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Stimulated geologic hydrogen: from mechanistic control to engineered rock transformation

Geologic hydrogen (GeoH 2 ) generated from subsurface iron-rich rock–water reaction (i.e., serpentinization) is emerging as a promising candidate for the next primary energy source. Yet, accelerating GeoH 2 production from geological to human timescales via enhanced serpentinization remains a formidable scientific and technical challenge. Here, in this Review, we decipher the mechanistic control and explore strategies for accelerating in situ, engineered iron-rich rock transformation into carbon-free GeoH 2 by orders of magnitude. Serpentinization rate is hindered by low porosity and permeability of source rocks, suboptimal temperatures, unfavorable water chemistry, inefficient Fe 2+ -to-Fe 3+ conversion, thermodynamic constraints, and low reactive surface area. While closed-system experiments provide valuable mechanistic insights, open-system conditions with fluid circulation are more crucial for economically viable GeoH 2 production. We assess stimulation techniques from enhanced hydrocarbon and geothermal recovery as tools to be adopted or adapted for increasing reactive surface areas for stimulated GeoH2 production. We estimate that 7.40 × 10 5 to 1.73 × 10 6 million metric tons (Mt) of hydrogen could be engineered over 20 to 50 years from about 10% iron-rich rocks within 10 km depth of continental crust. Enabling GeoH 2 as a viable energy source requires not only advancing scientific frontiers but also forming a global GeoH 2 research network and innovation ecosystem to address the critical scientific, technical, societal, economic, and policy challenges.

08 HYDROGEN↗

Enhanced H 2 production from subsurface through organic acids stimulation

Geologic hydrogen (H₂) generation through serpentinization of ultramafic rocks presents a promising alternative to conventional hydrogen production, utilizing Earth's abundant magnesium- and iron-rich minerals. This study explores the use of short-chain organic acids (specifically malic acid, MA; and citric acid, CA) to enhance hydrogen yields by stimulating mineral dissolution and iron oxidation from ultramafic rock samples. Batch experiments were conducted with crushed peridotite samples from the Tamarack Complex (Minnesota) and Del Puerto Ophiolite (California). Experiments employed 0.05 M and 0.1 M solutions of MA or CA, under 500 psi (35 bar) nitrogen pressure, at temperatures up to 150 °C. Real-time gas monitoring, aqueous chemistry and solid-phase analyses were performed to track reaction progress and hydrogen production.

08 HYDROGEN↗

Geochemical and Hydromechanical Stimulation for Reaction Acceleration (GeoHydRA) of Serpentinization for In Situ Hydrogen Production

The project team aims to develop an innovative approach to stimulate geological hydrogen generation by enhancing in-situ serpentinization of ultramafic rocks. This method can maximize hydrogen production by promoting reactive surface areas through controlled fracturing and optimizing fluid chemistry and flow rates. Key objectives include establishing optimal conditions for hydrogen generation, investigating subsurface limitations, and sustaining production via hierarchical crack systems.

08 HYDROGEN↗

Enhanced H 2 production from subsurface through organic acids stimulation Report

Geologic hydrogen (H 2 ) generation through serpentinization of ultramafic rocks presents a promising alternative to conventional hydrogen production, utilizing Earth's abundant magnesium- and iron-rich minerals. This study explores the use of short-chain organic acids (specifically malic acid, MA; and citric acid, CA) to enhance hydrogen yields by stimulating mineral dissolution and iron oxidation from ultramafic rock samples. Batch experiments were conducted with crushed peridotite samples from the Tamarack Complex (Minnesota) and Del Puerto Ophiolite (California). Experiments employed 0.05 M and 0.1 M solutions of MA or CA, under 500 psi (35 bar) nitrogen pressure, at temperatures up to 150 °C. Real-time gas monitoring, aqueous chemistry and solid-phase analyses were performed to track reaction progress and hydrogen production.

