Earth-Science Reviews 230 (2022) 104063

Contents lists available at ScienceDirect

Earth-Science Reviews
journal homepage: www.elsevier.com/locate/earscirev

Molecular hydrogen in surface and subsurface natural gases: Abundance,

origins and ideas for deliberate exploration
Alexei V. Milkov
Colorado School of Mines, Golden, CO, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Geologic molecular hydrogen (H2) occurs in the subsurface and vents and seeps at the surface. However, this
Hydrogen valuable natural resource is under-utilized in the economy because the distribution, abundance and origins of H2
Serpentinites are poorly understood. I studied a global dataset of 6246 natural gases with reported H2 concentrations from 16
Natural gas
different geological habitats. The average H2 concentration in all gas samples is 3.5%, but the median concen­
Isotopes
tration is only 0.01%. Gases sampled in Mid-Ocean Ridges and in serpentinites have the highest average con­
centrations of H2 (~24% and ~21%, respectively). More than 30 different processes may produce H2 observed in
natural gases. Hydrogen isotopic composition (expressed as δ2H-H2 values) may indicate crustal (<-650‰) or
mantle and primordial (from -650‰ to -100‰) sources of H2, or may result from temperature-dependent
equilibration of H2 with water. Much of crustal H2 may be sourced by the reactions of serpentinization, while
the quantitative significance of other H2-generating processes such as radiolytic decomposition of water and
hydrocarbons, fracture-induced reduction of water, petroleum cracking and coal metamorphism remain specu­
lative. Primordial H2 perhaps vents in some volcanic settings. Provided better understanding of H2 abundance
and origins in different geological settings should enable the purposeful exploration for geologic H2 and the
assessment of its economic resources.

1. Introduction
Hydrogen, the most abundant element in the Universe, was recog­
nized in 1776 by Henry Cavendish, and its name was coined in 1783 by
Antoine Lavoisier (Brophy and Schimmelmann, 2017). Molecular
hydrogen (H2) is important in modern economy and industry. Currently,
it is used mostly in ammonia production and petroleum recovery and
refining (IEA, 2021). Hydrogen gas is an excellent clean fuel because it
contains more energy per unit weight than most other fuels, is carbon-
free, and its combustion in fuel cells emits only water (World Energy
Council, 2019; Truche and Bazarkina, 2019; Farias et al., 2022).
Therefore, H2 can play an important role in the energy transition away
from fossil fuels as either an energy vector or a zero-carbon source of
energy (Hanley et al., 2018; Murray et al., 2020). The vast majority of
the H2 currently utilized in the economy is produced using methods
collectively known as “thermal processes”, and steam reforming of
methane and other light hydrocarbons is the most common industrial
process of H2 generation (Nuttall and Bakenne, 2020; Timmerberg et al.,
2020).
Molecular H2 occurs in the subsurface and seeps and vents at the
surface (Zgonnik, 2020; Etiope et al., 2011; Combaudon et al., 2022).
This geologic (natural, native, gold) H2 is already utilized as a source of
energy (electricity) in a village in Mali (Hydroma, 2022), and should be
used more widely around the globe if available, producible and
economically viable (Smith, 2002; Larin et al., 2015; Truche and
Bazarkina, 2019; Gordienko, 2019; Gaucher, 2020; Boreham et al.,
2021a; Lefeuvre et al., 2021; Yedinak, 2022).
Hydrogen and other reduced gases support unique ecosystems with
chemolithoautotrophic metabolic pathways on the modern deep sea­
floor (Takai et al., 2004; Ohara et al., 2012), may provide energy for
long-term survival of microbial cells (Morita, 2000) and may have
contributed to the origin of life on Earth and perhaps other planets
(Nisbet and Sleep, 2001; Oze and Sharma, 2005, 2007; McCollom and
Seewald, 2013; Holm et al., 2015; Glein and Zolotov, 2020; McCollom
et al., 2022). Molecular H2 plays a significant role in the formation of
natural hydrocarbon gases via the processes of microbial hydrogeno­
trophy (Wagner et al., 2018; Katz, 2011; Milkov, 2011, 2018) and
Fischer-Tropsch synthesis (Etiope and Whiticar, 2019), and may play a
role in the formation of liquid petroleum fluids (Pratt, 1934; Szatmari,
1989; Levshounova, 1991; Kenney et al., 2002; Wang et al., 2019).

E-mail address: amilkov@mines.edu.

