Low‐temperature dunite hydration: evaluating CH4 and H2 production from H2O and CO2

Abiotic methane (CH4) and hydrogen (H2) produced after hydration of mafic/ultramafic rocks represent energy sources for microbes that may thrive in the deep subsurface regions of Earth and possibly on other planets. While H2 is a direct product of serpentinization, CH4 can form via Fischer–Tropsch Type (FTT) reactions (carbon reduction) that, due to potential H2 migration, can be spatially and temporally detached from serpentinization. We tested an alternative process hypothesized by some scholars, in which CO2 can be reduced through dunite hydration without initially added H2, implying that CH4 can form in the same serpentinized fluid–rock system. The experiment used natural dunite sand (Forsterite 92), CO2 with δ13C ~ −25‰ (VPDB), and a 1 mm dissolved SiO2 solution mixed in 30 glass bottles (118 mL) stored for up to 8 months at low temperature (50°C) to simulate land-based serpentinization systems. In addition, 30 control bottles without olivine were used as blanks. Trivial amounts of CH4 (orders of 0.2–0.9 ppmv) were detected in both samples and blanks, likely representing analytical noise; essentially, no significant amount of CH4 formed under the experimental conditions used in this work. Low amounts of H2 (~2.55 ± 1.39 ppmv) were generated, with production yields that were one order of magnitude lower than in previously published experiments. Moderate concentrations of SiO2 appeared to hinder low-temperature H2 production. Our experiment confirms that the low-temperature reduction of CO2 into CH4 through direct olivine hydration, without initial H2, is sluggish and not straightforward, which is consistent with previous studies. The presence of substantial amounts of H2, as well as suitable metal catalysts, appears to be essential in the low-temperature production of abiotic CH4, as observed in published FTT experiments

Acoustic Scattering from Mud Volcanoes and Carbonate Mounts

Submarine mud volcanoes occur in many parts of the world’s oceans and form an aperture for gas and fluidized mud emission from within the earth’s crust. Their characteristics are of considerable interest to the geology, geophysics, geochemistry, and underwater acoustics communities. For the latter, mud volcanoes are of interest in part because they pose a potential source of clutter for active sonar. Close-range (single-interaction) scattering measurements from a mud volcano in the Straits of Sicily show scattering10–15dB above the background. Three hypotheses were examined concerning the scattering mechanism: (1) gas entrained in sediment at/near mud volcano, (2) gas bubbles and/or particulates (emitted) in the water column, (3) the carbonate bio-construction covering the mud volcano edifice. The experimental evidence, including visual, acoustic, and nonacoustic sensors, rules out the second hypothesis (at least during the observation time) and suggests that, for this particular mud volcano the dominant mechanism is associated with carbonate chimneys on the mud volcano. In terms of scattering levels, target strengths of 4–14dB were observed from 800to3600Hz for a monostatic geometry with grazing angles of 3–5°. Similar target strengths were measured for vertically bistatic paths with incident and scattered grazing angles of 3–5° and 33–50°, respectively

Methane Seepage on Mars: Where to Look and Why

Methane on Mars is a topic of special interest because of its potential association with microbial life. The variable detections of methane by the Curiosity rover, orbiters, and terrestrial telescopes, coupled with methane's short lifetime in the martian atmosphere, may imply an active gas source in the planet's subsurface, with migration and surface emission processes similar to those known on Earth as “gas seepage.” Here, we review the variety of subsurface processes that could result in methane seepage on Mars. Such methane could originate from abiotic chemical reactions, thermogenic alteration of abiotic or biotic organic matter, and ancient or extant microbial metabolism. These processes can occur over a wide range of temperatures, in both sedimentary and igneous rocks, and together they enhance the possibility that significant amounts of methane could have formed on early Mars. Methane seepage to the surface would occur preferentially along faults and fractures, through focused macro-seeps and/or diffuse microseepage exhalations. Our work highlights the types of features on Mars that could be associated with methane release, including mud-volcano-like mounds in Acidalia or Utopia; proposed ancient springs in Gusev Crater, Arabia Terra, and Valles Marineris; and rims of large impact craters. These could have been locations of past macro-seeps and may still emit methane today. Microseepage could occur through faults along the dichotomy or fractures such as those at Nili Fossae, Cerberus Fossae, the Argyre impact, and those produced in serpentinized rocks. Martian microseepage would be extremely difficult to detect remotely yet could constitute a significant gas source. We emphasize that the most definitive detection of methane seepage from different release candidates would be best provided by measurements performed in the ground or at the ground-atmosphere interface by landers or rovers and that the technology for such detection is currently available

