Zgonnik2020 Hydrogen

Earth-Science Reviews 203 (2020) 103140
Contents lists available at ScienceDirect
Earth-Science Reviews
journal homepage: www.elsevier.com/locate/earscirev
The occurrence and geoscience of natural hydrogen: A comprehensive T

review
Viacheslav Zgonnik
Natural Hydrogen Energy LLC, French branch: 31 rue Raymond Queneau, 92500 Rueil Malmaison, France
ARTICLE INFO ABSTRACT
Keywords: Using an interdisciplinary approach, this paper reviews current knowledge in the field of natural hydrogen. For
Hydrogen the first time, it combines perspectives on hydrogen from the literature of the former Eastern bloc with that of
Natural hydrogen the West, including rare hardcopies and recent studies. Data are summarized and classified in three main sec-
Gas seeps tions: hydrogen as a free gas in different environments, as inclusions in various rock types, and as dissolved gas
Faults
in ground water. This review conclusively demonstrates that molecular hydrogen is much more widespread in
Earthquakes
Atmosphere
nature than was previously thought. Hydrogen has been detected at high concentrations, often as the major gas,
Microorganisms in all types of geologic environment. A critical evaluation of all the proposed mechanisms regarding the origin of
Energy natural hydrogen shows that a deep-seated origin is potentially the most likely explanation for its abundance in
nature. By combining available data, an estimate of 23 Tg/year for the total annual flow of hydrogen from
geologic sources is proposed. This value is an order of magnitude greater than previous estimate but most likely
still not large enough to account for recently discovered worldwide diffusive seepages. Hydrogen could play a
critical role in mechanisms taking place in both the shallow and deep geospheres and it can influence a very wide
range of natural phenomena. Hydrogen is an essential energy source for many microorganisms. Sampling for
hydrogen can be a useful tool in studying natural environments, geologic mapping, monitoring of earthquakes,
plotting fault traces and resource exploration. Hydrogen of geologic origin has the potential to become the
renewable energy source of the future, with exploratory projects ongoing at the present time. The topic of
natural hydrogen is therefore relevant from many different perspectives.
1. Introduction analyzers used in the natural sciences include a hydrogen sensor in their
design. It is difficult to estimate how many times hydrogen has not been
“From a geological perspective, hydrogen has been neglected”. This was identified in H2-rich samples because of the lack of a suitable detection
written by Nigel Smith and colleagues more than a decade ago in a technique to measure hydrogen concentrations.
2005 paper, which appears to be the latest initiative in a review of For example, hydrogen was not measured (de Boer et al., 2007;
natural hydrogen (Smith et al., 2005). In 2019 this statement still holds Hosgörmez, 2007) at a location in Turkey, where it is known to occur
true. I suspect this is because of an existing prejudice that free hydrogen naturally at concentrations of up to 11.3%. The presence of hydrogen at
in nature is rare, and descriptions of the few known discoveries are this location has been confirmed by other studies (Hosgörmez et al.,
anecdotal and for some reason garner very little notice. Therefore, if no 2008; Vacquand, 2011). At the location in Turkey, hydrogen-rich nat-
one expects to find free hydrogen, no one samples for it. This prejudice ural gas seeps to the surface and burns spontaneously. The flames from
influences the way gas samples are analyzed and sampled, but also the this natural gas seep have been known since antiquity and are believed
way detection systems are designed. The standard analytical approach to be the source of the first Olympic flame. Another study reporting on
for gas chromatography often uses hydrogen as a carrier gas (Angino the analysis of gas from Poison bay, New Zealand, did not include hy-
et al., 1984). Because of this, if there is any hydrogen in a gas sample it drogen (Lyon and Giggenbach, 1994) as a constituent, though it had
will not be detected. It was reported that even in the 1990’s, many been documented by others (Wood, 1972) to be at concentrations as
surveys were not equipped to analyze for hydrogen (Smith, 2002). It high as 75.8%.
still holds true, to this day, that only a few modern portable gas In view of the above, gas analyses from databases should be
Abbreviations: BTU, British thermal unit; c, concentration; MCFD, Million cubic feet per day; NH, Northern hemisphere; NR, not reported; PSIG, Pounds Per Square
Inch Gauge; Tg, Teragram, equal to 1012 gram or 1 million ton.; SH, Southern hemisphere
E-mail address: zgonnik@nh2e.com.
https://doi.org/10.1016/j.earscirev.2020.103140
Received 16 July 2019; Received in revised form 14 February 2020; Accepted 18 February 2020
Available online 24 February 2020
0012-8252/ © 2020 Elsevier B.V. All rights reserved.
V. Zgonnik Earth-Science Reviews 203 (2020) 103140
Fig. 1. (a) Map of hydrogen detections in various environments at concentrations > 10% vol. Note: the high density of placemarks across Eastern Europe and
Northern Asia is due to the fact that researchers from these regions were looking for hydrogen more frequently, and not because these regionsare richer in hydrogen.
The area highlighted by the orange rectangle is shown on the (b). Data on each placemark are available in the corresponding tables of this review and in a .kmz file
provided in the Supplementary Information. (b) A detail map of the area highlighted by the orange rectangle on the (a).
regarded with caution before any generalized conclusions are made as unable to detect hydrogen at concentrations of less than 1 or 2%
to the rarity of hydrogen. For example, only 5 out of 14,242 samples of (Headlee, 1962; Войтов and Осика, 1982). Even when hydrogen was
natural gas from wells across the USA reported hydrogen at con- detected, such analyses were considered erroneous (Войтов and Осика,
centrations greater than 10% (Moore and Sigler, 1987). However, it is 1982). And even at the time of this writing, recent databases with gas
very likely that many of these samples were not tested for hydrogen for analyses contain only a small number of hydrogen detections. The
the aforementioned reasons. The lack of hydrogen testing may be at- United States Geological Survey's (USGS) Energy Geochemistry Data
tributed to antiquated analytical techniques and protocols. Indeed, the Base (EGDB) has103,000 records of worldwide gas samples with only 8
absence of hydrogen in analyses of natural gases during the 1930’s and detections of hydrogen at concentrations > 10%. Another database, the
1960’s can be readily explained by inadequate analytical equipment, Global Onshore Gas-Oil Seeps Dataset (GLOGOS), does not contain any
2
hydrogen entries at all. Examples of this kind have led some authors to hydroarbons. Many papers and books have been published on natural
conclude that the number of known detections of gas with high con- hydrogen in the Eastern European states, but so far there has been no
centrations of molecular hydrogen is small (Voitov and Rudakov, single review combining all the data from Eastern and Western coun-
2000). However, through this comprehensive literature review it is tries. This current work attempts to cover this gap. Also, it presents the
possible to confirm the original statement cited above, that the im- data of hydrogen discoveries in a sorted and easy to use format.
portance of naturally occurring hydrogen has largely been overlooked. Previous reviews on naturally occurring hydrogen have stated that
An important reason for this situation, besides imperfect analytical it is time to take hydrogen more seriously (Smith, 2002) and that this
techniques, is that most wells drilled worldwide have been drilled in gas is much more widespread than previously thought (Войтов and
sedimentary basins, which make up half of the Earth’s surface, how- Осика, 1982; Несмелова and Рогозина, 1963). This review fully
ever, these are not the most likely places for hydrogen to be most supports these statements. The goal in writing this paper has been to
abundant (Smith, 2002; Truche and Bazarkina, 2019). Another issue show how overlooked natural hydrogen is and how important a role it
preventing hydrogen from being discovered are its diffusive and che- plays in Earth processes.
mical properties. Being the lightest of all the gases, it diffuses rapidly in
air, but also in different materials. Therefore, it quickly leaves the place 2. Summary and classification of hydrogen discoveries
of its generation and can not be retained in geologic traps for long
periods of time (Осика et al., 2002; Johnsgard, 1988). For this reason, In this section, reported discoveries of hydrogen are separated into
samples with hydrogen gas should be handled in a specific way. It is three main categories: hydrogen as a free gas, hydrogen as inclusions
also very reactive and when it combines with oxygen it yields water, and hydrogen as dissolved gas in water. Each category is then divided
leaving no trace of it having been there in the first place as a free gas. into sub-categories, classifying discoveries by type. In many cases it was
Moreover, it is rapidly consumed by microorganisms, representing for very difficult to classify them, therefore these categorizations remain
them a valuable source of energy. subjective. The main criterion I used to attribute a hydrogen discovery
All these properties of H2 have puzzled many researchers, some of to a specific category was the way the author of the original work was
whom have reported the presence of hydrogen in diverse situations, making the attribution, whether advertently or inadvertently. This re-
completely independent of tectonic, stratigraphic or lithological con- view does not cover discoveries of hydrogen in samples from mid-ocean
ditions. Hydrogen concentrations appear to be independent of the ridges and other locations in the ocean because they have already re-
productivity of the stratum being sampled. No regularities in the hy- ceived a lot of attention from the scientific community and have been
drogen distribution appear to be apparent, even in a single well reviewed elsewhere (see, for example, (Cannat et al., 2010) and refer-
(Стадник, 1970). It was reported, that even in the same well, sampling ences therein).
results varied: a second sample from the same hydrogen-rich well Everywhere in this article the word hydrogen means naturally oc-
during the same day always resulted in a higher hydrogen concentra- curring H2, except if otherwise specified, and all concentrations are
tion (Goebel et al., 1984). One could suppose that this result is probably given by volume. Discoveries of hydrogen are presented and sorted by
due to replenishment of otherwise consumed or diffused H2. their concentration. The content of the gas is given when possible. A
Therefore, it is not surprising, that hydrogen gases are sometimes choice was made to report only discoveries with concentrations greater
identified later than other gases. For example, H2-rich combustible than 10%, because the number of observations at lower concentrations
gases in Khibiny, Russian Federation, were discovered only after 20 would be too exhaustive to collect in one work, and also because it is a
years of research work in the region. Later more detailed studies re- round number that approximately represents the minimum concentra-
vealed such gases were present in all types of ore in the mines studied tion of hydrogen necessary for ignition in air (assuming that all other
(Онохин, 1959).These same studies showed that hydrogen concentra- gases of a mixture are not also combustible). In some articles, hydrogen
tions varied greatly in space and time: it was reported that even in 50 content was reported in a way impossible to convert it into a percentage
cm-spaced monitoring holes, H2 concentrations could be 3 and 7000 (for example, in cm3/kg of rock, without reference to its’ content of
ppm simultaneously. Even more surprising, monitoring at several lo- other gases). Such results were not included in this review, as it was not
cations situated up to 50 km apart showed H2 concentrations increasing possible to know if hydrogen was a significant constituent.
simultaneously but independently of local meteorological conditions
(Satake et al., 1985), suggesting a global-scale process as being the 2.1. Hydrogen as a free gas
cause of this synchronous behavior.
Indeed, the presence of hydrogen can be used as a diagnostic tool for Free hydrogen has been encountered by humans since ancient time.
geological processes that involve hydrogen in one way or another, be- The continuously burning gas seep at Chimaera (sometimes also called
cause its concentration in the atmosphere is normally very low. As will Yanartaş), near Antalya, Turkey, has 7.5–11.3% H2 and these active
be shown, it can be used for different monitoring studies. But because of vents have been known for more than 2500 years (Fig. 2). They are
its physicochemical properties it is not an easy compound to work with. believed to be the source of the first Olympic flame. It has been reported
Hydrogen has primarily been studied as an atmospheric gas, but geo- that they are subject to seasonal variations, being more vigorous in the
logic hydrogen is so poorly understood, that none of the articles on winter months (Hosgörmez et al., 2008). Another similar occurrence
hydrogen budget accounted for geologically generated hydrogen. was discovered in the Philippines more than two centuries ago, where
The earliest published analysis of a natural gas sample containing flames of burning gas have been continuously active. The place is called
hydrogen it was possible to find while doing this review, is in an 1888 “Los Fuegos Eternos” (the eternal flames) with measured hydrogen
report by D. Mendeleev on the composition of gas seeping from frac- concentrations ranging from 41.4 to 44.5% depending on the vent
tures in coal from a mine near the city of Makiivka, in the Donetsk (Vacquand, 2011; Abrajano et al., 1990). Continuous monitoring of
region of Ukraine. Mendeleev documented that the gas contained these vents has shown that the hydrogen content of these gases has been
5.8–7.5% hydrogen (Менделеев, 1888). It is notable that most of the stable over a 25-year period (Abrajano et al., 1990).
later discoveries of hydrogen have been made in the same part of the Both of the above-mentioned instances are associated with ophio-
world, mostly in Eastern Europe and Northern Asia (Fig. 1). This is not lites, which are regions where oceanic crust has been theorized to have
because this region of the world is richer in hydrogen, but because been uplifted by tectonic forces or "obducted" onto the surface of a
researchers were looking for hydrogen more frequently. In part this continental margin. Table 1 summarizes other reported discoveries in
reflects the popularity of an abiogenic theory for the generation of oil equivalent environments. Recent work documented in the literature has
and gas in countries which were previously part of the Soviet camp. compared multiple parameters for gases from ophiolitic complexes and
This theory requires a sustained flux of hydrogen for generation of concluded that all such gas samples could be categorized into four
3
groups: H2-rich, N2-rich and mixed N2-H2-CH4 or H2-CH4. These dif-

ferences have been explained as reflecting different zones of generation
(Vacquand et al., 2018).
A map showing all places described in this section is given in Fig. 3.
Ophiolites have received a lot of attention from scientists because
hydrogen from these locations is attributed to the process of serpenti-
nization (discussed in the idem Section 3.2). Other locations such as rift
zones have received attention from researchers for the presence of re-
duced gases (those which can react with oxygen). A lot of the hydrogen
observed and reported in the scientific literature has been sampled from
the mid-ocean rift zones, which are not covered in this review (for
examples see this publication (Cannat et al., 2010) and references
therein). However, onshore hydrogen discoveries attributed by scien-
tists to rift systems remain rare (Table 2).
Many hydrogen discoveries are associated with rocks of
Precambrian age (Table 3). One of the highest reported concentrations
of hydrogen (84%) detected while drilling a well in South Australia was
in free gases sampled from deep Precambrian rocks (Ward, 1933). A
similar situation was reported by different authors where the highest
hydrogen concentrations were detected in deeper, Precambrian sections
of wells (Table 3).
Hydrogen was frequently observed in superdeep wells (drilled to 5
km or deeper). For example, gases from samples of the Kola superdeep
drilling project (deepest well in the world, project name SG-3) are
Fig. 2. Picture of the continuously burning gas seep at Chimaera, near Antalya, mainly nitrogen-hydrogen rich (Войтов, 1990). Hydrogen was detected
Turkey. The gas contains 7.5–11.3% H2. These active vents have been known
from 1 to 11 km. Starting at 8.5 km, an increase in hydrogen was ob-
for more than 2500 years and are believed to be the source of the first Olympic
served (Карус et al., 1984). It is interesting to note, that at depths
flame. Picture from Wikimedia by W. Neuheisel distributed under the cc-by-2.0 li-
cense.
greater than 8.9 km no zones of free water were detected. This ob-
servation puts constraints on the hypothesis that the detected hydrogen
is the product of reactions with water (Боревский et al., 1984). Hy-
drogen was reported to be a major constituent of gas detected during
Table 1
Hydrogen discoveries associated with ophiolites.
H2, % Comments Country Name of placemarka Reference
7.5–11.3 Eternal flames of burning natural gases Chimaera. Total H2flow about 2 Turkey Chimaera, 11.3 (Hosgörmez et al., 2008; Vacquand,
kg/day from the entire site. Proposed origin: mixture of organic 2011; Etiope et al., 2011)
thermogenic gas and abiogenic gas
15.7 Bubbles from ultra-basic springs. Proposed origin: serpentinization USA Austin Creek, 15.7 (Morrill et al., 2013)
35.1 Free gas seeps on the surface. Proposed origin: serpentinization Philippines Mangatarem, 35.1 (Vacquand, 2011)
26.8–36.1 Gas-bearing springs in ophiolites of New Caledonia. Proposed origin: New Caledonia Kaoris, 32.9; Carenage, (Vacquand et al., 2018; Deville and
serpentinization 36.1 Prinzhofer, 2016)
34–39.2 Bubbles from ultra-basic springs. Proposed origin: serpentinization USA Barnes Spring, 39.2 (Morrill et al., 2013)
41.4–44.5 Free gas seeps on the surface. Proposed origin: serpentinization Philippines Los Fuegos Eternos, (Vacquand, 2011; Abrajano et al., 1990)
44.5
41.4–45.6 Burning gas in peridotites of the Zambales ophiolite complex. Proposed Philippines Mt. Lanat, 45.6 (Thayer, 1966; Abrajano et al., 1988)
origin: serpentinization
48.3 Gases in hyperalkaline groundwaters of the serpentinized Dinaride Bosnia and Vaiceva voda, 48.3 (Etiope et al., 2017)
ophiolite belt Herzegovina
50.9 Bubbles from ultra-basic springs. Proposed origin: serpentinization USA Camp Spring, 50.9 (Morrill et al., 2013)
58.5 Free gases seeps on the surface. Proposed origin: serpentinization Philippines Nagsasa, 58.5 (Vacquand, 2011; Sherwood Lollar et al.,
2014)
37.1–60.5 Gas from bubbling in hyperalkaline spring (Tahtakopru) and free Turkey Kurtbagi, 38.4 (Yuce et al., 2014)
spontaneously igniting gas (Kurtbagi). Proposed origin: serpentinization Tahtakopru, 60.5
39–69 Gas seeps on the surface. Proposed origin: serpentinization Oman Howqain, 69 (Vacquand, 2011; Sano et al., 1993; Neal
and Stanger, 1983)
37.3; Gases from bubbles in different water sources in Oman ophioliteb. Oman Abyiad, 37.3; (Vacquand, 2011; Zgonnik et al., 2019)
68.1; Proposed origin: serpentinization Alkar, 68.1;
73.4; Halhal, 73.4;
77; Haylayn, 77;
85.9 Hawasina, 85.9
61; Gases from bubbles in different water sources in Oman ophiolite. Oman Lauriers Roses, 61; (Vacquand, 2011; Boulart et al., 2013)
75.2; Proposed origin: serpentinization Kufeis, 85.4;
85.4; Barrage, 75.2;
87.3 Magniyat, 87.3
81–97 Gas seeps on the surface Oman Bahla, 97 (Vacquand, 2011; Sano et al., 1993; Neal
Ain Al-Waddah. Proposed origin: serpentinization and Stanger, 1983; Boulart et al., 2013)
22–99 Bubbles in springs. Proposed origin: Fe2+ oxidation by water Oman Nizwa, 99 (Neal and Stanger, 1983)
a
The .kmz Google Earth file with placemarks is available in Supplementary information.
b
A video from the Haylayn site in Oman is available online: https://www.youtube.com/watch?v=9Qnt_XENDrI
4
Fig. 3. (a) Map of hydrogen detections in free gases in various environments at concentrations > 10% vol. Note: the high density of placemarks across Eastern Europe
and Northern Asia is due to the fact that researchers from these regions were looking for hydrogen more frequently, and not because these regions are richer in
hydrogen. The area highlighted by the orange rectangle is shown on the (b). Dataon each placemark are available in the corresponding tables of this section and in a
.kmz file provided in the Supplementary Information. (b) A detail map of the area highlighted by the orange rectangle on the (a).
the Ural superdeep drilling project (SG-4). The quantity of hydrogen gas associated with igneous rocks. There were a few other reports of hy-
was reported to increase with depth (Башта et al., 1991). The amount drogen detections and Table 4 summarizes other reports of hydrogen in
of hydrogen was also reported to increase with depth during the su- such rocks.
perdeep drilling program (SG-8) in Kryvyi Rih, Ukraine (Курлов, Many studies have reported hydrogen in volcanic gases, despite the
2003). High concentrations of hydrogen, 13.8–28.1%, were detected fact that hydrogen is a reactive gas which is readily oxidized by oxygen
during the drilling of the Aralsor superdeep well in Kazakhstan (Войтов either in the air or oxygen bonded to certain minerals. Such reactions
and Осика, 1982; Перевозчиков, 2011; Войтов et al., 1967; Соколов, produce water vapor, a main component in volcanic gases. The detec-
1971; Шорохов and Шишенина, 1967). Up to 2% of hydrogen was tion of hydrogen (Table 5) implies it can be sufficiently abundant to
detected during the drilling of the superdeep Gravberg-1 in the Siljan override the oxidizing capacity of fluids/rocks in volcanic settings.
crater in Sweden. Observed hydrogen increased at depths below 6 km Hydrogen has been reported in volcanic gases throughout the world.
(Smith, 2002; Николаевский, 1988). Spectroscopic studies of burning gas from the Hawaiian volcanoes show
Hydrogen discoveries in the Kola and Ural superdeep wells were that the flame is originating from the combustion of H2 in air
5
Table 2
Hydrogen discoveries associated with rift zones.
V. Zgonnik
H2, % Comments Country Name of placemark Reference
33.7 Gas from the Willey #1well. Proposed origin: associated with mid-continent rift system USA Willey #1, 33.7 (Moore and Sigler, 1987; Coveney et al., 1987)
57.3 Gas from a geothermal well in Namafjall. Measured δD = -499 ‰, δD of water = -97.7; c (H2S) = 16% Iceland Namafjall, 57.3 (Sano et al., 1985; Кононов, 1983)
64.0 Gas from a borehole. Proposed origin: unknown Iceland Namaskard, 64.0 (Sigvaldason, 1966)
96.3 Gas from the Hofmann #3 well. Proposed origin: associated with mid-continent rift system USA Hofmann #3, 96.3 (Angino et al., 1984; Moore and Sigler, 1987; Coveney et al., 1987)
6
Table 3
Hydrogen discoveries associated with Precambrian rocks.
H2, % Comments Depth, m Country Name of placemark Reference
12.8 Gas from well Juuka 116, drilled on Fennoscandian shield into Karelian Up to 1122 Finland Juuka, 12.8 (Sherwood Lollar et al., 1993a; Sherwood Lollar et al., 2007)
Supracrustals complex, dated 1900–2100 Ma. Proposed origin: serpentinization
17.2 Free gas from Wilson #1 well drilled into Precambrian basement rocks. Quantity 1446–1732 USA Wilson well, 17.2 (Newell et al., 2007)
28–70 L H2 per 1 L of pumped water; c (He) = 1.5%. Proposed origin:
serpentinization
3.9–27.3 Free gases from the well #1886 1323 Russian Pechengskaya, 27.3 (Войтов, 1990)
Federation
30.4 Well Pori-D on Fennoscandian shield. Proposed origin: serpentinization > 300 Total well depth Finland Pori, 30.4 (Sherwood Lollar et al., 1993a; Sherwood Lollar et al., 2007;
is 7300 m Sherwood Lollar et al., 1993b)
34.9 Gas from a well on the Baltic shield (old craton) 2300 Russian Pechenegskaya, 34.9 (Войтов and Осика, 1982)
Federation
56, up to Free gas from the Scott well. Maximum H2 content associated with Precambrian 666 USA Scott well, 56 (Vacquand, 2011; Goebel et al., 1984; Coveney et al., 1987; Newell
basement. Proposed origin: mixed (from different sources) et al., 2007; Angino et al., 1990; Goebel et al., 1983; Guélard et al.,
2017)
68.6 Well drilled into Precambrian. Located on Kangaroo Island. Proposed origin: 290 Australia Penneshaw, 68.6 (Ward, 1933)
reaction of water with ferrous compounds or magmatic (from high-temperature
reactions)
80, up to Free gas from the Heins well. Maximum H2 content associated with Precambrian 661 USA Heins well, 80 (Vacquand, 2011; Goebel et al., 1984; Coveney et al., 1987; Newell
basement. Proposed origin: mixed et al., 2007; Angino et al., 1990)
84 Gas from a well, drilled into Precambrian metamorphic rocks. Yorke Peninsula, 508 Australia Minlaton, 84.0 (Войтов and Осика, 1982; Ward, 1933; Woolnough, 1934)
Australian shield
91.8, up to Free gas from the Sue Duroche2 well. Maximum H2 content associated with NR USA Sue Duroche2 well, 91.8 (Guélard et al., 2017)
Precambrian basement. Proposed origin: mixed
(Cruikshank et al., 1973). Gases sampled from the Icelandic volcano

Surtsey were reported to contain 1.7–3.1% H2 (Smith, 2002). In Japa-
(Войтов, 1990; Карус et al., 1984; Войтов, 1986; Ikorsky
(Angino et al., 1984; Bogdanowicz, 1934; Заварицкий,

nese volcanoes, hydrogen was detected mainly in gases collected from
liquid magma but not from hot sources and fumaroles. To explain this
the authors of the published studies proposed that hydrogen was re-
acting with SO2 before reaching the surface (Соколов, 1966a). During
(Стадник, 1970; Черепенников, 1936)
the eruption of Mount St. Helens, USA continuous soil gas monitoring of
hydrogen concentrations at a “non-fumarole” site was performed.
(Соколов, 1971; Пиковский, 1963)
Abrupt increases in H2 concentrations in the surface air were recorded a

few days before the eruption. After a few to several hours following
1928; Лидин et al., 1982)
seismic and volcanic events, H2 concentrations were observed to have

increased in the soil (Sato and McGee, 1981). Another soil gas survey
(Башта et al., 1991)
carried out at the Sabatini volcanoes in Italy, showed generally low

levels of hydrogen. In such cases it was hypothesized that these low
et al., 1999)
levels were a function of high permeability at depth (Bertrami et al.,

1990). Plots of hydrogen concentration in soil gases in the Canadas
kmz
caldera, Canary Islands, identified anomalous hydrogen concentrations

in places where the most recent eruption of the Tenerife Island oc-
Ural superdeep, > 50
Kola superdeep, 20.6
curred. The distribution pattern was shown to be associated with vol-

Nizhny Tagil, 80.5
canic tectonic lineaments (Hernández et al., 2000).

Iriklinskoe, 80.4
Tubinsky, 38.2
Table 6 lists examples of hydrogen observed in geysers and hydro-

thermal systems associated with volcanic activity along with a hy-
drogen discovery in a standalone gas seep in France and in mud vol-
kmz
canoes in Azerbaijan. In Iceland, it was reported that hydrogen is one of

the major constituents of all natural gas samples. When geysers were
Russian Federation
Russian Federation
Russian Federation
Russian Federation
Russian Federation
studied based on δD measurements (ratio of deuterium to protium, two

stable isotopes of hydrogen) the calculated equilibrium temperature
between H2 and H2O (246°C) was reported to be much lower than the
observed temperature of the aquifer (465°C) (Sano et al., 1985), which
kmz
shows that hydrogen was likely not produced in the ground water. The
discovery of hydrogen in hot hydrothermal systems is not unique. It was
1100–1140, and up to 11
reported that hydrogen-rich hydrothermal systems such as those in

Iceland have the highest heat values, up to 108 kcal/s, and very high
temperatures, up to 350°C. Similar conditions were observed in hy-
drothermal systems in California, USA (Sonoma), El Salvador (Ahua-
2930–3080
3450–3770
chapan) and Japan (Arima) (Кононов, 1983). High values of the heat
flow may be related to the process of hydrogen oxidation.
40.6
kmz
600
Hydrogen discoveries in kimberlite pipes have been reported in only

km
NR
a few instances (Table 7), however, one of these holds the record for the
In gas, seeping for 2 weeks from the well #1 drilled in dunites. Initial pressure was 60
Kola superdeep drilling SG-3. Volume of hydrogen up to 0.3 m3 per 1 m3 of drilled
highest reported flow of natural hydrogen. Well #42 in the Udachnaya

kimberlite pipe blew out during drilling, creating a huge flare of
burning gas (Fig. 4). The estimated initial flow from the well was
Ural superdeep drilling, hydrogen is a major gas in the drilling mud when
100,000 m3 H2/day. The gas burned for 3 days, after which the well
started to produce water as a result of an “air-lift effect” (when ex-
panding gase draw fluids to the surface) and was capped. The measured
hydrogen concentration on the second day was in the range
27.4–46.6%. After a month, measured H2 concentrations were around
Iriklinskoe canyon, well #14 drilled in extrusive rocks.
intercepting fracture zones in volcanic tuff and basalt.
10% (Фомичев, 2008). Hydrogen measurements were also taken from

other kimberlite pipes in the area: Internatsionalnaya and Mir each
Tubinsk, Gas from well drilled into volcanic pipe
bar. Proposed origin: mixed, mostly inorganic.
reported values of H2 of up to 6% at depths of 550 to 1300 m

Hydrogen discoveries associated with igneous rocks.
(Сороченко and Дроздов, 2010).