https://doi.org/10.1016/j.earscirev.2022.104063
Received 29 January 2022; Received in revised form 16 May 2022; Accepted 22 May 2022
Available online 28 May 2022
0012-8252/© 2022 Elsevier B.V. All rights reserved.
A.V. Milkov
Emissions of combustible and explosive H2-containing gases during the
mining of ore deposits represent a known hazard (Nivin, 2019) and need
to be predicted and mitigated.
In spite of the clear importance of geologic H2 as a clean fuel, a
source of energy for life and a geohazard, the current understanding of
geologic H2 occurrences is rather limited, and the in-place, recoverable
and economic resources of geologic H2 have not been adequately
quantified. The main reason for that is the lack of fundamental under­
standing of the prevailing reaction mechanisms and rates associated
with geochemical processes of H2 formation, and how H2 migrates and
fractionates in the Earth. More than 30 different mechanisms and pro­
cesses of H2 production in Earth have been proposed in the literature.
However, the relative importance of these processes and their contri­
butions to global H2 budget remain unknown. This is partly due to the
fact that geochemical tools aimed at distinguishing these processes are
poorly developed. Further, various different processes that consume H2
in the subsurface and lithologies that can form effective seals for H2-
bearing reservoirs are not well understood.
Here, I use a large global dataset of natural gases to document the
abundance of molecular H2 in various geological settings. Then, I
investigate how to distinguish numerous proposed processes of H2
generation in the subsurface and which of them may be quantitatively
significant on Earth by using H2 isotopic composition and other asso­
ciated geological and geochemical characteristics (including noble
gases) of H2-bearing gases. A better understanding of processes that
generate H2 will help constrain the rates of geologic hydrogen produc­
tion in Earth, which may be significant (up to ~30% of global industrial
hydrogen production, Sherwood Lollar et al., 2014) but are highly un­
certain (Zgonnik, 2020). It will also lay out the foundation for the
assessment of potentially recoverable resources of geologic H2 around
the world and help formulate exploration strategies for this valuable gas.
2. Current knowledge of hydrogen occurrences, origins and
sinks
2.1. Occurrences of molecular H2 on Earth
The H2 molecule has a small size, is extremely mobile and can be
rapidly consumed by redox reactions mediated by microbes and/or
mineral catalysts (Brophy and Schimmelmann, 2017; Truche et al.,
2018). As a result, H2 does not accumulate easily in the crust, which led
to a misconception that it does not occur freely in the subsurface (Smith
et al., 2005). However, several recent reviews (Gregory et al., 2019;
Truche et al., 2020; Zgonnik, 2020; Rusakov, 2020) highlighted that
concentrations of molecular H2 can be very high (up to 99 vol.%) in
ophiolites and associated seeps (e.g., Neal and Stranger, 1983; Vacquand
et al., 2018) and in kimberlite pipes (e.g., Fridman, 1970, also note that
H2 is a major gas released from diamonds, Melton and Giardini, 1974).
Other geologic settings with significant H2 occurrences include graphite
deposits, volcanic systems, geothermal systems, crystalline basement,
potash and evaporite deposits, cataclasites, and anoxic sediments
(Gregory et al., 2019; Zgonnik, 2020) as well as some conventional oil
and gas accumulations (Bohdanowicz, 1934; Headlee, 1962; Molcha­
nov, 1981; Angino et al., 1984; Coveney Jr. et al., 1987; Perevozchikov,
2011; Zinger, 1962; Kraychuk, 1976; Prinzhofer et al., 2018).
2.2. Origins of molecular H2 in natural gases
There are numerous proposed origins and generation mechanisms of
H2 observed in the subsurface and in seeps/vents at the surface and the
ocean floor, as previously reviewed by Lin et al. (2005a, 2005b), Truche
et al. (2020), Klein et al. (2020), Zgonnik (2020) and Boreham et al.
(2021a). I identified 32 processes previously described in the literature
and list them below grouped as natural abiotic, natural biotic, and
anthropogenic processes.
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Earth-Science Reviews 230 (2022) 104063
2.2.1. Natural abiotic processes
Natural abiotic processes of H2 generation in Earth include water-
rock interactions involving iron, degassing from the mantle, radiolysis
and other abiotic processes in the geosphere:
1. Serpentinization (metamorphic hydration and oxidation) of ul­
tramafic rocks such as peridotites, dunites and kimberlites composed
mostly of Mg and Fe2+ silicate minerals olivine and pyroxene (Fridman,
1970; Moody, 1976; Coveney Jr. et al., 1987; Sleep et al., 2004; Oze and
Sharma, 2005, 2007; Russell et al., 2010; Klein et al., 2013; Mayhew
et al., 2013; Holm et al., 2015; Miller et al., 2017; Preiner et al., 2018;
Huang et al., 2019; Truche et al., 2020; Worman et al., 2016, 2020;
Zgonnik, 2020; Albers et al., 2021). Serpentinites are water-rich rocks
that contain mostly serpentine-group minerals (chrysotile, lizardite and
antigorite) and varying amounts of brucite, magnetite, and/or FeNi al­
loys (Sleep et al., 2004). They form from relatively low-temperature
(<300◦ C) hydration of mantle-derived ultramafic rocks, during which
Mg-rich olivine and orthopyroxene are altered to serpentine minerals
(Guillot and Hattori, 2013; Evans et al., 2013).
Modern serpentinites in oceans are present along the axis of slow and
very slow spreading ocean ridges where the mantle is too cool to form
significant basalt (Charlou et al., 2002; Dick et al., 2003; Worman et al.,
2020), magma-poor transform margins (such as the Iberian Margin,
Skelton et al., 2005; Albers et al., 2021) and in the subduction zones
(some forearc environments, for example, in the serpentinite diapirs in
the Mariana forearc, Wang et al., 2009; Fryer, 2012). Ancient serpen­
tinites on continents are exposed as ophiolites in suture zones associated
with closure of paleo-oceans. The largest (by area) examples include the
Semail ophiolites (~10,000 km2) in the Sultanate of Oman and the
United Arab Emirates (Barnes et al., 1978; Neal and Stranger, 1983; Fritz
et al., 1992; Kelemen and Matter, 2008) and the Massif du Sud (~6000
km2) in New Caledonia (Barnes et al., 1978; Deville and Prinzhofer,
2016; Monnin et al., 2021). Ophiolites with smaller areas are present in
New Zealand (Wood, 1972), Philippines (Thayer, 1966; Abrajano et al.,
1988; Sturchio et al., 1989), Japan (Suda et al., 2014, 2017), China (Ye
et al., 2007), Turkey (Etiope et al., 2011; Yuce et al., 2014; D’Alessandro
et al., 2018), Bosnia and Herzegovina (Barnes et al., 1978; Etiope et al.,
2017), Greece (Daskalopoulou et al., 2018; Li Vigni et al., 2021), Italy
(Boschetti et al., 2013), Spain (Etiope et al., 2016), Portugal (Etiope
et al., 2013; Marques et al., 2018), Norway (Daae et al., 2013), Mali
(Caby, 2014), Costa-Rica (Crespo-Medina et al., 2017), USA (Morrill
et al., 2013; Lazar and Cooperdock, 2021), Canada (Szponar et al., 2013)
and in other countries, on all continents, including Antarctica. Guillot
and Hattori (2013) estimated that >3% of the Earth’s surface is made up
of serpentinites and serpentinized peridotite.
Serpentinization of peridotite is accompanied by the release of H2
and other reduced gases. Olivine is the main mineral of the upper
mantle. The general reaction that describes serpentinization of olivine is
(McCollom et al., 2022):
Olivine + H2O → Serpentine ± Brucite ± Magnetite + H2
Generation of H2 during serpentinization reactions has been
demonstrated in laboratory experiments (Miller et al., 2017; Huang
et al., 2019; Barbier et al., 2020; Song et al., 2021). Serpentinization is
thought to be the major process responsible for some of the highest
concentrations of H2 in natural gas seeps (Abrajano et al., 1988; Etiope
et al., 2013) and in subsurface gas reservoirs (Coveney Jr. et al., 1987;
Briere et al., 2017). Serpentinization of iron-rich olivine on Mars, icy
moons, and other planetary bodies may be a significant source of
hydrogen, which has a potential to support extra-terrestrial biological
communities (McCollom et al., 2022).
2. Release of H2 during volcanic activity and from hydrothermal
vents, when equilibrium reactions in the C-H-O-S system in magmas
favor H2, for example (Apps and van de Kamp, 1993; Holland, 2002):
CO + H2O ↔ CO2 +H2
H2S + 2H2O ↔ SO2 + H2
SO2 + 2H2O ↔ H2SO4 + H2
3. Cooling and decompression in a hydrothermal CO2-CH4-C fluid
A.V. Milkov
system (Tsunogae and Dubessy, 2009).
4. Late stage crystallization of basic magma where dissolved water
oxidizes ferrous iron Fe2+ (in Fe2+-bearing minerals) to ferric iron Fe3+
(Stevens and McKinley, 1995; Schrenk et al., 2013; Sherwood Lollar
et al., 2014; Etiope and Whiticar, 2019; Nivin, 2019). An example re­
action would be decomposition of fayalite without serpentinization
(Arrouvel and Prinzhofer, 2021):
3Fe2SiO4 (fayalite) + 2H2O(l) → 2Fe3O4 (magnetite) + 3SiO2(­
quartz) + 2H2(g)
5. Degassing of primordial H2 that has been present in the Earth since
its formation (Chamberlin, 1909; Larin, 1993; Gilat and Vol, 2005,
2012; Larin et al., 2015; Yang et al., 2016).
6. Metasomatism of upper mantle and crustal rocks with the infil­
tration of metal hydrides from the deeper mantle (Walshe, 2006).
7. Hydration of biotite in felsic rocks such as granite (Murray et al.,
2020).
8. Hydrothermal hydration of siderite in sedimentary basins (e.g., in
the Solimões basin in Brazil, Milesi et al., 2016) and metasedimentary
rocks according the following reaction (Seewald, 2001; Milesi et al.,
2015):
3FeCO3 (siderite) + H2O (l) ↔ Fe3O4 (magnetite) + 3CO2 (g) + H2
(g)
9. Oxidation of Fe2+ from magnetite to Fe3+ to crystallize hematite
(Arrouvel and Prinzhofer, 2021):
2Fe3O4 (magnetite) + H2O(l) → 3Fe2O3 (hematite) + H2 (g)
Geymond et al. (2022) suggested that weathering of banded iron
formations can result in significant H2 generation in iron mines in
Australia, Brazil and South Africa.
10. Reactions linked to pyritization. Under acidic conditions (such as
in some hydrothermal sites, fumaroles from volcanic activities), the
reactions are simulated with H2S (g) (Arrouvel and Prinzhofer, 2021):
Fe2O3 (hematite) + 4H2S (g) → 2FeS2 (pyrite) + 3H2O (l) + H2 (g)
Fe3O4 (magnetite) + 6H2S (g) → 3FeS2 (pyrite) + 4H2O(l) + 2H2(g)
Reactions may also be with siderite and with pyrrhotite, which may
also be mediated by microorganisms (Drobner et al., 1990; Hofstra and
Cline, 2000; Thiel et al., 2019).
11. Water hydrolysis accompanying Fe and Fe2+ oxidation (anaer­
obic corrosion) most likely catalysed by metal hydroxides at low tem­
perature, crustal weathering and by Ca produced from the radioactive
decay of 40K (Neal and Stranger, 1983; Guélard et al., 2017; Worman
et al., 2020).
12. Radiolysis of water by alpha, beta and gamma radiation released
in the radioactive decay of U-, Th- and K-bearing minerals (Boyd et al.,
1973; Vovk, 1987; Dubessy et al., 1988, 1989; Spinks and Woods, 1990;
Smith et al., 2005; Lin et al., 2005a, 2005b; Blair et al., 2007; Dzaugis
et al., 2016; Bouquet et al., 2017; Parnell and Blamey, 2017b; Truche
et al., 2018; Wang et al., 2019; Zgonnik, 2020; Sauvage et al., 2021).
When ionizing radiation passes through water, it leads to the formation
of ionic and excited states, which further decompose or recombine to
produce radical and molecular species according to the following
equations (Pastina and LaVerne, 2001; Wang et al., 2019):
H2O (ionizing radiation) → H⋅ + OH⋅ + H+ + OH− + e−
e− + → e−aq (hydration)
e−aq + H+ → H⋅
e−aq + e−aq +2H2O → H2 + 2OH−
e−aq + H⋅ + H2O → H2 + OH−
H⋅ + H2O → H2 + OH⋅
H⋅ + H⋅ → H2
13. Radiolytic dehydrogenation of organic matter and kerogen, for
example, in shales, which generates gases dominated by H2 and CO2
(Lewan et al., 1991; Wang et al., 2022). The generation of H2 appears to
be due to C-H scission and double-bond formation (Yamazaki and Shida,
1960; Frolov et al., 1998).
14. Radiolytic dehydrogenation of crude oil molecules (Frolov et al.,
1998; Larter et al., 2019; Silva et al., 2019).
15. Radiation-induced polymerization of methane into H2 and C2+
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Earth-Science Reviews 230 (2022) 104063
hydrocarbons (Boreham and Davies, 2020).
16. Fracture-induced reduction of water: cataclastics (cohesive
granular faulted rock) of silicates in the presence of water and in igneous
rocks and associated with upper crustal processes (e.g., earthquakes)
(Kita et al., 1982; Sugisaki et al., 1983; Apps and van de Kamp, 1993; Ito
et al., 1999; Freund et al., 2002; Saruwatari et al., 2004; Kameda et al.,
2004; Hirose et al., 2011, 2012; Klein et al., 2020). The mechanism is
likely mechanoradical where 2(≡Si⋅) + 2H2O → 2(≡SiOH) + H2, with
the potential for subsequent redox conversion of hydroxyl (2(≡Si–OH)
or 2(–OH)) to peroxy links (≡SiOOSi≡ (or -OO-)) + H2.
17. Mechanochemical reaction of phosphate to produce phosphine
(PH3) and its subsequent hydrolysis to H2 (Hoeman, 1944; Glindermann
et al., 2005).
18. Natural release of H2 from fluid inclusions. This process appears
to be widespread in Precambrian basement rocks, particularly granites.
The eroded basement remnants in sedimentary basins may be a signif­
icant H2 resource (Parnell and Blamey, 2017a).
19. Decomposition of methane (CH4) to form graphite and H2 at high
(>600◦ C) temperatures during metamorphism (Galimov et al., 1973;
Hahn-Weinheimer and Hirner, 1981; Apps and van de Kamp, 1993;
Holland, 2002; Smith et al., 2005; Dzaugis et al., 2016; Bouquet et al.,
2017; Parnell and Blamey, 2017a, 2017b; Truche et al., 2018; Boreham
and Davies, 2020; Zgonnik, 2020):
CH4 ↔ C(graphite) + H2
That CH4 may be biotic or abiotic, but the formation of H2 is an
abiotic process. Hydrogen can also be generated from carbonaceous
material during graphitization (Suzuki et al., 2017).
20. Oxidative coupling of methane catalyzed by alkali metal and
lanthanide oxides. This process has been demonstrated in the laboratory
at high (>650◦ C) temperatures, and similar reactions may potentially
occur in the subsurface with the involvement of O2 from water radiolysis
(Lunsford, 1990; Lehmann and Baerns, 1992).
21. Mixing of waters with differing ionisation potentials, i.e. fresh
and saline groundwaters (Goebel et al., 1984).
22. Release from ammonium (NH+ 4 )-bearing minerals oxidized by
reacting with sulfate at high temperatures (Dubessy et al., 1989; Li et al.,
2009), which may happen in anhydrite-rich marine salt deposits
(Dubessy and Ramboz, 1986):
2-
8NH+ 4 + 3SO4 ↔ 4N2 + 3H2S + 12H2O + 2H
+
23. Dehydrogenation of clay minerals that are abundant in many
shale formations (Truche et al., 2018).
24. Liberation of H2 from H2O at high metamorphic temperatures
(Suzuki et al., 2017).
2.2.2. Natural biotic processes
Natural biotic processes (both biologically-mediated processes and
processes that may be abiotic but which act upon biogenic substrates) of
H2 generation include:
25. Formation during biological activity (Ginsburg-Karagitscheva,
1933; ZoBell, 1947; Bokova, 1953; Ekzercev, 1960; Nandi and Sengupta,
1998; Gregory et al., 2019) via fermentation of organic matter (Gest,
1954; Krichevsky et al., 1961; Adams and Stiefel, 1988; Boone et al.,
1989; Adam and Perner, 2018; Hallenbeck and Benemann, 2002) by
certain anaerobic bacteria and cyanobacteria (Luo et al., 1991; Conrad,
1996; Morita, 2000; Ménez, 2020), by heterotrophic hyperthermophiles
(Mermelstein and Zeikus, 1998), by nitrogen fixing bacteria (Morita,
2000; Conrad, 1996), and through anaerobic carbon monoxide oxida­
tion and phosphate oxidation (Schwartz et al., 2013; Sipma et al., 2006).
During diagenesis, the polymerization of hydrocarbon C-H bonds results
in the formation of kerogen and release of H2.
26. Thermogenic liberation of H2 from cracking of C-H bonds by
aromatization, polycondensation or metathesis of hydrocarbons (Li
et al., 2015) during the generation of oil and gas (Bogomolov, 1976;