Mud volcanoes and microseepage: the forgotten geophysical components of atmospheric methane budget

Mud volcanoes and microseepage are two important natural sources of atmospheric methane, controlled by neotectonics and seismicity. Petroleum and gas reservoirs are the deep sources, and faults and fractured rocks serve as main pathways of degassing to the atmosphere. Violent gas emissions or eruptions are generally related to seismic activity. The global emission of methane from onshore mud volcanoes has recently been improved thanks to new experimental data sets acquired in Europe and Azerbaijan. The global estimate of microseepage can be now improved on the basis of new flux data and a more precise assessment of the global area in which microseepage may occur. Despite the uncertainty of the various source strengths, the global geological methane flux is clearly comparable to or higher than other sources or sinks considered in the tables of the Intergovernmental Panel on Climate Change

Methane concentration and isotopic composition (d13C-CH4) in the Nerja Cave system (South Spain)

Air in underground caves often has methane (CH4) concentrations below the atmospheric level, due to methanotrophic or other unkown CH4 consuming processes. Caves are thus considered a potential sink for atmospheric methane. If globally important, this underground CH4 oxidation should be taken into account in the atmospheric methane budget, in addition to the known soil methanotrophy and tropospheric/stratospheric sinks. A large set of data is however necessary to understand how and how much methane from external atmospheric air is consumed in the caves. While methane concentration data are available for several caves worldwide, its isotopic composition and variations in space and time are poorly documented. We measured methane concentration and stable C isotope composition (d13C) in the Nerja cave (Southern Spain) air during two surveys in March and April 2015. CH4 concentration decreases progressively from the more external cave rooms, with atmospheric levels of 1.9 ppmv, to the more internal and isolated rooms down to 0.5 ppmv. d13C increases correspondingly from -47 h to -41 h (VPDB). CH4 is systematically 13C-enriched (d13C > -45 permil) in areas of the cave where the concentration is below 1.4 ppmv. This combination of concentration decrease and 13C-enrichment towards the more internal and isolated zones of the cave confirms the importance of CH4 oxidation, likely driven by methanotrophic bacteria. Further data, including stable H isotope composition of subatmospheric CH4 concentrations, CO2 and microbial analyses, shall be acquired over time to assess the actual role of methanotrophic bacteria and seasonal controls in the CH4 consumption process.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Vadose zone air as a biogenic source of methane in Nerja Cave system (South of Spain)

Subterranean air in karst cavities has often low methane contents in comparison to atmosphere and so karst systems have been considered a sink of atmospheric methane. Methane-oxidizing bacteria have been hypothesized as responsible for CH4 depletion in many caves around the world, although ionization radiation was also proposed as possible mechanism for this process. We measured CO2 and CH4 concentration and their C isotopic composition (d13C-CO2 and d13C-CH4) over 2 years within the Nerja cave system (South Spain) and in 9 boreholes drilled into the vadose zone (Triassic carbonate aquifer) surrounding the cave. According to d13C-CO2 and d13C-CH4 vadose zone of this karst system is a source of biogenic methane, produced both by acetate fermentation and CO2 reduction. Biogenic and atmospheric methane flows (along fractures from the vadose zone, and through ventilation, respectively) into the cave, where it is oxidized by methanotrophic bacteria that we detected on soil samples into the cave.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

