Enhanced Gas Recovery and Stimulation by Thermal Methods in Depleted Hydraulically Fractured Gas Wells in Shales
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03 NATURAL GAS↗
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A phase-field fracture formulation for generalized standard materials: The interplay between thermomechanics and damage
Accurately modeling fracture of ductile materials poses open challenges in the field of computational mechanics due to the multiphysics nature of their failure processes. Integrating the interplay between thermodynamics and damage into ductile fracture models is vital for predicting critical failure modes. Here, in this paper, we develop a versatile phase-field (PF) framework for modeling ductile fracture, taking into account finite-strain elasto-plasticity. The framework stems from a variational formulation of constitutive relations for generalized standard materials (GSMs), whose response is described by a Helmholtz free energy and a dissipation pseudo-potential. Its variational structure is based on a minimum principle for a functional that expresses the sum of power densities for reversible and irreversible processes. By minimizing this functional with a constraint on a von Mises yield function, we derive the evolution equation for the equivalent plastic strain and an associative flow rule. This constrained optimization problem is analytically solved for a wide class of thermo-viscoplasticity models. The key innovations of the current work include (i) a cubic plastic degradation function that accounts for a non-vanishing damage-dependent yield stress, (ii) closed-form expressions of the Helmholtz free energy and dissipation pseudo-potential for three thermo-viscoplasticity models, (iii) an extended Johnson–Cook plasticity model with a nonlinear hardening law, and (iv) a plastic work heat source that depends on the plastic degradation function and a variable Taylor–Quinney (TQ) coefficient. The capabilities of the proposed framework are tested with the aid of four ductile fracture problems, including the Sandia Fracture Challenge. In each of these problems, we examine the evolution of relevant field variables such as the PF order parameter, the equivalent plastic strain, the temperature, and the internal power dissipation density, in addition to the overall structural response quantified by the force–displacement curve. These numerical studies demonstrate that the proposed framework effectively represents ductile fracture, yielding computational results that exhibit good agreement with experimental data.
36 MATERIALS SCIENCE↗
Orthotropic fracture using a singular isoparametric element
The six noded quarter point natural isoparametric triangular element is employed to obtain displacement and stress distributions in the vicinity of the crack tip in a center cracked tensile coupon of unidirectional graphite epoxy. The material is considered to be homogeneous, elastic and orthotropic. The finite element results are compared to the analytical solution of anisotropic elasticity. Convergence as a function of mesh parameters is studied for isotropic and orthotropic materials. It is shown that displacements converge faster than stresses and that meshes which are convergent for isotropic and orthotropic materials. It is shown that displacements converge faster than stresses and that meshes which are convergent for isotropic materials are not completely convergent for the highly orthotropic graphite epoxy.
Gregory, M. A.↗
Geochemical Modeling of Celestite (SrSO 4 ) Precipitation and Reactive Transport in Shales
Celestite (SrSO 4 ) precipitation is a prevalent example of secondary sulfate mineral scaling issues in hydraulic fracturing systems, particularly in basins where large concentrations of naturally occurring strontium are present. Herein, we present a validated and flexible geochemical model capable of predicting celestite formation under such unconventional environments. Simulations were built using CrunchFlow and guided by experimental data derived from batch reactors. These data allowed the constraint of key kinetic and thermodynamic parameters for celestite precipitation under relevant synthetic hydraulic fracturing fluid conditions. Effects of ionic strength, saturation index, and the presence of additives were considered in the combined experimental and modeling construction. This geochemical model was then expanded into a more complex system where interactions between hydraulic fracturing fluids and shale rocks were allowed to occur subject to diffusive transport. We find that the carbonate content of a given shale and the presence of persulfate breaker in the system strongly impact the location and extent of celestite formation. The results of this study provide a novel multicomponent reactive transport model that may be used to guide future experimental design in the pursuit of celestite and other sulfate mineral scale mitigation under extreme conditions typical of hydraulic fracturing in shale formations.