Gregory et al., 2019, and references therein), in oil accumulations
(Zinger, 1962), during petroleum cracking (Briere et al., 2017) and
during coal metamorphism (Zgonnik, 2020). During metagenesis, the
A.V. Milkov
progressive aromatisation of the residual kerogen leads to production
predominantly of CH4 but also some H2 (Tissot and Welte, 1984; Hunt,
1996; Horsfield et al., 2022). Suzuki et al. (2017) found significant
concentrations of presumably organic H2 in gases released from pul­
verized thermally mature shales and matapelites. Liberation of molec­
ular H2 from shales and coals during laboratory pyrolysis experiments
was demonstrated in numerous studies (Jüntgen and van Heek, 1979;
Campbell et al., 1980; Li et al., 2015, 2017; Horsfield et al., 2022).
However, the specific mechanisms of H2 generation (cracking of hetero-
bonds, demethylation, aromatization, condensation) and the role of H2
in the transformation of organic matter into hydrocarbons are still
poorly constrained (Behar et al., 1997; Li et al., 2015, 2017).
27. Thermal decomposition of alkanes and carboxylic acids at tem­
peratures >200◦ C and CH4 at temperatures >500◦ C, which results in the
release of H2 (Tissot and Welte, 1984; Seewald, 2001).
28. H2 release during sulfur incorporation into hydrocarbon com­
pounds during thermochemical sulfate reduction (Ostertag-Henning and
Scheeder, 2009).
2.2.3. Anthropogenic processes
Anthropogenic processes in which H2 results from artificial processes
during drilling and metal corrosion include:
29. Drill bit metamorphism, bit burning and cracking of organic
matter by excessively hot drill bit (Halas et al., 2021).
30. The oxidation of steel drill pipes and well casings in the presence
of natural gas with a high CO2 content (“CO2 corrosion”) (Meincke,
1967; Mørkved et al., 2009).
31. Corrosion of steel well casing from exposure to H2S (Lyon and
Hulston, 1984).
32. Corrosion reactions between acids either naturally present in
ground waters at low pH conditions (Zinger, 1962) or introduced during
wellbore cleaning operations (Feldbusch et al., 2018) and iron in well
casings, steel drilling shavings and lithic fragments (Bjornstad et al.,
1994), for example:
2H3O+ + Fe → 2H2O + H2 + Fe2+
When nuclear waste is disposed, corrosion of steel canisters can
produce copious amounts of hydrogen (Truche et al., 2020). Other ref­
erences describing these anthropogenic processes include Goebel et al.
(1984), Merlivat et al. (1987), Zimmer (1993), Zimmer and Erzingeer
(1995), Messer et al. (2008), Wersin et al. (2008), Erzinger et al. (2006),
Wenger et al. (2009), Thiessen et al. (2009).
2.3. Sinks of H2 on Earth
Based on the available evidences, it appears that virtually all of the
H2 generated in the subsurface is converted to methane (and other hy­
drocarbons) via biotic and abiotic processes (Conrad, 1995). Hydro­
genotrophic microbes (Wagner et al., 2018; Adam and Perner, 2018)
utilize H2 and CO2 to produce primary microbial gas (mostly methane)
in marine sediments (e.g., Katz, 2011) and secondary microbial gas in
shallow cool petroleum reservoirs (Milkov, 2010, 2011, 2018).
Abiotic methane (Potter and Konnerup-Madsen, 2003; Etiope and
Sherwood Lollar, 2013; Etiope and Whiticar, 2019) forms from H2 via
Fischer-Tropsch Type reactions (FTT, Fischer and Tropsch, 1926). The
FTT chemical reactions have been widely studied and applied in in­
dustrial catalysis for synthetic fuel and chemicals production and CO2
consumption (Anderson, 1984; Schulz, 1999; Wang et al., 2011). The
general form of the FTT reaction is:
(2n + 1)H2 + nCO = CnH2n+2 + nH2O
The highly exothermic hydrogenation of CO is a basic FTT reaction
(Rӧper, 1983; Szatmari, 1989). The Sabatier reaction of slightly endo­
thermic CO2 hydrogenation is another form of FTT (Sabatier and
Senderens, 1902). In this process, CO is formed first, and is then hy­
drogenated to hydrocarbons (Weatherbee and Bartholomew, 1984).
Etiope and Whiticar (2019) suggested that most abiotic methane forms
from CO2 hydrogenation (Sabatier reaction) in water-free (or
4
Earth-Science Reviews 230 (2022) 104063
unsaturated) rocks, at relatively low temperatures, in the presence of
minerals that can act as FTT catalysts (e.g., chromium and/or
ruthenium-based minerals in ophiolites).
There may be many inorganic sinks of H2 in the subsurface (reactions
with pyrite or other sulphides, oxidation to water and others). For
example, Suzuki et al. (2017) suggested that the dehydration of hydrous
minerals could be responsible for consumption of H2 during
metamorphism.
Some geologic H2 escapes into the atmosphere and the ocean, for
example, in areas where H2-rich gases seep at the surface (Etiope et al.,
2011) and vent at the seafloor (Charlou et al., 2002). However, the
models and budgets of H2 in the atmosphere currently do not account for
the geologic H2 (Price et al., 2007; Ehhalt and Rohrer, 2009; Pieterse
et al., 2011). Although H2 is commonly considered as
environment-friendly gas (World Energy Council, 2019), its natural or
industrial combustion adds water vapor to the atmosphere, which is the
most abundant and powerful greenhouse gas (Sherwood et al., 2018). In
addition, leakage of H2 into the atmosphere reduces global levels of the
hydroxyl radical OH and therefore increases the lifetime and forcing of
the second most powerful greenhouse gas CH4 (Warwick et al., 2004). A
recent study estimated that, over a 100-year time period, one metric ton
of H2 in the atmosphere will warm the Earth some 11 (± 5) times more
than one metric ton of CO2 (Warwick et al., 2022). An increase in the
atmospheric H2 also increases the concentration tropospheric ozone
(O3), important to both air quality and climate (Warwick et al., 2022).
3. Dataset
Compilation of a large global dataset of ~34,500 gas samples from
100 countries and territories across seven continents (~370 basins) was
done using data from ~1200 publications and public databases. Gas
samples were taken at depths ranging from the surface to 8600 m below
surface/seafloor. Gas samples came from 16 different geological habitats
listed below (note that the references cited below are not the sources of
all of the data from the given habitat but rather provide further details
about the gas type, collection method or source of the samples typical for
that habitat).
A. Conventional oil and gas reservoirs. These reservoirs do not
require stimulation such as fracking or heating to recover oil and
gas. The gases were sampled either from wellheads or separators
at the surface (Liu et al., 2013) or directly from producing for­
mations (mostly with formation testers such as Modular Dynamic
Formation Tester, Milkov et al., 2007; Petersen et al., 2019).
B. Coals. These gases came from coal mines and coal seams (known
as coal bed methane (CBM) or coal seam gas (CSG)) (Milkov,
2021). They were sampled from producing wellheads (Bao et al.,
2014) or from degassed coals placed in desorption canisters
(Bannerjee et al., 2021).
C. Shales. These gases came from geological formations with true
shale lithology such as the Marcellus Formation in the USA and
the Wufeng-Longmaxi Formation in China and from unconven­
tional “tight” reservoirs composed of very fine-grained sand­
stone/siltstone (e.g., the Bakken Formation, USA) and some
mixed clastic/carbonate reservoirs (e.g., the Niobrara Formation,
USA) where gases were generated within these formations or in
immediately surrounding rocks (Milkov et al., 2020a). The gases
were sampled during production at wellheads (Feng et al., 2017)
or after degassing from rocks placed in desorption jars and can­
isters (Chatellier et al., 2013; Chen et al., 2020).
D. Hydrocarbon seeps and mud volcanoes. These gases were
sampled at the surface/mudline from actively or passively
degassing petroleum seeps and mud volcanoes in sedimentary
basins (Etiope et al., 2009).
E. Marine sediments. These gases were sampled in marine sediments
with no obvious indication of petroleum or volcanic/magmatic
A.V. Milkov
seeps or discharge from hydrothermal systems, and recovered by
piston coring (Bernard et al., 1977, 2013) or during ocean drilling
(Choi et al., 2016). Such gases are usually water-dissolved in the
subsurface, and were sampled after being released into gas voids
(Milkov et al., 2004) or into headspace (Luong et al., 2021).
F. Gas hydrates. These gases were sampled during the decomposi­
tion of gas hydrates recovered from marine (Milkov, 2005) and
continental (Liu et al., 2020; Hachikubo et al., 2020) sediments.
G. Continental sediments (including lakes and swamps). These gases
were sampled in continental settings (Hendrix, 2009) in sedi­
ments and rocks with no obvious indication of petroleum or
volcanic/magmatic seeps or discharge from hydrothermal sys­
tems. They were recovered by shallow coring and drilling (Lecher
et al., 2017) or deep drilling (Wiersberg and Erzinger, 2008), and
were usually dissolved in water (Gruca-Rokosz and Koszelnik,
2018).
H. Aquifers/groundwater. These gases, typically dissolved in water,
were sampled from water wells drilled into underground layers of
water-bearing permeable rocks, rock fractures or unconsolidated
materials (Darrah et al., 2014; Goetz, 2021). This category ex­
cludes gases from volcanic/magmatic hydrothermal systems,
sedimentary hydrothermal systems, and serpentinites (see
below).
I. Non-sedimentary hard rocks. These gases were sampled from
non-sedimentary igneous and metamorphic rocks (but not ser­
pentinites, see below), typically in cratonic settings (Potter et al.,
2013; Boreham et al., 2021b). The gases were obtained during
crushing of the hard rocks (Potter et al., 2013) or came from
pores/cavities (Galimov and Petersil’ye, 1967; Jeffrey and
Kaplan, 1988) and even as gas jets and seeps (Voytov, 1992).
J. Volcanic/magmatic seeps. These gases were sampled at the sur­
face/mudline from actively (via eruptions) or passively (via fu­
maroles) degassing onshore and offshore volcanoes (excluding
vents in Mid-Ocean Ridges, see below) associated with magmatic
processes (Bergfeld et al., 2014; Fischer and Chiodini, 2015;
Fiebig et al., 2019).
K. Volcanic/magmatic vents in Mid-Ocean Ridges (MORs). These
gases were sampled from vents in the Mid-Atlantic Ridge (Konn
et al., 2022), Mid-Cayman Rise (McDermott et al., 2018), East-
Pacific Rise (Proskurowski et al., 2008a, 2008b), Juan de Fuca
Ridge (Lilley et al., 1993), and the Central Indian Ridge (Kawa­
gucci et al., 2010).
L. Volcanic/magmatic hydrothermal systems. These gases sampled
below surface (in aquifers) were clearly related to volcano-hosted
hydrothermal systems in which the heat and volatiles are sup­
plied from magma (Fischer and Chiodini, 2015; Fiebig et al.,
2019). In the classification of Moeck (2014), these are
convection-dominated volcanic type and plutonic type
geothermal plays exemplified, for example, by the Reykjanas
system in Iceland (Arnason, 1977; Byrne et al., 2021) and the
Larderello system in Italy (Leila et al., 2021).
M. Hot springs in sedimentary hydrothermal system. These gases
sampled at the surface/mudline were apparently associated with
deep hydrothermal systems in sedimentary rocks, with no
obvious relation to adjacent recent volcanic/magmatic activity.
Examples include hot springs in the Baikal rift zone (Kalmychkov
et al., 2020).
N. Sedimentary hydrothermal system. These gases came from hot
aquifers in sedimentary rocks that do not have clear association
with volcanic/magmatic systems. In the classification of Moeck
(2014), these are conduction-dominated geothermal plays in
intracratonic basins (e.g., North German basin, Feldbusch et al.,
2018), orogenic belts and basements. The extensional domain
plays with no obvious recent volcanic/magmatic activity such as
in the Western Turkey (Tut Haklıdır et al., 2021) are also included
in this category.
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Earth-Science Reviews 230 (2022) 104063
O. Springs. These gases were sampled at the surface/mudline from
some degassing features that do not have obvious known asso­
ciation with either hydrocarbon seeps (and underlying petroleum
systems) or with degassing volcanoes associated with magmatic
processes (and having obvious thermal anomalies). Examples
include springs along the Dead Sea Fault system (Gasperini et al.,
2020). Many of the springs from the database of Mariner et al.
(2006) were included in this category simply because there was
no clear geological information to classify them as either volca­
nic/magmatic seeps or hot springs in sedimentary hydrothermal
system.
P. Serpentinites. These gases came from springs, seeps/vents and
aquifers, located both onshore and offshore, that clearly associate
with serpentinites (Etiope et al., 2017; Nothaft et al., 2021). Some
gases in volatiles released from crushed ultramafic rocks appar­
ently affected by serpentinization (Zhang et al., 2017) are also
included in this category.
There are some overlaps and uncertainties in the definitions of these
geological habitats. For example, gas hydrates occur in marine (Milkov,
2010) and in continental (Lu et al., 2011), including lake (Hachikubo
et al., 2020), sediments. However, gas hydrates contain concentrated
gases (Milkov, 2005), which are potentially important resources (Mil­
kov, 2004), and the process of gas hydrate formation fractionates gases
(Sassen et al., 2000; Milkov et al., 2004). Therefore, I differentiate gas
hydrates as a separate geological habitat. Similarly, and highly impor­
tant for this study, I differentiate serpentinites as a separate habitat.
Even though gases in that category are sampled both at the surface/­
mudline (seeps, springs) and in the shallow fractured aquifers, I differ­
entiate that habitat strictly based on the mineralogy of the hosting rocks,
due to the unique H2-enriched gases generated in that setting. Serpen­
tinization process can contribute to gases sampled from other habitats
such as aquifers (Sherwood Lollar et al., 2007), volcanic/magmatic
seeps and vents in MORs (Charlou et al., 2000), sedimentary hydro­
thermal systems (Hao et al., 2020), conventional reservoirs (Coveney Jr.
et al., 1987; Briere et al., 2017), and non-sedimentary hard rocks (Kelley
and Früh-Green, 1999). However, unless the sampled gases directly
emanate from serpentinites, they have been labelled as corresponding to
other geological habitats. Gases from springs and hydrothermal systems
may also be difficult to assign to one of the defined habitats. For
example, I classified Bazman thermal springs in the southeast Iran
(Deshaee et al., 2020) as “hot springs in sedimentary hydrothermal
systems” even though there are nearby volcanoes with recent activities
because it appears that these volcanoes contributed heat but not vola­
tiles to the thermal springs. In spite of the listed limitations, the
assignment of gases to specific geological habitats enables the holistic
geological and geochemical interpretation of natural gases.
The data for gas samples include information on location, sampling,
depth, temperature, formation, fluid type and molecular and isotopic
compositions. Gas concentrations are recorded as vol.% on water-free
basis. Parts of this dataset were previously described and studied by
Milkov and Etiope (2018), Milkov et al. (2020a, 2020b), Snodgrass and
Milkov (2020) and Milkov (2021).
A total of 34,290 samples in the dataset have identified geological
habitats (one of the 16 habitats discussed above, Fig. 1A). 6246 of these
samples have reported H2 concentrations (Fig. 1B). The concentration
data come from published papers, reports and publicly available gov­
ernment databases, and the validity of specific measurements is
impossible to check. Gases with reported H2 concentrations occur in 50
countries and territories and in MORs (Fig. 2). Most gases come from the
USA (n = 2481) and China (n = 816). A fraction of samples (n = 484)
have measured δ2H-H2 values.
A.V. Milkov Earth-Science Reviews 230 (2022) 104063