Many instances of naturally occurring hydrogen have been reported
from various mining sites, exploring for iron, gold, uranium, mercury,
nickel, copper and polymetallic ores such as niobioum-tantalum and
tungsten-molybdenum. Table 8 lists instances of hydrogen detected in
association with many different types of ore. Several estimates are
rocks; c (He) = 1.5%
available for the quantity of gas: in the Khybiny massif, Russian Fed-
eration, the flow rates of gas are in the range of 0.05–5 L/min per in-
dividual borehole or gryphon (seep) (Nivin, 2009) and 0.5 ml/min/m2
in the Lovozero loparite deposit mine or 0.2–1.6 m3 of total gas per 1
m3 of undisturbed rock (Nivin, 2016). The duration of gas seepage
kmz
ranges from several days to up to 20+ years (Nivin, 2009; Nivin, 2016).
A systematic study of these gases has divided them into three types: free
50, at least
35.1–38.2
(seeping from the fractures), occluded (stored in closed pores), and

Table 4
diffusively-dispersed (intermediate between the two previous types

20.6
80.4
80.5
kmz
(diffusively dispersed gases refer to gas stored in micropores, mostly in
7
Table 5
Hydrogen in volcanic gases.
10.8 Gas from small low-temperature fumarole. Proposed origin: H2S Washington, USA Mount St. Helens, (Evans et al., 1981)
reaction with water; c (H2S) = 2.16% 10.8
14 Volcanic gases in Askja volcano Iceland Askja, 14 (Кононов, 1983)
14.9 Volcanic gases from the rift-zone-related to the Nyiragongo volcano; c Democratic Republic Nyiragongo, 14.9 (Canfield et al., 2006)
(SO2) = 18.3% of Kongo
6–16 Fumarole gases from Shiveluch volcano Russian Federation Shiveluch, 16 (Соколов, 1966a)
16.6 Gas from fumarole from Kverkfjöll volcano Iceland Kverkfjöll, 16.6 (Sigvaldason, 1966)
18 Gases from fumaroles in Iwo Jima volcano Japan Iwo Jima, 18 (Соколов, 1971)
25 Volcanic gases in Showashinzan volcano; c (NH3) = 0.06% Japan Showashinzan, 25 (Кононов, 1983)
0.002–25.5 Composition of dry gases separated from water vapor (~90 % of the Russian Federation Tolbachik, 25.5 (Gilat and Vol, 2005)
gas volume) by condensation, taken from the hot (1000°C ± 65°C)
liquid lavas during the 1975–1976 Tolbachik volcano fissure eruption
14.4–29.2 Fumarole gases, South-East vent, Trident volcano; c (He) = 1.8–2.8% USA Trident, 29.2 (Symonds et al., 2003)
34.4 Volcanic gases in Surtsey volcano Iceland Surtsey, 34.4 (Кононов, 1983)
51.5 Fumarole gases, Spine vent, Augustine volcano; c (He) = 4.5% USA Augustine, 51.5 (Symonds et al., 2003)
Up to 54 High-temperature volcanic gases in Eldfell volcano Iceland Eldfell, 54 (Кононов, 1983)
Up to 57.8 Hot gases from fumaroles and during the eruptions of the volcano Italy Etna, 57.8 (Войтов and Осика, 1982; Соколов, 1971;
Etna. c (O2) = 34.5% Соколов, 1966a; Соколов, 1966b;
Huntingdon, 1973)
Up to 67 Gases from Hekla volcano Iceland Hekla, 67 (Соколов, 1971; Соколов, 1966a)
15.3–69.5 Klyuchevskaya Sopka volcano, gases from various volcanic craters Russian Federation Kliuchevskoi, 82.2 (Пиковский, 1963; Соколов, 1966a;
Up to 82.2 and fumaroles. In total 672 analyses of gases from 15 side craters; c Куликова, 1966; Фроловская, 1964)
(CO) up to 34% (Башарина, 1963)
72–90.2 Gases from Mihara volcano Japan Mihara, 90.2 (Войтов and Осика, 1982; Соколов,
1966a; Соколов, 1966b)
63–93 Volcanic gases from Plosky Tolbachik volcano Russian Federation Plosky Tolbachik, 93 (Щека and Гребенников, 2009)
Table 6
Hydrogen in gases of geysers, hot springs, mud volcanoes and standalone seeps.
2.4–12.5 Gas from hot springs and geothermal wells China Jimo hot spring, 12.5 (Hao et al., 2020)
14.1 Gas from mofetta (gas seep) France Les Tiogaux, 14.1 (Blavoux and Dazy, 1990)
14.7 Gas from the hot geyser “Old Faithful”; c (H2S) = 1.7% California, USA Sonoma, 14.7 (Кононов, 1983; Соколов, 1971)
15.4 Gases from mud volcano Azerbaijan Baladzhary, 15.4 (Фроловская, 1964)
22.2 Free gases from hydrothermal spring in vapour/hydrothermal Iceland Torfajokull, 22.2 (Кононов, 1983)
system; c (H2S) = 1.7%
24.1 Gases of Namafjall geysers. Estimated daily flow 1000 m3/day Iceland Namafjall, 24.1 (Войтов and Осика, 1982; Кононов, 1983; Shcherbakov
of H2; c (H2S) = 32.8% and Kozlova, 1986)
9–36 Gases from hydrogenous hot springs of Icelandic type Iceland Landmannlaugar, 36 (Smith et al., 2005)
Kerlingerfjoll, 36
10–40 Free gases from the well #1 in vapor/hydrothermal system El Salvador Ahuachapan, 40 (Кононов, 1983)
46.4 Free gases from hydrothermal site in vapor/hydrothermal Iceland Nesjavellir, 46.4 (Кононов, 1983)
system; c (H2S) = 7.6%
51.4 Free gases from hot spring in hydrothermal system Japan Arima, 51.4 (Кононов, 1983; Nakamura and Meda, 1961)
an adsorbed state and which can be degassed from a sample shortly concentrations in Eastern Siberia wells systematically increase with
after sample collection). By analysing these three types of gas in more depth (Levshounova, 1991). Recent studies from the Volga-Ural oil and
than 10,000 samples it was shown that the average concentrations for gas province have shown that hydrogen has been systematically logged
each type were very similar. However, the volume of gases sampled during drilling and that it is present across the entire sedimentary
varied by up to 6 orders of magnitude (Нивин, 2013). Another study section with peak-values correlating to hydrocarbon peak values
reported that during the drilling of a well in the Tyrnyauz mine, in the (Шевченко and Силкин, 2015). A probable causal link between hy-
Caucasus mountains of the Russian Federation, at a depth of 763 m a drocarbons and hydrogen is discussed in the Section 5.5 Oil, gas and
flow of hydrogen gas with up to 87.3% H2 was encountered. It con- minerals.
tinued to flow for several months, and hydrogen concentrations pro- Besides association with oil & gas fields, coal basins are another
gressively declined to 0.5%, being totally replaced by CO2. The calcu- common locale where significant quantities of hydrogen have been
lated volume of total degassed hydrogen was 3237 m3. The authors observed (see Table 10). As already mentioned above, the first dis-
suggested that it was a local accumulation of natural hydrogen covery of natural hydrogen was made in gas from a coal mine in Uk-
(Гуревич et al., 1960). raine (Менделеев, 1888). Sometimes, hydrogen can be the main
Another important instance of naturally occurring hydrogen is that component of gas sampled from coal mines: it was detected at different
associated with the exploration for oil and natural gas (Table 9). In concentrations in 60% of gas samples from coal mines in the Russian
some cases, it has been shown that hydrogen is one of the main com- Far East (Гресов et al., 2010).
ponents of gases associated with hydrocarbon deposits. It has been re- Multiple discoveries of hydrogen have been reported in sedimentary
ported that almost all of the combustible gases derived from the Cam- rocks (Table 11). This is not surprising, because sedimentary basins
brian of Eastern Siberia contain hydrogen, at concentrations as high as make-up about half the world’s surface area, and have been thoroughly
10% and higher (Войтов and Осика, 1982). Another study comple- drilled (Smith, 2002) in the search for hydrocarbons. It been suggested
ments this observation, reporting that hydrogen and helium that hydrogen is present in any sample of gas from sediments, however,
8
(Войтов and Осика, 1982; Соколов, 1971; Войтов, 1986;

(Соколов, 1971; Фридман, 1970)
Фомичев, 2008; Дроздов, 2011)

Reference
Name of placemark
Udachnaya, 58.9
Zheldon, 48.8
Russian Federation
Russian Federation
Country
Fig. 4. Burning gas from well #42 in the Udachnaya kimberlite pipe. Picture
365–367 (well #42);
from (Фридман, 1970).

370 (well #217)
special conditions are required for it to accumulate and reach high

Depth, m
concentrations (Молчанов, 1981).

Salt deposit hydrogen discoveries are presented in a separate
Table 12, because the origins of hydrogen discovered in salt is debated
(see Section 3.4 Water radiolysis). It has been proposed that high
Gas from wells #42 and 217 in kimberlite pipe Udachnaya. Estimated initial flow
In gas-water released from a well drilled into kimberlite or volcanic pipe Zheldon
concentrations of hydrogen in salt deposits can be explained by the fact

that hydrogen can be effectively trapped by alternating layers of clays
and salt (Суббота and Сардонников, 1968).
2.2. Diffusive flow
Hydrogen is the most diffusive of all gases and for this reason one
would expect it to exist mainly in a diffused state in the natural en-
vironment and not concentrated as has been presented in the examples
above. Indeed, many studies have shown that hydrogen diffuses
through the Earth’s crust to reach the surface. Soil gas measurements
from well #42: 100,000 m3 H2/day
carried out at the surface over an area of more than 7000 km2 show a
zone of anomalously high hydrogen concentrations extending as much
as 85 km west of certain hydrogen-rich wells in Kansas, USA (described
in the Table 3). Abnormally high, up to 6000 ppm (0.6%) hydrogen
Hydrogen discovered in kimberlite pipes.
concentrations were observed in soils sampled in Kansas. The area with

anomalously high hydrogen soil gas concentrations appears to correlate
with gravity and magnetic anomalies defining the North American Mid-
Comments
Continent Rift System (Angino et al., 1990; Angino et al., 1988). A very
recent study reports that hydrogen along with other gases has been
III
mapped over a variety of sites in Ukraine (165 in total), mostly in oil

and gas fields, but also coal mines, astroblemes and offshore continental
58.9 in well #217
shelf areas. The authors conclude that hydrogen is a useful tool for geo-
51 in well #42
ecological research and prospecting (Багрій et al., 2019).

Indeed, hydrogen plotting appears to be a useful technique in geo-
Table 7
H2, %
logical analysis and the locating of deep structures. For instance, it was
48.8
used to identify zones of high fluid conductivity on the East-European
9
Table 8
Hydrogen discoveries associated with orebodies.
V. Zgonnik
8.3–11.8 Seeping of gas and water from the well during 5 days in an apatite-nepheline ore 53 Russian Kukisvumchorr, 11.8 (Фридман, 1970; Nivin et al., 2005)
mine; c (NH3) = 0.05% Federation
13.7 Free gas in production zone of iron ore mine Lenina. Estimated flow into two 825 Ukraine Kryvyi Rih, 13.7 (Войтов and Осика, 1982; Войтов, 1986; Войтов,
ventilation galleries 734.4 m3/day; c (He) = 1.1% 1971)
13.9 Gas seep from the ijolit-urtites (igneous rocks consisting essentially of nepheline) Russian Yuksporsk, 13.9 (Онохин, 1959; Nivin et al., 2005; Войтов, 1962)
in apatite-nepheline ore mine of Yuksporsk orebody Federation
15.2 Gas, which exploded and then continued to burn. Horizontal tunnel in quartzites 1621 South Africa Robinson Deep, 15.2 (Фридман, 1970)
of gold mine
16.3, up to During drilling, when encountering crushed and hydrothermally modified ore in Russian Belokamennoe, 16.3 (Фридман, 1970)
mercury orebody mine Federation
17.6 Gas–air mixtures from boreholes in Khibiny alkaline igneous complex Russian Eveslogchorr, 17.6 (Nivin et al., 2005)
Federation
17.9 Gas–air mixtures from boreholes in Khibiny alkaline igneous complex Russian Apatitovyi Tsirk, 17.9 (Nivin et al., 2005)
Federation
19 Free gas in production zone of iron ore mine “Hvardiiska”. Estimated flow in two 680 Ukraine Kryvyi Rih, 19 (Войтов, 1971)
ventilation galleries 5438 m3/day
19.0, up to, in free gases in mine; Free gas in the mine #8 orebody goldfield. Hydrogen in drilling mud: 36.6–68.9 316 Russian Taseevskoe, 19.0 (Куликова, 1972)
2.6–14.0 in drilling mud cm3/per kg of drilled rock Federation
1.4–19.5 in gryphons; 20.1, up to, in Free gas seeps in the railway tunnel blast-hole #28 in Mount Rasvumchorr. Russian Rasvumchorr, 20.1 (Войтов and Осика, 1982; Войтов, 1986; Кривцов
drilled holes in mine Linearly distributed seeps, several tens per 100 m2 in late Devonian-early Federation et al., 1967; Хитаров et al., 1979; Петерсилье, 1964)
Carboniferous urtites. Estimated flow of H2 0.1–0.2 L/min per seep; c (He) up to
3.67%; c (Ar) up to 6%
7.1–20.3 Gas from drilling mud in a well in gold ore. Volume of hydrogen 37–69 cm3/L of Russian Baleysky graben, 20.3 (Куликова, 1966)
drilling mud. Maximum content in Cretaceous-Jurassic sandstones Federation
21.5 Gas seeping from a well drilled in nickel mine. Flow rate up to 6 L H2/min. Russian Zapolyarny, 21.5 (Фридман, 1970)
10
Proposed origin: magmatic Federation
24 Gas seep in tunnel of gold mine #4. The seep was located near a fault 2192 South Africa City-Dan, 24.0 (Фридман, 1970)
24.6 In chalcopyrite orebody copper mine Russian Kizil-Dere, 24.6 (Войтов and Осика, 1982)
Federation
25.1 Gas seeping from well drilled into nickel ore intrusion. Flow rate 32 cm3/L of Russian Imangda Rudnaya, 25.1 (Фридман, 1970)
drilling mud. Proposed origin: magmatic Federation
34.8 Gospodskaya shahta mine, situated in dunite massif Nizhne-Tagilsky 183 Russian Gospodskaya shahta, 34.8 (Черепенников, 1936; Заварицкий, 1928; Лидин
Federation et al., 1982)
50 St. Helena Gold Mine, African shield South Africa St. Helena Gold Mine, 50 (Войтов and Осика, 1982)
40–70 in free gas; 26, up to, from Urupsky chalcopyrite orebody mine: Hydrogen content in drilling mud up to 157 Russian Urupsky, 70 (Соколов, 1966a; Соколов, 1966b; Фридман, 1970;
fractures in mine cm3/L. Federation Войтов, 1962)
43.3 in drilling mud Gas from fractures depleted in hydrogen after 2 days. Proposed origin: action of
hydrogen flow on shales
77.5 Gas, which exploded and was burning 4 days after drilling in quartzites in gold 1426 South Africa Crown mine, 77.5 (Фридман, 1970)
mine. Later, gas was seeping for a long time without burning.
80, up to In drilling mud of a well drilled in copper mine. Flow rate up to 120 cm3 H2/L of 350–460 Russian Vlasenchihinskoe, 80 (Фридман, 1970)
drilling mud. Proposed origin: magmatic Federation
79.4–81.8 Gas from #1 well drilled in dunite massif of mine Krasny Ural 600 Russian Krasny Ural, 81.8 (Войтов and Осика, 1982; Стадник, 1970)
Federation
63.2–82.6 Strong degassing for 3–4 years in wells #2 and #27 of Kyzylkolskoe mine. Russian Hudesskoe, 82.6 (Войтов and Осика, 1982; Фридман, 1970; Войтов,
Well #7 in chalcopyrite orebody copper mine. Hydrogen concentration decreased Federation 1962; Фридман, 1961)
progressively by 2.5–5%. Proposed origin: magmatic
87.4, up to Gas from well #104 in tungsten-molybdenum mine Tyrnyauz. Total volume of 763 Russian Tyrnyauz, 87.4 (Войтов and Осика, 1982; Войтов, 1986; Соколов,
degassed hydrogen estimated 3237 m3 Federation 1966b; Гуревич et al., 1960; Гуревич, 1967)
90.6, up to Free gases in Lovozero loparite mine. Mean concentration 35.6% Russian Lovozero, 57.8 (Nivin, 2016)
Federation
37.8–96.8 Gas from drilling mud for a well drilled in porphyry and diabase of nickel Russian Norilsk, 96.8 (Соколов, 1966a)
orebody mine Federation
98 100 Uzbekistan Rudnoe, 98 (Перевозчиков, 2011)
(continued on next page)
Table 8 (continued)
V. Zgonnik
Hydrogen seeped for several weeks from a well drilled into metamorphic
Ordovician-Silurian uranium ore deposit
93.5–98.5 Gas from chromites and serpentinized dunites in chromite mine Molodezhnaya in 300–513 Kazakhstan Khromtau, 98.5 (Лидин et al., 1982; Уханов et al., 1987; Уханов et al.,
Kempirsae massif. Gas was identified as the fuel for a flame which was stable for 1984)
12 h. Also, in several places in the shaft with bubbling. Estimated flow 0.1–20
m3/day. Measured δD = -766‰, δD of water = -122‰. Proposed origin: deep-
seated
11
Table 9
Hydrogen discoveries associated with oil & gas fields.
6–10 In oilfield gases Russian Federation Lenno-Viluisk, 10 (Гресов et al., 2010)

11.0 Moiseevskaya oil field, well #2 2576–2589 Russian Federation Moiseevskaya, 11 (Молчанов, 1981)
11.5 Gas from the Navajo No1A well drilled into Pennsylvanian age Hermosa Formation, Paradox Basin USA, near 2365 USA Navajo, 11.5 (Headlee, 1962; Boone, 1958; USGS, 2009)
Rattlesnake and Hogbackoil pools. BTU value = 238. Proposed origin: igneous or coal.
12.7 Gas from well #17 in ozokerite, oil and sulfur field Shor-Su Uzbekistan Shor-Su, 12.7 (Черепенников, 1936)
14.7 Hydrocarbon well #1, parcel 573 Azerbaijan Absheron, 14.7 (Молчанов, 1981)
17.9 Kama field. BTU value1778, open flow 7000 mcfd 2262 USA Jeffers, 17.9 (USGS, 2009)
19.5 Gas from the well drilled into Devonian strata. Vaughn field, Cascade County, MT. Reported wellhead 965 USA Cascade, 19.5 (Moore and Sigler, 1987; Headlee, 1962; Anderson
pressure 50 psig, open flow rate 10 mcfd and Hinson, 1951)
20.4 Pinta Dome hydrocarbon field, Late Triassic, Chinle formation in. BTU value = 60; c (He) = 4% 325 USA Hortenstein, 20.4 (USGS, 2009)
20.8 Gas in well drilled in Glacial deposits. Gas may be related to Baltic Cambrian reservoirs in offshore Swedish 27 Estonia Koksher, 20.8 (Smith et al., 2005; Bogdanowicz, 1934)
gas field
26.3 Gas from Horse point 1-X well drilled into Cretaceous rocks. BTU value = 744, wellhead pressure 999 psig, 2472 USA Horse point, 26.3 (Moore and Sigler, 1987; USGS, 2009)
open flow 2169 mcfd
27.3 Upper Miocene gas well. Max pressure 0.15 atm, flow rate 2–3 m3/s. Proposed origin: mixed, mostly Russian Federation Stavropol, 27.3 (Angino et al., 1984; Bogdanowicz, 1934)
inorganic
27.3, up to Free gases #1-PR well. Russian Federation Verhne-Bureinsk, 27.3 (Гресов et al., 2010)
30, up to In the drilling mud of well #16 drilled into Cambrian sediments 2530 Russian Federation Iki-Burul, 30 (Левшунов, 1972)
40, up to Gas from hydrocarbon field Russian Federation Markovskoe, 40 (Молчанов, 1981; Левшунов, 1972)
47.3 Well #101 in Severnaya oil field 2261–2263 Russian Federation Severnaya, 47.3 (Молчанов, 1981)
52.5–95.2 Drilling mud #2-R well drilled into Carboniferous sediments 1105 Belarus Yelskaya, 95.2 (Шорохов, 1960)
Table 10
Hydrogen discoveries associated with coal basins.
10 In gases from drilling muds. Karagandinsky coal basin Kazakhstan Karagandinsky, 10 (Зингер, 1962)
18.4 In gases from drilling muds. Kuznetsk coal basin Russian Federation Kuznetsky, 18.4 (Зингер, 1962)
20 Gas seep in mine Kirova, horizon 35. Kuznetsk coal basin Russian Federation Leninsk-Kuznetsky, 20 (Молчанов, 1981; Гуревич,
1946)
10.9–21 in the mine In coal mine and gas samples from the Luhanska well 1500. Donbas coal Ukraine Luhanska, 23.1 (Молчанов, 1981)
23.1 in the well basin
21.2–27 Gas from reservoirs in coal basins Uglovsky, Partizansky and Sakhalinsky. Russian Federation Uglovsky, 27 (Гресов et al., 2010)
Estimated volumes 100–1,000,000 m3 Partizansky, 27
Sakhalinsky, 21.2
40, up to In gases from drilling muds. Donbas coal basin Ukraine Donetskyy, 40 (Зингер, 1962)
87.2 In gas from well #110. Berzassk region of Kuznetsk coal basin Russian Federation Berzassk, 87.2 (Стадник, 1970)
95.4, up to Drilling mud gas, coal mine well #V-335. 539 out of 820 samples contained Russian Federation Kayerkan, 95.4 (Молчанов, 1981; Сивак,
> 10% of hydrogen 1962)
platform (Козлова, 2004). It has been shown that the source of H2 is in the Russian Federation and USA give volumes of up to 27,000 m3 H2
natural and that hydrogen anomalies related to anthropogenic factors per day. It is possible that the hydrogen flow at such locations has been
are localized to small areas of only a few square meters (Гусев, 1997). continuous for thousands of years.
The plotting of hydrogen concentrations in subsurface soil has proved Some evaluations are available for diffusive flow of hydrogen at
to be useful in identifying geological structures over large areas of other locations. The volume of hydrogen degassing from the entire re-
Uzbekistan in the Gazli gas field area. Regions where no detect values gion of Kryvyi Rih, Ukraine, was estimated to be 120,000 m3/day
were measured were interpreted to be areas where the upward migra- (Войтов, 1971). Another study estimated the flow of hydrogen from the
tion of hydrogen was obstructed by ground water (Перевозчиков, Ukrainian shield to be 10–12 cm3 of H2 per year per square meter. On
2012). Indeed, studies have shown that hydrogen flux through water- the alkaline massifs of the Ukrainian shield, this number is estimated to
saturated porous media is reduced by a factor of ten compared to hy- be 100–120 cm3 of H2 per year per m2 (Войтов, 1975). Indeed, when
drogen flow through pure water. This retardation of hydrogen diffusion estimated hydrogen releases from the alkaline rocks of Khybiny and
by water-saturated sediments may be related to the Van der Waals radii Lovozero massifs in the Russian Federation were compared with re-
(the distance at which Van der Waals forces become effective). The leases from alkaline rocks from the eight massifs of the Ukrainian
study’s authors note that molecular hydrogen and cetrain noble gases shield, the latter were shown to be less rich in hydrogen. At the same
have similar radii, and as a result the migration properties of these time, alkaline rocks of Khybiny and Lovozero massifs are characterized
gases in porous media are similar. In this case, the migration of hy- by a high oxidized iron content (Kryvdik et al., 2007), contrary to what
drogen coud possibly be retarded by traps and aquifers (Vacquand, would be expected, if the rate of hydrogen production was related to
2011). However, the Van der Waals radius of the hydrogen molecule iron oxidation.
varies depending on pressure and the presence of other molecules and In a recent study of hydrogen in Oman, a general diffused flow of
other factors (Batsanov, 1999). In the gas phase the Van der Waals molecular hydrogen was observed to emanate from the Western Hajar
radius of H2 is equal to 152 pm, which is closer to that of Neon atom mountains (Zgonnik et al., 2019). Notably, the most significant flows
(155 pm), rather than that of Argon (188 pm). Therefore, it seems that were observed to emanate from the deeper underlying structural units
depending on the geology, hydrogen can diffuse more or less efficiently and not the ophiolites which suggests a probable deep source for the
as a function of multiplicity of factors. hydrogen. Minimum estimated H2 flows from the Oman study range
It should be noted that plots of hydrogen concentration in soil-gas from 73 to 147 m3/km2 per day from the Oman peridotites and up to
have limitations. This is because soils have been proven to efficiently 1300 m3/km2 per day in the shales and marbles of the Oman Upper
decompose hydrogen (Conrad and Seiler, 1981).These reactions are Proterozoic. Another study recently done in the French and Italian
discussed in more detail the Section 3.5 Biological activity. The im- Western Alps also detected hydrogen seepage (Dugamin et al., 2019).
plications are that in soil covered areas subsurface hydrogen seepage
will be taken up by soil and microorganisms. Therefore, for hydrogen to
2.3. Relationship of hydrogen with faults and with some noble gases
be observed in soil, the influx of hydrogen must be greater than the
hydrogen consumption rate. For hydrogen flux to be accurately eval-
Numerous studies show an association of hydrogen with faults be-
uated it should be sampled in strata below any zones of biologic and/or
cause they represent a natural pathway for fluids. It was in Japan that
soil activity.
the first experiments were carried out showing that hydrogen con-
Recent studies have identified thousands of sites in the Eastern
centrations are strongly correlated with the faults and their activity
Russian Federation (Larin et al., 2015; Sukhanova et al., 2013), along
(Wakita et al., 1980). Later, H2 concentrations of up to 9.36% were
the Atlantic Coastal Plain of the USA (Zgonnik et al., 2015), and more
recorded from some Japanese faults (Sugisaki et al., 1983). As a result,
recently in Mali (Prinzhofer et al., 2018) and Brazil (Prinzhofer et al.,
hydrogen was confirmed as a useful tool for mapping faults (Ware et al.,
2019), where hydrogen has been measured seeping from "pockmarked
1985). Table 13 summarizes a few examples from the literature.
shaped" surface depressions referred in the literature as "Zapadyny",
Studies of hydrogen in soil gas were carried out in the USA over the
"Carolina Bays" and other local terms for a charcteristic circular topo-
San Andreas (California) and Duchesne (Utah) fault systems. Hydrogen
graphic feature. These shallow sub-circular depressions range from a
and helium soil gas concentrations show a clear association with deep-
hundred meters to several kilometers in diameter. There are thousands
seated fault zones. Concentrations of helium in soil gas at some loca-
of them in certain areas worldwide. It has been postulated that hy-
tions were as high as 1243 ppm, which indirectly proves that when it is
drogen originates from deep below the sedimentary section and mi-
associated with helium, hydrogen is of geologic provenance (Jones and
grating upwards the Earth’s surface. The observed circular depressions
Pirkle, 1981). Geochemical sampling for hydrogen in USA has been
are interpreted by the authors of two of the above cited papers as being
used to map faulting associated with mineral deposits in the Trans-
the result of localized collapse caused by the alteration of rock along
Challis fault systems of Idaho and the Carlin trend in Nevada. It was
hydrogen migration pathways. Estimated flow rates at some locations
suggested that based on anomalous concentrations useful fault zone
12
V. Zgonnik
Table 11
Hydrogen discoveries associated with sedimentary rocks.
4.2–10.7 Gas discovered in 1906 Russian Novo-Usensk, 10.7 (Rogers, 1921)

