H 2 -rich fluids from serpentinization: Geochemical and biotic implications
Open accessAbstract
Metamorphic hydration and oxidation of ultramafic rocks produces serpentinites, composed of serpentine group minerals and varying amounts of brucite, magnetite, and/or FeNi alloys. These minerals buffer metamorphic fluids to extremely reducing conditions that are capable of producing hydrogen gas. Awaruite, FeNi3, forms early in this process when the serpentinite minerals are Fe-rich. Olivine with the current mantle Fe/Mg ratio was oxidized during serpentinization after the Moon-forming impact. This process formed some of the ferric iron in the Earth's mantle. For the rest of Earth's history, serpentinites covered only a small fraction of the Earth's surface but were an important prebiotic and biotic environment. Extant methanogens react H2 with CO2 to form methane. This is a likely habitable environment on large silicate planets. The catalytic properties of FeNi3 allow complex organic compounds to form within serpentinite and, when mixed with atmospherically produced complex organic matter and waters that circulated through basalts, constitutes an attractive prebiotic substrate. Conversely, inorganic catalysis of methane by FeNi3 competes with nascent and extant life.
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The H2 in hydrothermal vents comes from serpentinization.
“The H2 in hydrothermal vents comes from a geochemical process called serpentinization [21–25].”
From Early bioenergetic evolution (2013) · cites this paper as [22]
Serpentinization occurs because suboceanic crust consists of iron-magnesium silicates such as olivine with Fe2+, and seawater at high pressure and around 150°C oxidizes Fe2+ to Fe3+ while water is reduced to H2.
“Serpentinization takes place because most of the suboceanic crust consists of iron–magnesium silicates like olivine, in which the redox state of the iron is Fe2+. Seawater penetrates the ocean floor crust, reaching depths on the order of 3–5 km below the surface. There at high pressure and temperatures of around 150°C, water oxidizes the Fe2+ to Fe3+, the water being reduced to H2 with the oxygen”
From Early bioenergetic evolution (2013) · cites this paper as [22]
The production of H2 via serpentinization has probably been taking place since there was liquid water on Earth and continues today because the amount of Fe2+ in the crust is inexhaustible relative to the amount of water on Earth.
“The production of H2 via serpentinization has probably been taking place since there was liquid water on the Earth [22], and it continues today because, relative to the amount of water on the Earth, the amount of Fe2+ in the crust is inexhaustible.”
From Early bioenergetic evolution (2013) · cites this paper as [22]
On the early Earth, serpentinizing systems were probably more abundant than today.
“On the early Earth they were probably more abundant than today.”
From Serpentinization as the source of energy, electrons, organics, catalysts, nutrients and pH gradients for the origin of LUCA and life (2023) · cites this paper as Sleep et al., 2004
In subsurface reduction models, the source of reductant for origins is geochemical and continuous: H2 supplied by serpentinization.
“In subsurface reduction models, the source of reductant for origins is geochemical and continuous: H2 supplied by serpentinization.”
From Serpentinization as the source of energy, electrons, organics, catalysts, nutrients and pH gradients for the origin of LUCA and life (2023) · cites this paper as Sleep et al., 2004
The electrons released by serpentinization reduce H2O to H2 which in turn reduces CO2 to CH4 and organics.
“The electrons released by serpentinization reduce H2O to H2 which in turn reduces CO2 to CH4 and organics (Sleep et al., 2004; Martin et al., 2008; Sleep et al., 2011; McCollom and Seewald, 2013).”
From Serpentinization as the source of energy, electrons, organics, catalysts, nutrients and pH gradients for the origin of LUCA and life (2023) · cites this paper as Sleep et al., 2004
On the early Earth the lithosphere was not yet differentiated and higher mantle temperatures allowed ultramafic lava to erupt on Earth's surface, such that ultramafic rocks were probably much more exposed to the surface oceans than today, meaning that serpentinization was almost certainly much more prevalent on early Earth than now.
“On the early Earth the lithosphere was not yet differentiated and higher mantle temperatures allowed ultramafic lava to erupt on Earth’s surface, such that ultramafic rocks were probably much more exposed to the surface oceans than today, meaning that serpentinization was almost certainly much more prevalent on early Earth than now (Sleep et al., 2004, 2011; McCollom and Seewald, 2013; Schrenk et”
From Serpentinization as the source of energy, electrons, organics, catalysts, nutrients and pH gradients for the origin of LUCA and life (2023) · cites this paper as Sleep et al., 2004
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“The electrons released by serpentinization reduce H 2 O to H 2 which in turn reduces CO 2 to CH 4 and organics (Sleep et al., 2004; Martin et al., 2008; Sleep et al., 2011; McCollom and Seewald, 2013).”
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- Authors
- Sleep, N. H., Meibom, A., Fridriksson, T., Coleman, R. G., & Bird, D. K.
- Affiliations
- Stanford University (US)
- Departments of Geophysics and Geological and Environmental Sciences, Stanford University, Stanford, CA 94305
- Venue
- Proceedings of the National Academy of Sciences
- Publisher
- National Academy of Sciences
- Published
- 2004-08-23
- Volume
- 101
- Issue
- 35
- Pages
- 12818-12823
- ISSN
- 0027-8424 (ISSN-L)
- 1091-6490
- PMC
- PMC516479
- OpenAlex
- W2153323573
- Cited by
- 568
- References
- 4
- Citations by year
- 2026: 43 · 2025: 35 · 2024: 26 · 2023: 32 · 2022: 29 · 2021: 37 · 2020: 34 · 2019: 17 · 2018: 25 · 2017: 38 · 2016: 23 · 2015: 25 · 2014: 19 · 2013: 34 · 2012: 24
- FWCI
- 7.86
- Type
- journal article
- Language
- en
- Open access
- green
- europepmc.org
- Locations
- Proceedings of the National Academy of Sciences (publishedVersion)
- Europe PMC (PubMed Central) (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- Infoscience (Ecole Polytechnique Fédérale de Lausanne) (submittedVersion)
- Infoscience (Ecole Polytechnique Fédérale de Lausanne) (submittedVersion, cc-by-nc-nd)
- Topics
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Physical Sciences › Earth and Planetary Sciences › Geophysics › Geological and Geochemical Analysis
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Keywords
- serpentinization, hydrogen production, serpentinite, ultramafic rocks, metamorphic fluids, awaruite, FeNi3, prebiotic chemistry, methanogenic archaea, methane, Earth's mantle, Moon-forming impact, brucite, magnetite
- MeSH terms
- Hydrogen, Nickel, Thermodynamics, Moon, Asbestos, Serpentine, Earth, Planet, Natural History, Iron Compounds
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