08 HYDROGEN↗

On the viability of stimulated hydrogen generation from iron-rich formations

Hydrogen-based technologies present a promising solution for the global energy transition. In addition to electrolytic production, subsurface geological formations provide a potential natural source of hydrogen. Iron-rich ultramafic rocks, in particular, are favorable for hydrogen generation through natural processes such as serpentinization. Naturally occurring reactions and migration can be enhanced through various types of stimulation, including thermal, hydraulic, and chemical treatment. Through numerical simulations, we analyzed the complex interplay of factors influencing the production and migration within the subsurface, emphasizing the importance of different stimulation techniques, catalysts, and conditions. Our findings indicate that key parameters, such as damage zone permeability and width, significantly impact producible hydrogen mass. Our results indicate that a combination of large damage zone widths, high permeability, and a stimulated reaction rate of 1 × 10 -9 can yield economically viable production rates of up to 1 kg s -1 at the wellhead. Moreover, the availability of ferrous iron, rather than the serpentinization rate itself, has been identified as the primary limiting factor in achieving economically sustainable hydrogen production. In conclusion, while an unstimulated rock volume of 0.165 km 3 yields only 45t of hydrogen in two years, various stimulation techniques can increase production to 18500t.

08 - HYDROGEN↗

Geologic hydrogen: a review of resource potential, subsurface dynamics, exploration, production, transportation, and research opportunities

Hydrogen is a versatile resource with critical roles in decarbonization, industrial manufacturing, and energy integration. However, most hydrogen today is produced from fossil fuels, resulting in high emissions and energy consumption. Although low-carbon hydrogen production methods, such as steam methane reforming with carbon capture and renewable-powered electrolysis, are advancing, their high costs hinder large-scale deployment. Identifying alternative pathways for producing low-cost, low-emission hydrogen is therefore essential. Geologic hydrogen, referring to natural and stimulated hydrogen generated in the Earth's subsurface, has attracted growing attention as a potential source of sustainable, economically viable, and environmentally favorable hydrogen. This paper provides a comprehensive review of geologic hydrogen, covering its resource potential, origins, migration and trapping mechanisms, exploration techniques, production strategies, and pipeline transportation. It also identifies key knowledge gaps and proposes a roadmap for future research. The review indicates that geologic hydrogen has vast resource potential and can leverage existing subsurface technologies and geophysical exploration methods. However, major challenges persist, including uncertain hydrogen generation rates, limited understanding and control of serpentinization processes, costly transportation infrastructure, the lack of validated techno-economic analysis, and potential social and environmental issues. As the field is still in its early stages, progress will require interdisciplinary collaboration spanning geoscience, engineering, economics, environmental science, and policy and regulation.

42 ENGINEERING↗

Geologic hydrogen: From natural occurrences to anthropogenic generation – A review of fundamentals, potential, challenges and prospects

Growing demand for hydrogen is exposing the environmental and economic limits of reforming-based and carbon-managed supply chains, while the scale-up of electrolytic capacity remains capital-constrained. Geologic hydrogen, defined as molecular H₂ generated and stored within the Earth's crust offers a complementary, potentially lower-cost resource, yet exploration is still ad hoc. This review (1) revisits a global inventory of confirmed hydrogen seeps and subsurface occurrences; (2) analyzes the controlling reactions, migration pathways, and trapping conditions governing these occurrences; (3) proposes a process-based geologic hydrogen system concept analogous to, yet distinct from, the petroleum system; and (4) evaluates potential geologic hydrogen systems within the United States as a representative case study. Here, we contrast natural systems powered by serpentinization, mantle degassing or radiolysis with anthropogenic systems that stimulate the same reactions or convert in-situ hydrocarbons. Stable hydrogen accumulations require generation rates that outpace combined physical, chemical and microbial losses; the Bourakébougou field (Mali) exemplifies a self-recharging, free-gas reservoir sustained by meteoric-water serpentinization beneath an efficient caprock. Prospective geologic hydrogen resources are likely to occur in regions where iron-rich lithologies, deep-seated faults, and low-permeability sealing formations coexist. Applying this principle, we highlight three promising hydrogen play types in U.S. geological terrains: ophiolite belts (Appalachian and Californian regions), the Midcontinent Rift and the Lake Superior banded‑iron formations. Multiphysics numerical models and positive-unlabeled machine-learning workflows help to accelerate play screening and de-risk future production; yet, reaction kinetics, stimulation strategies, and full techno-economic and life-cycle assessments remain pivotal knowledge gaps.

