Widespread abiotic methane in chromitites

Recurring discoveries of abiotic methane in gas seeps and springs in ophiolites and peridotite massifs worldwide raised the question of where, in which rocks, methane was generated. Answers will impact the theories on life origin related to serpentinization of ultramafic rocks, and the origin of methane on rocky planets. Here we document, through molecular and isotopic analyses of gas liberated by rock crushing, that among the several mafic and ultramafic rocks composing classic ophiolites in Greece, i.e., serpentinite, peridotite, chromitite, gabbro, rodingite and basalt, only chromitites, characterized by high concentrations of chromium and ruthenium, host considerable amounts of 13C-enriched methane, hydrogen and heavier hydrocarbons with inverse isotopic trend, which is typical of abiotic gas origin. Raman analyses are consistent with methane being occluded in widespread microfractures and porous serpentine- or chlorite-filled veins. Chromium and ruthenium may be key metal catalysts for methane production via Sabatier reaction. Chromitites may represent source rocks of abiotic methane on Earth and, potentially, on Mars

Identifying thermogenic and microbial methane in deep water Gulf of Mexico Reservoirs

The Gulf of Mexico (GOM) produces 5% of total U.S. dry gas production (USEIA, 2016). Despite this, the proportion of microbial and thermogenic methane in discovered and producing fields from this area is still not well understood. Understanding the relative contributions of these sources in subsurface environments is important to understanding how and where economically substantial amounts of methane form. In addition, this information will help identify sources of environmental emissions of hydrocarbons to the atmosphere. We apply stable isotopes including methane clumped-isotope measurements to solution and associated gases from several producing fields in the U.S. Gulf of Mexico to estimate the proportions, properties and origins of microbial and thermogenic endmembers. Clumped isotopes of methane are unique indicators of whether methane is at thermodynamic isotopic equilibrium or affected by kinetic processes. The clumped methane thermometer can provide insights into formation temperatures and/or into kinetic processes such as microbial methanogenesis, early catagenetic processes, mixing, combinatorial processes, and diffusion. In this data set, we find that some fluids have clumped isotope methane apparent temperatures consistent with the methane component being produced solely by the thermogenic breakdown of larger organic molecules at substantially greater temperatures than those reached in shallow reservoirs. A portion of these reservoirs with hot clumped isotope methane temperatures are consistent with exhibiting a kinetic isotope effect. Other reservoirs have clumped isotope methane apparent temperatures, and other isotopic and molecular proportions, consistent with mixtures of microbial and thermogenic methane. We show that in certain cases the evidence is most consistent with formation of the microbial methane in the current reservoir. However, in other cases the methane is produced at significantly shallower depths and is then transported to greater depths as a result of post generation burial of methane bearing sedimentary sequences to the current reservoir conditions. For the first time, we show that methane of an unambiguously purely microbial origin (i.e. those that do not contain obvious contributions of thermogenic methane) is dominantly generated at temperatures less than 60 °C, despite burial to greater depths. This finding suggests that, while microorganisms are able to generate methane at temperatures up to 105 °C under laboratory conditions (Brock, 1985), in the Gulf of Mexico, microbial methane is dominantly produced in the 20–60 °C window

The Effects of Dissolved Methane upon Liquid Argon Scintillation Light

In this paper we report on measurements of the effects of dissolved methane upon argon scintillation light. We monitor the light yield from an alpha source held 20 cm from a cryogenic photomultiplier tube (PMT) assembly as methane is injected into a high-purity liquid argon volume. We observe significant suppression of the scintillation light yield by dissolved methane at the 10 part per billion (ppb) level. By examining the late scintillation light time constant, we determine that this loss is caused by an absorption process and also see some evidence of methane-induced scintillation quenching at higher concentrations (50-100 ppb). Using a second PMT assembly we look for visible re-emission features from the dissolved methane which have been reported in gas-phase argon methane mixtures, and we find no evidence of visible re-emission from liquid-phase argon methane mixtures at concentrations between 10 ppb and 0.1%.Comment: 18 pages, 11 figures Updated to match published versio

TAP investigations of the CO2 reforming of CH4 over Pt/ZrO2

The adsorption and reaction characteristics of methane, carbon dioxide, carbon monoxide, and hydrogen have been investigated over a ZrO2support and a Pt/ZrO2catalyst by using a temporal analysis of products reactor system. It was observed that on Pt/ZrO2both methane and carbon dioxide dissociate independently of one another. The dissociation of carbon dioxide acts as an oxygen supplier, while the decomposition products of methane scavenge the oxygen from the catalyst. When an abundance of oxygen is present, pulsing of methane leads to the production of carbon dioxide. It is concluded that both the selectivity with which methane produces carbon monoxide or carbon dioxide and the carbon dioxide conversion is determined by the same reaction: COads+Oads CO2,ads

Methane emissions from the 2015 Aliso Canyon blowout in Los Angeles, CA.