An overview of sedimentary volcanism on Mars

Extensive fields of sub-kilometre-to kilometre-scale mounds, cones, domes, shields, and flow-like edifices cover large parts of the martian lowlands. These features have been compared to structures on Earth produced by sedimentary volcanism &ndash; a process that involves subsurface sediment/fluid mobilization and commonly releases methane to the atmosphere. It was proposed that such process might help to explain the presence of methane in martian atmosphere and also may have additionally produced habitable, subsurface settings of potential astrobiological relevance. However, it remains unclear whether sedimentary volcanism on Earth and Mars share genetic similarities; hence whether methane, or other gases were released on Mars during this process. The aim of this review is to summarize the current knowledge about mud-volcano-like structures on Mars, address the critical aspects of this process, identify key open questions, and point to areas where further research is needed to understand this phenomenon and its importance for the red planet&rsquo;s geological evolution. We show here that after several decades of exploration, the amount of evidence supporting a martian sedimentary volcanism scenario has increased significantly, but as critical ground truth is still lacking, alternative explanations cannot always be ruled out. We also highlight that the lower gravity and temperatures on Mars compared to Earth control the dynamics of clastic eruptions as well as surface emplacement and resulting morphologies of erupted material. This implies that shapes and triggering mechanisms of mud-volcano-like structures may be different from those observed on Earth. Therefore comparative studies should be done with caution. To provide a better understanding of the significance of these abundant features on Mars, we argue for follow-up studies targeting putative sedimentary volcanic features identified on the planet&rsquo;s surface and, if possible, for in situ investigations by landed missions such as that currently in progress by the Zhurong rover.</p

Mud volcanoes and methane seeps in Romania: main features and gas flux

Romania is one of the European countries with the most vigorous natural seepage of methane, uprising from pressurised natural gas and petroleum reservoirs through deep faults. The largest seepage zone is represented by large mud volcanoes, with CH4 >80% v/v, occurring on the Berca-Arbanasi hydrocarbon-bearing faulted anticline, in the Carpathian Foredeep. Smaller mud volcanoes have been identified in other areas of the Carpathian Foredeep, in the Transylvanian Depression and on the Moldavian Platform. New surveys carried out in Transylvania allowed us to discover the richest N2 mud volcano zone in the world (N2>90% v/v), with a remarkably high He content and a helium isotopic signature which highlights a contribution of mantle-derived source. The large mud volcanoes are generally quiescent, with rare explosive episodes and provide a methane flux in the order of 102-103 t km?2 y?1. Independently from mud volcanism, a remarkable dry macroseepage, however, has been found, with a degassing rate up to three orders of magnitude higher than that of mud volcanoes (i.e. 103-105 t km?2 y?1). The total gas flux from all investigated macroseepage zones in Romania is estimated in the range of 1500-2500 t y?1. The emission from microseepage, pervasively occurring throughout the hydrocarbon-prone basins, has yet to be assessed and added to the total gas output to the atmosphere

The importance of multi-parametric analysis in long-term submarine gas emission monitoring : the SN4 observatory at the north anatolian fault (marmara sea,turkey)

Peer Reviewe

The Benthic Boundary Layer: geochemical and oceanographic data from the GEOSTAR-2 observatory

Geochemical and oceanographic data, acquired throughout 6 months by the GEOSTAR-2 benthic observatory in southern Tyrrhenian Sea, evidenced ocean-lithosphere interactions in the 1900-m deep Benthic Boundary Layer (BBL), distinguishing two water masses with different origin and, possibly, benthic residence time. Gas concentration, helium isotopic ratios, radioactivity, temperature, salinity and vertical component of the current converged towards the indication of a BBL characterised by a colder and fresher western water (WW), which is episodically displaced by the cascading of the warmer and saltier Eastern Overflow Water (EOW). The benthic WW has higher concentration of geochemical tracers diffusing from the seafloor sediments. The data set shows the potential of long-term, continuous and multiparametric monitoring in providing unique information which cannot be acquired by traditional, short-term or single-sensor investigations