Anthropogenic hydrogen generation↗

Induced microseismicity and tremor signatures illuminate different slip behaviours in a natural shale fault reactivated by a fluid pressure stimulation (Mont Terri)

SUMMARY Fault slip induced by fluid perturbation in shale formations may only lead to a sparse seismicity. However, fault slip may strongly impact the integrity of shale formations that serve as caprocks for geological reservoirs holding buoyant fluids such as CO2, natural gas or hydrogen. A better understanding of the fluid reactivation processes of fault and the seismic triggering process is therefore critical for reservoir monitoring and fault stability. Here we analyse the seismic responses of a shale fault exposed to fluid pressurization during an in situ field-scale injection experiment at ∼340 m depth in the Mont Terri underground research laboratory (Switzerland). Two main types of seismic signals are observed as the fault was activated and started to slowly slip. After an aseismic phase, we observed tremor signatures and an increase in noise amplitude, which were directly associated with the slowly propagating fault slip in response to fluid injection. These signatures were later followed by micro-earthquakes that seem to occur further away from the fluid-pressurized area. We interpret these micro-earthquakes to be triggered by stress perturbations from the main slip growth. These two classes of seismic responses therefore highlight two different processes. Tremors seem to be a more direct observation for the fluid-induced slip propagation than micro-earthquakes. Even hidden in the noise, they precede earthquake failures, thus providing a useful tool for monitoring fluid leakage activated by slow deformation on low permeable shale faults, with applications for sealing integrity of caprocks.

De Barros, Louis (ORCID:0000000255419162)↗

R&D Effort of Geologic Hydrogen Production at the National Renewable Energy Lab (NREL)

Geologic hydrogen (geoH2) is an emerging technology with massive current market interest and distinct potential to change the paradigm of hydrogen production. Two major subsurface processes influence the amount of geoH2 that are available for energy extraction: 1) geochemical reactions of H2O and Fe2+-bearing rocks which can produce hydrogen in the subsurface environment, where 2) various active microbial communities consume hydrogen as an energy source before the hydrogen reaches the surface. The net gain of hydrogen from these two competing processes dictates the production rate of geoH2. A recent study (Templeton et al., 2024) suggested that for most natural geoH2 systems, five orders of magnitude of production rate enhancement are needed to make geoH2 production economical in the near term. Effective enhancement of the production rate requires an in-depth understanding of the two geoH2 processes, in order to promote the H2-generating geochemical processes and suppress the H2-consuming microbial processes. However, current significant knowledge gaps in these two processes hinders the efforts to formulate strategies to enhance geoH2 production. The National Renewable Energy Laboratory (NREL) is a U.S. Department of Energy National Laboratory with the core mission of leading research, innovation, and strategic partnership to deliver solutions for a clean energy based economy. NREL's extensive research portfolio in hydrogen, bioenergy, geothermal, industrial decarbonization, and energy analysis makes us well positioned to conduct interdisciplinary research and facilitate technology deployment in the geoH2 space. In this presentation, we will discuss ongoing geoH2 research and engagement efforts at NREL, including: 1) geochemical investigation to understand the reaction mechanisms and production rate and potential of different source minerals and rocks, 2) microbiological investigation to understand methanogenesis and acetogenesis in the subsurface geoH2 environment, and identify effective inhibitors for these microbial processes, and 3) preliminary analysis for geoH2 production in the State of Minnesota, where abundant Fe-rich rocks for stimulated geoH2 production and ample opportunity to utilize geoH2 in transforming iron and steel industries are currently available.

08 HYDROGEN↗

The Search for Life on Mars - Current Knowledge, Earth Analogues, and Principal Issues

For centuries, the planet Mars has been imagined as a possible abode for life. Serious searches for life's signatures began in the 19th century via ground-based visual astronomy that stimulated a vibrant fantasy literature but little lasting scientific knowledge. Modern scientific inquiry has emphasized the search for chemical signatures of life in the soil and rocks at the planet's surface, and via biomarker gases in the atmosphere. Today, investigations are based on high-resolution spectroscopy at Earth's largest telescopes along with planet orbiting and landed space missions. Methane has assumed central importance in these searches. Living systems produce more than 900/0 of Earth's atmospheric methane; the balance is of geochemical origin. Abundant methane is not expected in an oxidizing atmosphere such as Mars', and its presence would imply recent release - whether biological or geochemical. F or that reason, the quest for methane on Mars has been a continuing thread in the fabric of searches conducted since 1969. I will review aspects of the discovery and distribution of methane on Mars, and will mention ongoing extended searches for clues to its origin and destruction. On Earth, hydrogen (generated via serpentinization or radiolysis of water) provides an important 'fuel' for carbonate-reducing and sulphate-reducing biota (CH4 and H2S producers, respectively). Several such communities are known to reside at depth in continental domains (e.g., Lidy Hot Springs, Idaho; Witwatersrand Basin, S. Africa). If similar conditions exist in favourable locations on Mars, organisms similar to these could likely prosper there. Geologic (abiotic) production will also be mentioned, especially abiotic methane production associated with low-temperature serpentinization (e.g., terrestrial ophiolites). It is vitally important to pursue evidence for geochemical and biological production with equal vigour and intellectual weight lest unwanted and unintended bias contaminate the results. Finally, I will touch upon unresolved questions and issues posed by the methane detections.