Single-point failures of natural gas infrastructure can hamper methane emission control strategies designed to mitigate climate change. The 23 October 2015 blowout of a well connected to the Aliso Canyon underground storage facility in California resulted in a massive release of natural gas. Analysis of methane and ethane data from dozens of plume transects, collected during 13 research-aircraft flights between 7 November 2015 and 13 February 2016, shows atmospheric leak rates of up to 60 metric tons of methane and 4.5 metric tons of ethane per hour. At its peak, this blowout effectively doubled the methane emission rate of the entire Los Angeles basin and, in total, released 97,100 metric tons of methane to the atmosphere

THERMODYNAMIC ANALYSIS OF SYNTHESIS GAS AND HIGHER HYDROCARBONS PRODUCTION FROM METHANE

This chapter focused on thermodynamic chemical equilibrium analysis using method of direct minimization of Gibbs free energy for all possible methane reactions with oxygen (partial oxidation of methane), carbon dioxide (CO2 reforming of methane), steam (steam reforming of methane), and autothermal reforming. Effects of feed ratios (methane to oxygen, carbon dioxide, and/or steam feed ratio), reaction temperature, and system pressure on equilibrium composition, conversion, and yield were studied. In addition, operating regions of carbon and no carbon formation were also considered at various reaction temperatures and feed ratios in the equilibrium system. It was found that the reaction temperature above 1100 K and CH4/CO2 ratio unity were favorable for synthesis gas production for methane – carbon dioxide reaction. The Carbon Dioxide Oxidative Coupling of Methane reaction to produce ethane and ethylene is less favorable thermodynamically. In addition, steam reforming of methane is the most suitable for hydrogen production from methane with low coke formation from thermodynamic point of view

Hypotheses for near-surface exchange of methane on Mars

The Curiosity rover recently detected a background of 0.7 ppb and spikes of 7 ppb of methane on Mars. This in situ measurement reorients our understanding of the Martian environment and its potential for life, as the current theories do not entail any geological source or sink of methane that varies sub-annually. In particular, the 10-fold elevation during the southern winter indicates episodic sources of methane that are yet to be discovered. Here we suggest a near-surface reservoir could explain this variability. Using the temperature and humidity measurements from the rover, we find that perchlorate salts in the regolith deliquesce to form liquid solutions, and deliquescence progresses to deeper subsurface in the season of the methane spikes. We therefore formulate the following three testable hypotheses. The first scenario is that the regolith in Gale Crater adsorbs methane when dry and releases this methane to the atmosphere upon deliquescence. The adsorption energy needs to be 36 kJ/mol to explain the magnitude of the methane spikes, higher than existing laboratory measurements. The second scenario is that microorganisms convert organic matter in the soil to methane when they are in liquid solutions. This scenario does not require regolith adsorption, but entails extant life on Mars. The third scenario is that deep subsurface aquifers produce the bursts of methane. Continued in situ measurements of methane and water, as well as laboratory studies of adsorption and deliquescence, will test these hypotheses and inform the existence of the near-surface reservoir and its exchange with the atmosphere.Comment: Accepted for publication on Astrobiolog

Evening Methane Emission Pulses from a Boreal Wetland Correspond to Convective Mixing in Hollows

Spatial and temporal heterogeneity of methane flux from boreal wetlands makes prediction and up-scaling challenging, both within and among wetland systems. Drivers of methane production and emissions are also highly variable, making empirical model development difficult and leading to uncertainty in methane emissions estimates from wetlands. Previous studies have examined this problem using point-scale (static chamber method) and ecosystem-scale (flux tower methods) measurements, but few studies have investigated whether different processes are observed at these scales. We analyzed methane emissions from a boreal fen, measured by both techniques, using data from the Boreal Ecosystem-Atmosphere Study. We sought to identify driving processes associated with methane emissions at two scales and explain diurnal patterns in emissions measured by the tower. The mean methane emission rates from flux chambers were greater than the daytime, daily mean rates measured by the tower, but the nighttime, daily mean emissions from the tower were often an order of magnitude greater than emissions recorded during the daytime. Thus, daytime measurements from either the tower or chambers would lead to a biased estimate of total methane emissions from the wetland. We found that the timing of nighttime emission events was coincident with the cooling and convective mixing within hollows, which occurred regularly during the growing season. We propose that diurnal thermal stratification in shallow pools traps methane by limiting turbulent transport. This methane stored during daytime heating is later released during evening cooling due to convective turbulent mixing

A primordial origin for the atmospheric methane of Saturn's moon Titan

The origin of Titan's atmospheric methane is a key issue for understanding the origin of the Saturnian satellite system. It has been proposed that serpentinization reactions in Titan's interior could lead to the formation of the observed methane. Meanwhile, alternative scenarios suggest that methane was incorporated in Titan's planetesimals before its formation. Here, we point out that serpentinization reactions in Titan's interior are not able to reproduce the deuterium over hydrogen (D/H) ratio observed at present in methane in its atmosphere, and would require a maximum D/H ratio in Titan's water ice 30% lower than the value likely acquired by the satellite during its formation, based on Cassini observations at Enceladus. Alternatively, production of methane in Titan's interior via radiolytic reactions with water can be envisaged but the associated production rates remain uncertain. On the other hand, a mechanism that easily explains the presence of large amounts of methane trapped in Titan in a way consistent with its measured atmospheric D/H ratio is its direct capture in the satellite's planetesimals at the time of their formation in the solar nebula. In this case, the mass of methane trapped in Titan's interior can be up to 1,300 times the current mass of atmospheric methane.Comment: Accepted for publication in Icaru