54 ENVIRONMENTAL SCIENCES↗
Quantum algorithms for geologic fracture networks
Abstract Solving large systems of equations is a challenge for modeling natural phenomena, such as simulating subsurface flow. To avoid systems that are intractable on current computers, it is often necessary to neglect information at small scales, an approach known as coarse-graining. For many practical applications, such as flow in porous, homogenous materials, coarse-graining offers a sufficiently-accurate approximation of the solution. Unfortunately, fractured systems cannot be accurately coarse-grained, as critical network topology exists at the smallest scales, including topology that can push the network across a percolation threshold. Therefore, new techniques are necessary to accurately model important fracture systems. Quantum algorithms for solving linear systems offer a theoretically-exponential improvement over their classical counterparts, and in this work we introduce two quantum algorithms for fractured flow. The first algorithm, designed for future quantum computers which operate without error, has enormous potential, but we demonstrate that current hardware is too noisy for adequate performance. The second algorithm, designed to be noise resilient, already performs well for problems of small to medium size (order 10–1000 nodes), which we demonstrate experimentally and explain theoretically. We expect further improvements by leveraging quantum error mitigation and preconditioning.
58 GEOSCIENCES↗
Preliminary results of geologic and remote sensing studies of Rima Mozart
In order to better understand the processes responsible for the formation of lunar sinuous rilles, a study of Rima Mozart was conducted using a variety of geologic, photographic, and remote sensing data. The apparent source of this rille is located in a highlands unit of known composition and it is hypothesized that thermal and mechanical erosion played an important role in the formation of Rima Mozart. Excellent photographic, topographic, multispectral, and radar data exist for this rille. The preliminary results of an analysis of this data are presented. Photographic data indicates the presence of two volcanic source vents for Rima Mozart: Kathleen and Ann. It is suggested that Rima Mozart, like many other lunar sinuous rilles, was most likely formed by a combination of events. Rima Mozart does follow a pre-existing, dominant NW/SE structural trend suggesting the influence of structural features on the rille, however, the tectonic influence is not the sole source for the formation of the rille, as suggested by the presence of the two source vents and the spatter around Ann. It is suggested that the rille formation began with an explosive eruption at Kathleen which later calmed down to a pulsating, high volume, low-viscosity lava flow. The rapid effusion rate of the magma as well as its high temperature and turbid nature helped carve the sinuous rille into the fractured and structurally weak Apennine Bench Formation underneath. Similar eruptions and subsequent flows were also created at Ann and joined to the main channel by a NE-trending secondary rille.
Coombs, C. R.↗
Giant radiating dyke swarms on Earth and Venus
On Earth, giant radiating dyke swarms are usually preserved as fan-shaped fragments which have been dismembered from their original configuration by subsequent plate tectonic rifting events. Analysis of the largest fragments and consideration of their original configuration has led to the idea that many swarms are plume related, and that dyke swarms radiate away from plume centers. Magellan radar data reveal abundant intact giant radiating swarms on Venus which are similar in scale and pattern to those on Earth. The absence of intense weathering and plate tectonic processes on Venus accounts for the preservation of the primary radiating patterns. It is characteristic of both Earth and Venus that giant radiating dikes are emplaced laterally for distances of at least 2000 km away from plume centers. At distances beyond the influence of the plume on both Earth and Venus, the radiating dyke pattern is often swept into a linear pattern aligned with the regional stress field. There is tremendous potential synergism between the characterization and analysis of terrestrial dyke swarms (where significant erosion has revealed their structure and emplacement directions at depth) and the giant swarms of Venus (where the complete circumferential structure is preserved, and the surface fracture systems above near surface dikes and the nature of the central source regions are revealed). In this study, we report on the characteristics of radial dyke swarms on Earth and Venus and draw some preliminary comparisons from the two perspectives. In summary, on both planets there is evidence for plume-related magmatic centers associated with vertical and lateral injection of magma over considerable distances (up to at least 2000 km). The abundance of very broadly radiating swarms on Venus supports the notion that the swarms on Earth were radiating over broad sectors at the time of intrusion but were dissected by later events. The Venus data show that a swarm can change from radiating (proximal) to regional (distal) subparallel orientations. An implication for Earth is that many regional linear swarms which do not have a radiating pattern may be due to fragmentation of the swarm during later plate tectonic rifting. Completion of the global classification and census of Venus features, comparison to the terrestrial synthesis, and documentation of the mode of emplacement of dikes in these environments (buffered and unbuffered conditions) should lead to additional general insight into mechanisms of formation and evolution and their relation to plumes.