Federation
13.6 Well #1-P drilled in Lower Carboniferous. Proposed origin: deep-seated 4140–4155 Russian Sukhoi Hrebet, 13.6 (Суббота and Сардонников, 1968)
Federation
16.6 Well #2-Tdrilled in Paleocene, sandstone and gravel; c (CO) = 35.4%. Proposed 1135–1170 Kyrgyzstan Frunzenskaya, 16.6 (Суббота and Сардонников, 1968)
hydrogen origin: deep-seated
18.6 Gas discovered during construction of tunnel #5, Black Sea railroad Russian Mamayka, 18.6 (Молчанов, 1981)
Federation
18.9 Gas from a water well USA Bernalillo, 18.9 (Moore and Sigler, 1987)
20 Gas from well #2. Paleocene-Eocene epoch; c (CO) = 20% 2954–2980 Kyrgyzstan Serafimovskaya, 20 (Войтов and Осика, 1982; Суббота and Сардонников, 1968)
7.3–21.2 Gas seeping for 1 month from a well drilled into Middle Jurassic. Pressure at the 2849–2888 Uzbekistan Alambek, 21.2 (Войтов and Осика, 1982; Бетелев, 1965)
wellhead 2 bar. Proposed origin: deep hydrogen rising in a fault
26.7 Drilling mud gas, R-1 well drilled into Silurian sediments 910 Latvia Bauska, 26.7 (Шорохов, 1960)
13.8–28.1 Gas from Triassic sediments during the Superdeep drilling SG-2 5475–5500 Kazakhstan Aralsor superdeep, 28.1 (Войтов and Осика, 1982; Перевозчиков, 2011; Войтов et al.,
1967; Соколов, 1971; Шорохов and Шишенина, 1967)
37.5 In the drilling mud of the well 1-R drilled into Permian sediments 1185 Russian Kaliningradskaya, 37.5 (Шорохов, 1960)
Federation
42.3; 11.3 Drilling mudgas two wells: #1-RA and #2-RA. Proposed origin: biological 908; 1076 Russian Ivanovka, 42.3 (Несмелова and Рогозина, 1963)
Federation
42.3 Drilling mud gas, well #68 drilled into Devonian sediments 330 Latvia Loknovskaya, 42.3 (Шорохов, 1960)
31.7–43.5 Free gas from well #1-R drilled into Cambrian sandstones in Nukuty 2503–2520 Russian Nukuty, 43.5 (Несмелова and Рогозина, 1963; Пиковский, 1963; Фроловская,
13
Federation 1964)
20–50 During testing of wells drilled into Mesozoic sediments. Gas pressure 20–64 atm Russian Prikumskoe, 50 (Осика et al., 2002)
Federation
56.9 In the drilling mud, well R-1 drilled into Devonian sediments 846 Russian Lubimskaya, 56.9 (Шорохов, 1960)
Federation
57.6 Drilling mud gas, well 3-R drilled into Permian sediments 365 Russian Anybskaya, 57.6 (Шорохов, 1960)
Federation
57.7 Gas from the well Slope Indicator hole #6 drilled into Cretaceous 40 USA O'Neil pumping plant, 57.7 (Moore and Sigler, 1987)
73.1 Gas associated with sediments. Proposed origin: mixed, mostly inorganic Poland Lubina, 73.1 (Angino et al., 1984; Coveney et al., 1987)
75.8 Bubbling on the surface and seabed offshore, associated with Metamorphic rocks. New Zealand Poison bay, 75.8 (Wood, 1972)
Estimated flow 0.7–1.4 m3/day per bubbling. Proposed origin: serpentinization
76.9, up to In the drilling mud of a well drilled into Permian sediments 860–867 Russian Oparinskaya, 76.9 (Шорохов, 1960)
Federation
80, in average Gas from Tertiary sediments Russian Barguzin, 80 (Пиковский, 1963; Бодунов-Скворцов, 1958)
Federation
80, in average Gas from Tertiary sediments Russian Tunka, 80 (Пиковский, 1963; Shcherbakov and Kozlova, 1986; Бодунов-
Federation Скворцов, 1958)
86.6 In the drilling mud, Structural well drilled into Cambrian sediments 1475 Russian Povarovskaya, 86.6 (Шорохов, 1960)
Federation
90.5 In the drilling mud of the well 2-R drilled into Cambrian sediments 760 Russian Krestetskaya, 90.5 (Шорохов, 1960)
Federation
78–95 Gas from Tertiary sediments Russian Selenga, 95 (Пиковский, 1963; Shcherbakov and Kozlova, 1986; Бодунов-
Federation Скворцов, 1958; Сывороткин, 2002)
98 First producing hydrogen well. Opened in 2012 and as of 2018 has produced hydrogen 109 Mali Bourakebougou, 98 (Guélard, 2016; Prinzhofer and Deville, 2015; Briere and
without a decrease in pressure Jerzykiewicz, 2016; Prinzhofer et al., 2018)
Table 12
Hydrogen discoveries associated with salt deposits.
11.3 Gas from potash mine in Salzmunde Germany Salzmunde, 11.3 (Черепенников, 1936)
12–12.9 Gas from potash mine in Rossleben Germany Rossleben, 12.9 (Черепенников, 1936)
8.4–13.3 Gas from potash mine in Siegfried-Giesen Germany Siegfried-Giesen, 13.3 (Черепенников, 1936)
16 Gas in association with potash deposit Denmark Tonder, 16 (Smith, 2002)
17.4 Gases from well drilled into carnallite zone Russian Chusovskie Gorodki, (Bogdanowicz, 1934)
Federation 17.4
22.1 Gas from potash mine in Eristgal Germany Eristgal, 22.1 (Черепенников, 1936)
24.6 Gas from potash mine in Burbach Germany Burbach, 24.6 (Черепенников, 1936)
32.9, up to Gas from wells and mines in Solikamsk potassium field. 5.3–18.5 Russian Solikamsk, 32.9 (Черепенников, 1936; Молчанов, 1981;
in carnallite zones; 32.9 in bubbles on the border of the lake Federation Savchenko, 1958)
> 50 Main component of the gas in a potash deposit France Wittelsheim, > 50 (Молчанов, 1981)
54.3, up to Gas in carnallite and sylvinite layers. Proposed origin: from Russian Verhnekamsk, 54.3 (Войтов and Осика, 1982; Молчанов, 1981;
organic matter Federation Морачевский et al., 1937)
61.5 Gas from a well (probably) in a salt deposit. Proposed gas origin: Germany Muhlhausen, 61.5 (Angino et al., 1984)
mixed, mostly inorganic
82.3–93 Gas from potash mine in Leopoldshall potassium field near Germany Stassfurt, 93 (Черепенников, 1936; Rogers, 1921)
Stassfurt. Was seeping for at least for 4.5 years with flow 3.6 m3/
day
maps could be prepared (McCarthy and Kiilsgaard, 2001; McCarthy and they show a close relationship in their behavior and distribution.
McGuire, 1998). Based on an assumption for annual hydrogen flow of Geochemical maps of hydrogen and helium concentrations in ground
2.7 * 104 t/year (Giardini and Melton, 1983) a flow rate for H2 mi- water and soil gas were made for a study of a large area of Uzbekistan in
grating along the faults was estimated at 3.6*10−7 cm3/cm2·s (Su et al., the Gazli gas field area. Anomalous helium and hydrogen concentra-
1992), which is a very conservative number when compared to other tions were well correlated and related to zones of high fluid con-
estimates (see Table 25). ductivity. Hydrogen concentrations were usually two orders of magni-
Data on hydrogen from hundreds of soil gas measurements in North- tude greater than those of helium. At locations where helium was not
Central Kansas, USA suggests that fractures act as preferential conduits detected hydrogen was also not detected (Перевозчиков, 2012). He-
for the vertical migration of free hydrogen (Johnsgard, 1988). Another lium and hydrogen anomalies were studied in Uzbekistan over an area
study of soil gas sampled near hydrogen-rich wells in Kansas suggests a of 100,000 km2. Anomalous concentrations of both gases appeared to
relationship between anomalous hydrogen concentrations and faulting be associated with fault zones. The bivariate correlation coefficient of
(McCarthy et al., 1986). In an extensive review of the occurrence of hydrogen and helium is 60%, which suggests a linkage between them.
hydrogen in Ukraine and Belarus the highest concentrations of hy- No indicators were detected for an anthropogenic origin of these gases
drogen were found in subsurface fluids from the North Pryp'yat fault (Перевозчиков, 2011).
zone (Shcherbakov and Kozlova, 1986). Another study analyzed more Radon levels are commonly monitored for environmental safety
than two thousand detections of hydrogen in ground water and con- reasons. Since the properties of hydrogen and radon are diametrically
cluded that the hydrogen content of ground water associated with deep opposed, monitoring of these two gases might be useful in obtaining
faults is two orders of magnitude greater than that of ground water complimentary information about the properties of the environment.
sampled from background areas (Щербаков, 1985). One attempt to simultaneously monitor both gases was done in a 1-
A geophysical study of deep faults in the Moscow region of the month study near the city Essentuki in the Stavropol region of the
Russian Federation with the simultaneous plotting of subsurface hy- Russian Federation. No obvious correlations were reported (Рудаков
drogen concentrations showed a correlation between the highest ob- and Уточкин, 1993). However, later studies of hydrogen/radon mon-
served concentrations and deep faults (Rogozhin et al., 2010). In an- itoring in Belarus demonstrated that temporary variations in con-
other study, the concentrations of hydrogen-rich gases in kimberlitic centration of these gases correlated in time (Гусев, 1997). More re-
pipes were shown to be related to the presence of fractures which were cently, hydrogen was simultaneously measured with radon
the likely conduits for the migration of these gases in the subsurface concentrations and the electrical conductivity of the air at the surface. It
(Сороченко and Дроздов, 2010). was shown, that peaks of hydrogen correlate with peaks of Rn and the
Hydrogen subsurface concentrations were monitored over large electrical conductivity of the air over fault zones. It was suggested, that
areas of south-western Belarus. It was shown that areas of abnormally hydrogen plays a role as a carrier for radon gas (Козлова et al., 1999;
high hydrogen concentration were associated with deep faults. In such Войтов et al., 2000). In later studies, hydrogen and radon were con-
cases hydrogen concentrations were 10–50 times higher than back- tinuously monitored for 1.5 years at two locations in the Russian Fed-
ground concentrations, which were also close to hydrogen concentra- eration, one in a seismically active area and the other over a seismically
tions in air. A correlation coefficient of 0.7 between H2 and helium more stable area. It was concluded that the variations observed were a
concentrations suggests an association of high hydrogen and helium response to planetary scale geodynamic events and could be used for
concentrations with deep faults (Гусев, 1997; Гумен and Гусев, 1997). the monitoring of such events (Рудаков and Цыплаков, 2011).
It is commonly acepted that faults control the flow of the mantle
fluids into a sedimentary basin. A well-studied example from North Sea
2.4. Periodic variations in concentration
oil fields, where analyses using multiple isotope systems (Os, C, He, Ar,
Ne, O and D isotopes) to identify fluid sources elucidated a mantle
Variations in hydrogen concentration are not stable with time when
component in the origination of fluids trapped in the field (Ballentine
measured in natural environments. For example, hydrogen monitoring
et al., 1996; Fallick, 1993; Finlay et al., 2010). Apparently, hydrogen
over active faults in Japan on a regular basis shows that H2 con-
flux was not directly addressed, but helium flux may serve as a proxy
centrations fluctuate spatially and temporally (Sugisaki et al., 1983).
for hydrogen, what has been demonstrated in the other works discussed
Continuous monitoring of hydrogen concentration along the San An-
above.
dreas and Calaveras faults in California, USA, from 1980 to 1984 re-
Because hydrogen and helium have similar diffusive properties,
vealed diurnal changes in H2 concentration with abrupt increases
14
correlating with tectonic events (Sato et al., 1986).It has been proposed
(Wiersberg and Erzinger, 2008)

that these variations are the result of hydrogen being a very mobile gas,
the measured concentrations of which are sensitive to weak forces such
as tides (Хитаров and Войтов, 1982). Multiple studies have shown
(Sugisaki et al., 1983)
(Ware et al., 1985)

periodic changes in H2 concentration over time. Indeed, it is well
known that gas seeps from the Earth have a periodic character. A
possible mechanism to explain such phenomena could be tide-induced
Reference
sorption-desorption (Хитаров and Войтов, 1982).

A large amount of data on variations in hydrogen concentration
with time was collected in the Khibiny massif on the Kola peninsula in
Name of placemark
the Russian Federation. The first measurements were started in the

1960s and showed a relationship between hydrogen and hydrocarbons
SAFOD, 13.3
in the Khibiny gas seeps. These variations demonstrated a 14 days

Atera, 9.4
Burro, 70
periodic trend corresponding to lunar tides with a correlation coeffi-

cient of 0.65. This trend was stable and only interrupted by seismic
events, which changed the chemical composition of the seeping gases
(Хитаров and Войтов, 1985). Later studies showed that the ratio of
Country
Japan
hydrogen to hydrocarbons changes periodically with time and pro-

USA
USA
nounced peaks at 2 weeks and 6 months were observed (Кривцов et al.,

1967). Another study of periodic trends in gas concentration in the
Mud logging samples from the drilling of 3433 m borehole for the San Andreas Fault Observatory at Depth (SAFOD) project. Proposed origin of gas: water
Khibiny massif showed evidence of tidal effects (Хитаров et al., 1979).

Later, the intensity of hydrogen-rich gas seeps was monitored in the
Khibiny and Lovozerk massifs continuously for 5 years, with measure-
ments being taken at 5-min intervals. These data showed the intensity
varying with time in a complex way, including periodic and non-peri-
odic trends and that major factors influencing gas seeps are probably
tectonic and cosmic in nature. Hydrogen concentrations increased
during the summer months, and became very unstable during the sy-
zygy of Moon, Earth and Sun. Other regular trends include monthly,
daily, half- and quarter-daily cycles (Нивин, 2013; Nivin et al., 2016).
More recent interpretations of the same data lead the authors to con-
Burro mountain, bubbles of gas in strike-slip fault in dunites. Proposed origin of gas: decomposition of Fe(OH)2
clude that the most important factors controlling the dynamics of H2

concentration are changes in atmospheric pressure and mining activity
(Nivin et al., 2018; Nivin, 2019).
It has been shown that hydrogen concentrations respond to ongoing
tectonic activity. In one study, subsurface hydrogen concentration were
monitored in Belarus at 1-min intervals. A cyclicity of 12- and 24-h
changes in hydrogen concentration was observed, which was attributed
Measurements at 1 m depth in active faults. Proposed origin of gas: rock-water reactions
to tidal influences. A correlation coefficient of 0.6–0.75 confirmed at-

tribution to theoretical tidal deformations, while taking into account
that peaks were appearing with a delay of 2–4 h (Гусев, 1997). The
study also showed a perfect correlation with measured deformations of
the Earth’s crust (Гумен and Гусев, 1997). Longer cycles of 10–18 and
22–32 days were attributed to lunar tides of 14 and 28 days (Гусев,
1997). A later study, which compared tidal effects in wells to predicted
effects showed a perfect correlation (Гумен, 2000).
During several months, hydrogen soil gas concentrations were
monitored constantly at several points in a tectonically stable region of
Belarus. Some locations were situated over known faults, and others on
what were believed to be un-faulted areas. The results unambiguously
demonstrated that hydrogen concentrations varied periodically ac-
cording to 12 and 24-h cycles that were not related to changes in
temperature or biological activity, but according to the diurnal solid
Hydrogen discoveries associated with faults.
tides of the Earth. The highest amplitudes in concentration variations

reactions with fresh fractures
were observed at locations situated on faults. These variations were

attributed to the higher sensitivity of such zones to the Earth’s tidal
deformations. Hydrogen concentrations also showed a weak correlation
with changes in atmospheric pressure. Moreover, in winter months,
concentrations were lower, which the authors attributed to the sealing
Comments
of soil porosity by frost. A single instance of a sharp increase in H2

concentration was observed, which was attributed to the activation of a
deep fault zone (Гумен et al., 1998).
Another study, which monitored hydrogen concentrations in soil
13.3, up to
gas from surface and subsurface deposits at several locations in the city
Table 13
H2, %
of Obninsk in the Russian Federation, pointed to higher H2 content

9.4
70
during summer months and a decrease during autumn (Войтов et al.,
15
Fig. 5. Map of hydrogen detections in inclusions in various environments at concentrations > 10% vol. Note: high density of placemarks across Eastern Europe and
Northern Asia is due to the fact that researchers from these regions were looking for hydrogen more frequently, and not because these regions are richer in hydrogen.
Data on each placemark are available in the corresponding tables of this section and in a .kmz file provided in the Supplementary Information.
1995). In the Gomel region of Belarus and in the town Essentuki, Hydrogen concentrations were also monitored as a function of
Stavropol Krai, Russian Federation, H2 concentrations showed monthly depth, where atmospheric conditions would be supposed to have less
peaks of 12–75% above background concentrations (Войтов et al., effect. Measurements were made on an hourly basis in two wells in
1995). Hydrogen monitoring on the South Coast of Crimea, Ukraine, Moscow (at depths of 399 m and 1013 m respectively) for 455 days.
showed high background concentrations with frequent and non-regular Periodic cycles of 0.5, 1, 1.74, 21.33 and 85 days were observed. After
changes in peak amplitude probably related to tectonic processes analyzing the results, it was determined that variations in hydrogen
(Войтов et al., 1995). concentration could be attributed to geodynamic processes (Козлова,
When hydrogen concentrations are monitored in soil, many factors 2004). In the same study, the authors monitored hydrogen concentra-
may affect the measurements. For instance, the effect of soil humidity tions in the Moscow metro network. The study revealed a high degree
was studied showing that with an increase in soil humidity con- of heterogeneity in hydrogen concentration from station to station. At
centrations of hydrogen also increase, which is attributed to a decrease certain times, concentration differences ranged up to 100 ppm. It was
in soil permeability. Also, the highest hydrogen concentrations were concluded that the variations in hydrogen concentration were not
detected during winter months, when soil freezes (Гусев, 1997). An- connected to anthropogenic sources but rather to be natural (Козлова,
other study indicated that concentrations of hydrogen increase several 2004).
times at the contact between permafrost and talik (an area of unfrozen Periodic changes in global hydrogen degassing were deduced by
ground surrounded by permafrost) (Гресов et al., 2010). A recent study studying changes in the thickness of the ozone layer (see Section 5.3
of the causes of formation of Yamal crater, formed in 2014 in Yamal Atmosphere) (Сывороткин, 2013).
peninsula by an explosion of permafrost, demonstated that concentra- The above cited examples demonstrate that hydrogen, being the
tions of hydrogen in the permafrost could be very high, from 13 to 63% most mobile component of geologic fluids, responds to tides more than
(Vorobyev et al., 2019). This is probably due to low permeability of other gases. Even though tidal effects are several orders of magnitude
permafrost for gases. weaker than the stresses associated with an earthquake or other seismic
Correlations between atmospheric pressure, air temperature and event, they are nevertheless sufficient to dynamically influence un-
hydrogen concentration in soil gas were studied in the two fields in stable processes (Довбнич and Солдатенко, 2008) such as the release
Belarus. The maximum observed correlation coefficient was 0.45 with of H2 molecules (which are very light) from within the geosphere. The
less than a 1 day delay. There appeared to be zero correlation with air relationship of hydrogen to strong seismic events is described in the
temperature (Гусев, 1997). In a recent monitoring study of hydrogen Section 5.4 Earthquakes.
seepage at a circular surface depression in Brazil it has been demon-
strated that concentrations vary greatly between day and night 2.5. Hydrogen in inclusions
(Prinzhofer et al., 2019). The authors proposed that daily increases
correlated with the solar radiation, but the mechanisms of causation are Analyses of gases extracted from inclusions in rock samples has long
not fully understood and may be related to increases in temperature been considered useful by investigators. However, attention should be
affecting soil evaporation effects, microbiological activity, H2 detectors’ paid to the methodology used to extract gases from rock samples. When
efficiency depending on temperature etc. rock samples are heated to high temperatures or melted, or dissolved in
16
acid, it is not possible to determine whether or not hydrogen was in the
(Андреева and Молчанов, 1978)

sample. For example, it was reported that gases from samples of the
Kola superdeep drilling were mainly nitrogen-hydrogen rich. To de-
termine their composition, two types of degassing were used: me-
chanical, by crushing in argon atmosphere and chemical, by dissolution
(Велинский, 1978)
in hydrochloric acid. Chemical degassing produces gas enriched in
hydrogen, compared to gas from crushed samples (Войтов, 1990),
Reference
which indicates that some hydrogen may have been a by-product of
chemical reactions between the sample and acid. On the other hand,
when samples are heated or melted, any hydrogen in the original
sample will be destroyed by such analytical procedure. Therefore,
analyses of samples subjected to excessive heat or chemical agents were
Koriaksko-Kamtchatskaya orogen, 15
excluded from this review.
Anadyrsko-Kamchatskaya, 100
Hydrogen has been detected as a major occluded gas (trapped inside
of rock in form of inclusions or in adsorbed form) in a variety of dif-
ferent rock types. Each type of rock releases gas with a characteristic
Name of placemark
composition (Giardini et al., 1976; Fong-liang and Gui-ru, 1981).
Gornaya Shoria, 61
However, the number of instances where hydrogen has been extracted
from inclusions in rocks derived from the same environment of de-
position has yielded results that are not always consistent. Fig. 5 shows
all placemarks from the tables of this section.
While there are many studies describing instances of the detection
of hydrogen as a free gas in an ophiolitic context (Table 1), only one
Russian Federation
Russian Federation
Russian Federation
very recent study was found with analyses of hydrogen gas in inclusions
in such rocks. It was shown that in inclusions in olivine samples from
Zambales in Phillipines hydrogen is the dominant component (Grozeva
Country
et al., 2020). Such small number of articles on this topic begs the
question: was hydrogen not detected within rock inclusions in other
places, or was hydrogen overlooked because researchers were not
looking for it? I’m convinced that it is the last one, because the recent
Gas inclusions in basic and ultrabasic rocks. Highest concentration detected in serpentinites.
analyses of samples taken during by our group the field trip in Oman
(Zgonnik et al., 2019) demonstrated that inclusions in rocks are hy-
drogen-rich (results were not published yet).
Only two instances of hydrogen from inclusions in ultrabasic rocks
have been referenced. (Table 14). The source of the hydrogen is be-
lieved to be related to water-rock reactions (see Section 3.2 Serpenti-
nization).
It has been reported that minerals from rift zones have gas inclu-
sions high in hydrogen. In oceanic rifts the average hydrogen con-
In serpentinites of Koriaksko-Kamtchatskaya orogen region
centration found in inclusions is 21.4% (Моисеенко and Сахно, 1982).

However, no studies with analyses of hydrogen inclusions in rocks from
cratonic rift zones were found by this review.
More hydrogen detections were reported for inclusions in rocks of
Precambrian age (Table 15). As in the free gas data, increases in hy-
drogen concentration with depth with the highest values observed in
Hydrogen discoveries in inclusions in samples from ultrabasic rocks.
Precambrian basement from inclusions sampled (Зорькин et al., 1984).

Inclusions in dunite and peridotite
A recent study of Precambrian samples from around the globe de-

monstrated that hydrogen is consistent component and it mean con-
centration is 0.14%, while in younger basement samples concentrations
are lower by one order of magnitude (Parnell and Blamey, 2017a).
A large number of detections of hydrogen in gas inclusions was
reported for rocks of igneous origin (Table 16). The examples from this
table do not support the idea proposed in one paper that “under crustal
Comments
conditions, typical water-saturated granitic rocks could contain only minor

quantities of hydrogen” (Apps and Van De Kamp, 1993). Indeed, it was
reported in another study that the concentration of hydrogen in inclu-
sions in granites is very high, up to 99% (Петерсилье and Припачкин,
Content, cm3/kg
1979).
Samples of volcanic rocks often contain hydrogen in gas inclusions
6.3, up to
2.4–3.9
(Table 17). Reported average concentrations of hydrogen degassed

from fresh volcanic rocks is 45% (Соколов, 1966b).
Samples from kimberlite pipes were reported to have a high per-
centage of hydrogen in gas inclusions (Table 18). Fluid inclusions in
100, up to
xenoliths from the Kimberlite pipe Obnazhonnaya in the Russian Fed-

Table 14
39.8–61
H2, %
eration demonstrate that fluids at a depth of more than 70 km consists

15
mainly of hydrogen (Петерсилье and Припачкин, 1979). Also,
17
hydrogen appears to be always present in inclusions in diamonds, often
Молчанов,
Молчанов,
Молчанов,
Молчанов,
as a major gas (Федоров, 2001; Smith et al., 2016; Melton and Giardini,
(Konnerup-Madsen and Rose-Hansen, 1982)

1974). Another study confirms that hydrogen content increases with
depth by measuring hydrogen to water ratios in gases from diamond
inclusions. These studies showed that hydrogen is 140 times higher for
(Молчанов, 1981; Андреева and

(Petersilye and Sörensen, 1970)

diamonds estimated to have been generated at a depth of 400 km versus
those deemed to have been generated at depths of 120 km (Перчук,
2000).
Hydrogen was discovered in inclusions in minerals from different
mines and orebodies, such as: iron, uranium, gold, nickel, chrome and
(Войтов, 1990)
polymetallic ores (Table 19). It was shown that the concentration of H2
Reference
in quartz inclusions in gold and tungsten ore deposits increased with

1978)
1978)
1978)
1978)
depth (Letnikov and Narseev, 1991). Other studies report that hydrogen
is often present in gold mines. Its concentration in gold-bearing veins
can be extremely high, from 200 to 460 cm3/kg of rock, which is
Kangerdluarssuk, 12.6; Tunugdliarfik, 12.6
hundreds of times higher than the adjacent rocks (Фридман, 1970).

The same study indicates that hydrogen is present as inclusions in rock
samples from mercury orebodies with contents as high as 144 cm3/kg of
rock. In some inclusions hydrogen concentrations attained values of
19% (Фридман, 1970). Analyses of gas inclusions in silver and poly-
Sukhaya Tunguska, 69.5
Nijnaya Tunguska, 87.7
Minnibaevskaya, 97.8
metallic hydrothermal minerals in the Kurusaisk mining district in

Name of placemark
Uzbekistan show concentrations of up to 42.6% H2 with a content of

Igdlunguaq, 68.4
Ilímaussaq, 18.8
Miroediha, 26.1
102 cm3/kg in a sample of quartz. Other minerals contain (percent/

Narssaq, 93.1
Igarka, 89.5
Kotuy, 95.5
(cm3/kg)): 23/36 in garnet, 12/15 in sphalerite, 4/1.9 in calcite, 11.6/

2.6 in galena, 7.1/6.8 in barite (Соколов, 1971; Hawkes, 1980). It was
reported that hydrogen in high concentrations is present as an occluded
gas in most samples of rock from the Tyrnyauz tungsten-molybdenum
Russian Federation
Russian Federation
Russian Federation
Russian Federation
Russian Federation
mine in the Caucasus mountains of the Russian Federation (Гуревич

et al., 1960). A borehole drilled in Tyrnyauz mine produced hydrogen-
Greenland
Greenland
Greenland
Greenland
rich gas for several months (see Table 8).

Country
Many papers report on the results of studies of gas in Khibiny and

Lovozero massifs, on the Kola peninsula in the Russian Federation. The
highest hydrogen gas content in the ore-rich region of the massifs was
found in rocks surrounding apatite-nepheline ores. Gas is concentrated
Inclusions in augite and syenite; inclusions in sodalite and fayaite from
Inclusions in rocks from Precambrian igneous intrusions. Maximum in
in water-free blocks with a well-developed network of microfractures

surrounded by low permeability blocks (Нивин, 2013). A study of the
Inclusions in arfvedsonite and lujavrite from igneous intrusions
difference between open and closed pores, showed that most of the gas
Gases from crushed basement rocks from the well #20000
in Khibiny massif is present in closed pores, and the gas content of open
Inclusions in olivine and gabbro from igneous intrusions
pores is limited (Онохин, 1959). A study and analysis of diffusively

disseminated hydrogen–hydrocarbon gases in the rocks of both massifs,
In siliceous rocks: precipitates from thermal fluids
which compared their distribution with gases occluded in fluid inclu-

sions and free gases in fractures showed that hydrogen is the pre-
dominant diffusively disseminated gas in the undisturbed massif (Nivin,
Gas in siliceous concretions in gypsum
2009). The mean hydrogen content of the gas phase in the Khibiny
In precipitates from thermal fluids
massif was measured at 4% in occluded gases, and 20% in gases from

Hydrogen discoveries in inclusions in samples from Precambrian rocks.
fractures (Nivin et al., 2005). Hydrogen concentration in occluded gases

was seen to decrease with depth (Нивин, 2013). No correlations were
found between methane-hydrogen ratios (CH4/H2) in free and occluded
igneous intrusions
gases (Нивин, 2013) and between hydrogen and hydrocarbon con-

In siliceous rocks
centrations (Нивин, 2007). A very recent review summarized the data

arfvedsonite
Comments
for this region (Nivin, 2019).

