Monday, March 27, 2023

Natural Hydrogen: Exploring for H2 Through the Drillbit: Reserves and Economic Estimations

 

     Until very recently, I was unaware as a geologist that hydrogen can occur in significant volumes as a natural reservoir gas to be able to be produced. Hydrogen has developed quite a color scheme: black = coal sourced; brown = biomass sourced; gray = natural gas sourced; blue = natural gas w/carbon capture; green = renewables powered electrolysis; turquoise = combo of renewables and blue H2 such as methane pyrolysis; pink = nuclear sourced; gold = H2 from wells in depleted oil reservoirs. Natural hydrogen has been proposed to be called ‘white hydrogen’.

     Hydrogen is the most abundant element in the universe. However, free hydrogen in nature at significant volumes has long been thought to be quite rare. It may not be as rare as thought. Hydrogen is quite reactive and diffuses quickly. Its high reactivity makes it seemingly less likely to occur in a pure gaseous form. That may not be wholly true. H2 has not been looked for or recorded in many chemical analyses of subsurface gases and it may occur in different conditions than hydrocarbons or mineral ores so many potential accumulations may be very much under-explored. It is thought that free hydrogen in the vicinity of hydrocarbon systems will become bound up with those hydrocarbons but may appear unbound where there are no hydrocarbon systems.  

 

The processes that create natural hydrogen are not fully understood. It is found in a large range of geological settings – in oceanic and continental crust, volcanic gases and hydrothermal systems.”

     Mechanisms of subsurface hydrogen generation are thought to include:

● degassing of magmas and deep-seated hydrogen from the Earth’s core and mantle

● cataclasis

● oxidation of divalent iron (Fe2+) rich minerals and lithologies through rock-fluid interaction (e.g. serpentinisation); equivalent redox reactions may also occur using other multivalent elements such as sulfur, nitrogen and manganese

● natural radiolysis of water

● biogenic and abiogenic decomposition of organic matter

● a combination of coincident genetic factor

Hydroma’s website gives the four main means of generating hydrogen: serpentinization, radiolysis (separation of H2 from water), degassing from earth’s crust, and rock crushing along fault lines.

     It is found in some geothermal brines. Natural hydrogen can have both abiotic (non-life) and biogenic sources. Natural hydrogen has been ignored by explorers. However, it has been known to occur in non-negligible quantities in a few places for about a hundred years. It occurs in both sedimentary and igneous rock settings. It has yet to be determined if natural hydrogen occurs in quantities that can be commercially produced, aside from the accumulation in Mali, but it seems quite likely.



Global Locations of Natural Hydrogen Anomalies. Source: Current perspectives on natural hydrogen: a synopsis. Betina Bendall. Energy Resources Division, Department of Energy and Mining. MESA Journal 96, 2022 (37–46).
 Current perspectives on natural hydrogen: a synopsis (pir.sa.gov.au)

     One interesting factor in natural hydrogen exploration is that hydrogen can occur with associated helium, which is a commercial drilling target as well. The company Natural Hydrogen Energy, LLC, with offices in France and the U.S., is pursuing hydrogen and helium prospects. Helium is a rare gas and demand currently exceeds supply. The company believes they can produce both hydrogen and helium commercially.

     Hydrogen was known in the past from some natural seeps. There was a seep into a German salt mine in the early 1900’s that kept up a similar rate for several years. A groundwater aquifer in Mali in West Africa was known to contain H2 from the late 1980’s but in 2012:

 

Hydroma Inc. (a Canadian company previously known as Petroma Inc.) re-discovered a hydrogen-rich aquifer in Bourakébougou, Mali and, moreover, managed to flow the natural hydrogen to the surface in commercial quantities.”

 

The hydrogen accumulation in Mali has a content of 98% H2. It is apparently trapped and sealed differently than local hydrocarbons so there may be differences in the trapping and sealing mechanism for hydrogen vs. hydrocarbons.

 

     In 2019 Natural Hydrogen. LLC drilled an exploration well in Nebraska, the Hoarty NE3, that reported hydrogen. Volumes are unknown but the well is apparently still being evaluated. The target is hydrogen sourced in Precambrian basement rocks. In nearby Kansas there have been hydrogen shows recorded:

 

“In Kansas, hydrogen is present in several zones within late Mississippian sandstone, siltstone and limestone units, and an artesian aquifer directly overlying the Precambrian basement. Gas pressures and chemistry in the various Kansas drillholes appear to vary temporally and can be influenced by restricting exchange between the aquifer and the basement (Coveney et al. 1987; Guelard et al. 2017), suggesting recharge from an active hydrogen flux which may be migrating up adjacent fault structures from a deeper source (Coveney et al. 1987; Guelard et al. 2017).”