Fig. 1. Pie charts showing the number and proportions of gases from different geological habitats in the entire dataset of gas samples with known geological habitats
(A) and in the subset of gas samples with measured H2 concentrations (B).

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A.V. Milkov
Fig. 2. Distribution of samples with reported H2 concentrations across countries and territories (A) and across continents, including Mid-Ocean Ridges (B).
4. Results
4.1. Distribution of H2 in various geological habitats and depths
Concentrations of H2 in natural gases, when measured and reported
(n = 6246), range from 0% to 100% (Fig. 3), with average ~3.5% and
median ~0.01%. There are 4770 gas samples with H2>0%, and this
subset includes 1890 samples with H2>0.1%, 1012 samples with
H2>1%, and 621 samples with H2>5% (Fig. 3).
The distributions of H2 concentrations in gases from 16 geological
settings described above are presented as box plots in Fig. 4. Gases
sampled in MORs and in serpentinites have the highest average con­
centrations of H2 (~24% and ~21%, respectively). Other six settings
that contain less, but still appreciable amounts of H2, include non-
sedimentary hard rocks (average ~11%), volcanic/magmatic hydro­
thermal systems (~7%), sedimentary hydrothermal systems (~4%),
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Earth-Science Reviews 230 (2022) 104063
volcanic/magmatic seeps (~4%), aquifers (~3%), and conventional
petroleum reservoirs (~1%). The remaining eight geological settings
(marine sediments, shales, coals, hot springs in sedimentary hydro­
thermal systems, continental sediments, hydrocarbon seeps and mud
volcanoes, and springs) have either very low average concentrations of
H2 or/and small number of available gas samples, and I exclude them
from further consideration in this study.
Most gas samples with significant (>10%) H2 (also referred to as H2-
rich by Coveney Jr. et al., 1987) occur at the surface (as seeps and vents)
or in shallow (<2000 m) subsurface (Fig. 5). Among 1186 surface gas
samples with H2 measurements, the average concentration is ~10%. The
highest concentrations (>90%) are measured in gases seeping from
serpentinites (Neal and Stranger, 1983; Szponar et al., 2013) and vent­
ing from MORs (Proskurowski et al., 2008a, 2008b; Konn et al., 2022).
The average H2 in serpentinite seeps is ~23% (n = 239), and in MOR
vents it is ~24% (n = 131). In contrast, volcanic/magmatic seeps have
A.V. Milkov Earth-Science Reviews 230 (2022) 104063

Fig. 3. Distributions of H2 concentrations in gas samples with reported H2 concentrations. Panel A shows all available samples with bin size 0.1% and demonstrates
that the vast majority of samples has H2 concentrations <0.1%. Panel B shows all available samples with bin size 5% and also zooms into samples with H2 con­
centrations >5% (panel C) to demonstrate a relatively small number of such samples in the dataset.

significantly lower average H2 concentration of ~4% (n = 798).
At depth from >0 to 2000 m below the surface, the average H2 is
~2.8% (n=1296 samples). The highest concentrations >90% are
measured in gases dissolved in water held by serpentinites (Sader et al.,
2021; Nothaft et al., 2021), in conventional gas reservoirs (Prinzhofer
et al., 2018; Pudovskis, 1959) and in aquifers (Guélard et al., 2017). The
average H2 in volcanic/magmatic hydrothermal systems is ~18.4% (n
= 22, with highest concentrations up to 58.6% in wells from the Cerro
Prieto geothermal field, Welhan, 1981), in serpentinites ~15.5% (n =
65), in non-sedimentary hard rocks ~14.4% (n = 11), in aquifers ~6.6%
(n = 95), in sedimentary hydrothermal systems ~1.9% (n = 27), and in
conventional reservoirs ~1.2% (n = 997).
Samples from depth >2000 m are predominantly from conventional
reservoirs (Fig. 5). The average H2 concentration is ~1% (n = 666), but
that value is significantly affected by few gases from deep aquifers and
non-sedimentary rocks relatively enriched in H2.
It appears from the above statistics and displays in Fig. 5 that the
average concentration of H2 is greatest at the surface and decreases with
increasing depth. However, that observation results from a smaller
number of samples at great depths, which come predominantly from
conventional reservoirs. There are no clear trends of H2 increase or
decrease with increasing subsurface depth in studied geological settings.

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A.V. Milkov Earth-Science Reviews 230 (2022) 104063

Fig. 4. Concentrations of molecular H2 in natural gas samples (n=6246) from 16 geologic habitats (sorted by decreasing average values, letter labels are consistent
with text in section 3): K - Mid-Ocean Ridges; P – Serpentinites, I – Non-sedimentary hard rocks; L – Volcanic/magmatic hydrothermal systems; N – Sedimentary
hydrothermal systems; J – Volcanic/magmatic seeps; H – Aquifers/groundwaters; O – Springs; A – Conventional reservoirs; G – Continental sediments; E – Marine
sediments; F – Gas hydrates; C – Shales; B – Coals; M – Hot springs in sedimentary hydrothermal systems; D – Hydrocarbon seeps/mud volcanoes. The data are
displayed using a box plot, which shows distribution of values as histogram, average (mean) values as black stars (and 95% confidence level as black bars), median
values as dotted line, first quartile (Q1), third quartile (Q3), lower adjacent value (LAV), upper adjacent value (UAV), and outliers. The first quartile (Q1) is the
median of the lower half of the data set. This means that about 25% of the numbers in the data set lie below Q1 and about 75% lie above Q1. The third quartile (Q3) is
the median of the upper half of the data set. This means that about 75% of the numbers in the data set lie below Q3 and about 25% lie above Q3. The lower adjacent
value is the smallest observation that is greater than or equal to the lower inner fence, which is the first quartile minus 1.5×IQR, where IQR stands for the inter­
quartile range. The upper adjacent value is the largest observation that is less than or equal to the upper inner fence, which is the third quartile plus 1.5×IQR. Most
values are located in the lower part of the distributions, and displayed statistical boundaries are poorly distinguished on these box plots.

Fig. 5. Concentration of H2 (A – simple linear scale, B – logarithmic scale) at the surface and at subsurface depths in various geological habitats.

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A.V. Milkov Earth-Science Reviews 230 (2022) 104063

4.2. Associations of H2 with other natural gases He is generated in the crustal settings from the decay of radioactive
elements (Byrne et al., 2018), but crustal H2 either is limited at the
Hydrogen is the focus of this study, but it is, on average, not the most source or is largely consumed. On the other hand, a weak positive cor­
abundant gas even in geological habitats where it is present in relatively relation between H2 and He in gases from conventional reservoirs
high concentrations (Table 1). Other gases typically dominate, as, for potentially suggests that they are generated, migrate and/or become
example, N2 in serpentinites, CH4 in conventional reservoirs and in non- preserved in similar ways.
sedimentary hard rocks, and CO2 in volcanic/magmatic seeps and hy­
drothermal systems. Hydrogen is the second most abundant gas in MORs 4.3. Isotopic compositions of H2 and associated He
and in volcanic/magmatic hydrothermal systems. Helium is, on average,
less abundant than H2 in all these settings. Stable isotopes are a standard tool to evaluate the origin of hydro­
Fig. 6 compares concentration of H2 with the concentrations of other carbon gases, CO2, N2 and noble gases at the surface (seeps) and in the
major gases CH4, CO2 and N2 in different geological settings. Gases in subsurface (Milkov and Etiope, 2018; Lavrushin et al., 2020; Byrne et al.,
conventional reservoirs are clearly dominated by CH4, and volcanic/ 2018). Various tools ranging from two-dimensional genetic diagrams
magmatic gases are clearly dominated by CO2, and these observations (Milkov and Etiope, 2018; Milkov, 2021) to a web-based machine
are consistent with the main statistics in Table 1. There are no obvious learning tool (Snodgrass and Milkov, 2020) have been developed to
correlations between concentrations of H2 and concentrations of these interpret the origins of these gases based on large datasets of tens of
major gases in the studied geological settings. However, there is a weak thousands gas samples.
positive correlation between concentrations of H2 and He for all Geologic H2 contains two stable isotopes, 1H (protium, isotopic
considered gases (Fig. 7). Gases from MORs and volcanic/magmatic abundance ~99.972% of all hydrogen on modern Earth) and 2H
gases are more enriched in H2 and depleted in He (also see Table 1) than (deuterium). Isotopic composition of H2 is expressed as δ2H-H2 values in
gases from crustal settings. This may be because significant additional parts per thousand (per mil, ‰) referenced to Vienna Standard Mean
Ocean Water, or VSMOW (Schimmelmann and Sauer, 2017). Although
Table 1 δ2H-H2 can be indicative of H2 origin (Boreham et al., 2021a, 2021b;
Range, average and median concentrations of major gases (CH4, N2, CO2), H2 Schimmelmann and Sauer, 2017), the number of available δ2H-H2
and He in the six geological habitats with highest average H2 concentrations. measurements in natural gases is relatively small, there is a significant
Other gases that are present in smaller concentrations (e.g., ethane-pentane and overlap in δ2H-H2 values of H2 with different origins (Boreham et al.,
H2S) are not shown. The n indicates the number of samples with available 2021a, 2021b) and there is no comprehensive interpretation scheme to
concentration measurements. determine the origin of H2 based on its isotopic composition.
Geological CH4 N2 CO2 H2 He Gas Comparison of H2 concentrations with the isotopic composition of H2
habitat type suggests that there is no correlation between them for the entire set of
Mid-Ocean 0-73.3 0-88.8 0-99.9 0-97.1 0.01- CO2- gases (Fig. 8). However, there is a good separation between H2 in gases
Ridges Av. 6.7 Av. 21.6 Av. 50.6 Av. 0.05 H2- from MORs, volcanic/geothermal seeps and hydrothermal systems and
Med. 1.9 Med. 6.8 Med. 23.8 Av. N2 gases from serpentinites, conventional reservoirs and aquifers/ground­
(n = (n = 74) 47.6 Med. 0.04
waters, non-sedimentary hard rocks and sedimentary hydrothermal
137) (n = 4.1 Med.
112) (n = 0.04 system based on δ2H-H2 of -650‰.
137) (n = The distribution of δ2H-H2 values across various geological settings is
12) broadly trimodal (Fig. 9). Molecular H2 from serpentinites (Fig. 9b),
Serpentinites 0-95.1 0-99.5 0-99.9 0-100 0-0.01 N2- conventional petroleum reservoirs, aquifers, non-sedimentary hard
Av. 26.5 Av. 36.1 Av. 16.8 Av. Av. CH4-
Med. 9.7 Med. Med. 21.2 0.65 H2
rocks and sedimentary hydrothermal systems has δ2H-H2 values gener­
(n = 25.0 (n 0.05 (n Med. Med. ally more negative than -650‰ (mode around -730‰). Not included in
428) = 390) = 266) 4.8 0.01 Fig. 9 are gases extracted from shales and metapelites with δ2H-H2
(n = (n = values from -810 to -629‰ (Suzuki et al., 2017). In contrast, molecular
397) 248)
H2 from volcanic/magmatic seeps and hydrothermal systems is rela­
Non- 0.1-92.9 0-99.7 0-92.8 0-63.3 0-19.1 CH4-
sedimentary Av. 48.1 Av. 36.8 Av. 3.5 Av. Av. N2- tively enriched in 2H with δ2H-H2 values generally exceeding -650‰
hard rocks Med. Med. Med. 0.2 8.1 3.0 H2 (Fig. 9c), with apparent two modes around -530‰ and -370‰. Gases
52.0 32.4 (n = 70) Med. Med. sampled from vents in MORs are generally even more enriched in 2H
(n = 86) (n = 83) 3.0 (n 1.1 with δ2H-H2 values with a mode about -370‰ (Fig. 9d).
= 77) (n =
80)
These observations suggest that δ2H-H2 values may be indicative of
Volcanic/ 0-74.3 0-97.6 0-99.6 0-64.7 0-19.9 CO2- H2 origin: hydrogen with δ2H-H2 of <-650‰ has crustal origin, while
magmatic Av. 5.9 Av. 6.7 Av. 79.9 Av. Av. H2- hydrogen with δ2H-H2 of >-650‰ has mantle/primordial origin. Pri­
hydrothermal Med. 0.9 Med. 0.9 Med. 6.8 0.9 N2 mordial H2 was delivered by meteorites during accretion of the Earth
systems (n = (n = 84.1 (n Med. Med.
and preserved in the mantle and the core (Larin, 1993, 1995). The
156) 151) = 137) 1.6 (n 0.0
= (n = separation of crust-sourced and mantle-sourced gases based on δ2H-H2
149) 74) of -650‰ is supported by the well-established source fingerprinting
Volcanic/ 0-96.1 0-99.0 0-99.9 0-80 0-33.3 CO2- based on He isotopes as shown in Fig. 10 (3He/4He ratios are typically
magmatic Av. 2.1 Av. 10.5 Av. 81.4 Av. Av. N2- reported relative to the atmospheric ratio Ra and expressed as R/Ra).
seeps Med. 0.2 Med. 1.6 Med. 2.6 0.02 H2
(n = (n = 91.8 (n Med. Med.
Helium from the mantle is relatively enriched in 3He, which is a pri­
848) 817) = 803) 0.2 (n 0.00 mordial isotope made in the Big Bang and incorporated into Earth
= (n = during its initial accretion (Byrne et al., 2018). The association of 2H-
767) 640) enriched H2 with 3He-enriched He suggests that 2H-enriched H2
Conventional 0-100 0-97.8 0-100 0-97.4 0-9.0 CH4-
observed in volcanic/magmatic natural gases has mantle and/or pri­
reservoirs Av. 81.6 Av. 5.3 Av. 4.7 Av. Av. N2-
Med. Med. 1.7 Med. 1.0 0.9 0.15 CO2 mordial origin. Gas samples from the crustal geological settings are
87.1 (n (n = (n = Med. Med. relatively depleted in 3He and in 2H (Fig. 10). Specific sources of He and
= 10,251) 12,366) 0.0 (n 0.02 H2 in each gas sample from crustal settings can be different (e.g., He can
14,660) = (n = come from the decay of radioactive elements and from the air, while H2
2150) 2688)
is sourced by the reactions of serpentinization, Vacquand et al., 2018) or