Ernst, Richard E.↗
The Relationship Between Volatile Element Abundances and Iron Carrying Capacity in Lunar Volcanic and Impact Vapors
The highly volatile elements (e.g. H, C, S, Cl) released during lunar volcanism provide important insights into the bulk volatile composition of the Moon. Once erupted, some fraction of the species containing these elements may have migrated to the poles where they could have become sequestered in shadowed cold traps such as those found near the lunar South pole. The volatiles trapped in the lunar South pole are of great interest to the upcoming Artemis missions, which will be operating nearby and could sample some of those materials. Volcanic vapor deposits in the polar regions might also be supplemented by volatiles from other sources both exogenous (i.e. comets) and endogenous (i.e. remobilization of lunar volatiles by impact). Characterizing these endogenous sources is challenging because the highly volatile elements often leave little trace behind in the rocks themselves, which are inherently refractory by nature. Minerals are found on vug, vesicle, or fracture surfaces that have characteristics consistent with phases formed via direct deposition of a vapor, as opposed to crystallization from a liquid or via solid state decomposition. One common vapor-deposited species is metallic Fe, typically observed as subhedral to euhedral crystals found on vug or vesicle walls in mare basalts and on select breccia clast surfaces in regolith soil samples returned from the Moon. A particularly striking example is seen below in Fig. 1, where numerous Fe crystals are deposited onto the wall of a vug in Apollo 17 basalt sample 71036. Euhedral Fe crystals are not very common in Apollo breccia samples, though this may be from the limited number of systematic searches that have been performed. However, when Fe crystals are found, they can occur in extremely high abundance(e.g., sample 15402 which was specifically selected because of its numerous Fe crystals, was found to have a clast with 477 euhedral Fe crystals in a 570 x 570 μm area). What struck us as interesting about this was not only that it takes a large amount of Fe to make these crystal-rich deposits, but also that these crystal-rich deposits are not ubiquitous, and therefore they must be controlled by some aspect of their depositional conditions that varies. Since those conditions are inherently difficult to investigate and are critically interesting, we used thermochemical modeling as a tool to investigate the relationship between vapor-deposited Fe and various intensive and extensive parameters. We assumed that a high abundance of Fe in the vapor is required to form these crystals, thus the mass of Fe in the vapor was used to determine the plausibility of the vapor-deposited, euhedral Fe crystals observed in Apollo samples.
thermodynamics↗
Composite structure global fracture toughness via computational simulation
A computational method for the simulation of damage and fracture propagation in laminated composites is presented. A quantitative evaluation of the global fracture toughness of composites is shown as a tool for monitoring the fracture stability of composites under sustained loading. Changes in overall structural properties such as natural frequencies and the fundamental buckling load are also computed with increasing load-induced damage. Structural degradation, delamination, fracture, and damage propagation are included in the simulation. An angle-plied composite plate structure subjected to inplane tensile loading is used as an example to demonstrate some of the feature of the computational method.
