental peridotites: an integrated hydrogeological-bio-geochemical model from the Cabeço de Vide CH4-rich aquifer (Portugal)

Continental active serpentinization of ultramafic rocks is today recognized as a key process triggering a sequence of phenomena involving the passage from inorganic, to organic and metabolic reactions. These may have a role in the origin of life, and may explain the occurrence of abiotic hydrocarbons on Earth and other planets. Production of hyperalkaline waters and abiotic methane (CH4) are two critical steps in this sequence. They were described independently by specific hydrogeological and geochemical models. Here, we update and combine these models into a unified scheme using and integrating geological, hydrogeological, hydrogeochemical, gas-geochemical and microbial analyses acquired from 2002 to 2014 in the Cabeço de Vide (CdV) study site, Portugal. The hyperalkaline (pH > 10.5), Na-Cl/Ca-OH mineral water of CdV evolve from groundwater-peridotite interaction (serpentinization) generating hydrogen (H2), which, according to multiple theoretical, laboratory and field evidence, likely reacted with CO2 within metal- (catalyst) rich rocks, abiotically producing CH4 (up to 1.2 mg/L; -24.4°/oo < δ13C-CH4 < -14.0°/oo and -285°/oo < δ2H-CH4 < -218°/oo). The hyperalkaline water hosts hydrogen oxidizing bacteria “Serpentinomonas”, which may explain the paucity of H2 observed in the dissolved gas. The CdV gas-rich mineral waters ascend along a fault at the boundary of the peridotite intrusion. Temporal changes of pH and CH4 concentration result from episodic mixing with shallower Mg-HCO3-type waters. Soil-gas analyses show that methane migrates to the surface along the fault, also independently from the water emergences, consistently with non-aqueous abiotic CH4 production. Our integrated model is generally compatible with observations from other gas-bearing continental serpentinization sites.

Clay minerals trap hydrogen in the Earth's crust: Evidence from the Cigar Lake uranium deposit, Athabasca

Hydrogen (H2)-rich fluids are observed in a wide variety of geologic settings including gas seeps in serpentinized ultramafic rocks, sub-seafloor hydrothermal vents, fracture networks in crystalline rocks from continental and oceanic crust, and volcanic gases. Natural hydrogen sources can sustain deep microbial ecosystems, induce abiotic hydrocarbons synthesis and trigger the formation of prebiotic organic compounds. However, due to its extreme mobility and small size, hydrogen is not easily trapped in the crust. If not rapidly consumed by redox reactions mediated by bacteria or suitable mineral catalysts it diffuses through the rocks and migrates toward the surface. Therefore, H2 is not supposed to accumulate in the crust. We challenge this view by demonstrating that significant amount of H2 may be adsorbed by clay minerals and remain trapped beneath the surface. Here, we report for the first time H2 content in clay-rich rocks, mainly composed of illite, chlorite, and kaolinite from the Cigar Lake uranium ore deposit (northern Saskatchewan, Canada). Thermal desorption measurements reveal that H2 is enriched up to 500 ppm (i.e. 0.25 mol kg−1 of rock) in these water-saturated rocks having a very low total organic content (<0.5 wt%). Such hydrogen uptake is comparable and even exceeds adsorbed methane capacities reported elsewhere for pure clay minerals or shales. Sudoite (Al–Mg di-trioctahedral chlorite) is probably the main mineral responsible for H2 adsorption in the present case. The presence of multiple binding sites in interlinked nanopores between crystal layers of illite-chlorite particles offers the ideal conditions for hydrogen sorption. We demonstrate that 4 to 17% of H2 produced by water radiolysis over the 1.4-Ga-lifetime of the Cigar Lake uranium ore deposit has been trapped in the surrounding clay alteration haloes. As a result, sorption processes on layered silicates must not be overlooked as they may exert an important control on the fate and mobility of H2 in the crust. Furthermore, the high capacity of clay minerals to sorb molecular hydrogen may also open up new opportunities for exploration of unexpected energy resources and for H2 storage based on geo-inspired materials.

Methane clumped isotopes in the Songliao Basin (China): New insights into abiotic vs. biotic hydrocarbon formation

Abiotic hydrocarbon gas, typically generated in serpentinized ultramafic rocks and crystalline shields, has important implications for the deep biosphere, petroleum systems, the carbon cycle and astrobiology. Distinguishing abiotic gas (produced by chemical reactions like Sabatier synthesis) from biotic gas (produced from degradation of organic matter or microbial activity) is sometimes challenging because their isotopic and molecular composition may overlap. Abiotic gas has been recognized in numerous locations on the Earth, although there are no confirmed instances where it is the dominant source of commercially valuable quantities in reservoir rocks. The deep hydrocarbon reservoirs of the Xujiaweizi Depression in the Songliao Basin (China) have been considered to host significant amounts of abiotic methane. Here we report methane clumped-isotope values (Δ18) and the isotopic composition of C1–C3 alkanes, CO2 and helium of five gas samples collected from those Xujiaweizi deep reservoirs. Some geochemical features of these samples resemble previously suggested identifiers of abiotic gas (13C-enriched CH4; decrease in 13C/12C ratio with increasing carbon number for the C1–C4 alkanes; abundant, apparently non-biogenic CO2; and mantle-derived helium). However, combining these constraints with new measurements of the clumped-isotope composition of methane and careful consideration of the geological context, suggests that the Xujiaweizi depression gas is dominantly, if not exclusively, thermogenic and derived from over-mature source rocks, i.e., from catagenesis of buried organic matter at high temperatures. Methane formation temperatures suggested by clumped-isotopes (167–213 °C) are lower than magmatic gas generation processes and consistent with the maturity of local source rocks. Also, there are no geological conditions (e.g., serpentinized ultramafic rocks) that may lead to high production of H2 and thus abiotic production of CH4 via CO2 reduction. We propose that the Songliao gas is representative of an atypical type of thermogenic gas that can be mistaken for abiotic gas. Such gases may be encountered more frequently in future exploration of deep or over-mature petroleum systems.