Hydrogen was measured in gas inclusions of samples from different
coal basins (Table 20).
Only a few instances of hydrogen in sedimentary or metamorphic
7.48–43.2; 3.65–30.64
rocks have been reported in the literature (Table 21). Probably, because
6.88–25.8 cm /kg
sedimentary rocks have for the most part high porosity and perme-
Content, cm3/kg
ability, allowing hydrogen to readily diffuse out of the rock. However,

15.5–20.78
laboratory experiments on the hydrogen saturation in clastic and car-

bonate rocks show that the rock can adsorb very large quantities of
10.9
hydrogen (24–57 times) compared to their initial content and not to

release it for several days. The most absorptive rocks were found to be
13.1–69.5; 8–87.7
limestones (Levshounova, 1991). Laboratory analyses of hydrogen

68.4 in average
93.1 in average
content in different types of sedimentary rock showed that most sam-

17.5–26.1
61.1–97.8
12.6 (av.)
18.8 (av.)
ples have occluded hydrogen. The highest hydrogen contents were

Table 15
14–89.5
H2, %
observed in carbonates with up to 77.2 cm3/kg with an average of 14.8

95.5
cm3/kg. It has been suggested that carbonates are prone to absorb and
18
V. Zgonnik
Table 16
Hydrogen discoveries in inclusions in samples of igneous origin.
H2, % Content, cm3/kg Comments Country Name of placemark Reference
11.8 2.1 Gas occluded in granites of Elbrusskoe orebody mine Russian Federation Elbrusskoe, 11.8 (Фроловская, 1964; Гуревич et al., 1960)
13–21 In crushed diabases from Borjomi Georgia Borjomi, 21 (Соколов, 1971)
35.0, up to Inclusions in pegmatites from a plutonic body Canada Strange Lake, 35.0 (Salvi and Williams-Jones, 1997)
5.1–35.2 1.1–7.8 Gases in rocks of the Kola basic massifs. Highest concentrations Russian Federation Lovozero, 35.2 (Соколов, 1971; Potter et al., 2004)
in lujavrite.
8.8–40.8 71–84 In crushed quartz from the Mayndayntal igneous massif. Kazakhstan Mayndayntal, 40.8 (Соколов, 1971; Соколов, 1966a; Соколов, 1966b; Элинсон and
Proposed origin: deep-seated Йолыковский, 1961; Элинсон and Полыковский, 1961)
56.5 2.1 In crushed conglomerate of Sadonsky Igneous formation Russian Federation Sadonsky, 56.5 (Соколов, 1966b; Гуревич et al., 1960)
25.8–71 0.6–2 Inclusions in syenites and syenito-diorites of a granite massif Russian Federation Uibatsky, 71 (Андреева and Молчанов, 1978)
76.4 0.94 Inclusions in olivinite of a plutonic massif Russian Federation Kugda, 76.4 (Андреева and Молчанов, 1978)
79 In pyroxenites of Kola basic massifs Russian Federation Gremiaha, 79 (Соколов, 1971)
80.7, up to 5.3 Inclusions in granites and basic syenites of Middle Paleozoic Russian Federation Ulug-zassky, 80.7 (Андреева and Молчанов, 1978)
granite massif. Maximum H2 in granites
81.2, up to 0.25 In nephelines and nepheline syenites of Kola basic massifs Russian Federation Sakhariok, 81.2 (Соколов, 1971; Петерсилье and Припачкин, 1979)
82.7 0.24 Inclusions in miaskites Russian Federation Vishnevogorsk, 82.7 (Петерсилье and Припачкин, 1979)
19
83.7, up to 0.7–3 Inclusions in granites and syenites of a granite massif. Russian Federation Krasny Kamen, 83.7 (Андреева and Молчанов, 1978)
Maximum H2 in granites
47–85 In dunites 47%, in gartzburgites 67.5%, in gabbroids 85% of Russian Federation Koriaksko-Kamtchatskaya (Велинский, 1978)
Koriaksko-Kamtchatskaya orogen region orogen, 85
85.4, up to 0.2–10.2 Inclusions in granites, basic syenites and syeno-diorites of a Russian Federation Syrsky, 85.4 (Андреева and Молчанов, 1978)
granite massif. Maximum H2 in granites
85.8 In olivines of Kola basic massifs Russian Federation Afrikandsky, 85.8 (Соколов, 1971)
86.3 1.51 Inclusions in nepheline-syenites Russian Federation Goryachegorsk, 86.3 (Петерсилье and Припачкин, 1979)
76.7–87 0.63–0.89 Inclusions in pyroxenites and peridotites from intrusions Russian Federation Monchegorsk, 87 (Петерсилье and Припачкин, 1979)
49.9; 5.26; Inclusions in: Russian Federation Pechenga, 88.4 (Петерсилье and Припачкин, 1979)
61.5; 0.56; Gabbro from intrusions;
87.2; 3.97; Norite from intrusions;
88.4 11.18 Effusive diabase;
Effusive picrite-porfyritic rocks
90.5 In gneisses of Kola basic massifs Russian Federation Olenegorsk, 90.5 (Соколов, 1971)
93.8, up to 0.3 m3/m3 (up to) of Gases occluded in rocks. Kola superdeep drilling for 11 km Russian Federation Kola superdeep, 93.8 (Войтов, 1990; Карус et al., 1984; Войтов, 1986; Ikorsky et al., 1999)
drilled rocks
99.9 In apatites and olivines ofthe Kola basic massifs Russian Federation Kovdorsky, 99.9 (Соколов, 1971)
64–100 0.7–4.1 Inclusions in dunite and meimechite in a plutonic massif Russian Federation Gulinsky, 100 (Андреева and Молчанов, 1978)
store significant amounts of hydrogen (Левшунова, 1982). It has also

(Щека and Гребенников, 2009)
been reported that hydrogen is relatively abundant (up to 20–30% by
1982)
1982)
1982)
1982)
Сахно, volume) in association with anhydrite or gypsum (Smith et al., 2005).
Сахно,
Сахно,
Сахно,
In a recent experimental study, sandstones were exposed to pure H2 to
evaluate their properties as potential reservoir rocks for underground
storage of hydrogen. It was also shown by the same study that H2 in-
and
and
and
and
duced alteration of pore filling anhydrite and carbonate cements

(Моисеенко
(Моисеенко
(Моисеенко
(Моисеенко
Reference
(Flesch et al., 2018). Hydrogen has also been observed in organic-rich

shales and metapelites (Suzuki et al., 2017). A recent study of H2
content in the clay-rich rocks of the Cigar lake uranium deposit re-
ported that they are enriched in hydrogen. Measured values reached
Lesser Kuril Ridge, 24.1
0.25 mol per kg which is higher than the methane adsorption capacity
Name of placemark
Sikhote-Alin’, 19.2
Kliuchevskoi, 90.4
Milogradovo, 27.3
of clay rocks (Truche et al., 2018).

Semyachik, 34.5
Yakut-gora, 41
There have been several reported instances of hydrogen detected in

Terney, 27.3
Badjalsk, 19
salt sample inclusions (Table 22). It has been suggested that hydrogen
accumulates in salt deposits as a result of the absence of compounds
capable of reacting with hydrogen (Smith et al., 2005). Gas inclusions
from the German salt deposits in Hesse and Thuringia showed the
Federation
Federation
Federation
Federation
Russian Federation
Russian Federation
Russian Federation
presence of hydrogen in many samples, reaching maximum con-

centrations of 32.9% for samples from Thuringia and 26.4% for samples
from Hesse (Knabe, 1989).
Country
Russian
Russian
Russian
Russian
2.6. Hydrogen dissolved in ground water

Gas inclusions in andesite formations of the Badjalsk volcanic zone, including Laksky, Stanolirsky and Purilsky complexes
A significant number of instances of natural hydrogen as dissolved

gas in ground water have been observed. Fig. 6 shows a map with all
locations described in this sub-section. The number of such analyses is
large enough to allow researchers to look for correlations. In a review of
hydrogen occurrence in subsurface fluids in the territories of what was
formerly the soviet camp, a map of hydrogen anomalies was prepared
from more than 2000 analyses. This study showed that higher hydrogen
concentrations were observed in areas associated with recent tectonic
activity. In these areas high concentrations of free hydrogen gas was
Gas inclusions in basalts from different eruptions and craters of Kliuchevskoi volcano
observed in ground water monitoring wells (Shcherbakov and Kozlova,

1986). Another study of 2215 instances of hydrogen detected in ground
water showed hydrogen background levels of 50 mL/L in cratons, with
anomalous levels of up to 1500 mL/L and even higher associated with
deep faults and rift areas (Щербаков, 1985). Statistical studies of hy-
drogen occurrence in gases dissolved in ground water from Western
Siberia showed that 15% of all samples contained hydrogen. Hydrogen
concentrations (in ground water) ranged from trace amounts to tens of
Gas inclusions in liparites from Sikhote-Alin’ Outer range
a percent and there appeared to be a clear increase in the number of

Gas inclusions in basic basalts from Lesser Kuril Ridge
instances of hydrogen concentrations increasing with sampling depth

(Нечаева, 1968). It was reported recently that there is no evidence or
examples of natural springs waters rich in H2 (Ostojic, 2019). The au-
thor precise that measuring of hydrogen is not a part of a routine
Hydrogen discoveries in inclusions in samples from volcanic rocks.
analysis and is a difficult method, what may explain why there were no
discoveries yet.
High hydrogen concentrations were found in ground water sampled
Gas inclusions in ignimbrites
from fractured rock in 24 South African wells. Concentrations of dis-

Gas inclusions in basalts
solved hydrogen were not correlated with depth, salinity, pH, rock type,
Gas inclusions in rocks
borehole age, fractured aquifer age or any other measurement, but the
highest concentrations were typically found in the deeper, highly
saline, non-meteoric, older waters from fractured aquifers (Lin et al.,
Comments
2005a). Another study showed abnormally high hydrogen concentra-

tions in gases dissolved in ground water from wells in Idaho. Indications
were that the hydrogen was associated with a Pliocene age caldera
(Sidle and Hydrocarbon, 1982). 45 analyses of ground water from
Content, cm3/kg
Crimea in Ukraine contained dissolved hydrogen at concentrations

0.63, up to
ranging from 0.2 to 53.6%, with hydrogen concentrations and total

content increasing with depth by an order of magnitude. There ap-
2.08
peared to be no correlation between hydrogen concentration and dis-

solved iron content (Овчаренко, 1967). It is interesting to note that
34.5, up to
90.4, up to
19.2 (av.)
24.1 (av.)
27.3 (av.)
another study from the Volga Region in the Russian Federation reported
Table 17
19 (av.)
35–41
H2, %
an opposite finding: that high hydrogen concentrations in ground water

were often associated with high iron concentrations (328 mg/L) but
20
Table 18
Hydrogen discoveries in inclusions in samples from kimberlite pipes.
H2, % Content, cm3/ Comments Country Name of placemark Reference
kg
40, up to Inclusions in spherules of quartz and calcite. Proposed Russian Federation Udachnaya, 40 (Яценко et al., 2012a)
origin: endogenic
56, in average Inclusions in spherules of magnetite, wustite and Ukraine, Russian Priazovs’k pipes, 56 (Яценко et al., 2012a)
native iron. Proposed origin: endogenic Federation Udachnaya west, 56
29.4–59.0 Inclusions in diamonds South Africa Kimberly mine, 43.1 (Melton and Giardini, 1974)
Premier mine, 59
59.2–81.1 0.23–0.7 Inclusions in xenoliths Russian Federation Obnazhennaya pipe, 81.1 (Петерсилье and Припачкин,
1979)
also with low pH values (Зингер, 1962). hydrogen-containing compounds, together with the variety of me-
Measurements of dissolved hydrogen in ground water were pro- chanisms through which these compounds can be transformed gives
posed as a useful way for the monitoring of shallow aquifers con- way to a very large number of possible explanations for the genesis and
taminated by landfills (Bjerg et al., 1997), solvents and jet fuel origin of hydrogen. This is why it is often difficult to understand which
(Chapelle et al., 1996). Hydrogen plays the role of a redox indicator exact mechanisms could be involved in the production of hydrogen gas.
positively correlating with pollution plumes. It was suggested that a Moreover, hydrogen is a very diffusive gas, it is most likely not gen-
monitoring well should be allowed to equilibrate for up to 3 months erated in situ. Detection of hydrogen in the crust suggests that there is a
before taking measurements (Bjerg et al., 1997) and that H2 measure- constant supply of this gas (Молчанов, 1981). Its high reactivity and
ments are more useful than Eh (oxidation−reduction potential) mea- mobility, means hydrogen sources must be geologically relatively
surements for identifying anoxic redox processes (Chapelle et al., young (Войтов and Осика, 1982), at least in crustal settings.
1996). The following section critically reviews all possible sources of hy-
Table 23 summarizes reported observances of dissolved hydrogen in drogen, together with estimates for their hydrogen production poten-
ground water. tial. I will start with the description of deep-seated hydrogen, as po-
Hydrogen detections in water samples from hydrocarbon fields are tentially the most important source of natural hydrogen.
presented in a separate table, Table 24. Two studies appear to show that
ground water sampled close to oil fields contain higher hydrogen
concentrations than ground water sampled close to natural gas deposits 3.1. Deep-seated hydrogen
(Зингер, 1962; Нечаева, 1968).
Many studies point to the fact that the presence of hydrogen in
samples increases with depth: it is detected more often and in higher
3. Origin concentrations in gases coming from greater depths (Сороченко and
Дроздов, 2010). The authors of a 1986 review of hydrogen accumu-
As has been documented in the sections above, hydrogen has been lations concluded that higher H2 concentrations were observed in
detected in a variety of different environments. Several hypotheses abundance in deep and superdeep wells (Shcherbakov and Kozlova,
have been proposed by researchers as to the genesis and origin of hy- 1986). Another study reported that the number of H2 detections in-
drogen in the Earth's crust. creased from a few at depths of 500–600 m to tens of detections at
In summary these hypotheses include: 800–1000 m (Войтов, 1971). The amount of hydrogen was reported to
increase with depth during the superdeep drilling programs (SG-8) in
• degassing of deep-seated hydrogen from the Earth’s core and Kryvyi Rih, Ukraine (Курлов, 2003) and SG-4 in the Ural region of the
mantle, Russian Federation (Башта et al., 1991).
• the reaction of water with ultrabasic rocks or serpentinization, Such observations have led some scientists to conclude that hy-
• contact of water with reducing agents in the mantle, drogen has a “deep-seated origin”. As strict definition for deep-seated
• the interaction of water with freshly exposed rock surfaces, hydrogen has as yet to be agreed upon consequently, I propose to use
• decomposition of hydroxyls in the lattice structure of minerals, the term “deep-seated” for hydrogen originating from the Earth’s
• natural radiolysis of water, mantle or core, but not from crustal processes.
• decomposition of organic matter, Direct observations of deep-seated hydrogen are difficult for the
• biological activity, obvious reasons that drilling into the mantle or core is likely impossible.
• anthropogenic activities and more. However, researchers have proposed a deep-seated origin for hydrogen
found in soil gas in Kansas (Johnsgard, 1988; McCarthy et al., 1986), in
Some authors have proposed a mixed origin for hydrogen as a soil gas sampled from the East-European platform (Козлова, 2004;
combination of several different genetic factors (Angino et al., 1984; Ларин et al., 2010; Ларин and Ларин, 2007), from kimberlite pipes
Vacquand et al., 2018). Such a large number of proposed explanations (Сороченко and Дроздов, 2010), hydrocarbon wells in the Russian
for the origin of hydrogen demonstrates on the one hand the ubiquity of Federation (Шевченко and Силкин, 2015), in a chromite mine in Ka-
hydrogen, and on the other hand a lack of understanding of its' nature zakhstan (Лидин et al., 1982; Уханов et al., 1987; Уханов et al., 1984)
and behavior in the Earth. and for seeps in Khibiny massif on the Kola peninsula (Nivin, 2009;
Indeed, hydrogen being a very reactive element is present every- Кривцов et al., 1967; Хитаров and Войтов, 1982).
where in bonded form with other elements. It is the main element in Gas samples from the Kola superdeep drilling project, the deepest
molecules of water, in many types of minerals, in living beings, organic well in the world, are hydrogen rich (Ikorsky et al., 1999; Войтов,
matter and hydrocarbons. Under specific conditions these materials 1990). This has led researchers to conclude that the role of deep-seated
undergo chemical reactions which give as a product molecular hy- processes below the Earth's outer crust have not been adequately esti-
drogen. These materials may be transformed by redox reactions, which mated. Measurements of diffusive flow in Oman by the author of this
could be inorganic or driven by living organisms, and also by the action review and colleagues has demonstrated that the highest hydrogen flow
of temperature or radiation. The variety and omnipresence of rates were present in layers underlying the peridotites, implying input
21
V. Zgonnik
Table 19
Hydrogen discoveries in inclusions in samples from orebodies.
H2, % Content, cm3/kg Comments Country Name of placemark Reference
13.8, up to 1.1 In rischorrites intrusions. Concentration depends on sample type Russian Federation Apatitovaya Mt, 13.8 (Петерсилье, 1964)
19, up to In microscopic inclusions of fluid in quartz in Precambrian uranium Canada Cluff Lake, 19 (Dubessy et al., 1988)
deposits. Mixed with O2. Proposed origin: radiolysis
21, up to In microscopic fluid inclusions in quartz in Precambrian uranium deposits. Canada Rabbit Lake, 21 (Dubessy et al., 1988)
Mixed with O2. Proposed origin: radiolysis
10.5–21.4, (av.) 0.4–0.7 In apatite-nepheline. Concentration depends on sample type Russian Federation Suoluaiv, 21.4 (Петерсилье, 1964)
27.4, up to 0.6–2.7 In apatite-nepheline and in rischorrites intrusions. Average concentration Russian Federation Rasvumchorr, 27.4 (Петерсилье, 1964)
dependins on sample type
33, up to In crushed porfyric sand diabases of Norilsk nickel field Russian Federation Norilsk, 33 (Соколов, 1971; Соколов, 1966a)
34.6 Gases from pores in magnetite at Tunguska Podkamennaya river Russian Federation Kamyshevsky Baykitnik, 34.6 (Соколов, 1971; Фридман, 1970)
4–42.6 22–239 In crushed rocks of Kurusaisk polymetallic orebody near Karamazar. Uzbekistan Kurusaisk, 42.6 (Соколов, 1971; Hawkes, 1980; Элинсон
22
Maximum detected in quartz, minimum in calcite and Сазонов, 1966)
3–58 In purified chromite samples from the chrome orebody of Kempirsai Massif Kazakhstan Kempirsai, 58 (Melcher et al., 1997)
69.5, up to In massive ore samples from the chrome orebody of Kempirsai Massif Kazakhstan Stepninsk, 11.6 (Melcher et al., 1997)
Kempirsai MOF, 69.5
80, up to 20(up to) of rock Gas in cores from the superdeep drilling in Kryvyi Rih, SG-8. Iron orebody Ukraine Kryvyi Rih superdeep, 80 (Курлов, 2003)
in Paleoproterozoic syncline
10.8–70.7 in cores 89.8 (up 97–134in cores; 520, up Gas in core from 216 m borehole in gold orebody. Maximum in Cambrian- Russian Federation Baleyskoe, 89.8 (Куликова, 1966; Куликова, 1972)
to) in quartz to, in quartz Jurassic sandstones. In quartz, near the production zone
75–89.8 2.6–4.4 In magnetite iron ore samples Russian Federation Sheregesh, 89.8 (Андреева and Молчанов, 1978)
90, up to Adsorbed gases at 8–10 m depth in soil over uranium orebody Uzbekistan Uchkuduk, 90 (Перевозчиков, 2011; Перевозчиков, 2012)
47.4–91.1 0.9–6.3 In magnetite iron ore samples Russian Federation Abagas, 91.1 (Андреева and Молчанов, 1978)
60.4–93.3 1.1–4.1 In magnetite iron ore samples Russian Federation Abakan, 93.3 (Андреева and Молчанов, 1978)
37.8–98.7 1.1–52.4 In magnetite iron ore samples Russian Federation Krasnoyarovskoe, 98.7 (Андреева and Молчанов, 1978)
68.3–99.6 51(up to) In magnetite iron ore samples Russian Federation Tei, 99.6 (Андреева and Молчанов, 1978)
100 Fluid inclusions in chromites chrome orebody Cyprus Cyprus, 100 (McElduff, 1989)
100, up to In microscopic fluid inclusions in quartz of Precambrian uranium deposits. Gabon Oklo, 100 (Dubessy et al., 1988)
Proposed origin: radiolysis
Table 20
Hydrogen discoveries in inclusions in samples from coal basins.
11.4 Gas in the samples from the horizon 110 of a coal mine Russian Federation Baydaevka, 11.4 (Молчанов, 1981; Гуревич, 1946)
12.7, up to Gas in coal samples from nickel orebody. Content 0.083 m3/t rock Russian Federation Talnakh, 12.7 (Фридман, 1970)
18.4 Gas in the samples from horizon 197 in#4 coal mine Russian Federation Osinovka, 18.4 (Молчанов, 1981; Гуревич, 1946)
20, up to 40% of all coal samples contain up to 10% H2; 80% of rock samples contain Kazakhstan Karagandy, 20 (Соколов, 1971; Соколов, 1966a;
up to 18% H2 in Karagandy coal mines Молчанов, 1981)
20–21 Gas from coal samples of Pechora coal basin Russian Federation Vorgashor, 21 (Соколов, 1971)
25, up to Gas in liptobiolites samples from a coal basin. Content 0.5–1 m3/t coal Russian Federation Razdolnensky, 25 (Гресов et al., 2010)
25, up to Gas in liptobiolites of Lipovetskoe and Sangarskoe coal basins Russian Federation Lipovetskoe, 25 (Гресов et al., 2010)
Sangarskoe, 25
30–35 Gas in cores from wells in Kuzbass coal basin Russian Federation Shugurovo, 35 (Молчанов, 1981)
40, up to Content of H2 up to 40% in 95% of rock samples in Donbas coal basin Ukraine Donbas, 40 (Молчанов, 1981)
24–64 Gas in rapdopissites (coals with high content of leptynite) from Illytchevsk Russian Federation Illytchevsk, 64 (Гресов et al., 2010)
coal field. H2 content > 0.5 m3/t coal
76–81 Gas from sandstone samples of Pechora coal basin Russian Federation Pechora basin, 81 (Соколов, 1971; Молчанов, 1981)
of H2 from regions below the ophiolites (Zgonnik et al., 2019). hydrogen-rich (Rohrbach et al., 2007).
There are also indirect arguments for a deep-seated origin for hy- It seems increasingly accepted that the lower mantle is reduced such
drogen. Some researchers argue for a deep-seated origin because the that C-O-H fluids will be dominated by CH4/H2O/H2 rather than CO2/
presence of hydrogen is associated with fault zones (Войтов, 1971; H2O. What seems less clear and pertinent to this review are the con-
McCarthy et al., 1986; Овчаренко, 1967) and riftzones (Сывороткин, ditions at which H2 > > H2O, i.e. the redox conditions that would
2002). When helium and hydrogen anomalies were studied in different sustain reservoirs of genuinely hydridic fluids. Rohrbach et al.
investigations it was shown that the concentrations of both gases cor- (Rohrbach et al., 2007; Rohrbach et al., 2011) state that CH4 ± H2
relate, which, according to the authors, suggests a deep-seated origin occur with iron saturated fluids and that the metal saturated lower
for these gases (Перевозчиков, 2011; Гусев, 1997). Another indicator mantle is likely to have a redox state between IW (iron-wustite
for the deep-seated nature of hydrogen is the synchronous and rapid buffer)–0.5 and–2. This range of conditions suggests gradients exist in
behavior of widely separated, on the order of thousands of kilometers, the lower mantle between reduced fluids that still contain significant
seeps (Сывороткин, 2009). Some authors relate this unstable nature of water (relative to H2) and genuinely hydric fluids (H2/CH4/and other
deep seated hydrogen seeps to the geodynamic behavior of the Earth hydrides?) that must exist, based on, for example discoveries of metal
(Voitov and Rudakov, 2000). It was suggested that the isotopically-light inclusions in diamonds (Smith et al., 2016), occurrences of moissanite
hydrogen, observed in the study, is an indicator of its deep-seated origin (SiC) (Di Pierro et al., 2003) and various silicides (Muszer, 2014;
(Уханов et al., 1987). In another study of hydrogen occurrence in coal Геворк’ян et al., 1969; Яценко et al., 2012b). A heterogeneous dis-
basins the authors propose that in places where hydrogn is found at tribution of hydrogen in the lower mantle (c.f. the crust), possibly in-
anomalously high concentrations it could be of a deep origin (Гресов fluenced by hydrogen fluxes from the core, would therefore be possible.
et al., 2010). Other studies point out that because of the very diffusive Recent experimental work (Bali et al., 2013) shows that water and
nature of hydrogen its' detection in the crust suggests that there is a hydrogen can be immiscible at mantle conditions and this provides
constant supply of H2 from depth (Молчанов, 1981). another mechanism for creating heterogeneity in the distribution of
Various works suggest the version of a mantle source for hydrogen. hydrogen, at least in the upper mantle.
It has been suggested that the origin of the gas in the Khybyny Massif is Isotopic studies of hydrogen suggest that the mantle contains hy-
at least partially related to gas influx from the subcrustal layers (Nivin, drogen and that the mantle supplies it to crustal rocks i.e. "surface"
2009). Mantle outgassing was proposed as one of many possible sources rocks. This is because δD values of measured hydrogen are isotopically
for hydrogen-rich gas in Kansas (Coveney et al., 1987). A general light (have less deuterium), similar to the primordial δD values of the
analysis of the evolution of different Earth fluids has concluded that Solar System. This was pointed out by the observation of very low δD
mantle fluids are much more chemically reduced than those of the crust values in Hawaiian xenoliths (Deloule et al., 1991) and in a study of
(Перчук, 2000). Recent experiments have shown that hydrogen is so- anomalies in D/H (deuterium to protium) ratios of pore waters in se-
luble in minerals under mantle conditions (Yang et al., 2016). The diments from the Norwegian Sea (Lawrence and Taviani, 1988) (in the
authors suggest that significant amounts of hydrogen could be present Section 2.2 the examples are given illustrating mantle contribution of
in the Earth's mantle under reducing conditions. Analyses of metal in- fluids into crustal settings of the North Sea). The work of unravelling
clusions in diamonds derived from depths equivalent to that of the the isotopic record of the mantle is still ongoing. Recent studies (Clog
Earth's mantle showed the presence of hydrogen, confirming that it is et al., 2013; Loewen et al., 2019) suggest values of δD −60‰–−75‰
present in the mantle (Smith et al., 2016). Also, it has been demon- or lower.
strated that the Earth’s upper mantle and large portions of astheno- A review of hydrogen in the deep Earth concluded that a significant
sphere are metal-saturated. In such case, the main fluid should be quantity of hydrogen could be retained in the transition zone, lower
Table 21
Hydrogen in sedimentary or metamorphic rock inclusions.
H2, % Content, cm3/ Comments Country Name of Reference
kg placemark
5.2–19.7 175–460 Crushed Cretaceous argillites from the well #118. Depth 1580–1582 Russian Federation Igrim, 19.6 (Несмелова and Рогозина,
m. 1963)
56, (av.) Inclusions in spherules of magnetite, wustite and native iron. Ukraine, Russian Ilyinets crater, 56 (Яценко et al., 2012a)
Proposed origin: endogenic Federation Kara crater, 56
66.6, (av.) Inclusions in glass spherules with perovskite, native iron, silicides, Ukraine Boltysh Crater, (Яценко et al., 2012a)
moissanite and titanium oxides. Proposed origin: endogenic 66.6
23
mantle or core (Williams and Hemley, 2001). It was suggested that
(Черепенников and Рогозина, 1964)

presence of hydrogen could be responsible for the anomalous electrical
(Ковалевич and Сворень, 1975)

conductivity of the asthenosphere (Karato, 1990). Recent studies in-
dicate that a large quantity of hydrogen can be stored in the mantle in
the form of hydrated minerals (Schmandt et al., 2014). A very recent
(Зорькин et al., 1984)
(Зорькин et al., 1984)

(Savchenko, 1958)
discovery of first natural hydride (VH2) proves the presence of hy-
(Savchenko, 1958)
drogen-dominated fluids in the mantle (Bindi et al., 2019) and should
attract more attention for this topic.
Several works suggest a core source of hydrogen. Hydrogen allows
Reference
for resolution of the so-called core deficit problem the Earth’s core,
which is about 10% lighter than Fe-Ni alloy at the same pressure and
temperature (Poirier, 1994; Isaev et al., 2007; Yagi and Hishinuma,
Name of placemark
Starobinskoe, 23.9
1995; Murphy, 2016; Rumyantsev, 2016). It was reported that adding

Solikamsk, 34.6
Berezniki, 32.6
Kenkyak, 26.7
1% by wt of hydrogen to the core resolves this issue (Poirier, 1994).