 

     The hydrogen in Kansas and Nebraska is associated with the Mid-Continental Rift System, a long buried, failed rift system. Basement hydrogen outgassing is known around the world from active oceanic rift systems, ie. the Mid-Ocean Ridges. The H2 in Kansas occurs with N2, He, and occasionally CH4 (methane). The proposed mechanism for hydrogen generation there is “deep crustal H2: water reduction associated to iron oxidation in the Precambrian basement.” Some of the hydrogen was also thought to be generated by chemical reaction within the well-tubing which has high amounts of reduced iron and/or dissolved organic carbon in the water.

     Natural Hydrogen Energy, LLC seems to think that hydrogen reservoirs are fed in such a way that they will not deplete like hydrocarbons do after significant production. They estimate a production cost for natural hydrogen at $0.1-1 per kg. Associated helium production is also expected to improve economics.

     As noted, natural hydrogen can be generated in a number of geologic conditions. In the discovery in Mali the hydrogen was sealed by dolerite that formed a volcanic sill. From the article in Geoscientist magazine:

 

Denis Briere introduced the concept of Hydrogen System Logic (as opposed to the traditional approach of Petroleum System Logic). Derived from his work on the Bourakébougou discovery in Mali, in the Hydrogen System Logic model the hydrogen reservoir is not a pressurised stagnant reservoir trapped under impervious shale barrier, but a slowly flowing accumulation being regenerated in the fractures and matrix. Natural hydrogen is periodically replenished via migration of hydrogen through fractures and then the subsequent diffusion into a host rock.”  

 

Host Rocks and Seal Rocks (Dolerite) in the Natural Hydroegn Accumulations in Mali, West Africa. Source: Hydroma's website: Activities – Natural Hydrogen – Hydroma


     It is not known whether hydrogen is stored as gas reservoirs over geologic time periods as oil and gas is. It is thought that salts/halite, intrusions like the dolerite sills in Mali, and clay-rich rocks like shales could act as hydrogen seals and barriers to migration. The Mali hydrogen accumulation is thought to be more than 8km in areal extent and to be producible from five stacked reservoirs. The potential of this prospect is that it will be cheaper to produce than to manufacture hydrogen, either through electrolysis or through fossil fuels. 24 wells were drilled in 2017-2019 to assess the accumulation. Hydroma began a new drilling campaign in Mali in May 2022. Thus far gas with over 95% H2 content has been recovered in all wells drilled.

     Hydrogen generation in the subsurface may be much different than that of hydrocarbons. Betina Bendall writes that:

 

“It is possible then that some natural hydrogen accumulations are long-lived dynamic systems resulting from continuous, diffuse generation of hydrogen approaching a steady state in the crust, similar to conductive geothermal systems, rather than static accumulations more akin to oil and gas fields. The permeability of individual rock layers and the presence of aquifers, together with subsurface hydrogen-fixing reactions, may mediate the balance between rates of migration from active generation sites and rates of continuous surface seepage.”

 

     Natural hydrogen exploration is taking off in some parts of the world but has yet to be supported at the level of decarbonized manufactured hydrogen, ie. blue and green hydrogen. There has been some legislative support in South Australia where several exploration wells have been permitted. High hydrogen content was found in gas samples in old wells. In two shallow wellbore examples hydrogen makes up to 84% of the gas which also contains nitrogen and lesser amounts of oxygen, CO2, and methane.

 

     Bendall (2022) provides a recent synopsis of the geology of natural hydrogen occurrences and exploration methodologies. Potential exists for natural hydrogen plays in South Australia – Gaucher (2020) indicated that there are two main geological settings where hydrogen could be generated - Proterozoic crystalline shields and serpentinized ultramafic rocks in mid-ocean ridges and in land-based ophiolite-peridotite massifs. Potential natural hydrogen source rocks include ultrabasic rocks and iron-rich cratons (hydrogen generation from the oxidation of Fe(II) bearing mineral such as siderite, biotite, or amphibole by water) and uranium-rich basement with hydrogen generated by radiolysis of water (Gaucher, 2020).”  

 

     Salt/halite and possibly volcanic intrusives are considered the best seal rocks for hydrogen in South Australia. Despite H2 being a small molecule with low density it has a similar seal capacity to methane and better than CO2. This is, of course, why hydrogen can be successfully stored in underground storage reservoirs, particularly salt dome storage fields as exist in the U.S.

     Yet to be determined are reserves estimates of local and regional deposits and what the carbon intensity of drilling and producing natural hydrogen will be. Certainly, the carbon intensity will be far less than natural gas, since burning hydrogen produces no CO2 and there are no fugitive ghg emissions. One preliminary analysis suggests that it will be much less carbon intensive (4 times less) than even green hydrogen. That will depend on the production volumes and length of time the wells produce. However, the energy produced per well or per projects will likely be far less than natural gas and the energy content of hydrogen is also much less (about two-thirds) than that of natural gas.