Minnetyan, L.↗
Leakoff assessment of nanoparticle-stabilized CO 2 foams for fracturing applications
The leakoff of multiphase systems through porous media is a complicated process. In this study, we have designed an experimental setup that is used to assess the leakoff of the liquid and gas phase under pressurized conditions. The novelty of this study is that while most previous studies utilized fluid/gas in the aqueous phase, nanoparticles are introduced in this study, which formed a solid/fluid/gas multiphase system to boost foam performance and reduce leakoff. In the parametric experimental analysis, the effects of foam quality, core permeability, surfactant concentration, and polymer concentration on the dynamic and static leakoff rates of liquid and gas are evaluated. It was found that core permeability affects the leakoff of foam the most with a leakoff coefficient of up to 1.37015 $ft/\sqrt{min}$ for gas and up to 0.1056 $ft/\sqrt{min}$ for liquid under the experiment settings herein. The leakoff rate of gas is generally several magnitudes higher than that of the liquid. When CO 2 gas is present in the foam, the leakoff coefficient falls in the range between 0 and 1.37015 $ft/\sqrt{min}$ for gas, and between 0.0005 and 0.1056 $ft/\sqrt{min}$ for liquid. Finally, the methodology and results of this study shed light on the mechanistic understanding of the leakoff properties of multiphase systems and could be used to assist the design of foam fracturing for reservoir stimulation.
03 NATURAL GAS↗
Accelerating Hydraulic Fracture Imaging by Deep Transfer Learning
Deep transfer learning has a great success story in computer vision (CV), natural language processing, and many other fields. In this communication, we are going to push forward the deep transfer learning to the hydraulic fracture imaging problem by proposing a two-step approach: 1) train a convolutional neural network (CNN) to reconstruct target geometries by a relatively large amount of approximated field patterns generated from a simplified model and 2) fine-tune the top layers of transferred CNN by a small amount of true field patterns generated through a full model. The advantages include the rapid generation of large amount of data through the simplified model and the high reconstruction accuracy through a careful design of the deep transfer learning. Here, the CNN trained through the deep transfer learning can accurately reconstruct the lateral extent and direction of fractures with unseen conductivity and white Gaussian noise, showing a notable acceleration/accuracy enhancement over the previous CNN trained by mixing a small number of true data into the approximated data as data augmentation.
02 PETROLEUM↗
CO2 injection with fracturing in geomechanically protected caprock: Task 6 of LLNL's Research Activities to Support DOE's Carbon Storage Program (FWP-FEW0191) (Final Technical Report)
Conventional principles of the design and operation of geologic carbon storage (GCS) require injecting CO 2 below the caprock fracturing pressure to ensure the integrity of the storage complex. In non-ideal storage reservoirs with relatively low permeability, modest injection rates can lead to pressure buildup and hydraulic fracturing of the reservoir and caprock. While the GCS community has generally viewed hydraulic fractures as a key risk to storage integrity, the actual behavior of a caprock hydraulic fracture, particularly from a geomechanical perspective, has not been thoroughly studied. The prevailing method of treating a hydraulic fracture as a high-permeability wing of the storage reservoir might have resulted in erroneous understanding of caprock hydraulic fracture behavior. Comprehensive analyses of monitoring data from the In Salah project suggested that one or more hydraulic fractures may have been created in the reservoir and lower caprock system during injection operations, but did not cause detectable leakage of CO 2 out of the storage complex. This observation coincides with a well-known phenomenon in the oil and gas industry: sedimentary rock formations have many inherent features that naturally protect the formations from unbounded vertical growth of hydraulic fractures.