Stebnyk, 34
Inder, 17.2
Kalush, 34
Studies suggest that iron hydride is stable under the Earth's mantle and
core conditions (Isaev et al., 2007). A review of deep-seated hydrogen
estimates that the core itself could contain, in the form of hydrides of
iron, up to100 times more hydrogen than in the hydrosphere (Williams
Russian Federation
Russian Federation
and Hemley, 2001). A recent study proposed that the core might con-
tain 80 times more hydrogen than of the mass of all hydrogen in the
Kazakhstan
Kazakhstan
ocean (Ikuta et al., 2019). One report suggests that an FeH0.14 com-
Country
Ukraine
Belarus
position for the inner core produces a reasonable agreement with

seismic observations (Murphy, 2016). For the outer core an alloy of
Fe0.88Si0.12H0.17 containing 0.32 wt% hydrogen was reported to match
Gases extracted from carnallite from Bereznikovskii salt mine. Concentration in free gas of mine: 7.8%. Proposed origin:
density and seismic profiles (Tagawa et al., 2016). However, there

doesn’t appear to be a consensus in the literature on the question of
what element is responsible for the core density problem and different
research teams propose admixture of different elements like carbon,
silicon, sulphur, oxygen, etc. The idea of hydrogen as a main light
element in the core has not received more attention because it does not
altogether support traditional views on the Earth's formation, which
postulate that it was accreted from volatile-depleted material (Harry
et al., 2010). From this viewpoint reduced species are expected to be
present in only minor quantities in the upper mantle (Apps and Van De
Kamp, 1993). However, in this model the origin of volatiles, and
especially water, remains unclear and is still debated (Harry et al.,
Gases sampled from salt-bearing strata from well #88. Depths 1046–2826 m.
2010; Morbidelli et al., 2012).

The discussion on how hydrogen could arise in the Earth’s core is
Gases from salt-bearing strata from well #10153. Depths 251–998 m.
open. It has been proposed that the Earth could have accreted a large
quantity of hydrogen during its formation. When discussing hydrogen
sources some authors are specifically referring to the flow of “pri-
mordial hydrogen”, which they hypothesize to have been present in the
Earth since its formation (Gilat and Vol, 2005; Gilat and Vol, 2012;
Gases sampled from sylvinite samples from 414 m
Walshe, 2006; Walshe et al., 2005; Larin, 1993). As to possible me-

reaction of newly formed elements with water
chanisms, some studies show that it is possible that hydrogen was likely
In carnallite from Solikamsk potassium field
incorporated into iron during an early stage in the Earth’s evolution

Hydrogen discoveries in inclusions in samples from salt deposits.
(Rumyantsev, 2016; Iizuka-Oku et al., 2017). Others propose a reaction

of iron with water yielding separate phases of iron oxide and iron hy-
dride (Yagi and Hishinuma, 1995; Fukai, 1984; Fukai and Suzuki, 1986;
Okuchi, 1997; Mao et al., 2017). Another idea is based on the dis-
Gases in sylvinite samples
covered relationship between the ionization potential of elements and

their distribution in Solar system. Calculations show that the primordial
Earth's composition was highly enriched in hydrogen (Larin, 1993). The
Earth therefore could have stored some portion of this hydrogen in its
Comments
interior. This hypothesis was proposed by Vladimir Larin (Ларин,

1973) and developed into a fundamental study of primordially hy-
drogen-rich Earth years later (Larin, 1993; Ларин, 2005; Ларин, 1991).
The underlying idea was recently re-examined using the methods of
Content, cm3/kg
statistical physics to confirm that the initial bulk composition of the

Earth was hydrogen-enriched (Toulhoat et al., 2015). Hervé Toulhoat
et al. have suggested that the inner Earth may have contained 5.1 wt %
0.49
0.32
of hydrogen in bonded state in the form of hydrides (Toulhoat et al.,

2015). This number is of the same order as previous estimates of 0.61–
23.9, up to
34.6, up to
17.2 (av.)
26.7 (av.)
1.1–32.6
4.72 wt% (Larin, 1993; Williams and Hemley, 2001; Сывороткин,

Table 22
H2, %
2002).
6–34
The idea of a hydrogen-enriched Earth is not completely new. It was
24
Fig. 6. (a) Map of hydrogen detections in dissolved gases in various environments at concentrations > 10% vol. Note: the high desity of placemarks across Eastern
Europe and Northern Asia is due to the fact that researchers from these regions were looking for hydrogen more frequently, and not because these regions are richer
in hydrogen. The area highlighted by the orange rectangle is shown on the (b). Data on each placemark are available in the corresponding tables of this section and in
a .kmz file provided in the Supplementary Information. (b) A detail map of the area highlighted by the orange rectangle on the (a).
first hypothesized at the beginning of 20th century by Vladimir Taking into account the considerations from this section, natural H2
Vernadsky (Вернадский, 1960). Later authors also speculated on the can be classified into two groups: primary hydrogen (stored in the
formation and evolution of an initially hydrogen-enriched Earth mantle or the core and progressively degassed to the surface), and
(Маракушев and Маракушев, 2008a; Семененко, 1990; Маракушев, secondary hydrogen (produced in the mantle or the crust by various
1999). The controversial nature of these works probably explains why chemical reactions), which is more general than the assumption that
they have not got much attention. However, they illustrate the interest natural hydrogen is only produced from water (Молчанов, 1981).
of scientists in the idea of a primordially hydrogen-rich Earth and its
potential to explain various geologic and terrestrial phenomena.
25
Table 23
Hydrogen discoveries in water samples.
V. Zgonnik
H2, % Content Comments Depth, m Country Name of placemark Reference
0.05–10.3 7410 μmol/L (for the sample In waters from fractured Precambrian shield rocks in well 3200 South Africa Driefontein, 10.3 (Sherwood Lollar et al., 2007; Sherwood Lollar et al.,
with highest concentration #DR548. Value of δD = -706‰; c (He) = 3%. Proposed 2006)
10.3%) origin: unknown, probably radiolysis
10.7 216.9 cm3/L Water from Early Riphean horizon of Lubimskaya well #3-L; 2984–3004 Russian Lubimskaya, 10.7 (Мухин, 1970)
c (He) = 0.5% Federation
10–11.1 In water from Lower Cambrian dolomites and anhydrites 1210–1215 Russian Elovka, 11.1 (Пиковский, 1963)
from well #1-bis Federation
11.2 Gas from ground water Russian Kulomzin, 11.2 (Levshounova, 1991)
Federation
11.4 Water from migmatitic biotite, plagioclase gneiss and 407 Finland Ylistaro, 11.4 (Sherwood Lollar et al., 2014; Sherwood Lollar et al.,
associated mica and amphibolite schists. 1993b)
3.3–11.5 3714 μM/L (for the sample In ground water from fractured Precambrian shield rocks in 2825 South Africa Mponeng, 11.5 (Sherwood Lollar et al., 2007; Sherwood Lollar et al.,
with highest concentration well #MP104. Value of δD = -684‰; c (He) = 12.3%. 2006)
11.5%) Proposed origin: unknown, probably radiolysis
11.8 62 cm3/L Water from Devonian deposits in well Zvenigorodskaya #3; 788–900 Russian Zvenigorodskaya, 11.8 (Мухин, 1970)
c (He) = 0.9% Federation
3
12 540 cm /L In deep waters from Paleozoic deposits of Kalininskaya field, 2797–2803 Russian Kalininskaya, 12 (Стадник, 1970)
Zhivetsky horizon, well #2 Federation
3
12.1 84.2 cm /L Water from Earlypaleozoic deposits in Boenskaya well #2- 1138–1400 Russian Boenskaya, 12.1 (Мухин, 1970)
TsBL; c (He) = 0.7% Federation
12.5 662 cm3/L In deep waters from Paleozoic deposits of Gorno-Vodianaya 3176–3182 Russian Gorno-Vodianaya, 12.5 (Стадник, 1970)
field, Voronezhsky horizon, well #14 Federation
0.1–12.7 In fracture waters from Precambrian shield rocks in a well. 2072 Canada Timmins, 12.7 (Sherwood Lollar et al., 2014; Sherwood Lollar et al.,
Value of δD = -725 to -737‰. Proposed origin: 2007)
serpentinization
26
13.2 In water from Low Cambrian, diabases in the well #1-0 2608–2615 Russian Zayarsk, 13.2 (Пиковский, 1963)
Federation
14.5 Peschany Umet field, Bobrikovsky horizon, well #57 1140–1142 Russian Peschany Umet, 14.5 (Стадник, 1970)
Federation
6.5 1082 cm3/L in the well #12 Uritskaya field, Tulsky horizon, wells #32, #69, #12 1521–1529 (well Russian Uritskaya, 15.4 (Стадник, 1970; Зингер, 1962)
(well #32); Dissolved gases in waters. #32); Federation
8.8 In the well #32 hydrogen-producing bacteria was detected 1504–1511 (well
(well #69); #69);
15.4 1500
(well #12) (well #12)
15.73 553 cm3/L In deep waters from Paleozoic deposits of Petrushinskaya 2727–2737 Russian Petrushinskaya, 15.7 (Стадник, 1970)
field, Vorobievsky horizon, well #7 Federation
3
15.9 25.7 cm /L Devonian aquifer well Chapliginskaya #1-Ch; c (He) = 678–690 Russian Chapliginskaya, 15.9 (Мухин, 1970)
0.6% Federation
3
16.2 293 cm /L In deep waters from Paleozoic aquifer of Novo-Kubanskaya 2114–2128 Russian Novo-Kubanskaya, 16.2 (Стадник, 1970)
field, Evlanovsko-Livensky horizon, well #12 Federation
15.7–16.5 Gases associated with Artesian water Australia Coonanna, 16.5 (Woolnough, 1934)
16.7 739 cm3/L In deep waters from Paleozoic aquifer of Rahmanovskaya 2924–2962 Russian Rahmanovskaya, 16.7 (Стадник, 1970; Зингер, 1962)
field, Zhivetsky horizon, well #12 Federation
2–17 18–29 cm3/L Gases dissolved in waters of sediments Russian Pochep, 17 (Соколов, 1966a)
Federation
3
17.4 244 cm /L In deep waters from Paleozoic deposits of Grazhdanskaya 2446–2449 Russian Grazhdanskaya, 17.4 (Стадник, 1970)
field, Nizhneschegrovsky horizon, well #91 Federation
17.4 Associated with Artesian water from upper zone of the Australia Mungyer, 17.4 (Woolnough, 1934)
Mungyer well
10.6–18.7 Lower Cambrian dolomites aquifer, in the well #1-R 918–968 Russian Ust'-Kut, 18.7 (Пиковский, 1963)
Federation
18.9 Water from Earlypaleozoic aquifer, Redkino well #2 1498–1500 Russian Redkino, 18.9 (Мухин, 1970)
Federation
Table 23 (continued)
V. Zgonnik
3
19.2 52.6 cm /L Devonian aquifer, in Zhavinskaya well 920–923 Russian Inzhavinskaya, 19.2 (Мухин, 1970)
Federation
3
19.5 17.8 cm /L Early Riphean aquifer, Klintsovskaya well #5808; c (He) = 739–755 Russian Klintsovskaya, 19.5 (Мухин, 1970)
0.5% Federation
18.4–20.1 91.2 cm3/L Residual soil ground water in crystalline basement, well 553 Russian Strugova Buda, 20.1 (Мухин, 1970)
#3345 in Strugova Buda Federation
18.8–20.5 Lower Cambrian dolomite and limestone aquifer, well #1-R 540–550 Russian Schukina, 20.5 (Пиковский, 1963)
Federation
3
20.9 312 cm /L Deep Paleozoic aquifers Kuleshovskaya field, 1779–1784 Russian Kuleshovskaya, 20.9 (Стадник, 1970)
Nizhnebashkirsky horizon, well #59 Federation
22.2 832 cm3/L Deep Paleozoic aquifers Bagaevskaya field, Bobrikovsky 1620–1622 Russian Bagaevskaya, 22.2 (Стадник, 1970)
horizon, well #12 Federation
8.86 Kudinovskaya field, Bobrikovsky horizon, well #26 1744–1760 Russian Kudinovskaya, 22.3 (Стадник, 1970)
(well #26); (well #26); Federation
16.4 Nizhnebashkirsky horizon, well #93
(well #82); 2824–2850
(well #82);
22.3 Pashysky horizon, well #82 1407–1474
(well #93) (well #93)
24.2 360 cm3/L Devonian–Lower Carboniferous aquifers, well Rybinskaya 1063–1075 Russian Rybinskaya, 24.2 (Мухин, 1970)
#5-R Federation
3
23.3–25 754 cm /L Deep Paleozoic aquifer of Sokolovaya gora field, 1063–1065 Russian Sokolovaya gora, 25 (Стадник, 1970; Зингер, 1962)
Bobrikovsky horizon, well #33 Federation
25.4 Fresh water beds in Jurassic sediments from the Robe well 917 Australia Robe, 25.4 (Headlee, 1962; Woolnough, 1934)
25.6 In fresh water aquifer USA Belleville, 25.6 (Headlee, 1962; Newcombe, 1935)
26.0 Fresh water aquifer J. Polasky 1 well. Proposed origin: USA Washtenaw, 26.0 (Headlee, 1962; Newcombe, 1935)
27
mixed, mostly inorganic
26.4 187.5 cm3/L Devonian–Lower Carboniferous aquifer, Kuvshinoskaya well 583–600 Russian Kuvshinoskaya, 26.4 (Мухин, 1970)
Federation
27 Gases dissolved in water from the superdeep drilling SG-2 3350 Kazakhstan Aralsor superdeep, 27 (Соколов, 1971)
28 1129 cm3/L In deep waters from Paleozoic aquifer, Lemeshkinskaya 2174–2184 Russian Lemeshkinskaya, 28 (Стадник, 1970)
field, Evlanovsko-Livensky horizon, well #16 Federation
13.5–29.5 28.7–58.2 cm3/L Devonian aquifer Smolenskaya well #2; c (He) = 1.1–2.1% 614–640 Russian Smolenskaya, 29.5 (Мухин, 1970)
Federation
25–30 Well water. Proposed origin: deep from basement Russian Chesnokovka, 30 (Щербаков et al., 1972)
Federation
30, up to In waters of a copper mine Russian Hudesskoe, 30 (Фридман, 1970)
Federation
10.5–32.1 Aquifer in residual soil in crystalline basement, 540–552 Russian Borisoglebskaya, 32.1 (Мухин, 1970)
Borisoglebskaya well Federation
18–31.9 89.7 cm3/L Dissolved gases in ground water Lower Riphean aquifer, 2027–2033 Russian Pereyaslavl-Zalesskaya, (Мухин, 1970)
well #1-P in Pereyaslavl-Zalessk; c (He) = 0.7% Federation 31.9
3
32.8 (well 879 cm /L in the well #319 Deep paleozoic aquifer Bahmetievskaya field, 638–655 Russian Bahmetievskaya, 32.8 (Стадник, 1970)
#319); Verhnebashkirsky aquifer, well #319; Bobrikovsky aquifer, Federation
11.6 (well well #445
#445)
34.7 Deep Paleozoic aquifers of Furmanovskaya field, 964–966 Russian Furmanovskaya, 34.7 (Стадник, 1970)
Verhnebashkirsky aquifer, well #21 Federation
Up to 36.3 Sparkling water from Triassic aquifer 1077–1082 Ukraine Sahaidakske, 36 (Шорохов, 1960; Зингер, 1962)
1.7–37.7 Gases in aquifers from the well #5. Proposed origin: deep- 2892–2914 Ukraine Henicheska, 37.7 (Овчаренко, 1967)
seated
47.5 Deep Paleozoic aquifer of Sherbakovskaya field, Sakmarsko- 1755–1790 Russian Sherbakovskaya, 47.5 (Стадник, 1970)
Artinsky horizon, well #19 Federation
3.2. Serpentinization
Sherwood Lollar et al., 1993a; Sherwood Lollar et al.,

2007; Sherwood Lollar et al., 2006; Sherwood Lollar
(Стадник, 1970; Фроловская, 1964; Зингер, 1962)
Serpentinization is a metamorphic process in which mainly ultra-
(Smith et al., 2005; Sherwood Lollar et al., 2014;

basic rocks are oxidized by water into serpentine producing hydrogen.
It is generally considered that ultramafic rocks are the main con-
stituents of the Earth’s mantle explaining why serpentinization as a
process attracts so much attention from Earth scientists. It has been well
studied with many works published (see for example, these articles
(Стадник, 1970; Зингер, 1962)

(Vacquand et al., 2018; Suzuki et al., 2015; Mayhew et al., 2013) and
references therein). A comprehensive review of the serpentinization
literature will exceed the scope of this article and has already been done
(Овчаренко, 1967)
in cited works therefore only a resume of the current literature is pre-
(Стадник, 1970)
sented herein.
et al., 1988)
A typical mantle rock is peridotite which is mainly composed of the

Reference
mineral olivine. This is a mineral which is likely to react with water.

Olivine, (Mg,Fe)2SiO4, is a solid solution series between forsterite
(Mg2SiO4) and fayalite (Fe2SiO4). Iron in the fayalite has the oxidation
state Fe2+, which allows it to react with water. During the reaction iron
Rodionovskaya, 60.6
oxidizes to Fe3+ and hydrogen in water reduces to H20:

Name of placemark
Nyzhnohirska, 53.6
Zhirnovskaya, 49.1
Klenovskaya, 76
3 Fe2 SiO4 + 2 H2 O Fe3 O4 + 3 SiO2 + 2 H2

Sudbury, 57.8
Forsterite is often the dominant mineral in the structure of olivine. It

reacts with excess silica to give serpentine:
3 Mg2SiO4 + 4 H2 O + SiO2 Mg3Si2O5 (OH)4
Forsterite can also react with water to give serpentine and magne-
Federation
Federation
Federation
sium hydroxide, which drastically increases the pH of the solution:

Country
Ukraine
Russian
Russian
Russian
Canada
2 Mg2SiO4 + 3 H2 O Mg3Si2O5 (OH)4 + 2 Mg2 + + 2OH
It has been reported that serpentinization is most active in the

1027–1029 (well
1044–1049 (well
1050 (well #39)
1350 (well #31)
temperature range of 200 to 310 °C (Mccollom and Bach, 2009). At

850–884 (well
lower temperatures, the rate of reaction becomes very limited, and at

2836–2858
1795–1810
Depth, m
higher temperatures the reaction rate rapidly decreases because of

#641)
#790)
1333
#53)
thermodynamic constraints. While some authors suggest that hydrogen

could be produced by low-temperature reactions, a recent rigorous
study demonstrated that hydrogen generation in such experiments is
Deep Paleozoic aquifer of Zhirnovskayafield, Tulskyhorizon,
Deep Paleozoic aquifer of Rodionovskaya field, wells #790

Gases in aquifers from the well #6. Proposed origin: deep-
also generated by contamination from commonly used reaction vessels

Fractured Precambrian shield aquifer Copper Cliff well
#CCS4572. δD= -637 to -738‰; c (He) = 2.6–6.7%.
Deep Paleozoic aquifer of Klenoskaya field, Dankovo-
which were also generating hydrogen when compared to control ex-

periments done without minerals (McCollom and Donaldson, 2016).
It should also be noted that the alteration of peridotites to serpen-
tinite decreases the permeability of the rock which inhibits further
access to water (Apps and Van De Kamp, 1993). It is also useful to
Lebediansky horizon, wells #4, #10
mention that some authors consider hydrogen to not only be the pro-
Proposed origin: serpentinization
duct of serpentinization but also to be a reagent producing "structural"

and #31, Kungursky horizon
water in serpentinite (Юркова et al., 1982; Юркова and Воронин,

2008). This important point requires further study.
wells #53, #641, #39
Serpentinization has been well studied in places where outcrops of

mantle material are exposed at the surface. Mantle comes close to the
surface in rift zones, but these are mainly situated beneath oceans. Rare,
Comments
but more accessible locales are the ophiolite belts, where oceanic crust
seated
with underlying mantle is uplifted and exposed above the sea level.
Table 1 summarizes documented locations of hydrogen-rich gas seeps
associated with ophiolitic outcrops. Estimates of present-day hydrogen
1306 cm /L in the well #53;
946 cm3/L in the well #39
flow from oceanic crust serpentinization are on the order of 0.8–1.3 *

1011 mol/year (0.16–0.26 Tg/year) (Canfield et al., 2006). Other stu-

dies have made the assumption that 10% of the seafloor is serpentinite,
to derive a maximum possible annual flux of H2 equal to 0.38 Tmol/
year (0.76 Tg/year) (Sleep and Bird, 2007). In other studies authors
3
96 L/day
used drill-samples of oceanic crust to obtain hydrogen flux values of

Content
4.5 ± 3.0 × 1011 mol H2/year (0.89 ± 0.6 Tg/year) (Bach and
Table 23 (continued)
Edwards, 2003). Applying a recently derived estimate by this author

41.5 (well #53)
49.1 (well #39)
14.7 (well #31)
et al. for hydrogen flow from the Semail ophiolite in Oman (Zgonnik
76 (well #4);
6.2 (well
et al., 2019) to the total surface area of the ophiolites throughout the
#641)
#790)
14.2 (well
60.6 (well
#10)
1.8–53.6
9.9–57.8
world (Vacquand, 2011) we obtain 0.18–0.36 Tg/year, which is in the