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Fig. 6. Concentration of H2 versus concentrations of CH4, CO2 and N2 in natural gases from various geological habitats. See Fig. 5 for symbol legend.

Fig. 7. Concentration of H2 versus concentrations of He in natural gases from various geological habitats. See Fig. 5 for symbol legend. Samples that contain one gas
(for example, H2), but not the other (respectively, He), as, for example, some gases emanating from serpentinites in Oman (Zgonnik et al., 2019) are not displayed on
this log-log plot.

the same (Naumenko-Dézes et al., 2022).
Gases venting at MORs have a wide range of δ2H-H2 values from -823
to -231‰ (n = 52). Three samples from the East Pacific Rise extremely
depleted in 2H (δ2H-H2 values around -800‰, Fig. 9d) are likely sam­
pling artifacts (Merlivat et al., 1987). Ten samples with δ2H-H2 values
between around -700 and -600‰ come mostly from the Lost City, where
the process of serpentinization is very well documented (Lang and
Brazelton, 2020). The vast majority of MOR samples have δ2H-H2 values
between -500‰ and -230‰ (Fig. 9d), suggesting mostly mantle/pri­
mordial origin.
The isotopic composition of molecular H2 in volcanic and magmatic
settings is distinct, with δ2H-H2 values generally greater than -700‰ and
as high as -110‰. This H2 is associated with mantle/primordial He, and
may have mantle/primordial origin. Among these samples, δ2H-H2
values closer to -700‰ may indicate H2 of mixed mantle/crustal origin,
for example in some samples from the Yellowstone (Welhan, 1981). δ2H-
H2 values closer to -400‰ (as in MOR samples, Fig. 9) and to -100‰ (as
in the Mid-Icelandic volcanic belt, Sigvaldson and Elisson, 1968; Arna­
son and Sigurgeirsson, 1968) may indicate H2 from processes in the
mantle, and perhaps some H2 of primordial origin. Such interpretation is
consistent with δ2H-H2 values mostly between -95‰ and -35‰ in min­
erals and fluid inclusions in mantle-derived rocks (Kyser and O’Neil,
1984; Deloule et al., 1991; Kingsley et al., 2002; Loewen et al., 2019),
the suggestion that primordial H2 has δ2H-H2 of about -75‰ (Craig and