58 GEOSCIENCES↗
Oil and Natural Gas Development near and beneath Uranium Tailings Cells and Other Remediated Sites - 20358
DOE LM is responsible for maintaining remedies at more than 50 remediated sites that require active long-term surveillance and maintenance (LTS and M). Institutional controls (ICs) were established to limit human and environmental exposures to residual contamination by controlling land use, restricting access to potential hazards, and making the public aware of potential dangers from the residual contamination. ICs for each site were developed based on current and foreseeable conditions; however, these controls should evolve to mitigate potential human health and other environmental risks from unanticipated changes in activities or site conditions. Activities conducted beyond the DOE long-term care boundaries by non-DOE parties may impact the effectiveness of ICs or even the long-term stability of disposal cells and groundwater remedies. Several sites that LM manages or that will transfer to LM for LTS and M are in active oil and gas production basins. The sites are associated with uranium ore milling or nuclear test sites and have been remediated or are in the process of remediation and have no ongoing DOE mission. Particularly since 2005, hydraulic fracturing ('fracking') combined with directional drilling has dramatically increased oil and natural gas (oil/gas) production in the United States, now making it the number one hydrocarbon-producing country. Fracking has allowed production from shale and other rocks of low natural permeability that were historically not considered viable oil/gas resources. Also, because wellbores can now be drilled as many as 5 kilometers or more horizontally, hydrocarbons can be recovered from zones without having access to the surface above them. Drilling activity near Rulison, Colorado, the location of an underground nuclear detonation managed by LM, has raised public concerns that remnant radioactivity in the detonation zone could migrate to producing wells and enter the natural gas distribution system. At sites like the Falls City, Texas, Disposal site, transitioned to LM with a split estate, increased production in the region has resulted in wellbores beneath the long-term care boundary of the site. While the DOE license for Falls City was approved by the NRC in 1997 without the acquisition of the subsurface rights, NRC has raised concerns on whether this activity impacts the integrity of the cell and/or groundwater remedies. In Wyoming, LM is anticipating receiving the license for the Bear Creek site and manages the Spook site, both locations of uranium mill tailings disposal cells. These Wyoming sites are in an active region of major oil and gas development. This change in surrounding land use will require LM to work collaboratively with NRC to address these concerns. At several DOE sites radioactive waste, and often intermixed nonradioactive constituents, is permanently isolated in engineered disposal cells. At other sites, residual contamination can be present in groundwater, blast cavities, and infinite amounts within soil. Areas targeted for oil and gas development at the Texas and Wyoming sites range from depths of 2440 to 3350 meters (8000-11000 feet) below ground surface. When most site remedies were designed, oil and gas development was not considered to be an issue within the site boundary. With the more recent uses of directional drilling, fracking, and associated wastewater injections, the evaluative criteria for incoming sites and ICs for managing long-term protectiveness and regulatory compliance are changing. Although DOE surface ownership was previously thought to be a robust IC to prevent surface and subsurface development, particularly at disposal sites, that may no longer be the case. Whereas the subsurface development at Texas and Wyoming sites is currently occurring at thousands of meters beneath the surface, shallower and direct onsite development would be more of a concern for LM. The energy introduced when a well is hydraulically fractured causes microseismic events (magnitude -2 to 1.0) as the fractures propagate but does not directly cause seismic events (earthquakes) of sufficient magnitude to damage surface structures. Additionally, the extent of the hydraulic fractures is limited to the targeted depths, which are far below the surface. However, earthquakes of sufficient magnitude to damage surface structures have been attributed to the injection of wastewater into disposal wells. States that have experienced these effects have enacted regulations that limit the rate and pressures that wastewater can be injected into disposal wells. Items LM may consider are the need for monitoring the volume of water injected into nearby disposal wells and possibly installing seismic stations at sites most susceptible to damage. While the need to demonstrate that no impact from oil and gas extraction activities on a site groundwater remedy or disposal cells will vary from site to site, LM is assessing risk criteria for this activity. Though LM has not experienced an issue yet at a uranium tailings disposal site, it cannot assume that there will be none, and must address NRC concerns. LM is building on past experiences at other sites and beginning to form new processes with the hope that these concepts can be applied for other future sites. (authors)
04 OIL SHALES AND TAR SANDS↗