H2, %
same order of magnitude as the above cited estimates. It was also

suggested that olivine might function as a source of hydrogen for
28
V. Zgonnik
Table 24
Hydrogen detected in water sampled from hydrocarbon fields.
3
10.9 1163 cm /L of total gas Dissolved gas in ground water from Jurassic strata. Velichaevsko-Kolodeznoe 3160–3164 Russian Velichaevsko-Kolodeznoe, 10.9 (Зорькин, 1989)
oil field Federation
11.2 Dissolved gas in water, Luginetskaya field, well #159 2224–2232 Russian Luginetskaya, 11.2 (Молчанов, 1981)
Federation
13.1 Dissolved gas in water from Devonian strata. Rechytskoe oil field 2423–2438 Belarus Rechytskoe, 13.1 (Зорькин, 1989)
12.2–14.2 139–230 cm3/L of total gas Dissolved gas in water from Carboniferous strata. Mukhanovskoe oil field 2208–2138 Russian Mukhanovskoe, 14.2 (Зорькин, 1989)
Federation
9.1 (well #2) In deep water in oil-gas field from the hydrocarbon free horizon in the wells: 2858–2878 (well Russian Katchalinskaya, 15.8 (Стадник, 1970)
#2 of Oksko-Serpuhovsky horizon and #3 of Vereisky horizon in #2) Federation
15.8 (well #3) Katchalinskaya field 2456–2460 (well
#3)
16.4 270 cm3/L of total gas Dissolved gas in water from Devonian layers of Ostashkovichskoe oil field 2835–2855 Belarus Ostashkovichskoe, 16.4 (Зорькин, 1989)
5.1 (well #5) In deep water in contact with gas from wells #5 and #82 of Nizhnebashkirsky 534–535 (well #5) Russian Abramoskaya, 18.2 (Стадник, 1970)
18.2 (well #82) horizon in Abramoskaya hydrocarbon field 2399–2407 (well Federation
29
#82)
21.0 Dissolved gas in water from Bolsherechenskaya field, well #3 3145–3250 Russian Bolsherechenskaya, 21 (Молчанов, 1981)
Federation
28, up to Dissolved gas in water from Ayyuvinskoe hydrocarbon field Russian Ayyuvinskoe, 28 (Соколов, 1966a; Молчанов,
Federation 1981)
11.2 (well #21) 650 cm3/L in the well# 48; In deep waters from Paleozoic deposits of Korobkovskaya field, 1780 (well #21) Russian Korobkovskaya, 30.6 (Стадник, 1970; Зингер,
571 cm3/L in the well# 21 Nizhnebashkirsky horizon, wells #48, 50 Federation 1962)
22.3 (well #48) Bobrikovsky horizon, well #21 1439–1447 (well
#48)
30.6 (well #50) Water in contact with hydrocarbons 1447–1466 (well
#50)
33.9 In deep water in contact with oil-gas from the well #6 of Turneisky stage in 1345–1352 Russian Staritskaya, 33.9 (Стадник, 1970)
Staritskaya field Federation
37.7 286 cm3/L of total gas Dissolved gas in water from Proterozoic strata of Davydovskoe oil field 3490–3500 Belarus Davydovskoe, 37.7 (Зорькин, 1989)
58.0 Dissolved gas in water from Megionskaya field, well #1 2727–2734 Russian Megionskaya, 58 (Молчанов, 1981)
Federation
24.2–86.6 Dissolved gas in water from Severnaya field, well #101 2329–2595 Russian Severnaya, 86.6 (Молчанов, 1981)
Federation
90–98 Hydrogen dissolved in oil well water 2450 Kazakhstan Gagarinskaya, 98 (Перевозчиков, 2011)
energy applications(Schuiling, 2013). during rock displacement along fractures (Suzuki et al., 2015). How-
Total estimated hydrogen flux from the global mid-ocean rift system ever, the chemical reactions taking place are not fully explained. Other
is 0.12 Tg/year (Welhan and Craig, 1979). In comparison with ophio- articles propose that hydrogen is generated in a reaction between free
lites this number looks rather low. Other authors used H2/3He and 3He/ radicals on fresh rock surfaces with water (Sugisaki et al., 1983;
heat ratios to estimate a global H2 flux for slow-spreading ridges to Wiersberg and Erzinger, 2008). Yet such reactions must simultaneously
obtain 89 * 109 mol/year (0.18 Tg/year) (Charlou et al., 2012). Esti- produce oxidized species such as peroxides or oxygen in addition to
mated hydrogen flux from slow-spreading ridges of about 16.7 * 1010 hydrogen. The pathways of oxidized compounds are not addressed.
mol/year (0.33 Tg/year) are published in (Cannat et al., 2010). Later Moreover in the laboratory, rock samples taken from the fault zone with
study gave a close estimate of 19 * 1010 mol/year (0.38 Tg/year) (Keir, the highest observed hydrogen concentration were incapable of gen-
2010). Another more recent work integrated in their model the erating H2 (Sugisaki et al., 1983), which puts into question the pro-
spreading rate and demonstrated that hydrogen generation is higher, in posed mechanism for hydrogen generation. More recent laboratory
the order of ~1012 mol/year (Worman et al., 2016). experiments with different types of dry and wet rocks showed that
Moreover, hydrogen is produced exclusively by oceanic crust. hydrogen was generated (Hirose et al., 2011; Hirose et al., 2012),
Recent studies suggest that production of hydrogen from the however, the authors did not explore the possible mechanisms for this
Precambrian has been underestimated. The authors of the study esti- process and the role of oxygen in the reaction chain. The authors used
mated that the hydration process (reactions of rocks with water) may their results to estimate annual global hydrogen flow generated by rock
contribute 0.2–1.8 * 1011 mol per year (0.04 –0.38 Tg/year) (Sherwood friction during earthquakes. They concluded that it is equal to 2.3 * 102
Lollar et al., 2014). mol/m2year, which gives 235,000 Tg of H2 per year, which appears to
Mantle rocks are not the only rocks which react with water to be an unrealistic value, given that it is 3–4 orders of magnitude greater
produce hydrogen. Basalt-water reactions were also shown to be pos- than all other geological estimates combined together (see Table 25).
sible (Stevens and McKinley, 2000). A study of samples of basaltic Moreover, such a rate of production would appear to have consumed all
oceanic crust from the Integrated Ocean Drilling Program (IODP) de- available water on Earth in only in 0.2 million years.
monstrated that they were enriched in hydrogen (Lin et al., 2014). The During displacement of rocks along faults friction creates fresh
entire basaltic layer of the oceanic crust may contribute 17*109 mol H2/ surfaces which can allow water to contact and react with Fe(II)-con-
day (12.6 Tg/year) (Holloway and O’Day, 2000). Other authors esti- taining minerals. Hydrogen has been generated in the laboratory by
mated the global flux of H2 from basaltic oceanic crust could result in combining water with fine minerals, crushed in situ with a mill
3.75 Tmol/year of H2 (7.5 Tg/year) (Sleep and Bird, 2007). Another (Молчанов, 1968; Голосов et al., 1966). Even after 7 weeks of
study suggests that hydrogen can be produced by the reaction of water grinding, hydrogen was still being produced. The authors of this study
with Fe2+-containing minerals at the depths of 10–15 km. The per- propose that the hydrogen generated is the result of a reaction between
meability of microcracks in excess of 10−14 cm2 can extend to depths of Fe particles (formed in the iron mill) with water (Голосов et al., 1966)
15 km. According to the authors of this study such permeability is en- and from the reaction of Fe (II)-containing minerals (Молчанов, 1968).
ough to permit substantial fluid movement. It is estimated that basaltic One of the authors developed the idea and published an entire book
rock in equilibrium with water should contain 7 ppm of H2 by weight. (Молчанов, 1981) proposing that hydrogen could form naturally when
This is equivalent to 75 cm3 per kg of rock or 12 L H2 per L of water in minerals are ground together in fault zones. However, the possibility
equilibrium with the rock (Hawkes, 1980). However, some works that the released hydrogen could be either pre-existing hydrogen stored
suggest that basalt-groundwater interaction can not produce large in pores or hydrogen migrated along faults from depth, and not gen-
quantities of hydrogen because the surfaces of water-mineral contacts erated by friction, was not evaluated.
quickly become de-activated by their reaction products (Anderson, Cataclasis is a term applied to the crushing of minerals during me-
1998). tamorphism. Laboratory experiments performed to investigate the ef-
Other minerals, containing Fe(II) could yield H2 in reactions with fects of crushing on wet granite and quartz samples demonstrated that
water. It was shown that siderite could generate hydrogen under certain hydrogen can be generated as a result of cataclasis (Saruwatari et al.,
conditions (Milesi et al., 2016). 2004; Kita et al., 1982; Parkes et al., 2018). However, hydrogen has
This question related to water consumption should be addressed in also been generated in experiments crushing synthetic materials like
detail, as the majority of currently considered geologic sources of hy- pyrex, alumina and silica (Kita et al., 1982; Parkes et al., 2018). More
drogen imply a reaction of water with minerals speculated to be the surprisingly, high values for generated hydrogen have been reported in
only source for natural hydrogen (via serpentinization or other reac- experiments where samples were dry milled without water, and the
tions discussed below). Because this reaction is irreversible, it is ne- authors have not addressed the issue of possible sources of hydrogen
cessary to estimate the rate of water consumption. With a hydrogen generated in these experiments. Another study obtained hydrogen by
production rate on the order of 23 ± 8 Tg/year via different geological crushing rock samples from the Arctic and Antarctic and making them
mechanisms (Table 25), assuming all of them are consuming water, the react with 0°C water (Telling et al., 2015). Based on analyses of fluid
entire hydrosphere (1.4 *1024 g) would be consumed in a time frame of inclusions in rocks from fault zones the authors of another study pro-
6.6 ± 3 billion years. Of course, some portion of hydrogen produced is posed that hydrogen is formed by brittle fracturing (McMahon et al.,
recycled back to water abiogenically and/or via biological consumption 2016). Nevertheless, the authors of the aforementioned studies do not
(bypassing through organic compounds), but oxygen still remains address the fate of any excess in oxygen produced by the reactions of
bonded in rocks. Therefore, the processes of hydrogen generation water with free radicals which were proposed as a mechanism for the
through water reaction with rocks can be seen from another perspec- generation of hydrogen. This question was not addressed because half-
tive: as a process by which surface oxygen from water is redistributed reactions were used rather than balanced full equations. Assuming that
through burial in rocks. water reacts with silica or that silicates give off hydrogen, excess in
oxygen can yield either unstable peroxides or molecular oxygen. An-
3.3. Other reactions in minerals other part of the water molecule in the mechanism proposed by the
authors yields hydroxyl groups in silicates. However, as already pointed
Several other mechanisms have been proposed to explain how hy- out in other research, exposed mineral surfaces quickly become de-ac-
drogen may form in rocks. A frequently cited article suggests that hy- tivated in natural environments by reaction products, principally silica
drogen can be produced from the reaction of water with fresh rock gels. Such gels limit the diffusion of water to the underlying unreacted
surfaces along active fault zones (Wakita et al., 1980). Recent friction surfaces and reduce their capacity to produce H2 (Anderson, 1998).
experiments on rocks showed that fault systems may produce hydrogen Hydroxyl groups are at the core of another mechanism, which was
30
proposed as an explanation for the release of hydrogen when the rocks the energy of radioactive decay in water/rock systems has the effect of
are under stress. It was suggested that H2 could be formed by the re- oxidants being simultaneously produced with reducers like hydrogen,
action of two hydroxyl groups, forming H2 and a peroxide anion O22−, i.e. components with opposite chemical properties (Vovk, 1982). In the
which in turn would make a peroxide bridge between two silicon atoms case of water decomposition, this should mainly be hydrogen peroxide,
in silicates (Freund, 1984; Freund et al., 2002). Based on the results of H2O2, which should quickly decompose to O2. Indeed, experiments with
laboratory experiments the authors estimate that this mechanism could irradiation of water/mineral mixtures consisting of the most common
produce 0.005 m3 of H2 per m3 of rock. In comparison, the serpenti- rock-forming minerals resulted in the generation of a hydrogen-oxygen
nization process can produce 20 m3 H2 per m3 of rock. Although peroxy gas mixture with O2 concentrations of up to 30–35% (Вовк, 1979). One
bonds were observed in pure synthetic compounds, there is a lack of should therefore expect to find nearly stoichiometric proportions of H2
evidence for them in natural rocks (Kubatko et al., 2003). Probably to O2 gas at locations where water radiolysis is thought to have oc-
because peroxides are unstable compounds and should quickly de- curred, but this is not the case. Oxygen has not been measured in stu-
compose giving off O2. It was later suggested that peroxy bonds break dies exploring chemical composition of inclusions (Parnell and Blamey,
under stress, producing according to the paper’s authors terminology 2017a). Moreover, pure hydrogen was detected by Raman spectroscopy
“positive holes” (chemically equivalent to O–), which rapidly propagate in fluid inclusions in quartz from a Precambrian uranium deposit in
to unstressed rock. As the "positive holes" cross the rock-water Oklo, Gabon while fluid inclusions from two other Precambrian ur-
boundary, the rock turns into a hydrous silica gel and cations are re- anium deposits (in Canada) are almost pure oxygen (Dubessy et al.,
leased, leading to the dissolution (“electrocorrosion”) of the rock 1988). If the origin of these gases is radiolysis, the stoichiometry of the
(Freund and Freund, 2015; Scoville et al., 2015; Balk et al., 2009). gas mixtures (no oxygen in the Oklo inclusions and no hydrogen in the
However, the fate of any remaining oxygen after the breakage of peroxy samples from Canada) can not be explained.
bonds, remains unclear. In another study hydrogen yield was estimated for the entire re-
sidence-time of water in an aquifer, which was expected to range from 3
3.4. Water radiolysis to 80 million years. Comparisons of calculated values with measured H2
concentrations in natural environments show numbers of the same
Radiolysis of water is often cited as a possible source of hydrogen. order of magnitude (Lin et al., 2005b). However, hydrogen is a very
The energy from radioactive decay is high enough to break apart mo- mobile gas, so its diffusion rate should have been taken into account,
lecules of water into their component parts, oxygen and hydrogen, and which was not done. The analyses of inclusions in rocks of different age
the Earth’s crust contains significant quantities of radioactive elements, show no correlation between hydrogen concentration and the age of the
mainly U, Th and K. This idea of rock alterations by ionizing ratioation rock (McMahon et al., 2016) while another study has opposite con-
was proposed in 1930's by V. I. Vernadsky (Vovk, 1982). According to clusions, that Precambrian samples contain more hydrogen than
some authors, no other known H2-generating mechanism can produce younger ones (Parnell and Blamey, 2017a).
large amounts of hydrogen (Lin et al., 2005a). When making estimates of hydrogen generation over geological
Ionizing radiation provokes excitation and ionization of molecules, time, one should always account for hydrogen diffusion. Because hy-
which leads to an increase in their reactivity and the formation of free drogen is continuously leaving the reaction zone, the oxidation state of
radicals, the most reactive chemical species. For example, a single, 1 the remaining fluid should increase (Dubessy et al., 1988). Estimated
MeV α-particle can ionize 105 molecules as it loses energy (Dubessy O2 production in the crust from water radiolysis during a period of
et al., 1988). When this energy is passed to water molecules, they can 4*109 years gives 1.91*1023 g –a quantity large enough to oxidize the
decompose to give H2 and H2O2, which will quickly decompose to O2 entire Earth’s crust (Вовк, 1979). Many studies citing water radiolysis
and water. It has been estimated that only 1% of the total energy from as a possible source for natural H2 do not address a probable con-
the radiogenic decay is absorbed by pore water. The rest is absorbed by comitant increase in oxygen and therefore omit to propose a pathway
the mineral matrix and converted to heat. Thus, H2 yield is proportional for any oxidized species produced by radiolysis. Hydrogen peroxide has
to the rock porosity filled with water (Lin et al., 2005b). In a book not been detected in rock samples considered to have been exposed to
dedicated to the role of radiolysis in geochemistry even smaller num- the action of ionizing radiation (Lin et al., 2005a). Examples of other
bers are given: only a small amount of radioactive energy (0.002–0.06% hyper-oxidized compounds in the crust are extremely rare and limited
in igneous rocks and 0.03–0.6% in clays) is consumed to transform the to two peroxide uranium minerals (Kubatko et al., 2003).
chemical potential of compounds while most of the energy is dissipated Another mechanism for hydrogen generation related to the radio-
as heat. In multicomponent systems radioactive energy is distributed active decay of elements is connected to the change in valence of atoms.
between all components, thus only a part of it is used in the radiolysis of During radioactive decay isotopes transform into new elements with
water (Вовк, 1979). In a recent experimental study it has been shown other chemical properties. Such elements may be more or less reactive
that the action of γ-radiation on hydrogen-containing molecules and with respect to their parent atoms. In fact, the cumulative reactivity of
mixtures, including water solutions, produces H2. Note, that higher new atoms to parent atoms exceeds 0.5 times the reactivity of parent
hydrogen yields were observed for brines compared to pure water isotopes. This excess reactivity is mainly caused by the accumulation of
40
(Wang et al., 2019). Nevertheless, some researchers have developed Ca and 87Sr formed from 40K and 87Rb. New elements could react with
models for hydrogen generation through radiolysis without making a water, producing hydrogen. Th(IV) and U(IV), in their turn, while be-
single H2 measurement (Blair et al., 2007). coming Pb(II) also liberate one additional atom of oxygen, thus in-
Estimates for possible hydrogen production from these mechanisms creasing the oxidation state of the medium. According to the authors of
vary greatly. One author estimated the volume of radiolytically dis- the study, the quantity of hydrogen generated should be comparable to
sociated water in the sedimentary section to be about 0.026 m3 per year that of radiogenic helium, because radioactive decay of Th and U
(it is possible that this is a typing error and the author meant km3, even produces helium. For 100 km3 of crustal rock, the estimated annual
in this case the value is not very high: only 0.00032 Tg H2 per year) production of H2 by this mechanism is equal to 0.15 m3 H2 (Savchenko,
(Vovk, 1982). The book on water radiolysis gives a much higher value: 1958).
0.24*1023 g during the period of 4*109 years (6 Tg/year) (Вовк, 1979). One separate case should be discussed in more detail. As is shown in
Recent estimates for radiolysis reactions in continental Precambrian Tables 12 and 22, high concentrations of hydrogen are systematically
crust give H2 generation rates of 0.16–0.47 * 1011 mol per year (0.03 detected in potassium salt deposits. It is commonly proposed that hy-
–0.09 Tg/year) (Sherwood Lollar et al., 2014). drogen may have a water-radiolysis origin because of K and Rb radio-
It is very important to keep in mind that during water decomposi- active decay (Вовк, 1978; Parnell and Blamey, 2017b). In carnallite and
tion by radiolysis hydrogen is not the only product. Transformation of sylvinite, irradiation from 40K acts on water molecules generating
31
hydrogen, which fills the pore spaces, sometimes reaching pressures on with a suitable hydrogen-utilizing organism (Nealson et al., 2005).
the order of megapascals (Vovk, 1982). At the same time, produced Thus, all biologically produced hydrogen is rapidly converted to other
oxidizing species transform iron to hematite which lends a red color to compounds (Morita, 1999; Gregory et al., 2019). Moreover, hydrogen
the salt (Savchenko, 1958). However, observed H2/Ar ratios and car- producers can not exist without hydrogen consumers because hydrogen
nallite/sylvinite H2 concentration ratios don’t support this idea (Вовк, inhibits their activity (Hoehler, 2005). A recent comprehensive review
1978). Another article provides an additional argument against a ra- combined the knowledge of microbiology in environments with ele-
diation-induced origin for hydrogen in K and Na minerals. In this article vated hydrogen content (Gregory et al., 2019).
describing experiments done on blue sylvinite, which has its coloration This topic deserves particular attention not for the production of
as a consequence of ionizing radiation, no detections of hydrogen were hydrogen, but for its consumption. Two mechanisms for hydrogen de-
reported (Морачевский et al., 1937). composition are possible: by microorganisms and by the soil itself
An alternative mechanism for hydrogen generation in salt deposits (Conrad and Seiler, 1981). Uptake of hydrogen by soil is responsible for
has been proposed. It was noted that the volumes of hydrogen extracted a loss of about 80% of atmospheric hydrogen (Constant et al., 2010;
from salt samples were higher when the salt blocks were dissolved in Rhee et al., 2006). Maximum H2 production and consumption activity
water compared to crushed salt samples (Вовк, 1978; Nesmelova and was found in the surface layer of soils, where most of the microbial
Travnikova, 1973). In potassium deposits the radioactive isotope 40K biomass is located (Conrad, 1996). Indeed, it was reported that hy-
undergoes branching decay with the formation of 40Ar (12%) and 40Ca drogen production by the soil itself was not observed, and the pro-
(88%). The Calcium-40 cannot be completely transformed into chloride duction rate of H2 was shown to be negligible compared to its' con-
and accumulate in the crystal structure of the salt minerals in its me- sumption rate (Conrad and Seiler, 1985). It was proposed, that non-
tallic state. During dissolution, elemental calcium readily reacts with biological processes are more important than microbial activity in H2
water yielding molecular hydrogen (Nesmelova and Travnikova, 1973). decomposition (Conrad and Seiler, 1981).
Another study proposed that in addition to 40Ca, 87Sr formed from 87Rb In studies of different soil types it was found that production of H2 in
could also react with water to give hydrogen. However, there are some wetland soils is intensive, but most of the produced hydrogen is im-
discrepancies between the calculated and observed quantities of hy- mediately converted by methanogens to CH4 (Conrad, 1996). In upland
drogen (Savchenko, 1958). The author of another study suggests that soils which are oxic soils, hydrogen is mainly produced by nitrogen-
reaction of 40Ca with water is not the only mechanism generating hy- fixing bacteria and consumed by abiotic enzymes rather than by mi-
drogen. The author proposes that water radiolysis is also involved at the croorganisms, while in wetland anoxic soils, hydrogen is produced by
same time (Вовк, 1979). Another reaction is possible during the dis- bacterial fermentation and consumed by methanogens, sulfate reducers,
solution of carnallite for the extraction of trapped gases. It has been denitrifiers, ferric iron reducers and Knall gas bacteria (Conrad, 1996;
proposed that some hydrogen could be formed by the reaction of the F- Seiler and Conrad, 1987). It has been reported that most hydrogen is
centers of the carnallite crystalline structure (created by the action of consumed within 1 cm of point sources, and its presence significantly
ionizing radiation) with water (Вовк, 1978). decreases the soil’s capacity to oxidize other reduced gases like CH4 and
Some other processes related to water radiolysis should also be CO (Piché-Choquette et al., 2018).
taken into account. Noble gases form during the radioactive decay of The hypothesis that ambient atmospheric concentrations of hy-
certain elements. Helium-4 is produced in the radioactive decay chain drogen are not sufficient for bacterial growth (Conrad, 1996) while
reactions of U and Th, and radioactive K decomposes to 40Ar. These enzymes remain active to rapidly consume hydrogen from the air, re-
gases should be present together with hydrogen if water radiolysis takes mained for decades the basic assumption of many soil uptake studies.
place in connection with the decay of those elements. Taking into ac- However, later Constant et al. identified an aerobic microorganism
count the above rates for the conversion of radioactive energy to hy- (Streptomyces sp. PCB7) that can consume H2 at tropospheric ambient
drogen (≤1%), the quantity of 4He should greatly exceed the quantity mole fractions, and suggested that active metabolic cells could be re-
of H2. Indeed, some studies note, that the quantity of hydrogen pro- sponsible for the soil uptake of H2 rather than extracellular enzymes
duced by water radiolysis could not exceed the quantity of radiogenic (Constant et al., 2010). They showed that uptake activity at ambient H2
helium (Savchenko, 1958). Moreover, any estimate of hydrogen pro- levels is widespread among the streptomycetes abundant in a broad
duction from radiolysis should take into account the rate of re- variety of settings including desert soils, forests and peatlands. They
combination of oxidized and reduced species, formed by the action of postulated that specialized H2-oxidizing actinobacteria are responsible
high energy particles on water. for the most important sink term in the atmospheric H2 budget
Therefore, water radiolysis never happens as a separate reaction, (Constant et al., 2010). Recently it was discovered that some micro-
but rather as a complex of connected processes. Being focused on ex- organisms in Antarctica use only atmospheric H2 as an energy source (Ji
plaining hydrogen generation, researchers often appear to have for- et al., 2017).
gotten or omitted the consideration that radiolysis generates oxidizing Therefore, soils are the primary sink in the atmospheric H2 budget.
chemical species at the same time. When hydrogen volumes are sig- It was proposed that the consumption rate of hydrogen by soils is
nificant it is not possible to attribute its origin to water decomposition strongly influenced by soil moisture and only slightly by its temperature
driven by radioactive decay. Indeed, it has been shown that radioactive (Conrad and Seiler, 1985). In more recent studies it has been shown
decay is insufficient to produce the measured volumes of hydrogen that the maximum hydrogen uptake by moderately humid soils takes
(Стадник, 1970). place at 30°C (Ehhalt and Rohrer, 2011). It is interesting, that soil re-
mains active in the uptake of hydrogen at temperatures below freezing,
3.5. Biological activity temperatures at which hydrogenase, the enzyme responsible for hy-
drogen consumption, remains active. This fact mitigates in favor of H2
Biological activity is often used as an explanation for the origin of uptake by living bacteria (Ehhalt and Rohrer, 2011).
natural hydrogen in natural gas samples. H2 can be produced biologi- Hydrogen consumption by soils drastically increases with con-
cally by the anaerobic decay of organic matter (Morita, 1999), fer- centration. When the concentration of H2 rises to its lower explosive
mentation (Conrad, 1996) and by nitrogen fixing bacteria (Morita, limit or LEL (~ 4%) the consumption rate by soil increases by up to
1999; Conrad, 1996; Conrad and Seiler, 1980). In the laboratory and 1000 times (Sukhanova et al., 2013). This can be explained by the
with sufficient substrate many different bacteria will generate hy- existence of two metabolically diverse groups of H2-oxidizing micro-
drogen, as shown in the next overview (Nandi and Sengupta, 1998). organisms displaying different kinetic rates for H2 consumption
Althrough it is true that microorganisms may produce hydrogen in vitro, (Constant et al., 2010). To predict a soils capacity for hydrogen uptake,
the fact is that in nature hydrogen-producing bacteria always co-exist based on the results of experiments, it was proposed that total carbon
32
content and relative abundance of H2-oxydizing bacteria be used hydrogen-producing and hydrogen-consuming bacteria. For 13 probes
(Khdhiri et al., 2015). It was reported that hydrogen can also be oxi- containing dissolved hydrogen almost no biological activity was de-
dized in the rootzone or rhizosphere (Conrad, 1996). A measure of the tected (Стадник, 1970). No bacterial activity was detected in hy-
strength of soil uptake for hydrogen is called deposition velocity, which drogen-rich water in aquifers close to petroleum deposits (Зингер,
ranges from 0.06 to 0.22 cm s−1 depending on the soil type (Chen et al., 1962). Only one paper indicated that hydrogen in a small number of
2015). Hydrogen deposition velocities for various ecosystems were samples originated from biological activity in drilling mud (Несмелова
collected (Ehhalt and Rohrer, 2009). Estimates of hydrogen uptake by and Рогозина, 1963).
soils vary from:120 Tg/year (Hawkes, 1980), 56 ± 41 Tg/year It should be noted that any hydrogen in samples from very deep
(Novelli et al., 1999), 90 ± 20 Tg/year (Conrad and Seiler, 1981; wells where temperatures and pressures are likely too high to sustain
Conrad and Seiler, 1980; Seiler and Conrad, 1987), 88 ± 11 Tg/year life are unlikely to be the result of bacterial activity (Войтов and Осика,
(Rhee et al., 2006) and 60+30 −20 Tg/year (Ehhalt and Rohrer, 2009). 1982). Hovewer, there are a growing number of examples of hydrogen-
Estimates are available for the production of hydrogen by biological based deep microbal communities, living at great depths in the ocean
processes. Given that soils are the main sink for hydrogen, it is difficult and in fractures in the Earth’s crust (see the Section on 5.2 Hydrogen
to differentiate the amount of hydrogen that goes into the atmosphere and life). Estimated rates of hydrogen consumption by such organisms
from that consumed by microorganisms and soil enzymes. It has been are not yet available, but it is probable that hydrogen consumption
suggested that the microbial production of hydrogen in soils plays only rates are higher than the diffusion rate. In which case low hydrogen
a minor role in the hydrogen atmospheric budget (Conrad, 1996). Based concentrations in the majority of environments can be explained by the
on field studies of hydrogen emissions from nitrogen-fixing legumes action of biological activity (Fedonkin, 2009).
(Conrad and Seiler, 1979), total H2 from biological N2 fixation is esti-
mated to be on the order of 2.4–4.9 Tg/year (Conrad and Seiler, 1980). 3.6. Atmospheric hydrogen
This number seems to be much higher than earlier estimates for total
biological H2 production from paddy soils, enteric fermentation of an- An average hydrogen concentration in the atmosphere has been
imals, upland fields and forests which totals to 0.017 Tg per year estimated to be 0.531 ppm (Novelli et al., 1999). However, average
(Koyama, 1963). Indeed, recent work suggests that 97% of hydrogen hydrogen concentrations vary between the equator and poles, reaching
produced by nitrogen-fixing bacteria is removed from the soil by mi- 545 ppb at the equator, compared to 535 ppb at 88°S and 490 ppb at
croorganisms and soil activity before entering atmosphere (Chen et al., 80°N (Ehhalt and Rohrer, 2009). Global trends of hydrogen con-
2015). centration show either an increase of 3.2 ± 0.5 ppb per year (Morita,
In its turn, the fermentation of organic matter does not give high 1999) or a decrease by 2.3 ± 0.5 ppb per year (Novelli et al., 1999). It
yields of hydrogen. The possibility of hydrogen being generated by the has been suggested that such discrepancies are related to the large