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A.V. Milkov
Fig. 8. Concentration of H2 versus δ2H-H2 in various geological habitats. See Fig. 5 for symbol legend. The value of δ2H-H2 -650‰ may separate crustal and mantle/
primordial H2 (see text for discussion).
Lupton, 1976; Taylor et al., 1983; Larin, 1995) and even greater 2H
enrichment in asteroids and comets (Dauphas et al., 2000).
The variations of δ2H-H2 in geological habitats are interpreted above
in terms of different sources and origins of H2 (also complicated by the
fact that the geological habitats do not exactly correspond to specific
sources of hydrogen). Variations in source water isotope composition
(δ2H-H2O) and temperature-dependent equilibrium isotopic fraction­
ation and kinetic 2H-1H exchanges between H2 and water (Pester et al.,
2018; Ricci et al., 2022; Löffler et al., 2022) provide additional reasons
for these variations or an alternative explanation of such variations. The
fractionation factor at equilibrium (αH2O-H2(eq)) is sensitive to tempera­
ture (Richet et al., 1977; Horibe and Craig, 1995). In general, H2
sampled at high temperatures and/or sourced by high-temperature
fluids should be more enriched in 2H (i.e., should have more positive
δ2H-H2 values) than H2 sampled at low temperatures. Data from natural
gases generally follow this trend (see Fig. 1 in Pester et al., 2018), but
there are many deviations from the equilibrium curve, which can be
explained by previous higher temperatures of the solutions. There is a
weak positive correlation between δ2H-H2 values and sampling tem­
perature in our dataset (Fig. 11), which is broadly consistent with
temperature-dependent isotopic fractionation between H2 and water.
4.4. Origins of H2-containing gases
Molecular H2 is commonly a relatively minor compound in natural
gases dominated by hydrocarbons (predominantly CH4), CO2 and N2
(Table 1). The origins of these major gases can be inferred from stable
isotopes (Milkov and Etiope, 2018; Snodgrass and Milkov, 2020; Milkov,
2021; Lavrushin et al., 2020). Figs. 12 and 13 show commonly used
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genetic diagrams with plotted gases that contain ≥1% of H2. It appears
that hydrocarbons and CO2 sampled from conventional reservoirs have
mostly thermogenic origin. Hydrocarbons and CO2 sampled from other
geological settings, especially volcanic gases, gases from serpentinites
and gases from non-sedimentary hard rocks have mostly abiotic origin.
However, it is important to note that the construction of gas genetic
fields on these diagrams was grounded in both geochemical and
geological arguments (Milkov and Etiope, 2018), so the conclusions
above are based on circular reasoning. In addition, many natural gases
are mixtures. Almost no gases that contain ≥1% of H2 have hydrocar­
bons and CO2 of microbial origin, which may be explained by the close
association of H2 producers and consumers in shallow cool marine
sediments and oil pools where microbial gases typically form.
The concentration of H2 has a weak correlation with the values of
δ13C-CH4 (Fig. 14). Methane in gas samples (all geological settings) with
>10% H2 has average δ13C value -21.8‰ (n = 172), while methane in
gas samples with H2 content >0% and ≤10% has average δ13C value
-38.0‰ (n = 1509). The presence of very high H2 concentrations
together with 13C-enriched methane likely indicates common abiotic
processes in which these gases are co-generated (Etiope and Sherwood
Lollar, 2013; Etiope and Schoell, 2014; Etiope and Whiticar, 2019).
Comparison of δ2H-H2 values with carbon and hydrogen isotopes of
co-existing CH4 suggests that crustal and mantle CH4 can be distin­
guished based on δ2H-CH4, with a separation at about -200‰ (Fig. 15).
While carbon isotopes of CH4 help distinguish between biotic and
abiotic processes, the plot of δ2H-H2 versus δ13C-CH4 highlights that
gases from crustal geological settings can have biotic or abiotic origins,
while mantle/primordial gases have abiotic origin.
A.V. Milkov
Fig. 9. Histograms showing distributions of δ2H-H2 values in gas samples from eight geological settings (A), and separately from serpentinites (B), volcanic/
magmatic settings (C) and MORs (D). The bin size is 20‰.
4.5. H2 in conventional reservoirs
Conventional reservoirs with reported H2 concentrations are the
most represented geological settings with the largest number of H2
measurements in the studied dataset (n = 2237). The average concen­
tration of H2 in gases from conventional reservoirs is ~0.8%, while the
median concentration is only 0.01% (Fig. 4). I note that these statistics
are for all samples in the dataset, and they are not weighted for gas
resources in conventional reservoirs. The average concentration value is
likely to be significantly pushed upwards due to 38 samples with >10%
of H2 from several poorly understood gas accumulations in Australia and
better studied accumulations in Kansas and in Mali.
High concentrations of H2 in conventional reservoirs in Australia
(Fig. 5) have been reported long time ago, for example 51-84% in the
Adelaide area within the Gawler Craton (Ward, 1933) and up to 95.3%
in the Meda field in the Canning Basin (Pudovskis, 1959). These high H2
concentrations were highlighted in the recent review by Boreham et al.
(2021a), but they should be validated with modern measurements
(including isotopes) to be better understood.
High concentrations of H2 were observed in the Heins and Scott wells
in Kansas (Fig. 5) where 31 gas samples have H2 concentrations ranging
from 1.4 to 70% (average ~32%), the remainder being N2 and traces of
hydrocarbons (McCarthy Jr. et al., 1986; Goebel et al., 1984; Coveney
Jr. et al., 1987; Guélard et al., 2017). The Sue Duroche #2 water well
drilled in the same area also contains high concentrations of H2 (Guélard
et al., 2017). These wells are near a major rift system with mafic rocks
and known kimberlites, which led to the initial interpretation that H2
originated from the reactions of serpentinization (Coveney Jr. et al.,
1987), although the later study presented a more complex interpretation
of both deep and shallow H2 origins (Guélard et al., 2017). The average
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Earth-Science Reviews 230 (2022) 104063
δ2H-H2 value in the Heins and Scott gases is -753‰ (n = 11), which is
close to isotopic composition of H2 sourced by serpentinites (Fig. 9b).
Gas with high (98%) concentration of H2 (Fig. 5) was serendipitously
discovered in the Bourakebougou area (Mali) by a water well (Briere
et al., 2017; Prinzhofer et al., 2018). The initial study speculated that
serpentinization of ultramafic rocks is one of the most likely mechanisms
of H2 generation in the area (Briere et al., 2017). The later, more detailed
integrated geological/geochemical study suggested that H2 (it has δ2H-
H2 value -702‰) comes from the basement, without specifying the
process of H2 generation (Prinzhofer et al., 2018). Serpentinized mantle
peridotites are present in the NE Mali (the Timétrine massif, Caby, 2014)
but the presence of serpentinites in the proximity of the Bourakebougou
area located within the West African craton in SE Mali is not apparent
from the literature review.
Curiously, very high concentration of H2 of 88.5% (with δ2H-H2
-742‰) was reported in an oil-associated gas from the Brent field (211/
29-B17) in the North Sea (UK OGA, 2021). That gas was unusual because
most gases from the Brent field do not contain H2. The high H2 was likely
formed via artificial processes such as metal corrosion. Apparently
artificial gases with high H2 (up to 90%) found in a well annuli on Troll A
platform offshore Norway have δ2H-H2 values about -750 to -725‰
(Thiessen et al., 2009). The δ2H-H2 values of artificial H2 may overlap
with the δ2H-H2 values of H2 from serpentinization (Fig. 9b), making
separation of these processes based on H2 isotopes alone rather
challenging.
Plotting of δ2H-H2 values versus concentrations of H2 in conventional
reservoirs (Fig. 16) reveals that: 1) there is a wide range of δ2H-H2 values
from -996‰ to -370‰ (n = 74), but most samples (n = 69) have δ2H-H2
values from -850‰ to -600‰; 2) there is essentially no correlation of
δ2H-H2 values and concentrations of H2. Three samples more depleted in
A.V. Milkov
2
H (δ2H-H2 <-850‰) than most other samples are from the West
Moonfish, Marlin and Basket wells in the Gippsland basin offshore
Australia (Boreham et al., 2021a). Such δ2H-H2 values are highly un­
usual in the studied dataset (Fig. 9a). There are two samples more
enriched in 2H (δ2H-H2 >-600‰) than most other samples (Fig. 16),
including one sample from Australia (the Katandra well in the Bonaparte
basin). Boreham et al. (2021a) suspected that artifacts accompanying
gas production, collection or storage caused unusual δ2H-H2 values in
these gases from Australia. The fifth unusual sample is from the Heins
well in Kansas, but that single value δ2H-H2 >-520‰ reported by
McCarthy Jr. et al. (1986) is outside of the range of the other 16 mea­
surements from -670‰ to -836‰ (average -779‰) in the Heins and
Scott wells (Goebel et al., 1984; Coveney Jr. et al., 1987; Guélard et al.,
2017), making that value suspicious.
Samples with a significant 2H enrichment may be contaminated with
H2 from corrosion of steel (Levshounova, 1991) or may contain abiotic
mantle-derived H2 from some undelaying deep-seated rocks (Smith
et al., 2005; Truche and Bazarkina, 2019). Still, gases in conventional
reservoirs have δ2H-H2 values mostly from -850‰ to -600‰ (Fig. 16),
suggesting that these processes may be not important in conventional
reservoirs.
Similarity of δ2H-H2 values between conventional reservoirs and
serpentinites (Figs. 9 and 16) suggests that reactions of serpentinization
may be responsible for the origin of H2 in some conventional reservoirs.
This is likely the case for the H2-rich gas in the Heins and Scott wells in
Kansas. Interestingly, methane in these wells has δ2H values from -477 to
-419‰ (n = 5) and plot on the genetic diagram of δ13C-CH4 versus δ2H-
CH4 in the area of abiotic gas near many samples from serpentinites
(Fig. 12). This methane may have formed via FTT reactions from the H2
that originated from serpentinization of mafic rocks and kimberlites
documented in the area (Coveney Jr. et al., 1987).
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Earth-Science Reviews 230 (2022) 104063
Fig. 10. Isotopic composition of He (expressed as R/
Ra, see Byrne et al., 2018) versus isotopic composi­
tion of H2 (δ2H-H2) in gas samples from eight
geological settings. Three sets of samples (labeled)
are displayed but excluded from interpretation:
samples from 13N East Pacific Rise (Merlivat et al.,
1987) and from Groß Schönebeck (Feldbusch et al.,
2018) were interpreted as artifacts in the original
studies, and one sample from the Semail ophiolite
(Sano et al., 1993) is an outlier from other samples
taken in the same area. The other samples are inter­
preted as groups of mantle and primordial He and H2
and as crustal He and H2. Still, δ2H-H2 values may
reflect temperature-dependent equilibrium isotopic
fractionation and kinetic exchanges between H2 and
water (see the text for that discussion).
Other gases with δ2H values from -850 to -600‰ displayed in Fig. 16
come from fields (e.g., Brent field in the North Sea) and basins (Bohai
Bay in China, Taoudeni in Mali, and Gippsland, Bonaparte, Canning and
Bass basins in Australia) that do not have known nearby occurrences of
serpentinites. Other crustal sources and H2 generation mechanisms may
be responsible for the presence of H2 in these gases. δ2H-H2 values in
conventional reservoirs are similar to δ2H-H2 values (from -810 to
-629‰) in H2 released from pulverized shales and metapelites and
supposedly liberated from the organic matter (Suzuki et al., 2017). This
suggests that H2 in conventional reservoirs may come from the organic
matter (Horsfield et al., 2022) and perhaps from the same source rocks
that supplied the major gases such as hydrocarbons and CO2. However,
it is not clear at this stage if other most often mentioned natural pro­
cesses (e.g., radiolysis or water or fracture-induced reduction of water)
or some other processes listed in Section 2.2. contribute H2 to conven­
tional reservoirs. A much larger dataset of δ2H-H2 values integrated with
the geological settings of the conventional wells is needed to answer this
question.
5. Discussion
5.1. The value and use of δ2H measurements in the interpretation of H2
origins
Although δ2H-H2 can be indicative of H2 origin (Schimmelmann and
Sauer, 2017; Boreham et al., 2021a, 2021b), previous studies evaluated
relatively small datasets of available δ2H-H2 measurements in natural
gases with significant overlaps in δ2H-H2 values of H2 with different
origins (Hao et al., 2020; Boreham et al., 2021a, 2021b) and did not
propose a comprehensive interpretation scheme to determine the origin
of H2 based on its isotopic composition.
A.V. Milkov Earth-Science Reviews 230 (2022) 104063

Fig. 11. Sampling temperature versus δ2H-H2 values in natural gases from different geological settings. See Fig. 5 for symbol legend. The dashed line represents
calculated δ2H-H2 values assuming δ2H-H2O=0‰ for equation α[H2O-H2] = 1.0473+201036/T2 + 2.060×109/T4 + 0.180×1015/T6, which describes temperature-
dependent (temperature is in Kelvin) hydrogen isotopic equilibrium (exchange) between H2 and H2O (Horibe and Craig, 1995; Kawagucci et al., 2010).

Fig. 12. Gas genetic diagrams (from Milkov and Etiope, 2018) with displayed gas samples that contain H2 concentrations ≥1%. See Fig. 5 for symbol legend. The
ratio of C1/(C2+C3) is the ration of methane to the the sum of ethane and propane, also known as “dryness” of the gas. Abbreviations: CR – CO2 reduction, F – methyl-
type fermentation, SM – secondary microbial, EMT – early mature thermogenic gas, OA – oil-associated (mid0mature) thermogenic gas, LMT – late mature ther­
mogenic gas.

The results of this study suggest that crustal and mantle/primordial
molecular H2 have distinctive δ2H-H2 values: crustal H2 is relatively
more depleted in 2H (δ2H-H2<-650‰) and mantle/primordial H2 is
relatively more enriched in 2H (δ2H-H2>-650‰). Further identification
of specific sources of H2 based on δ2H may be possible as discussed
below. Still, I caution that this discussion should be considered as pre­
liminary and subject to significant future revisions because the number
of currently available δ2H-H2 measurements is relatively small. Another
important consideration that should be integrated into the interpreta­
tion of δ2H-H2 values in natural gases is the variations in source water
isotope composition (δ2H-H2O) and temperature-dependent equilibrium
isotopic fractionation and kinetic isotope exchanges between H2 and
water (Horibe and Craig, 1995; Kawagucci et al., 2010; Simon et al.,
2011; Pester et al., 2018; Ricci et al., 2022). Many δ2H-H2 values in
natural gases plotted against temperature generally follow the theoret­
ical trend calculated for temperature-dependent hydrogen isotopic
equilibrium (exchange) between H2 and H2O (Fig. 11). Most δ2H-H2
values that deviate from that trend may be explained by fluid cooling
and the subsequent isotope equilibrium reaction (Kawagucci et al.,
2010) and the variations in source water isotope composition (δ2H-
H2O). It is possible that isotope exchange (equilibrium) reaction is a
dominant process that controls δ2H-H2 values in natural gases. The

15
A.V. Milkov
Fig. 13. Gas genetic diagram (from Milkov, 2021) with displayed gas samples
that contain H2 concentrations ≥1%. See Fig. 5 for symbol legend.
broad correlation of δ2H-H2 values with temperature (Fig. 11) does not
directly contradict the variation of δ2H-H2 values due to origins from
different geological settings. High-temperature geological settings such
as volcanoes may emit H2 that is relatively enriched in 2H because it has
primordial/mantle origin or/and because it is at equilibrium with water
vapor at that high temperature.
Molecular H2 most enriched in 2H (δ2H-H2>-350‰) perhaps is
mostly primordial. Degassing of primordial H2 at the Earth surface
Fig. 14. Concentration of H2 versus δ13C-CH4 in various geological habitats. See Fig. 5 for symbol legend.
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Earth-Science Reviews 230 (2022) 104063
(along with He and Ne) has been proposed a long time ago (Chamberlin,
1909; Craig and Lupton, 1976). The mantle/primordial H2 is docu­
mented by measurements in volcanic and magmatic gases (Fischer and
Chiodini, 2015), is theoretically feasible, and may be quantitatively very
significant (Gilat and Vol, 2005, 2012; Yang et al., 2016; Mao et al.,
2017; Komabayashi, 2021). The contribution of mantle-sourced H2 to
shallow gas accumulations has been previously discussed (Meng et al.,
2015). The amount of H2 in the Earth is debatable, but some studies
suggest that the interior of the Earth is enriched in H2 (Larin, 1993;
Walshe, 2006; Ikuta et al., 2019; He et al., 2022). Larin (1993) and
Toulhoat and Zgonnik (2022) estimated that the early Earth contained 4
wt.% initial H2. This H2 stored in hydrides could progressively decom­
pose and degass from the surface over geological time (Larin, 1993). The
H2 degassing was more significant for early Earth. It was proposed that
an Archean atmosphere contained up to 30% H2 (Wordsworth and
Pierrehumbert, 2013) and that gases in Archean igneous rocks contain
significantly more H2 than gases from more recent igneous rocks
(Chamberlin, 1909). Still, the importance of mantle and primordial H2 in
natural gases remains speculative (Zgonnik, 2020) and this origin
received no serious consideration in recent studies and reviews of H2
origins on Earth (Klein et al., 2020). Our results suggest that primordial
H2 may vent at the surface of the Earth in MORs and in some volcanic
settings (Sigvaldson and Elisson, 1968; Kiyosu, 1983; Lyon and Hulston,
1984). Primordial H2 may support unique ecosystems with chemo­
lithoautotrophic metabolic pathways on the modern deep seafloor
(Takai et al., 2004; Ohara et al., 2012), provide energy for long-term
survival of microbial cells (Morita, 2000) and contribute to the origin
of life on Earth and perhaps other planets (Nisbet and Sleep, 2001;
McCollom and Seewald, 2013; Holm et al., 2015; Glein and Zolotov,
2020).
Molecular H2 from volcanic/magmatic settings has a bimodal
A.V. Milkov Earth-Science Reviews 230 (2022) 104063

Fig. 15. δ2H-H2versus δ13C-CH4 (A) and δ2H-H2 versus δ2H-CH4 (B) in various geological habitats. Broadly defined fields of “crustal” and “mantle/primordial” gases
are outlined. See Fig. 5 for symbol legend.