Methane foam performance evaluation in water-wet unconsolidated porous media: A systematic experimental investigation at elevated pressure and temperature conditions
In the petroleum industry, enhanced oil recovery (EOR) techniques employ foam extensively to establish conformance control in heterogeneous and fractured reservoirs in order to increase the sweep efficiency. In such applications, foam performance evaluation under complex subsurface conditions is pivotal for the effective and optimized deployment of foam treatment. However, there is a scarcity of hydrocarbon gas foam generation and evaluation studies that examine the relationships between foam performance and the critical foam parameters at high-pressure and high-temperature conditions. Here, this study aims at methodically investigating the effects of several foam parameters on methane foam performance in water-wet proppant packs under harsh operating conditions. This is in relation to the technical needs of hydrocarbon foam injection into hydraulically-induced, propped fractures in unconventional oil reservoirs. To this end, a state-of-the-art experimental foam generation apparatus was designed, fabricated, and commissioned. We performed a large number of foam flow experiments on proppant packs using methane gas and different foaming agents at 3500 psi and 115°C. Anionic and amphoteric surfactants were employed to probe the effect of their ionic nature on foam performance. Foam performance sensitivities to various foam generation parameters and operating conditions, such as surfactant concentration, gas fraction, total injection rate, operating pressure, salinity, and proppant pack length were investigated. To this end, steady-state pressure drops across the proppant packs during foam generation and foam's apparent viscosity were measured to quantify the foam performance of surfactants. The results were then analyzed to determine optimum values of the foam parameters and the interplay between these parameters are discussed here. The systematic results achieved from this work are in agreement with the trends available in the literature and provide new insights into complexities of in situ foam generation in water-wet, unconsolidated porous media at extreme reservoir conditions.
03 NATURAL GAS↗
Organic Carbon Exists in Mars Meteorites: Where is it on the Martian Surface?
The search for organic carbon on Mars has been a major challenge. The first attempt was the Viking GC-MS in situ experiment which gave inconclusive results at two sites oil. After the discovery that the SNC meteorites were from Mars, reported C isotopic compositional information which suggested a reduced C component present in the Martian meteorites reported the presence of reduced C components (i.e., polycyclic aromatic hydrocarbons) associated with the carbonate globules in ALH84001. Jull et al. noted in Nakhla there was acid insoluble C component present with more than 75% of its C lacking any C-14, which is modern-day terrestrial carbon. This C fraction was believed to be either indigenous martian or ancient meteoritic carbon. Fisk et al. have shown textural evidence along with C-enriched areas within fractures in Nakhla and ALH84001. Westall et al. have shown the presence of a large irregular fragment of organic material completely embedded within a chip of ALH84001. Interior samples from the Naklnla SNC made available by the British Museum of Natural History, were analyzed. Petrographic examination of Nakhla showed evidence of fractures (approx.0.5 microns wide) filled with dark brown to black dendritic material with characteristics similar to those observed by. Iddingsite is also present along fractures in olivine. Fracture filling and dendritic material was examined by SEM-EDX, TEM-EDX, Focused Electron Beam microscopy, Laser Raman Spectroscopy, Nano-SIMS Ion Micro-probe, and Stepped-Combustion Static Mass Spectrometry. Observations from the first three techniques are discussed.
McKay, D. S.↗
Recent Advances in Pipeline Integrity for Transporting Blended Hydrogen-Natural Gas
To achieve US decarbonization goals, hydrogen is being considered as an alternative energy source to reduce carbon emissions. Blending hydrogen into existing natural gas pipelines is an intuitive first step to enable near term emission reductions. However, there are numerous challenges and uncertainties that complicate the transition to transporting hydrogen long-distance through existing natural gas pipelines. The main challenge is hydrogen embrittlement (HE), which reduces the ductility, fracture toughness and fatigue resistance of pipeline steels. This work delivers a technical review on HE effects on the material properties of pipeline carbon steels, such as Grade B, X52, X65, X70, X80, and X100. An important aspect of laboratory tests to capture the HE effect is the hydrogen test environment. This includes hydrogen pre-charged specimens tested in air and specimens tested in a hydrogen gas environment. A review of the mechanical properties of pipeline steel in different hydrogen environments determined through tensile testing is given first, which includes HE effects on yield strength, ultimate tensile strength, and ductility for blended hydrogen-natural gas pipelines. Then, the HE effects on fracture toughness and fatigue crack growth resistance are discussed. Last, impacts of HE to pipeline integrity and major technical challenges are discussed.