fermentation of complex organic molecules was evaluated with calcu- inter-annual or intra-annual variability in H2 mixing ratios (Ehhalt and
lations of the Gibbs free energy of fermentation, however, it was con- Rohrer, 2009). Recent studies have shown that the global mean δD
cluded that microbial fermentation is unlikely to be the generating value of atmospheric H2 is about +130‰ (Batenburg et al., 2011) and
mechanism for observed high hydrogen concentrations (Lin et al., values for different sources of hydrogen are reviewed in (Ehhalt and
2005a). Rohrer, 2009). The total volume of H2 in the atmosphere is estimated to
It is interesting to note, that termites and some Protozoa can also be around 155 ± 10 Tg (Novelli et al., 1999), while different estimates
produce H2. However, nothing has been published on higher organisms range from 76 to 172 Tg (Price et al., 2007).
which metabolize hydrogen (Conrad, 1996). Estimates show that ter- Atmospheric chemistry is complex, and a detailed description of
mites may emit up to 200 Tg of H2 per year (Zimmerman et al., 1982), reactions is beyond the scope of this paper. More information can be
which is very high number, when compared to other sources of H2 (see found in this comprehensive review of tropospheric hydrogen (Ehhalt
Table 25) and is considered to be too large by other authors (Ehhalt and and Rohrer, 2009) and in these books (Hewitt and Jackson, 2009;
Rohrer, 2009). Most of this hydrogen may be rapidly consumed in-situ Warneck, 1999).
by symbiotic methanogens. It was suggested that only a portion of the Hydrogen, being the lightest of all gases, readily escapes the Earth’s
produced hydrogen could be released to the atmosphere, on the order of gravitation, and in combination with its high reactivity, makes its re-
1 Tg per year (Ehhalt and Rohrer, 2009). sidence time in the atmosphere very short. Estimates range from 4 to 7
Ocean waters have often been reported to be supersaturated with years (Schmidt, 1974), 2–3 years (Novelli et al., 1999), 1.9 years
hydrogen relative to its atmospheric concentration (hydrogen con- (Bullister et al., 1982; Price et al., 2007) and even 1.4 years (Rhee et al.,
centrations are higher than equilibrium with the atmosphere) (Bullister 2006). A recent review of hydrogen in the troposphere proposes a 2
et al., 1982). The waters of the Caspian Sea were reported to contain up year residence time (Ehhalt and Rohrer, 2009). Such short-term re-
to 7.3 cm3 H2/L (Levshounova, 1991) with no explanation for the sidence times imply that there is a constant supply of hydrogen to at-
source of this gas. Some Atlantic waters are supersaturated by a factor mosphere. Researchers have proposed possible sources for atmospheric
of three (Schmidt, 1974). This means that the ocean should be a source hydrogen to be anthropogenic, biological and water photolysis
of this gas to the atmosphere. Estimates for hydrogen production in (Schmidt, 1974), as well as the oxidation of methane and other hy-
oceans are 3 ± 2 Tg/year (Novelli et al., 1999), 4 ± 2 Tg/year (Seiler drocarbons and also oceans and soils (Warneck, 1999). The annual
and Conrad, 1987) and 6 ± 3 Tg/year (Ehhalt and Rohrer, 2009). supply of hydrogen to the Earth's atmosphere from all sources was es-
Recent work, based on isotopic measurements of hydrogen dissolved in timated to be on the order of 40–130 Tg/year (Adushkin et al., 2006).
oceanic waters suggests that it is possibly produced by nitrogen fixing Other estimates give values of 81 Tg/year (Warneck, 1999), 73 Tg/year
organisms with input from a “significant different source” (Walter et al., (Price et al., 2007) and 76 ± 14 Tg/year (Ehhalt and Rohrer, 2009).
2016). The authors suggest that it may be of photochemical origin, but However, none of these estimates take account of geologically supplied
it is also just as likely that the source may be geological. Indeed, an- hydrogen.
other study suggests that concentrations of hydrogen do not undergo In addition to terrestrial sources of hydrogen, atmospheric hydrogen
diurnal variations, which appears to eliminate the photochemical and includes hydrogen produced in situ by photochemical reactions. Note
biological hypotheses for hydrogen sourcing (Bullister et al., 1982). that, according to (Berkner and Marshall, 1966), photodissociation of
There are experimentally proven examples for the absence of hy- water is not a significant source of hydrogen to the atmosphere. This is
drogen producing microorganisms in samples from wells with high as a result of not only the limited transfer of water to high altitudes
hydrogen content, such as in this reference (Войтов and Осика, 1982). through freezing, but also because oxygen in the atmosphere acts as a
Another study checked deep water samples for the presence of barrier to the photodissociation of water. A variation of only 0.001%
33
from the present day oxygen concentration in atmosphere is enough to measurements from the Atmosphere Explorer C satellite, equal to
stop the H2O photodissociation (Berkner and Marshall, 1966). The main 3.2 ± 1 *108 atoms/cm2*s (equivalent to 2.6 ± 0.8 kg H2/s or
reaction producing hydrogen in the atmosphere is oxidation of methane 0.08 ± 0.03 Tg/year) (Breig et al., 1976). It is also interesting to note
and other hydrocarbons, which passes through a photodissociation of that observations of Venus and other planets show hydrogen escaping
formaldehyde step (Warneck, 1999). Estimates from the oxidation of from their atmospheres. The calculated escape ratio for Venus is 0.2–2.7
methane yield 23 ± 8 Tg H2/year and 18 ± 7 Tg H2/year for other *107 atoms/cm2*s (0.02–0.22kg/s, 0.0005–0.007 Tg/year) (Hunten,
hydrocarbons (Ehhalt and Rohrer, 2009). Yields calculated by other 1990).
authors are available in the same study. While the oxidation of CH4 is Because it is assumed that the main mechanism for hydrogen gen-
considered to be the main source for H2 and CO in the atmosphere, eration is related to reactions of water, an important element in esti-
observed increases in CH4 and CO have not been accompanied by a mates for hydrogen loss that should be addressed are losses of hydrogen
corresponding increase in H2, which begs the question as to the me- to space. These losses are well defined, therefore there should also be
chanism proposed (Ehhalt and Rohrer, 2009). (as a result of these losses) a contingent decrease in planetary water
As has been shown above, the residence time of hydrogen in the volumes, the main hydrogen-containing compound on the surface of the
atmosphere is likely to be very short because it is rapidly consumed by Earth. Taking estimates of current hydrogen loss to space from
different processes and it also escapes into space. Another study gives Table 25, and a mass for the hydrosphere of 1.4 *1024 g and that the
estimates for the total consumption rate of hydrogen by the atmo- oceans started to appear 4.4 Gyears ago (Wilde et al., 2001), we can
sphere, or its' consumption by various so-called "sinks" at a rate of 70 obtain a cumulative total loss of water from the hydrosphere of
Tg/year (784 * 109 m3/year) (Warneck, 1999). In the Section 3.5 0.64–2.25 Tg water/year, which amounts to a cumulative loss of
Biological activity of this review it was shown that soils are very effi- 2.8–9.9* 1021 g (0.2–0.7 %) of the total ocean volume since the ocean’s
cient at consuming hydrogen. However, biologic activity is not the only initial formation. However, isotopic studies of deuterium to hydrogen
important sink for this gas. Atmospheric sinks include oxidation by (D/H) ratios in water samples from rocks and ocean water lead to
hydroxyl radicals and escape into space. Photolytic oxidation was es- higher percentages for the reduction in ocean volume through time. The
timated to consume 10 Tg/year (Hawkes, 1980) and 8 ± 3 Tg/year studies sugges that 26% (Pope et al., 2012) to 36% (Yung et al., 1989)
(Seiler and Conrad, 1987). More recent studies give a higher number of of the present ocean volume may already been lost. Indeed, some stu-
19 ± 5Tg/year (Ehhalt and Rohrer, 2009; Novelli et al., 1999). Pho- dies suggest that hydrogen losses in early Earth history of the Earth
tolytic oxidation is of great significance because it affects the ozone were much greater, up to 1–5 * 1014 H2 molecules cm−2 s−1 (Pepin,
cycle. It is described in more detail in the Section 5.3 Atmosphere. 1991), which is 6 orders of magnitude greater than present day loss
The escape of hydrogen from the atmosphere is an extremely im- estimates (see the Section 3.6 Atmospheric hydrogen). Such processes
portant aspect of this review because it is by this mechanism that the may have depleted the Earth of water contributing to the oxidation of
Earth loses part of its mass (discussed in the Section 5.1 Hydrogen as a its surface because the oxygen from original water would remain at the
component of Earth degassing). The three generally accepted mechan- Earth’s surface.
isms for hydrogen escape from the atmosphere are: thermal, non- On the other hand, there is the possibility of hydrogen being trapped
thermal and polar wind (Yung et al., 1989). Thermal escape is also in the form of protons from the Solar wind by the Earth’s magnetic field.
called "Jeans escape", which is described by a Maxwell distribution It was estimated that the mean flux of protons penetrating over one pole
accounting for the kinetic energy and mass of a molecule determining is 1024 protons/s with variations of one order of magnitude (Hardy
its velocity. The less massive is a molecule of gas, the higher is the et al., 1989). Assuming all protons recombine to H2, this gives 0.8 g/s
average velocity of the same molecule at a given temperature, and the (0.000025 Tg/year), a negligible number compared to estimates of
higher is the likelihood of that molecule reaching the Earth's gravita- hydrogen escape rates.
tional escape velocity. It is for this reason that hydrogen escapes more
readily from the atmosphere than any other gas. Models have shown 3.7. Volcanoes and hydrothermal systems
that the escape of hydrogen from the Earth's gravitation at 100 km of
altitude occurs by conversion of H2 into atomic hydrogen in the ther- Hydrogen is the third most prevalent volcanic emanation after
mosphere (Hunten and Strobel, 1974). Non-thermal escape involves water and CO2. The current hypothesis used to explain its presence
collisional processes energizing hydrogen species above thermal en- depends on the nature of the lava, because the composition of the gases
ergies. Polar wind is a term defined to explain the movement of charged are in thermal equilibrium with molten rock (Соколов, 1971). A con-
particles along the lines of the Earth’s magnetic field. Hydrogen escape centration of 1% H2 is expected at equilibrium temperatures of around
is also controlled by its source and the effectiveness of upward transport 500°C with an FMQ (Fayalite, Magnetite, Quartz) buffer (Arnorsson,
(Yung et al., 1989). The Earth’s geocorona, detected in 1968 by the 1985). It has been reported that in geothermal fluid systems the mole
observations from the OGO-5 spacecraft, is composed mainly of hy- fraction of hydrogen x(H2) is usually lower than 10−3 at 200°C
drogen atoms, and was also photographed by Apollo 16 Moon landing (Arnorsson, 1985). However, as shown in examples from Tables 5 and
expedition. A recent study demonstrated that a “geotail” composed of 6, hydrogen concentrations in volcanic gases and hydrothermal systems
hydrogen atoms extends beyond the orbit of the Moon (Baliukin et al., may be much higher than theoretical water equilibrium concentrations
2019). Because of the pressure generated by the Solar wind radiation, indicating that other sources are involved. Many studies suggest hy-
the geocorona is compressed on the day side and extended on the night drogen is at the origin of volcanic activity. They are discussed in the
side of the planet forming a hydrogen “tail” downwind the planet. Section 5.1 Hydrogen as a component of Earth degassing.
The calculated that hydrogen escape rate from Earth to space is 1–4 Simple thermal decomposition of water is improbable because the
*108 atoms/cm2*s (Hunten, 1990). Using the data from the article equilibrium of the reaction is unfavorable for hydrogen generation. The
(5*1026 atoms/s = 108 atoms/cm2*s) we obtain 0.8–3.3 kg/s. The water decomposition reaction is non-spontaneous except at very high
author states that the most probable value is 2.8*108 atoms/sm2*s, temperatures. Even at 1000–1500°C the percentage of thermally dis-
which is equivalent to 2.3 kg H2/s (0.07 Tg/year) (Hunten, 1990). This sociated water is low. It begins to become significant at the higher
is close to other estimates of 3 kg H2/s (0.09 Tg/year) (Catling and temperatures of 2000–3000°C and low pressure (0.1 bar) (Соколов,
Zahnle, 2009) and 8 kg H2/s (0.25 Tg/year) (Белов et al., 2009). An- 1966b; Lede et al., 1983).
other article suggests that the mean escape rate of hydrogen from the Calculated estimates of H2 released by volcanoes were only based on
atmosphere cannot be much more than about 2*108 cm−2s−1 the assumption that H2 and CO2 are in equilibrium with the FMQ
(equivalent to 2.4 kg H2/s or 0.08 Tg/year) (Brinkmann, 1971). It is buffer. Flow values of 4.8 ± 3.6* 1012 mol/year (9.6 ± 7.2 Tg/year)
very close to the estimated daytime flux of hydrogen based on in situ were estimated by (Holland, 2002). Hydrogen flow from the most
34
active volcano in Antarctica, Erebus, was estimated at 30 g/s (0.001 The most recent review gives a value of 15 ± 6 Tg/year (Ehhalt and
Tg/year) (Moussallam et al., 2012) and for Mt. Etna in Europe at Rohrer, 2009) for hydrogen produced from the burning of biomass.
0.00065 Tg/year (Aiuppa et al., 2011). Hydrogen fluxes from subaerial There are numerous discoveries of hydrogen in coal basins (see
volcanoes is estimated at 0.9–3.4*1011mol/year (0.18–0.7 Tg/year), Table 25). The highest hydrogen concentrations were observed for coal
and from mid-ocean ridge volcanoes at 0.07–0.27*1011mol/year samples associated with the final stages (V-VI) of coal maturation
(0.02–0.05 Tg/year) (Canfield et al., 2006). Another study indicates (Гресов et al., 2010). Indeed, it is likely that hydrogen in coal basins is
that annual hydrogen flow from subaerial volcanoes is poorly under- related to coal metamorphism. Total hydrogen on a global basis pro-
stood and estimates it at 0.24 Tg/year (0.24 Tg/year) (Stoiber, 1995). duced from coal fields is estimated to be around 0.0014 Tg/year
Isotope studies show that hydrogen released from hydrothermal (Koyama, 1963), a very low number when compared to other sources.
systems at mid-ocean ridges is of volcanic origin. Using δ13C data for
the coexistence of methane with carbon dioxide in hydrothermal fluids 3.9. Anthropogenic sources
from the East Pacific Rise, showed that these gases could have been in
isotopic equilibrium only at temperatures between 550 and 750°C. The Some studies suggest that hydrogen in the atmosphere comes from
study states that “at such high temperatures, neither methane nor hydrogen automobile tailpipe emissions (Barnes et al., 2003). Some authors even
could be generated by olivine or enstatite hydrolysis because these minerals consider the combustion of fossil fuels as a major source of atmospheric
are thermodynamically stable with respect to their hydrolysis products. The H2 (Ehhalt and Rohrer, 2009; Novelli et al., 1999; Warneck, 1999)
dissolved gases in high-temperature hydrothermal vents are therefore the which is not the case, as shown in the Table 25. Calculated anthro-
products of the degassing of molten or quenched basaltic magma with an pogenic hydrogen emissions are in the range of 4.28–5.13 kg/year* per
oxidation state in the region of the FMQ buffer” (Apps and Van De Kamp, person for the population of the North-East USA (Barnes et al., 2003).
1993). However, as has been shown in the Sections of this paper 3.1 Other studies have estimated anthropogenic emissions of H2 to be
Deep-seated hydrogen and 5.1 Hydrogen as a component of Earth de- 20 ± 10 Tg/year (Seiler and Conrad, 1987; Warneck, 1999), close to
gassing, the hydrogen derived from such places could be of a deeper further estimates of 15 ± 10 Tg/year (Novelli et al., 1999). The most
origin. recent review gives value of 11 ± 4 Tg/year (Ehhalt and Rohrer,
Decomposition of hydrogen sulfide has been mentioned in some 2009).
studies as a possible source of hydrogen. One study, where hydrogen When hydrogen was discovered in some wells, it was proposed that
was discovered in fumarole gases from the Mt St Helens volcano in the it formed as a result of the reaction of water with steel casing (Bjornstad
USA, suggests that hydrogen was produced by the reaction of H2S with et al., 1994a; Bjornstad et al., 1994b; Chapelle et al., 1997), iron casing
water (Evans et al., 1981). One more study suggests that hydrogen may (Chapelle et al., 1997), with tubing made of black iron (Bjerg et al.,
come from the reaction of various sulfides with water and atmospheric 1997) or equipment used for the extraction of gas and liquid from rock
oxygen (Молчанов, 1968). The authors propose that hydrogen could be (Левит, 1954). In another example hydrogen concentrations were ob-
generated through a similar process to that which results from the served to be rising in monitoring wells over time (Стадник, 1970).
crushing and grinding of minerals (Молчанов, 1981). On closer in- When all the water was pumped from the wells, hydrogen concentra-
spection this study reveals that the hydrogen detected was most likely a tions decreased to near-zero. The authors attributed the hydrogen to
by-product of the reaction of hydrogen sulfide with copper in the mill corrosion processes in the well (Стадник, 1970). However, if hydrogen
reaction chamber. Indeed, in all runs, where H2S solution was added, is generated by reactions of water with metal well casing it should be
yields of hydrogen were much higher than in experiments where no H2S observed systematicaly in most wells with iron casing worldwide (as-
was used. For this reason, hydrogen generation data from sulfide re- suming, of course, that it was being sampled), which is not the case
actions appear to be ambiguous with regard to whether the hydrogen (Войтов and Осика, 1982). A recent experiment has demonstrated that
generated was due to natural causes or experimental error. the generation of hydrogen by reaction of water with steel slag is
Decomposition of H2S was suggested as a possible source of hy- negligeble at neutral pH, but can be stimulated by the addition of acids
drogen in a study of the isotopic compositions of hydrogen from hy- (Crouzet et al., 2017).
drocarbon wells in the Russian Federation. It was shown that in some
cases the δD of free hydrogen was equivalent to the δD of water from 4. Total global hydrogen budget and hydrogen cycle
some aquifers, but in other cases the δD was too low to originate from
ground water (Зыкин, 2009). However, the mechanism used to explain By combining together numbers from the previous sections it is
the presence of hydrogen as being derived from H2S is likely valid in possible to compare them to get an idea for the total volume of natural
only a few rare cases, because H2 has been detected mainly in H2S-free hydrogen at the Earth’s surface. Table 25 contains the available esti-
zones, indicating that hydrogen is not likely to be related to the pro- mates from the literature and proposes a first approach for defining a
cesses of H2S decomposition (Войтов and Осика, 1982). global hydrogen cycle.
The first remarkable thing about this table is the wide range in es-
3.8. Decomposition of organic matter timates. Different authors sometimes differ by orders of magnitude, as is
the case for hydrogen production from the oceanic crust and its basaltic
Several studies mention the decomposition of organic matter as a layer. Also, estimates from different studies may overlap, for example,
possible source of hydrogen without going into details and providing with the values obtained for hydrogen produced from the oceanic crust.
solid arguments. One interesting study shows that ground water close to Another important point that all currently available estimates are based
petroleum deposits is richer in hydrogen than ground water close to on the assumption that hydrogen is generated mainly from water re-
natural gas deposits. The authors hypothesize the origin of this hy- actions with rocks. Therefore, all these estimates and their totals are
drogen to be the result of the decay of organic matter (Зингер, 1962). approximate and obviously should not be taken as definite numbers.
Laboratory experiments show that hydrogen, up to 10.9%, forms during Total hydrogen production obtained by the addition of different sources
the thermal decay of kerogen at 300°C (Богомолов, 1976). However, at is higher than estimates made by other authors (Seiler and Conrad,
such temperatures in the natural environment the hydrogen generated 1987; Novelli et al., 1999; Warneck, 1999). However, none of the ar-
would immediately be consumed in reactions with oxygen-containing ticles (Seiler and Conrad, 1987; Novelli et al., 1999; Schmidt, 1974) and
compounds to produce water which is thermodynamically more stable. books (Warneck, 1999) which attempted to evaluate a total planetary
Burning of biomass is considered by some studies as an important hydrogen budget accounted for a geologic source in their estimates!
source of hydrogen and it is estimated to give 20 ± 10 Tg H2/year It should be noted that to date (2019) there has been no compre-
(Seiler and Conrad, 1987) or 16 ± 5 Tg H2/year (Novelli et al., 1999). hensive and systematic attempt to evaluate the total volume of
35
Table 25
Estimates for sources and sinks of hydrogen in nature.
Sources x109m3 H2 /year Tg/year (=106 t/year) Reference
Geological
Mid-oceanic rift system 1.3 0.12 (Welhan and Craig, 1979)
2 0.18 (Charlou et al., 2012)
3.7 0.33 (Cannat et al., 2010)
4.3 0.38 (Keir, 2010)
Oceanic crust, by various oxidations 10 ± 7 0.9 ± 0.6 (Bach and Edwards, 2003)
Oceanic crust serpentinization 1.8–2.9 0.16–0.26 (Canfield et al., 2006)
8.5 0.76 (Sleep and Bird, 2007)
22.4 2 (Worman et al., 2016)
Ophiolite massifs 2–4 0.18–0.36 based on (Zgonnik et al., 2019)
Basaltic layer of the oceanic crust 84 7.5 (Sleep and Bird, 2007)
139 12.6 (Holloway and O’Day, 2000)
Precambrian basement 0.45–4.3 0.04–0.38 (Sherwood Lollar et al., 2014)
Volcanoes and hydrothermal systems 108 ± 81 9.6 ± 7.2 (Holland, 2002)
Subaerial volcanoes 2–7.7 0.18–0.69 (Canfield et al., 2006)
2.7 0.24 (Stoiber, 1995)
Mid-ocean ridge volcanoes 0.2–0.6 0.02–0.05 (Canfield et al., 2006)
Coal metamorphism 0.02 0.0014 (Koyama, 1963)
Deep-seated hydrogen ? ?
Sub-total for geologic 254 ± 91 23 ± 8
Estimates for total geologic hydrogen by other studies 67 6 (Gilat and Vol, 2005; Gilat and Vol,
2012)
6 0.54 (Voitov and Rudakov, 2000)
0.3 0.027 (Giardini and Melton, 1983)
Atmospheric
CH4 oxidation by OHa 257 ± 90 23 ± 8 (Ehhalt and Rohrer, 2009)
Oxidation of nonmethane hydrocarbonsa 202 ± 78 18 ± 7 (Ehhalt and Rohrer, 2009)
Sub-total for atmospheric 459 ± 119 41 ± 11 (Ehhalt and Rohrer, 2009)
Biological
Biological N2 fixationa 27–54 2.4–4.9 (Conrad and Seiler, 1980)
34 ± 22 3 ± 2 (Ehhalt and Rohrer, 2009)
Burning of biomassa 224 ± 112 20 ± 10 (Seiler and Conrad, 1987; Warneck,
1999)
Oceansa 45 ± 22 4 ± 2 (Seiler and Conrad, 1987)
Anthropogenic emissionsa 123 ± 45 11 ± 4 (Ehhalt and Rohrer, 2009)
Sub-total for biological 412 ± 106 37 ± 9.5
Estimates for total biological hydrogen by other studies 0.2 0.02 (Koyama, 1963)
Total for geological, atmospheric and biological 1125 ± 183 100 ± 16
Estimates for total for all sources by other studies (no geologic sources were taken into 974 ± 437 87 ± 39 (Seiler and Conrad, 1987)
account) 862 ± 179 77 ± 16 (Novelli et al., 1999)
907 81 (Warneck, 1999)
448–1456 40–130 (Adushkin et al., 2006)
Sinks
Oxidation by OHa 90 ± 34 8 ± 3 (Seiler and Conrad, 1987)
110 9.8 (Hawkes, 1980)
Uptake by soilsa 1008 ± 224 90 ± 20 (Conrad and Seiler, 1981; Seiler and
Conrad, 1987)
1344 120 (Hawkes, 1980)
672+336
−224 60+30
−20 (Ehhalt and Rohrer, 2009)
986 ± 123 88 ± 11 (Rhee et al., 2006)
Uptake by oceans ? ?
Consumption by deep microbial communities ? ?
Escape to space, estimates 0.8–2.8 0.07–0.25 (Hunten, 1990; Catling and Zahnle,
2009; Белов et al., 2009; Brinkmann,
1971)
Escape to space, estimates based on in situ satellite measurements 0.9 ± 0.3 0.08 ± 0.03 (Breig et al., 1976)
Total sinks 1142 ± 282 102 ± 25
Estimates of total sinks by other studies 1098 ± 258 98 ± 23 (Seiler and Conrad, 1987)
840 ± 459 75 ± 41 (Novelli et al., 1999)
780 70 (Warneck, 1999)
885+336
−224 79+30
−20 (Ehhalt and Rohrer, 2009)
a
More estimates from different authors are available in (Ehhalt and Rohrer, 2009; Price et al., 2007).
geologically generated hydrogen. In every study reviewed where a every one or two decades which is probably due to progress in an un-
value was given it was not the main subject of the study, but rather a derstanding of the widespread occurrence of natural hydrogen. In 1983
secondary topic (Voitov and Rudakov, 2000; Gilat and Vol, 2005; total hydrogen volumes were estimated to be 0.027 Tg/year (Giardini
Giardini and Melton, 1983; Gilat and Vol, 2012). It is interesting to and Melton, 1983), in 2000: 0.54 Tg/year (Voitov and Rudakov, 2000)
note, that estimates have been increasing by an order of magnitude and in 2005: 6 Tg/year (Gilat and Vol, 2005; Gilat and Vol, 2012). For
36
comparison purposes, the current world industrial production of hy- shown experimentally that in tectonites the velocity of fluid migration
drogen for 2015 was 97.4 Tg (Runte, 2015) and has been projected to is several orders of magnitude higher than in fractures. The mechanism
grow to 2750 Tg by 2080 at a peak hydrogen economy (Barreto et al., consists of sliding films of fluid along foliation surfaces in tectonites
2003). (Летников, 2000). Propagation of light gases during Earth degassing
This review shows that previous estimates of hydrogen flux pro- creates porosity with high internal pressures resulting in lithospheric
duced from geologic sources have largely been underestimated. It is instability. (Gufeld and Matveeva, 2011). Some researchers have pro-
interesting to point out, that the author of the most recent estimates for posed that variations in hydrogen concentration could be responsible
globally generated total hydrogen, before this review, reached the for changes in the velocity of seismic waves (Гуфельд, 2012).
conclusion that geological sources for hydrogen have been under- It is known that deep faults play a major role in the migration of
estimated (Voitov and Rudakov, 2000). It is very likely that current natural gases and other fluids (Перчук, 2000; Летников, 2000). It is
estimates in this review are lower than they should be, because they do possible that such zones are not only acting as conduits but can also be
not include the data on flux of hydrogen from recently discovered the result of diagenetic changes in porosity and permeability resulting
seepages with diffusive flow and for the flux of deep-seated hydrogen from the effects of highly chemically reactive gas such as hydrogen. It
from diverse geological settings. has been shown experimentally that exposure of non-metallic materials
such as calcite, dolomite, antigorite, etc. to hydrogen at low pressure
5. Hydrogen and natural phenomena reduces their microhardness and crystal constants. This means that
hydrogen diffusion can cause weakening and embrittlement of non-
This section discusses the role hydrogen plays in the Earth’s struc- metallic materials. As a result, hydrogen migration along fault zones
ture, how hydrogen flow influences natural phenomena and how hy- might indicate not only the location of fault zones, but also the activity
drogen can be used for the monitoring of natural environments. of the faults (Su et al., 1992). Another study showed experimentally
that the strength of limestone decreases by 1.5–1.7 times with an in-
5.1. Hydrogen as a component of Earth degassing crease in brittleness after being saturated with hydrogen at 100°C and
PH2 = 8MPa for 48 h (Levshounova, 1991). Based on the aforemen-
Earth degassing has been proposed as the source for Earth's atmo- tioned experiments hydrogen not only migrates along fractures but it
sphere (Хитаров and Войтов, 1985). It is believed that hydrogen may also affect their development and dispersion.
played a very important role in this process in the past and that the This property of hydrogen may be at the origin of recently dis-
early Earth’s atmosphere was hydrogen-rich (Tian et al., 2005). Hy- covered hydrogen seepages described in the Section 2.2 Diffusive flow.
drogen continues to play an important role if, as this author and others It is thought that hydrogen seepages can be identified on the surface by
propose, the Earth is constantly degassing hydrogen (Осика et al., topographic circular to sub-circular shallow depressions. The formation
2002; Моисеенко and Сахно, 1982). Some authors describe this proof these circular depressions seen as the result of a process of chemical
cess as gas “breathing” (Войтов and Осика, 1982; Войтов, 1975; dissolution (diagenesis) of the rock by hydrogen (Larin et al., 2015;
Шестопалов and Макаренко, 2013). However, a more correct phra- Zgonnik et al., 2015). Hydrogen may react with rocks creating porosity
seology could be “exhalation”. Degassing of the Earth is classified as because the products of hydrogen reactions with rock are water and
either “hot” or “cold” by these authors. Hot “exhalation” includes vol- soluble mobile compounds which may tend to migrate away from the
canic activity and can be mainly characterized by oxidized gas species. reaction zone. The porosity created by hydrogen flowing though hy-
Cold “exhalation”, which is sometimes called “cold degassing”, is re- drogen-enhanced porosity will in turn promote the creation of addi-
lated to gas seeping from surface depressions, faults, gas chimneys, tional porosity in the form of a preferential hydrogen migration
pockmarks, etc. By chemical type, gases from "cold degassing" are channel. I.e. more hydrogen will create more porosity. As a result, in-
mainly reduced. Because of its quiescent nature, cold degassing pro- itially diffused flow will concentrate in vertical “streams” or plumes.
cesses happen in background and are often poorly studied or not stu- The origin of hydrogen in such seepages may be related to the degassing
died at all. It is for this reason that volumes of gas from cold-degassed of deep-seated or primordial hydrogen (Larin et al., 2015; Zgonnik
gases have been underestimated (Шестопалов and Макаренко, 2013). et al., 2015).
Molecular hydrogen flow is thought to be very irregular and un- Indeed, some works (Gilat and Vol, 2005; Su et al., 1992;
stable in time (Voitov and Rudakov, 2000; Войтов et al., 1995). It is Овчаренко, 1967; Walshe, 2006) refer to a primordial origin as a
hypothesized to likely be controlled by the geodynamic activity deep possible explanation for the observed hydrogen (discussed in detail in
within the Earth's interior and in probable association with preferential the Section 3.1 Deep-seated hydrogen).
vertical permeability pathways (Войтов et al., 1995). Therefore, hy- The following works cited assume that the Earth has a deep re-
drogen should be an excellent indicator for processes happening in servoir of hydrogen that has been leaking upwards to the surface,
depth (Hernández et al., 2000). Hydrogen mapping should be capable probably episodically, through geologic time. While this is a plausible
of revealing structural, lithologic and geodynamic features otherwise model it should be noted that it has yet to be generally accepted and the
attributable to previously unidentified causes (Войтов et al., 1995). The cited works are theoretical. However, these theories propose that
extensive review of hydrogen occurrencies in the territories formerly should the Earth’s interior be rich in hydrogen, which is chemically
part of the soviet camp show spatial distributions of hydrogen de- bonded in the form of hydrides, their progressive decomposition would
tectionsto be a reflection of Earth degassing via geological structures sustain the continuous degassing of hydrogen over geologic time
and formations (Shcherbakov and Kozlova, 1986). (Сывороткин, 2002; Ларин, 2005; Бембель et al., 2011). These au-