Fig. 16. Concentration of H2 versus δ2H-H2 values in conventional petroleum accumulations and in serpentinites.

17
A.V. Milkov
distribution of δ2H values, with one mode around -380‰ (similar to the
MORs) and the second mode around -520‰ (Fig. 9c). This may indicate
that some volcanoes emit mostly primordial 2H-enriched H2, maybe
from the deeper mantle and from the core, for example, in the Mid-
Icelandic volcanic belt (Sigvaldson and Elisson, 1968; Arnason and
Sigurgeirsson, 1968). Other volcanoes emit relatively more 2H-depleted
H2 generated in the upper mantle or mixed with some crustal-generated
H2 (Welhan, 1981).
Serpentinization is one of the main processes that can result in high
H2 concentration in crustal geological settings (Coveney Jr. et al., 1987;
Etiope et al., 2011), and our results support this view. Gases sampled
from serpentinites contain molecular H2 with δ2H values around -715‰
(Fig. 9b). Such 2H-depleted H2 may be due to specific serpentinization
reactions or just a function of relatively low temperatures at which H2
equilibrates with water in serpentinite settings (Fig. 11).
Suzuki et al. (2017) report that H2 released from pulverized shales
and metapelites sampled in one well and in outcrops in Japan has δ2H
values from -810 to -629‰ (n = 15, average -696‰). They interpreted
that this H2 was liberated from the organic matter (kerogen) during
thermal maturation. These δ2H values are similar to δ2H values in gases
sampled from conventional reservoirs (n = 72, average -722‰, Fig. 9).
Although significant amounts of H2 were obtained during laboratory
pyrolysis of shale and coals (e.g., Li et al., 2015, 2017; Horsfield et al.,
2022), there are no isotope measurements on pyrolysis-derived H2 (to
our knowledge).
Radiolysis of water by alpha, beta and gamma radiation released in
the radioactive decay of U-, Th- and K-bearing minerals (Boyd et al.,
1973; Lin et al., 2005a, 2005b; Sauvage et al., 2021) and radiolytic
dehydrogenation of kerogen and hydrocarbon molecules (Frolov et al.,
1998; Larter et al., 2019; Wang et al., 2022) are among other commonly
discussed process that can explain the presence of H2 in the crustal gases
(Leila et al., 2022). Laboratory experiments indicate that gamma ray
irradiation of water results in δ2H-H2 values from -348 to -539‰ (Lin
et al., 2005a, 2005b) and gamma ray radiolysis of methane results in
δ2H-H2 values around -400‰ (Boreham and Davies, 2020). Molecular
H2 with such δ2H values is not present in crustal gas samples investi­
gated in this study. This may be because of relatively rapid (on
geological timescales) isotopic exchange between H2 and groundwater
(Lin et al., 2005a, 2005b; Ricci et al., 2022). Alternatively, radiolysis of
water and hydrocarbons is not a quantitatively significant process of H2
generation in the crust. Experimental data from Wang et al. (2020) show
that H2 generated from irradiated kerogen (δ2H-H2 value -170‰) has
δ2H-H2 values from -710‰ to -450‰. That range of δ2H-H2 value
partially overlaps with δ2H-H2 values in gases from conventional res­
ervoirs (Fig. 9). This suggests that radiolysis of kerogen may produce at
least some H2 observed in conventional reservoirs.
Reaction between groundwater and Si-O or Si- radicals that appear
on the fresh surfaces of fractured rocks in fault zones is another often-
implied mechanism of H2 generation in the subsurface (mechanor­
adical H2, Kita et al., 1982). Elevated concentrations of H2 often
observed in soil gases sampled along fault zones support this hypothesis
(Wakita et al., 1980; Sugisaki et al., 1983). Soil gases sampled from sites
along the Yamasaki fault (Japan) displayed molecular H2 concentrations
in the 0.7% to 3% range with δ2H-H2 values -770‰, -590‰, -510‰ and
-470‰ (Kita et al., 1980). Sugisaki et al. (1983) reported δ2H-H2 value
-675‰ in soil gas in the area of the Atera fault (Japan). High concen­
trations of H2 (up to 25%) were observed in gases extracted from a drill
core taken in the fracture zone in the Nojima Fault Zone in Japan (Arai
et al., 2001), but there were no isotope measurements. High concen­
trations of H2 (up to 6%) with δ2H-H2 values from -708‰ to -618‰ were
observed in drill-mud gases sampled in fractured zones around the San
Andreas Fault core penetrated by the SAFOD well in California (Wiers­
berg and Erzinger, 2008). The authors found that high H2 is consistent
with interaction of water with fresh silica mineral surfaces in the fault,
but noted that serpentinites were observed in drill-cuttings (Wiersberg
and Erzinger, 2008), and reactions of serpentinization could cause high
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H2 concentrations in the SAFOD well. In one experiment of simulated
faulting of a basalt specimen dampened with water with δ2H -40‰, the
δ2H-H2 value was -222‰ (Hirose et al., 2011). Mechanoradical H2 from
the single lab-simulating faulting experiment is significantly enriched in
2
H relative to the geologic H2 in fault settings. There may be many
reasons for that, including mixing of H2 with different origins in the
subsurface (e.g., H2 from serpentinites, from the mantle, or from other
subsurface processes may mix with H2 generated at surfaces of fractured
rocks), isotopic fractionation of mechanoradical H2 by H2-metabolizing
organisms around natural fault zones, and laboratory experiments
poorly imitating natural conditions. The quantitative significance of the
reaction between groundwater and Si-O or Si- radicals in the generation
of subsurface H2 remains unclear and more field and laboratory mea­
surements of H2 concentrations and δ2H-H2 values are needed to
constrain it.
The molecular H2 generated by microbes through hydrogenase re­
action in laboratory conditions has δ2H-H2 values between -814‰ and
-763‰ (Krichevsky et al., 1961). However, H2-enriched natural gases
usually do not have microbial origin (Fig. 12). This may be because in
geological settings favorable for the generation of microbial gases (e.g.,
shallow cool marine sediments), the H2 is rapidly consumed and
metabolized into hydrocarbons, mostly methane (Wagner et al., 2018;
Katz, 2011; Milkov, 2011).
Artificial H2 present in some sampled natural gases may complicate
the use of δ2H measurements in the interpretation of H2 origin. Artificial
H2 may be generated in the subsurface during drilling operations via
reactions between acids introduced into the wellbore or naturally pre­
sent in groundwaters and the iron in well casings, steel drilling shavings
and lithic fragments (Zinger, 1962; Bjornstad et al., 1994; Feldbusch
et al., 2018; Halas et al., 2021), as experimentally reproduced by
Bjornstad et al. (1994). The corrosion process have been invoked to
explain unusually high concentrations of H2 in several wells. For
example, Lyon and Hulston (1984) interpreted H2 in one geothermal gas
sample with anomalous δ2H-H2 values around -600‰ (compared to δ2H-
H2 values of >-525‰ measured for the rest of the samples in their study)
to result from many minor effects such as H2S reduction to H2 by reac­
tion with the steel well casing. Unusually high H2 (9.2%) with δ2H value
-277‰ in a gas sample from geothermal reservoir Groß Schönebeck
(North German Basin) was judged to result from corrosion during a long
exposure of steel well casing at pH 2 (Feldbusch et al., 2018).
Merlivat et al. (1987) observed unusual δ2H-H2 values from -823‰ to
-759‰ in H2-rich samples taken above hydrothermal vents in the East
Pacific Rise and interpreted such H2 as a result of a reaction between the
titanium sample bottles and the hot and acid hydrothermal solutions.
Such δ2H-H2 values are indeed anomalous among the larger dataset of
samples from MORs, where H2 commonly has δ2H values >-500‰
(Fig. 9d).
The δ2H-H2 values of samples with high (up to 90%) and apparently
artificial (due to CO2 corrosion) H2 in well annuli on Troll A platform
(North Sea, Norway) were mostly about -750 to -725‰ (Thiessen et al.,
2009; Mørkved et al., 2009). Using the H2O(LIQ)-H2 geo-thermometer
the predicted equilibrium temperatures were, with some exemptions,
in the temperature range of the Troll A well heads (15-50◦ C), where the
H2 likely formed. A sample with likely artificial H2 concentration 88.5%
from the Brent B platform has δ2H-H2 value -742‰ (UK OGA, 2021).
The preferential leakage of light isotope 1H during long-term
(months and years) storage of gas samples in steel cylinders may lead
to erroneously high δ2H-H2 values. This was noted, for example, for
some of the first samples collected at Heins and Scott H2-rich wells in
Kansas that had δ2H-H2 values from -510‰ to -340‰ after being stored
for >2 months (Goebel et al., 1984). These samples were significantly
more enriched in 2H than the H2 sampled in later studies and converted
to water right in the field (Coveney Jr. et al., 1987). Boreham et al.
(2021a) suspected that extreme enrichment of 2H (relative to other
gasses) in two gases in their dataset (from well Pinelands 3 (Surat Basin)
with δ2H-H2 value -389% and from well Katandra 1 (Bonaparte Basin)
A.V. Milkov
with δ2H-H2 value -370%, Fig. 8) point to the artifact accompanying gas
production, collection or storage.
The δ2H-H2 values of artificial H2 (from -823‰ to -277‰, based on
the above references) and of leaked gas samples (significantly 2H-
enriched) may overlap with the δ2H values of H2 in samples where these
issues are not suspected. This indicates a significant challenge for the
interpretation of δ2H-H2 values and highlights the need for careful
sampling procedures and a holistic approach to the interpretation of H2
origin when some geochemical anomalies or unusual gas sampling
conditions are present.
5.2. H2 in petroleum fluids
There are some petroleum (mostly natural gas) accumulations where
H2 is reportedly present in relatively large concentrations exceeding
10% (Bohdanowicz, 1934; Headlee, 1962; Molchanov, 1981; Angino
et al., 1984; Perevozchikov, 2011; Leila et al., 2022). Large concentra­
tions (up to 43%) of H2 were found in many water samples taken below
oil accumulations in Lower Volga region in Russia (Zinger, 1962). A well
targeting a petroleum prospect in Kazakhstan encountered a free water
flow with 90-98% of molecular H2 in dissolved gas (Kraychuk, 1976).
More recently, Prinzhofer et al. (2018) reported a unique serendipitous
discovery of a large free gas accumulation that contains 98% H2, 1% N2
and 1% of thermogenic hydrocarbon gases (mostly methane) in Prote­
rozoic sedimentary rocks in Mali. Some researchers compared that dis­
covery to the pioneering Drake’s well that set off the first oil rush in
1859 pointing out that the well in Mali can start the rush for H2
exploration (Gaucher, 2020). However, the fundamental understanding
of a connection between oil and gas and molecular H2 is lacking (Lev­
shounova, 1991; Smith et al., 2005).
Near-surface fermentation by microorganisms is the only biotic
process that is considered among main sources of H2 in the Earth’s crust
(Truche et al., 2020). Virtually all of that H2 is converted to methane and
the rest escapes into the atmosphere (Conrad, 1995). In deeper sedi­
ments, hydrogenotrophic microbes (Wagner et al., 2018) utilize H2 and
CO2 to produce primary microbial (e.g., Katz, 2011) and secondary
microbial (Milkov, 2011) gases (mostly methane), which together ac­
count for 8-15% of the global endowment of recoverable gas in con­
ventional petroleum reservoirs (Milkov, 2018). Levshounova (1991)
used observations from shallow sediments to propose that H2 can hy­
drate olefins (ethylene, propylene and buthylenes) resulting in the for­
mation of normal alkanes (ethane, propane, butanes) but that
hypothesis has not been sufficiently tested yet.
While the role of molecular H2 in making natural microbial gases (i.
e., hydrogenotrophic methanogenesis) is well recognized by petroleum/
organic geochemists, the role of H2 in making oils is highly debatable.
Theories of abiotic (abiogenic) origin of oil rely on the availability of
molecular H2 in the deep subsurface (e.g., Szatmari, 1989; Kenney et al.,
2002; Kutcherov and Krayushkin, 2010). However, the vast majority of
petroleum geoscientists and geochemists do not support theories of
abiotic origin of large natural accumulations of petroleum (Peters et al.,
2005; Glasby, 2006).
Based on our results (Figs. 9 and 15-16), H2 in conventional reser­
voirs is mostly crustal-sourced. Meng et al. (2015) interpreted small
(<0.1%) concentrations of H2 in conventional oil and gas reservoirs in