: Hydrogen Embrittlement↗
Elevated temperature crack growth in advanced powder metallurgy aluminum alloys
Rapidly solidified Al-Fe-V-Si powder metallurgy alloy FVS0812 is among the most promising of the elevated temperature aluminum alloys developed in recent years. The ultra fine grain size and high volume fraction of thermally stable dispersoids enable the alloy to maintain tensile properties at elevated temperatures. In contrast, this alloy displays complex and potentially deleterious damage tolerant and time dependent fracture behavior that varies with temperature. J-Integral fracture mechanics were used to determine fracture toughness (K sub IC) and crack growth resistance (tearing modulus, T) of extruded FVS0812 as a function of temperature. The alloy exhibits high fracture properties at room temperature when tested in the LT orientation, due to extensive delamination of prior ribbon particle boundaries perpendicular to the crack front. Delamination results in a loss of through thickness constraint along the crack front, raising the critical stress intensity necessary for precrack initiation. The fracture toughness and tensile ductility of this alloy decrease with increasing temperature, with minima observed at 200 C. This behavior results from minima in the intrinsic toughness of the material, due to dynamic strain aging, and in the extent of prior particle boundary delaminations. At 200 C FVS0812 fails at K levels that are insufficient to cause through thickness delamination. As temperature increases beyond the minimum, strain aging is reduced and delamination returns. For the TL orientation, K (sub IC) decreased and T increased slightly with increasing temperature from 25 to 316 C. Fracture in the TL orientation is governed by prior particle boundary toughness; increased strain localization at these boundaries may result in lower toughness with increasing temperature. Preliminary results demonstrate a complex effect of loading rate on K (sub IC) and T at 175 C, and indicate that the combined effects of time dependent deformation, environment, and strain aging may play a role. Fractography showed that microvoid coalescence was the microscopic mode of fracture in FVS0812 under all testing conditions. However, the nature of the microvoids varied with test temperature and loading rate, and is complex for the fine grain and dipersoid sizes of FVS0812.
Porr, William C., Jr.↗
Hydrogen in rocks: an energy source for deep microbial communities
To survive in deep subsurface environments, lithotrophic microbial communities require a sustainable energy source such as hydrogen. Though H2 can be produced when water reacts with fresh mineral surfaces and oxidizes ferrous iron, this reaction is unreliable since it depends upon the exposure of fresh rock surfaces via the episodic opening of cracks and fissures. A more reliable and potentially more voluminous H2 source exists in nominally anhydrous minerals of igneous and metamorphic rocks. Our experimental results indicate that H2 molecules can be derived from small amounts of H2O dissolved in minerals in the form of hydroxyl, OH- or O3Si-OH, whenever such minerals crystallized in an H2O-laden environment. Two types of experiments were conducted. Single crystal fracture experiments indicated that hydroxyl pairs undergo an in situ redox conversion to H2 molecules plus peroxy links, O3Si/OO\SiO3. While the peroxy links become part of the mineral structure, the H2 molecules diffused out of the freshly fractured mineral surfaces. If such a mechanism occurred in natural settings, the entire rock column would become a volume source of H2. Crushing experiments to facilitate the outdiffusion of H2 were conducted with common crustal igneous rocks such as granite, andesite, and labradorite. At least 70 nmol of H2/g diffused out of coarsely crushed andesite, equivalent at standard pressure and temperature to 5,000 cm3 of H2/m3 of rock. In the water-saturated, biologically relevant upper portion of the rock column, the diffusion of H2 out of the minerals will be buffered by H2 saturation of the intergranular water film.
Hydrogen/analysis↗