     Betina Bendall offers the following guidelines for exploring for natural hydrogen:

 

● Target basement areas which contain Fe2+ -rich and/or uranium-rich rocks as these have potential for generating hydrogen via oxidation and radiolytic processes, respectively (e.g. Archean greenstone and Precambrian basement terranes).

● If these potential source areas are fractured and seismically active, then deep-seated faults can act to both channel migrating hydrogen from deeper sources to surface and introduce water downward for further chemical reaction with exposed Fe2+-rich rocks.

● A sedimentary overburden may enable entrapment of migrating hydrogen, particularly if aquifer systems and/or evaporites are present in the sedimentary sequence. Evaporites may also constitute a hydrogen source.

● Targets may be associated with surficial hydrogen seeps. Seeps can be blind or coincident with visible subcircular topographic depressions on the metre to kilometre scale, often associated with perturbed vegetation cover. Soil gas monitoring over extended periods can identify an active hydrogen flux.

● Routine monitoring for hydrogen in mines, and groundwater, oil and gas drillholes is a worthwhile practice which should be encouraged to bolster our understanding and existing records of natural hydrogen occurrences.

 

     Company HHe Exploration Technologies Ltd. Utilizes unmanned aerial systems (UASs), or drones, to detect methane, hydrogen, and helium in anomalous quantities. They utilize a combination of optical gas imaging (OGI) and ambient air analysis in tandem to detect minute hydrogen and helium anomalies. They have entered into joint venture agreements to explore the ambient air over certain areas, including South Australia.


References:

Natural hydrogen: the new frontier. Phillip J. Ball and Krystian Czado. Geoscientist. March 1, 2022. Natural hydrogen: the new frontier - GEOSCIENTIST

Hidden hydrogen might be the key to carbon-free fuel for future generations. Zeleb.es. The Daily Digest. MSN. Hidden hydrogen might be the key to carbon-free fuel for future generations (msn.com)

Hydrogen in Australian natural gas: occurrences, sources and resources. Christopher J. Boreham A C, Dianne S. Edwards A, Krystian Czado B, Nadege Rollet A, Liuqi Wang A, Simon van der Wielen A, David Champion A, Richard Blewett A, Andrew Feitz A and Paul A. Henson A. Journal of the Australian Petroleum Production & Exploration Association (APPEA). Vol. 61. July 2021. CSIRO PUBLISHING | The APPEA Journal

Natural Hydrogen. Government of South Australia. Natural hydrogen | Energy & Mining (energymining.sa.gov.au)

Current perspectives on natural hydrogen: a synopsis. Betina Bendall. Energy Resources Division, Department of Energy and Mining. MESA Journal 96, 2022 (37–46). Current perspectives on natural hydrogen: a synopsis (pir.sa.gov.au)

Natural H2 in Kansas: Deep or shallow origin? J. Guélard, V. Beaumont, V. Rouchon,09 F. Guyot, D. Pillot, D. Jézéquel, M. Ader, K. D. Newell, E. Deville. Geochemistry, Geophysics, Geosystems. Volume18, Issue5. May 2017. Pages 1841-1865. Natural H2 in Kansas: Deep or shallow origin? - Guélard - 2017 - Geochemistry, Geophysics, Geosystems - Wiley Online Library

Discovery of a large accumulation of natural hydrogen in Bourakebougou (Mali). Alain Prinzhofer, Cheick Sidy Tahara Cissé, Aliou Boubacar Diallo. International Journal of Hydrogen Energy. Volume 43, Issue 42, 18 October 2018, Pages 19315-19326. Discovery of a large accumulation of natural hydrogen in Bourakebougou (Mali) - ScienceDirect

Press release from Hydroma Inc. August 6 2022. New Natural Hydrogen Drilling Campaign at Bourakougou. Hydroma-Press-Release-August-6th-2022-EN-.pdf

NATURAL HYDROGEN ENERGY LLC – PIONEER OF HYDROGEN EXPLORATION. Key Player’s Insights. H-Nat Summit 2022. Natural Hydrogen Energy LLC – pioneer of hydrogen exploration | H-NAT SUMMIT (hnatsummit.com)

CAN WHITE HYDROGEN SOFTEN NET ZERO’S INCONVENIENT TRUTH? Key Player’s Insights. H-Nat Summit 2022. Can white hydrogen soften net zero’s inconvenient truth? | H-NAT SUMMIT (hnatsummit.com)

HHE JUNE 2022 NEWSLETTER. Key Player’s Insights. H-Nat Summit 2022. HHe June 2022 Newsletter | H-NAT SUMMIT (hnatsummit.com)

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