the Bohai Bay Basin as mantle-derived, but our analysis in the contexts
of a large global dataset from various geological habitats suggests that
H2 there is sourced from the crust.
There are some ideas and hypotheses about how molecular H2 can
contribute to formation and destruction of oils that originated from
organic-rich petroleum source rocks (Zhu et al., 2017). For example, a
prominent petroleum geologist of the first half of the 20th century,
Wallace E. Pratt, proposed a model in which early-expelled relatively
heavy (i.e., low API gravity) oils rich in “unsaturated” hydrocarbons
turn into lighter oils more rich in “saturated” compounds via hydroge­
nation in the reservoirs (Pratt, 1934). This model was not generally
19
Earth-Science Reviews 230 (2022) 104063
accepted because W.E. Pratt “could not point to a quantitatively
adequate natural source of free hydrogen to account for the [hydroge­
nation] process” (Hawkes, 1972, p. 2268). Hawkes (1972) listed some
natural occurrences with high concentrations of molecular H2 that
became known since Pratt’s publication, but admitted that reports of H2
in the subsurface are subject to review due to extreme difficulties with
the reliable collection, transportation and analysis of gas samples with
significant H2.
The conventional theory of hydrocarbon formation in the subsurface
implies that organic matter in the source rocks supplies hydrogen to
form hydrocarbons (Tissot and Welte, 1984; Hunt, 1996), while the
influence of exogenous H2 on hydrocarbon generation is given little
consideration (Wang et al., 2018). It appears from this review that there
are various sources of H2 in sedimentary basins and petroleum systems.
Laboratory studies suggest that large amounts of H2 can be released from
the radiolysis of waters and from irradiation of organic matter in
uranium-rich shales (and other rocks). That H2, if indeed generated in
the subsurface in significant amounts, can react with undersaturated,
long-chain hydrocarbons as well as sulfur and nitrogen compounds to
produce saturated and short-chain hydrocarbons per following reactions
(Wang et al., 2019):
R’CH = CH2 + H2 (catalyst) → R’CH2CH3
RCH2CH2CH2R’ + H2 → RCH2CH3 + R’CH3
R-SH + H2 → RH + H2S
Results from a laboratory experiment by Wang et al. (2006) sug­
gested that water provided exogenous H2 for hydrocarbon generation
from lignite. Wang et al. (2018) discussed a significant possibility that
uranium abundant in the Chang 7 Member source rock in the Ordos
Basin (China) radiated formation water and produced H2 for hydrocar­
bon generation by that source rock.
Szatmari (1989) proposed that petroleum liquids can form by
Fischer-Tropsch synthesis on magnetite and hematite catalysts when
CO2 from metamorphic/igneous decarbonation of carbonates reacts
with H2 derived from serpentinization of shallow-mantle lithosphere
and ophiolite thrust sheets. The Fischer-Tropsch synthesis of natural
gases is supported by field observations and geochemical studied in
areas with serpentinites (Etiope et al., 2011, 2016; Etiope and Whiticar,
2019). Mostly gaseous hydrocarbons were produced during abiotic
synthesis under hydrothermal conditions in laboratory experiments
(McCollom and Seewald, 2006). Natural hydrocarbon gases clearly are
generated via the Fischer-Tropsch reactions in serpentinites settings, but
the proportion of such gases in the global endowment of hydrocarbon
gases (Milkov, 2018) is likely very small. Further, the existence of liquid
petroleum from Fischer-Tropsch synthesis in natural oil accumulations
remains unproven.
It has been hypothesized that H2 can originate from the thermal
decay of organic matter in oil accumulations and then accumulate in
underlying water legs (Zinger, 1962). Some laboratory experiments
indicate generation of H2 during thermal decay of kerogen (Bogomolov,
1976; Li et al., 2015, 2017). There are examples of high concentration
(>10%) of free H2 in coal basins (see Table 25 in Zgonnik, 2020), pre­
sumably from coal metamorphism. Alternatively, this H2 could be
generated at the early stages of organic matter maturation and remained
trapped or adsorbed within the micropores of coals (Truche and
Bazarkina, 2019). Hydrogen can also originate from dehydrogenation of
clay minerals that are abundant in many shale formations (Truche et al.,
2018). Such shale formations, when enriched in organic matter and
exposed to sufficiently high thermal stress (Pepper and Corvi, 1995),
serve as petroleum source rocks. Carbonate minerals may preserve H2 in
their crystalline structure (Levshounova, 1991) and release it during the
maturation and expulsion of petroleum from carbonate source rocks.
When some of the reservoir or source rocks contain evaporite/potash
deposits, radiolysis of water by the radioactive decay of potassium may
contribute H2 to petroleum fluids (Smith et al., 2005; Gregory et al.,
2019). On the other hand, free H2 can result from the destruction of
petroleum fluids, for example, it can be produced via radiolytic
A.V. Milkov
dehydrogenation of crude oil molecules (Frolov et al., 1998; Larter et al.,
2019). Free H2 likely plays a role in oil biodegradation and biological
aromatization of oil (Röling et al., 2003).
5.3. Exploration for geologic H2
At present, geologic H2 is produced and used as a source of energy
(electricity) only in the village of Bourakébougou in Mali (Hydroma,
2022). The discovery of a H2-rich gas accumulation there was seren­
dipitous because the exploration well targeted water and not H2 (Briere
et al., 2017; Prinzhofer et al., 2018). Serendipity also plays a role in the
discovery of petroleum accumulations (Milkov and Navidi, 2020), He-
rich accumulations and geothermal fields (Dobson, 2016). However, I
propose that specific exploration programs may be designed and carried
out in order to deliberately search for accumulations of natural H2-rich
gases.
Areas where H2-rich gases seep at the surface may be attractive for
initial H2 exploration. This concept is the same as seep-guided petroleum
exploration in 1800s – early 1900s (Link, 1952). First commercial nat­
ural gas production in the USA (Fredonia, NY) from the naturally frac­
tured shale reservoir (Devonian Dunkirk Shale) in 1825 resulted from
the observations of nearby gas seeps (Lash and Lash, 2014).
Onshore seeps of H2-rich gases occur in areas of serpentinites (Neal
and Stranger, 1983; Etiope et al., 2011), which make these areas a
possible target for dedicated H2 exploration. Natural gases sampled from
serpentinites contain not only H2, but also valuable CH4 (Table 1). It is
possible to directly capture H2-rich gases from serpentinite seeps and
vents, as a H2 production mechanism. The concept is comparable to steel
pyramids/tents above seafloor seeps near Platform Holly in the Coal Oil
Point field offshore California (Hornafius et al., 1999). H2-rich gases also
can be recovered during degassing of water produced from wells drilled
into fractured serpentinites (Boulart et al., 2013; Suda et al., 2014).
Surface H2 surveys may help find areas with potential sub-surface H2
accumulations (Prinzhofer et al., 2019; Frery et al., 2021). Shallow
aquifers and maybe even free gas accumulations in fractured serpen­
tinite reservoirs potentially can be identified with geophysical technol­
ogies, for example, by searching for magnetic anomalies (magnetite is a
product of serpentinization). The technology of hydraulic fracturing that
revolutionized petroleum industry at the beginning of the 21st century
(King, 2012) may potentially be utilized in serpentinite reservoirs.
Projects of H2 production from serpentinites may be further enhanced by
CO2 sequestration in serpentinite aquifers through formation of car­
bonate minerals (Power et al., 2013). Oman has well-documented sur­
face (Fritz et al., 1992) and subsurface (Boulart et al., 2013) occurrences
of H2-rich gases in the Semail ophiolites and well-developed petroleum
exploration and development infrastructure, which make this country a
potential candidate for favorable H2 exploration. Japan is another
country where H2 may be recovered from shallow aquifers within ser­
pentinized rocks. Degassing of H2-rich gas from water wells sourcing a
commercial spa may be already happening in the Hakuba Happo hot
springs areas, as is illustrated by Suda et al. (2014) in their Fig. 2.
Extraction from waters producing geothermal energy may be
another viable option for economic production of geologic H2. Subsur­
face volcanic/magmatic hydrothermal systems produce gases with sig­
nificant H2 (average ~7%, on water-free basis). Examples of systems
where H2 can be recovered during production of geothermal energy
include such H2-rich geothermal fields as Salton Sea (Welhan, 1981) in
the USA, Cerro Prieto in Mexico (Welhan, 1981), and Namafjall (Sano
et al., 1985), Nesjavellir (Marty et al., 1991) and Hellisheidi (Combau­
don et al., 2022) in Iceland. Subsurface sedimentary hydrothermal sys­
tems produce gases with relatively less H2 (average ~4%, on water-free
basis), and may be less attractive targets for H2 exploration.
Petroleum companies may be more comfortable with the idea of
exploring for H2-rich gases in conventional reservoirs. There are known
accumulations of H2-rich gas in conventional reservoirs (as reviewed by
Zgonnik, 2020), but only three such gas pools have been described in the
20
Earth-Science Reviews 230 (2022) 104063
literature in some details: two in Kansas (Coveney Jr. et al., 1987) and
one in Mali (Prinzhofer et al., 2018). The concept of “hydrogen system”
(Prinzhofer et al., 2018; Rezaee, 2021) can be formulated similarly to
the concept of “petroleum system” (Magoon and Dow, 1994), and as it
was done for “helium system” (McDowell et al., 2017; Danabalan et al.,
2022). This study addresses the origins of molecular H2, and it appears
that sources of hydrocarbons and H2 in the subsurface are very different.
Further, mechanisms and efficiency of migration, accumulation and
preservation of molecular H2 (much smaller, mobile, and less soluble in
water than hydrocarbon gases) may be significantly different from those
for hydrocarbon gases.
6. Conclusions
Geologic molecular H2 is most abundant in natural gases sampled
from volcanic/magmatic vents at MORs and in serpentinites. Hydrogen
isotope data may be used to distinguish broadly defined crustal (δ2H-H2
values <-650‰), mantle and primordial (δ2H-H2 values >-650‰) H2 in
natural gases, and integration with geological data and isotope data on
other associated gases such as He and CH4 improves reliability of such
interpretations. Identification of more specific mechanisms of H2 gen­
eration based on isotopic composition data remains problematic because
the empirical dataset of δ2H-H2 values is relatively small and there is
much overlap of values resulting from different generation processes.
Further complications arise from variations in source water isotope
composition and temperature-dependent equilibrium isotopic fraction­
ation and kinetic exchanges between H2 and water. It appears that H2
from serpentinization reactions has δ2H-H2 values around -715‰, and
H2 supplied by the deep Earth (perhaps directly from the deep mantle
and core) has δ2H-H2 values around -350‰. However, these δ2H-H2
values may also result from the temperature-dependent isotopic frac­
tionation between H2 and water. More field and experimental data is
needed to constrain δ2H-H2 values typical for specific potentially
important processes of H2 generation in the subsurface such as radiolysis
and fracture-induced reduction of water and thermogenic liberation of
H2 during petroleum cracking and coal metamorphism. This review
highlights the possibility of purposeful exploration for geologic H2,
which is a valuable natural resource. Onshore serpentinites with known
surface and subsurface occurrences of H2-rich gases are viable settings
for such exploration programs.
CRediT authorship contribution statement
Alexei V. Milkov: Conceptualization, Data curation, Formal anal­
ysis, Investigation, Methodology, Writing – review & editing.
Declaration of Competing Interest
The author declares that he has no known competing financial in­
terests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The author would like to thank Antonio Martín-Monge, Geoffrey
Ellis, Chris Boreham and an anonymous reviewer for providing useful
comments on the manuscript.
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