Mumma, Michael J.↗

Methanogenesis and Acetogenesis in Hydrogenotrophy with Carbonate Minerals: Dependence on Mineral Surface Area, Biofilm Growth, and Microbial Community

The production, storage, and use of hydrogen are anticipated to grow substantially to achieve energy and climate goals. Consequently, microbial communities in many terrestrial and subsurface Earth environments could be exposed to elevated hydrogen concentrations. Hydrogen stimulates metabolic processes that reduce aqueous chemical species, such as bicarbonate or sulfate, that can exchange with solid mineral phases, but the controls on microbial hydrogenotrophy with mineral sources of electron acceptors are not fully understood. Herein, we applied laboratory experiments and biogeochemical modeling to study the response of a natural microbial community to an elevated partial pressure of hydrogen in the presence of carbonate minerals of varying composition, solubility, and size. Experimental incubations and simulation results showed that hydrogen consumption by microbial communities was initially dominated by sulfate reduction and, subsequently, transitioned to acetogenesis and methanogenesis. The rates of acetogenesis and methanogenesis were not correlated with the solubility of carbonate minerals. Instead, we observed strong linear correlations between the rates and surface area of carbonate minerals. Methane and acetate production slowed down in all incubations after about 2 weeks of incubation, although biogeochemical modeling predicted that the metabolic processes were not thermodynamically limited. Electron microscopy and infrared spectroscopy showed that biofilms with diverse microorganisms grew on the carbonates during this period. The methane δ13C value significantly increased, consistent with slower growth at elevated pH. This work highlights that microbial communities form biofilm on carbonate mineral surfaces as a response to hydrogen and that biofilm formation could pose a strong kinetic limitation to hydrogenotrophic metabolism utilizing carbonate minerals.

Acetobacterium↗

Geomechanical in situ testing of fault reactivation in argillite repositories

Abstract. Pressurization of natural faults as a result of repository-induced effects can lead to their reactivation and permeability generation in case such features are present near disposal tunnels. Potential driving forces for such pressurization are the temperature increase caused by heat-producing high-level radioactive waste and the generation of hydrogen and other gases due to corrosion of engineered materials. We are primarily concerned about pressurization and fault activation in host rocks and faults that have very low natural permeability for pore pressure increases to dissipate, such as the argillite rocks currently investigated in Switzerland, France and other countries. This presentation discusses a series of in situ experiments of fault activation by fluid injection conducted in the argillite rock (Opalinus clay) at the Mont Terri underground research laboratory in Switzerland. A multi-model monitoring test bed was installed at Mont Terri that includes distributed fiber optics for strain, temperature, and acoustics; local fault pore pressure and three-dimensional displacement sensors; active seismic imaging; and passive seismic monitoring. The fault experiments (and their subsequent analysis via hydromechanical modeling) provide a new fundamental understanding of the coupling between pore pressure, fault deformation and permeability generation as a function of time and allow exploring how seismic and aseismic events may impact the integrity of faulted argillite host rock. Our experimental observations demonstrate that significant flow (and transport) can occur along the initially impermeable argillite fault when rupture is activated. However, the fault permeability decreases to almost its pre-activation value when fluid injection ceases and fluid pressure drops. Dilatant slip on the fault plane alone does not explain the observed increase in fault permeability; pressure-induced fault opening also plays a role, favored by the softness of the shale along with the fact that the structure of the fault zone prevents fluids from diffusing into the adjacent damage zone. Rupture initiation and permeability generation is initially aseismic, associated only with an increase in noise level and emerging tremors. Micro-earthquakes are initiated later in the experiments and typically occur away from the fluid-pressurized area. Hydromechanical models show that stress transferred from the initial aseismic deformation can build up to stress criticality and later induce seismic rupture. After presenting the experimental results, we will close the presentation with an outlook to future experimental campaigns using the fault test bed at Mont Terri. We are currently planning a controlled thermal stimulation of the fault, where instead of fluid injection as a trigger mechanism we will heat up the nearby rock volume and measure potential effects on fault stability. Lessons learned from our past and future experiments will help inform the safety assessment of geologic disposal in argillite host rock.

Birkholzer, Jens T.↗