Hydrogen affects the structure and chemical composition of the thors suggest that hydridic fluids from deep within the Earth are very
rocks it passes through (Гуфельд, 2012). It has been reported that sa- important in mineral systems. The action of hydridic fluids can effec-
turation of rocks with light gases changes their crystal structure, creates tively be used in theories of volcanism, mineral system formation, an-
porosity and changes their volume. The authors suggest that the crea- oxia, evolution of ocean chemistry, climate change, mass extinction and
tion of porosity and fracturing at the depths of the Mohorovicic dis- more. It is suggested that all these phenomena can be explained using a
continuity ("Moho") could be the result of hydrogen and helium seeping hypothesis of episodic hydrogen flow from the Earth's core (Walshe
from greater depths. They suggest that below the Moho layer, diffusion et al., 2005). Another work points out that flows of hydridic fluid from
of hydrogen and other gases is possible and mainly happens within the Earth's core can sustain a redox gradient between a reduced Earth
crystal lattice vacancies and dislocations (Гуфельд, 2012). Another core and oxidized outer layers. The authors argue that this gradient can
study suggests that at depths where there are no open fractures hy- be used to explain in simple ways many geologic phenomena (Walshe,
drogen and other fluids migrate via different mechanisms. It has been 2006). Another study advances the same idea, that hydrogen affects the
37
character of redox processes in the crust and their intensity (Войтов 5.2. Hydrogen and life
and Осика, 1982). Ascending hydridic flows from the mantle are pro-
posed to account for the melting of silicates. Others have suggested that Hydrogen is an excellent source of energy for living organisms
hydrogen plays a key role in volcanic activity (Gilat and Vol, 2005; (Morita, 1999; Gregory et al., 2019). In microbial systems H2 transfer
Gilat and Vol, 2012; Портнов, 2003; Портнов, 2010; Персиков et al., creates the basis for organism-to-organism interaction. It is an im-
1986; Велинский, 1970). In which case, it may play a dual role: that of portant mediator for electron transfer, energy regulation and commu-
a heat-transfer agent (Letnikov et al., 2011) and to release heat while nity interaction (Hoehler, 2005). Many bacteria, including the very
undergoing oxidation (Белов et al., 2009). Others note that hydrogen well-studied Escherichia Coli, are able to generate energy through the
plays a major role in the volcanic eruption of ignimbrites (Щека and oxidation of H2. As oxidizing agents bacteria can use not only oxygen,
Гребенников, 2009). A recent study proposed that a sudden release and but also carbon dioxide, nitrogen, sulfates, nitrates and other electron
ignition of hydrogen may explain the formation of Libyan desert glass, acceptors (Cammack, 2001).
which are fragments of molten silica found at the surface in Libya and Many prokaryotic microorganisms use H2 as an energy source,
Egypt (Saul, 2019). In one study, it was experimentally shown that competing for access to it (Fedonkin, 2009; Schwartz and Friedrich,
hydrogen can affect the process of differentiation of molten rocks 2006). They are confined to the base of the phylogenetic tree, which
(Персиков et al., 1986). It has been therized that hydrogen could play a means that hydrogen consumption is one of the oldest and most basic
role in the formation of outer core plumes (Letnikov and Dorogokupets, properties of life. Indeed, about 30% of microorganisms have genes
2001). Other works propose that hydrogen rising from depth plays a encoding hydrogenases, a principal type of enzyme for H2 metabolism
role in the formation of hydrothermal and ore-forming systems (Colman et al., 2017). A recent study sequenced and classified several
(Павлов, 1977) and also in the formation of "juvenile" water (newly thousand of hydrogenases (Greening et al., 2016). They were recovered
created water in the interior of the Earth) (Войтов and Осика, 1982). from all types of environment, indicating that hydrogenases are broadly
The origin of water on Earth is an extremely important topic but used and sustain the survival and growth of microoganisms in a variety
there has yet to be agreement on how it appeared. A widely accepted ecosystems. This signifies that hydrogen was a primary component of
hypothesis that water was delivered by comets has been criticized and redox chemistry in the first living systems. It also indicates that initial
seems to have been ruled out by isotopic constraints (Drake, 2005). levels of hydrogen in early Earth history might have been several orders
Proposed in its place, the hypothesis of so-called “wet accretion” states of magnitude higher than they are today. Even today hydrogen plays an
that water was trapped during the Earth’s formation, but does not ex- important role in microbial chemistry (Hoehler, 2005). Studies of mi-
plain how this water came to be preserved during the assumed stages of crobial communities show that the evolution of life on the Early Earth
the Earth’s melting and subsequent heavy bombardment by planetary was related to reactions of H2 with oxidizing compounds (Fedonkin,
debris. However, if the Earth was initially hydrogen-rich the origin of 2009; Schwartz and Friedrich, 2006). A strongly reducing atmosphere
water ceases to be an issue but rather becomes a logical consequence of is much more favorable to the synthesis of bioorganic molecules than
the planet’s continual degassing of hydrogen (Larin, 1993). Moreover, more oxidized atmospheres (Miyakawa et al., 2002). Indeed, it was
the quantity of water should increase with time, even at present, an proposed that an Archean atmosphere could have contained up to 30%
important point yet to be considered by scientists studying the rise and hydrogen (Wordsworth and Pierrehumbert, 2013). The emergence of
fall in sea levels over geologic time (an extremely significant point at life under such conditions would have been much more efficient than in
that, if it these hypotheses prove to be valid). hydrothermal systems (Tian et al., 2005). It also makes it probable that
A recent 632-page monograph in describes some aspects of Earth the first organisms used hydrogen rather than light as an energy source
degassing based on an analysis of published sources and research (Kral et al., 1998). An analysis of early anaerobic ecosystems shows that
(Шестопалов et al., 2018). Consideration is given to fluid-conducting an early-Earth hydrogen-based ecosystem may have been dynamic, but
systems in the crust, characterization of various types of conduit not as active as the present marine biosphere (Canfield et al., 2006).
structures created by or facilitating degassing, degassing cyclicity, role A readily available electron acceptor in many environments is
of degassing in the generation of oil and gas, its action on climate, carbon dioxide. Hydrogen together with water and a small amount of
evolution of the biosphere and hazards caused by degassing. The au- minerals is all that simple forms of life would need to exist. Most of
thors of the monograph highlight what they believe are the important, them survive by reducing carbon dioxide to produce methane, from
but still underestimated impacts of the Earth’s degassing of hydrogen whence comes the term "methanogen". Methanogens were reported to
and other fluids. be present in every type of soil, and even in dry desert environments
The hydrogen “exhalation” of our planet can be seen as the process (Conrad, 1996). Certain methanogens can consume hydrogen at partial
of our planet's loss of mass to space (Войтов and Осика, 1982). From a pressures as low as 4 Pa (Kral et al., 1998). However, ambient atmo-
thermodynamics point of view this allows for the characterization of spheric concentrations of hydrogen are not sufficient for their growth
the Earth as an open system (which is exchanging mass and energy with (Conrad, 1996) and require an external source of H2.
its surroundings) and not as a closed system (which is exchanging only Estimates show that 10–50% of the total methane produced in an-
energy). Current planetary models have considered mass exchange to oxic soils is synthesized by methanogenic microorganisms from hy-
be negligible but in view of the volumes of hydrogen being lost to space drogen (Conrad, 1996). Biogenic methane has been found all over the
discussed in this review this is not necessarily accurate. This point is world (Kotelnikova, 2002). It is produced not only in soils, but in the
important for interpretations of terrestrial evolution. It appears that Earth’s crust as well. It has been reported that deeply-buried hydrogen-
through geologic time the planet is evolving towards more structural based methanogenic communities exist within the planet (Chapelle
ordering (formation of the core, crust, mountains, etc.), i.e. entropy of et al., 2002). A large accumulation of methane thought to have been
the planet as a thermodynamic system is decreasing, which contradicts generated by hydrogenotrophic methanogens is believed to exist be-
the second law of thermodynamics if the Earth is considered to be a neath the West Antarctic ice sheet (Michaud et al., 2017). In deep
closed system. This is possible only if the planet is considered to be an aquifers chemolythoautotrophic (those obtaining energy from the oxi-
open system, where mass and energy are being exchanged with its dation of inorganic compounds) microorganisms consume hydrogen to
surroundings with a corresponding removal of entropy. Hydrogen lost produce methane. These microorganisms greatly outnumber those that
to space appears to be a good candidate for the role of an entropy re- could grow on organic compounds (Kotelnikova, 2002). It is interesting
moval agent (Larin, 1993; Ларин, 2005). to note, that isotopic studies of methane emissions into the atmosphere
Taking into account the considerations of this section, the topic of show that since 2006, biogenic CH4 has become a main source of this
hydrogen Earth’s degassing deserves more attention. greenhouse gas (Schaefer et al., 2016; Nisbet et al., 2019). This raises
the issue of whether there might be a causal link to the possible increase
38
in planetary hydrogen degassing with an increase in methane, because maintain the deep-crust habitats (Sleep and Zoback, 2007). The rate of
with added hydrogen, methanogens will generate more methane. hydrogen consumption by prokaryote organisms is probably greater
Moreover, as hydrogen inhibits the decomposition of methane in the than the rate of input of hydrogen to a hydrogentrophic habitat thereby
atmosphere (see Section 3.6 Atmospheric hydrogen) the overall quan- explaining the low hydrogen content in the majority of environments
tity of methane will increase, with consequences on climate change. (Fedonkin, 2009). The last remark is very important and should be
There are many examples of deep ecosystems using hydrogen as an considered in any study of natural hydrogen.
energy source, the so-called subsurface lithoautotrophic microbial Because hydrogen is readily used by microbial communities, which
ecosystems (SLiMEs) (Morita, 1999; Nealson et al., 2005). Such com- are widespread on the Earth’s surface and subsurface, they should be
munities were discovered in deep basalt aquifers (Stevens and taken into account during the design of geology-related projects. For
McKinley, 1995). There is strong evidence for hydrogen-driven eco- example, it has been proposed that a microbial hydrogen-consuming
systems hosted in deep granitic rock aquifers (Pedersen, 1999), for web can be integrated into the design of underground constructions
subsurface habitats within serpentinites (McCollom and Seewald, (such as nuclear waste repositories) to reduce risks associated with
2013), for hyperthermophilic communities beneath active deep-sea hydrogen build-up (Bagnoud et al., 2016). Another work shows that in
hydrothermal vents (Takai et al., 2004) and for microbial ecosystems in the presence of sulfates, they can be chemically reduced by hydrogen
seafloor fault zones (Suzuki et al., 2015). Hydrothermal hydrogen vents into a toxic hydrogen sulfide (Boylan et al., 2019). A recent compre-
are true oases of life in the deep ocean (Геворкьян et al., 1990), and hensive review combined many examples on how hydrogen-consuming
hydrogen flow could be used to identify an important feature of an microorganisms can impact underground projects like gas storage,
explanation for their existence. Taking into account facts about me- carbon capture and radioactive waste disposal (Gregory et al., 2019).
thanogens, the question arises as to the possible connection between the Recently, sub-circular depressions were discovered to be seeping
activity of methanogens on the ocean floor and hydrogen seeps molecular hydrogen (see Section 2.2 Diffusive flow). Observations show
(Mikucki et al., 2003) and the formation of methane hydrate deposits. A that soils at hydrogen seep locations lose their humus, reducing their
recent study reporting hydrogen and helium concentrations in hydrate- fertility (Суханова, 2012). This effect of hydrogen mediated soil ferti-
bearing marine sediments showed relatively high concentrations of lity loss has been confirmed though field observations and experimen-
these gases, and in particular, over fault zones (Шакиров et al., 2016), tally in the laboratory. Hydrogen also affects the diversity of microbial
which indicates that hydrogen and helium gases are likely seeping from communities in soils, decreasing their total mass and increasing the
depth. proportion of bacteria in soil (Sukhanova et al., 2013). Another work
Hydrogen-based microbial communities can exist under extreme confirms that at hydrogen seep locations the microbiota of soils is af-
conditions, such as the +122°C hot springs of mid-oceanic ridges fected. The total quantity and biomass of bacterial cells, as well as
(Colman et al., 2017) or -13°C cold brines of Antarctic lakes (Murray fungal spores and the length of fungal and actinomycetal mycelium, are
et al., 2012) where no other energy (food) sources are available. The decreased (Polyanskaya et al., 2014). In laboratory tests of soils treated
recent discovery of microorganisms in Antarctica that use only atmo- with hydrogen fungal spores numbers decreased to zero after a week
spheric H2, CO and CO2 as an energy source (Ji et al., 2017), greatly and after 2 weeks actinomycetes and fungal mycelium could not be
extends the limits within which life can exist. It is suggested that similar isolated (Polyanskaya et al., 2017). A very recent study confirmed ex-
life forms may exist on Mars and Europa (Gregory et al., 2019; Chapelle perimentally that treatement of soil samples with hydrogen changes the
et al., 2002). Finally, could it be possible that new life forms are pre- microbial community and this is probably a major sink for hydrogen
sently appearing in isolation deep within the Earth but in contact with a seeping from topographic depressions (Myagkiy et al., 2020).
source of hydrogen? Because if new life appeared once in the past, why Hydrogen may also affect the biochemistry of higher plants. One
would it not be possible for it to be an on-going process? study shows that plants growing in the presence of molecular hydrogen
The existence of a “deep hot biosphere” was predicted in the early in air, change their spectral parameters indicated by an increase in the
1990's (Gold, 1992). A recent paper comprehensively reviews the state quantity of chloroplasts and carotenoids (Тимченко et al., 2014). A
of the art 25 years later (Colman et al., 2017). It was proposed that the very recent study on the influence of hydrogen on plants under natural
total mass of the deep biosphere may be comparable to that of all life at and laboratory conditions demonstrated that prolonged exposure to
the Earth's surface (Gold, 1992). The model requires a continuous influx high concentrations of H2 led to inhibition or fading of agricultural
of hydrogen to maintain the activity of SLiMEs (Nealson et al., 2005; crops (Sukhanova et al., 2019).
Fedonkin, 2009). Indeed, genomic studies of deep-living microorgan- Some researchers, by assuming there is a high flow of deep-seated
isms show that they have an order of magnitude more copies of the hydrogen, propose that it may affect the biological productivity of the
hydrogenase sequence than organisms from surface environments, de- oceans and paleobasins (Syvorotkin, 2013), speciation and other bio-
monstrating the importance of H2 in their metabolism (Colman et al., logical processes (Сывороткин, 2013; Syvorotkin, 2010). Speciation is
2017). Another study proposed that the first life forms may have the evolutionary process by which new living species arise. It was no-
emerged in water-conductive ultramafic rock systems (Hellevang et al., ticed that areas with high biological diversity are also situated over
2011). Recent discoveries in the genomics of hydrogen-based subsur- regions of high geologic-tectonic activity, where one might expect
face Archea provide insights not only on their evolution but on the higher flows of hydrogen. Such zones, when they are situated close to
emergence of life as well (Colman et al., 2017). the equator, are also exposed to maximum solar radiation. Seeps of
For life to exist in deep-earth environments the flow of hydrogen hydrogen and methane entering the atmosphere damage the ozone
must be continuous, which rules out certain proposed mechanisms for layer (see the next Section 5.3 Atmosphere) and increase levels of ul-
hydrogen generation. For example, for SLiMEs discovered in basalt traviolet radiation coming to the surface of the Earth (Сывороткин,
aquifers, the source of hydrogen proposed was a water-basalt reaction 2012a). Areas impacted by high UV radiation from the Sun may un-
(Stevens and McKinley, 1995). However, other researchers disagree and dergo higher rates of speciation when compared to other regions of the
say that a basalt-groundwater reaction producing hydrogen is not Earth (Сывороткин, 2013; Syvorotkin, 2010), a hypothesis yet to be
possible under natural conditions. In natural environments, exposed verified.
mineral surfaces will quickly become de-activated by their reaction
products and reduce their capacity to produce H2 (Anderson, 1998). 5.3. Atmosphere
The authors suggest that deep subsurface microbial ecosystems would
grow on reduced gases if there is a constant supply of such gases from Hydrogen in the atmosphere was first detected as a by-product of
the depth. It has been suggested that rock faulting and continuous de- the liquefaction of air. There is an abundance of atmospheric hydrogen
formation of the brittle crust sustains the supply of hydrogen to concentration data because during the 1950–70s the atmosphere was
39
monitored for the presence of tritium, an atomic weapons testing in- Hawaiian Islands and the equatorial Pacific. Continuous observations of
dicator (Warneck, 1999). For estimates of hydrogen concentration in air hydrogen concentration over a period of 44 months in the Khibiny
see the Section 4 Total Global Hydrogen Budget and Hydrogen Cycle. mountains, showed that there is a relationship between abrupt in-
Research on hydrogen in the atmosphere is still ongoing. For ex- creases in hydrogen concentration and a subsequent decrease in stra-
ample, in a study (Barnes et al., 2003), hydrogen concentrations were tospheric ozone. It is therefore suggested that geologic hydrogen plays
monitored every 24 min for three years above Harvard forest, MA USA. an important role in the ozone planetary balance (Сывороткин, 2013;
The authors found that hydrogen concentrations in the air change Syvorotkin, 2010). Some studies suggest that hydrogen may be re-
seasonally, with a spring maximum and an autumn minimum. Diurnal sponsible for the formation of noctilucent clouds (Сывороткин, 2002;
changes include a morning minimum and an afternoon maximum. It is Маракушев, 1998b; Tromp et al., 2003), which consist of frozen water,
interesting to note that their calculated annual emissions over 3 years the product of hydrogen oxidation at high altitudes.
show a statistically significant decline in H2 concentrations and that the Based on continuous monitoring of hydrogen in soil gas, the author
diurnal hydrogen cycle is opposite to that of CO. These two facts appear of another study developed a method for quantitative estimation of
to contradict the study author’s suggestion that hydrogen in the at- hydrogen input into the atmosphere based on ozone data. The method
mosphere comes from automobile tailpipe emissions. Another study was confirmed by comparing hydrogen ground data concentrations
confirms a conclusion that hydrogen is not associated with anthro- with ozone levels. During sharp increases in hydrogen ground con-
pogenic pollution by showing that H2 concentrations around polluted centrations, ozone levels decreased over the region under observation.
areas are not significantly greater than in regions where the air is clean It was thereby possible to transform Dobson units (DU) to degassed
(Novelli et al., 1999). Another similar study conducted near Saint-Pe- hydrogen volumes. An increase of 1 ppm H2 in soil gas, corresponds
tersburg in the Russian Federation discovered that hydrogen con- approximately to a decrease in ozone of 1 DU (Сывороткин, 2013).
centrations varied greatly when the wind blew from the direction of the Critics of this method say that the estimated total known hydrogen
city but were almost stable when the wind came from the forest input to the atmosphere is insufficient to affect the ozone layer
(Образцова et al., 2011). When H2 soil to air exchange was monitored (Adushkin et al., 2006). However, as has been shown in some examples
for 1 year in a rural area of Canada, it was shown that the uptake rate cited in the Section 5.4 Earthquakes, hydrogen concentrations mea-
depended on temperature, with the highest values measured at the end sured at continuous monitoring sites show abrupt changes in con-
of summer and the highest emissions observed at snow-melting time in centration over several orders of magnitude, up to 106 times, in a short
spring. The average uptake rate was 0.34 mg H2 per m2 per day period of time (Сывороткин, 2013). In such cases, plumes of hydrogen
(Constant et al., 2008). may rise very quickly and reach the stratosphere. Indeed, at epicenters
To understand the global budget and distribution of hydrogen in the of large earthquakes a reduction in the ozone layer above them has
troposphere, studies were done in both hemispheres of the globe. Air been observed. This seems to confirm that hydrogen is released in large
samples were collected from ~50 sites all over the world and from a quantities during earthquakes (Сывороткин, 2011).
ship crossing the Pacific Ocean on regular basis. Clearly visible yearly Hydrogen seepage is a dynamic process which appears to be very
changes in both hemispheres were observed, with a maximum in late irregular in space and time (Сывороткин, 2013; Syvorotkin, 2010).
winter in the Northern hemisphere (NH) and correspondingly in early Nevertheless, it is not completely chaotic. Continuous monitoring has
summer in the Southern hemisphere (SH). The amplitude in the NH was revealed periodic changes, related to seasonal and tidal influences of
three times that of the SH, but mixing ratios were lower in the NH the Moon and Sun (see the Section 2.4 Periodic variations in con-
(Novelli et al., 1999). The authors of another paper observed seasonal centration).
variations in H2 at high latitudes. Such variations remain unexplained Some researchers have warned that ignoring hydrogen component
(Warneck, 1999). Seasonal variations in atmospheric hydrogen con- of Earth’s degassing is a significant error when addressing issues such as
centration exhibit several features not found for other trace atmo- the destruction of the ozone layer and climate change (Сывороткин,
spheric gases (notably CO) (Ehhalt and Rohrer, 2009). Isotopic studies 2010). It is important to note, that H2 increases the half-life of the
of atmospheric hydrogen in both hemispheres also showed seasonal greenhouse gas methane (CH4) via a competing reaction with the hy-
variations of δD value (Batenburg et al., 2011). droxyl radical (Warwick et al., 2004). It has been suggested that hy-
The relative quantity of hydrogen in the atmosphere is low, but drogen may be at the origin of significant weather events. In one study
because of its high reactivity it has a noticeable impact on some natural the author speculated that an El-Niño event can be caused by hydrogen
processes. Probably the most important consequence of the presence degassing. El-Niño events form over an active rift system, which is
hydrogen in the atmosphere is the direct impact it has on concentra- likely producing hydrogen. Periodically, hydrogen seepage increases,
tions of hydroxyl (OH) and ozone (O3) in the troposphere (Barnes et al., which causes damage to the ozone layer which in turn increases air and
2003). Many studies indicate that hydrogen participates in the deple- water temperatures which in turn causes hurricanes. Finally, the flow of
tion of the ozone layer (Сывороткин, 2002; Сывороткин, 2013; reduced gas may render seawater anaerobic, causing mass biota die-offs
Маракушев and Маракушев, 2008a; Syvorotkin, 2010; Маракушев, (Сывороткин, 2012b).
1998a). The below cited works assume a large reservoir of hydrogen is Other studies have proposed that a sudden release of a large
present deep within the Earth and a periodic release of this gas is hy- quantity of natural gas, including hydrogen, could have been re-
pothesized to affect natural processes. sponsible for the mysterious Tunguska event, a large explosion which
The interpretation of spatial distributions of negative ozone happened over the Russian Federation in 1908. This event flattened
anomalies from a geologic point of view suggests a relationship be- 2000 km2 of forest. There is an explanation scenario for the 1908
tween these anomalies and rift zones and hot spots (Сывороткин, 2013; Tunguska event which proposes a 10 Mt natural gas seep from the
Syvorotkin, 2010). The largest ozone anomaly is observed over Ant- Kulikovskiі crater paleovolcano (Kundt, 2001) with a subsequent high-
arctica, where three main oceanic ridges merge and the entire continent altitude blast of a giant hydrogen–methane jet and the propagation of a
is surrounded by a rift zone (Pavlenkova, 2009). The hole in the ozone combustion or detonation wave. Such a scenario would explain some of
layer above Antarctica has at times been observed to exhibit a tri- the identified paradoxes and contradictions related to the Tunguska
radiate shape with the rays radiating from the South Pole in the di- event (Gendugov et al., 2010). Indeed, there is a comprehensive ana-
rection of the mid-ocean rifts: the Atlantic, the East and the West Pacific lysis of the 255 article bibliography on the Tunguska event, the authors
rises (Сывороткин, 2009). Such a unique configuration can be ex- of which show that, despite the largely accepted comet impact hy-
plained with the concept that ozone depletion is related to hydrogen pothesis, many facts remain unexplained. The authors suggest that a
flux, assuming that it is important enough to make an impact. Other release of methane and hydrogen can explain all the facts of the Tun-
ozone anomalies have been observed over Iceland, the Red Sea, the guska event better than the meteorite or comet impact hypothesis. One
40
of the hypotheses proposes that on the night of the event a large amount large, M=7.7 earthquake in 1983. Hydrogen increases were observed
of gas was released, which formed a cylindrical cloud with an explosive before the earthquake at three locations and simultaneous with the
concentration of CH4 and H2. This 12 km in length cloud of explosive quakes at the other two. Sometimes simultaneous increases were re-
gas extended up to 3 km in altitude. The ignition of this cloud in its gistered at stations situated 50 km apart. It was shown that such
upper part, caused the Tunguska event (Petrov and Shamshev, 2008). changes were independent of meteorological conditions (Satake et al.,
According to the authors, this hypothesis is supported by isotopic ob- 1985). Hydrogen concentrations were continuously monitored for a
servations. period of 1 year along the Yoro-Ise Bay fault zone in central Japan. Pre-
Another recent study suggests that hydrogen may be at the origin of seismic increases were recorded for local microquakes and for moder-
other catastrophic natural events. The spatial distributions of wildfires ately large events within a 25 km radius (Ito et al., 1998). Soil gas
in the Russian Federation were shown in 2010 to correspond to geologic hydrogen concentrations were monitored continuously for almost a
structures. Spontaneous endogenous methane-hydrogen releases from year in Turkmenistan at two locations, one near Ashgabat and a second
depth were proposed as a possible trigger and back-up for these wild- in the northern part of the country. During the monitoring period in
fires (Марин and Скублов, 2011). 1994, two earthquakes took place within a 100 km radius of the
Several studies have suggested that a massive implementation of monitoring locations. At both locations, a continuous increase in H2
hydrogen technologies may affect atmospheric chemistry and ozone background concentration of 0.2–0.5 ppm per day was observed for
layer integrity (Tromp et al., 2003; Warwick et al., 2004), however, a several months prior to the earthquakes. A sharp multifold increase of
recent re-examination has demonstrated that the impact would be small H2 concentration was observed just after the earthquakes. Aftershocks
when compared to natural variability in stratospheric values for water were preceded by concentration increases, but after each new after-
vapor concentrations (Vogel et al., 2012). Moreover, any impacts re- shock the increases in hydrogen concentration were less and less pro-
sulting from a conversion of the main energy carrier from fossil fuels to nounced (Voitov and Rudakov, 2000; Ишанкулиев et al., 1997). Con-
hydrogen will largely be off-set by positive effects related to the re- tinuous monitoring of hydrogen in soil gas during the period from 1998
placement of fossil fuels and their pollutants (Ehhalt and Rohrer, 2009). to 2000 in Dagestan showed that all seismic events with a magni-
tude > 5 took place when H2 concentrations in soil gas were 3–5 times
5.4. Earthquakes higher than normal background levels (Урдуханов et al., 2002). In the
Khibiny Massif anomalous changes in hydrogen concentration were
Being the lightest of all the gases, hydrogen responds quickly to shown to be related to seismic activity. It was observed that before
even minor disturbances in the Earth’s crust. Hydrogen will mainly weak seismic events, hydrogen concentrations increased but before
dissipate through fracture zones. Moreover, faults, where high con- significant seismic events, it decreased (Нивин, 2013). Monitoring of
centrations of hydrogen have been detected, are mostly active. H2 in soil gas at the surface over a mine situated in Khibiny Massif,
Observed hydrogen anomalies associated with fault movements have showed that concentrations of hydrogen increased after seismic events,
either been synchronous or precursory (Su et al., 1992). A systematic but also after large explosions in the mine (Федотова and Жукова,
study of hydrogen in aquifers shows that H2 concentrations are in- 2014). Continuous observations of hydrogen in soil gas in Southern
versely correlated with the age of the area's last tectonic activity Kamchatka, during the 1999–2004 timeframe, showed a statistically
(Shcherbakov and Kozlova, 1986). Another study shows that hydrogen significant correlation (correlation coefficient > 0.99) between hy-
concentrations in earthquake-associated faults are usually much higher drogen concentration pulses and earthquakes, with measured hydrogen
than concentrations in non-earthquake faults (Sugisaki et al., 1983). concentration pulses 2-14 times over background. An earthquake event
The recent Wenchuan Earthquake Fault scientific drilling project was detected within a 2–4-week period, following a pulse in hydrogen
showed the presence of hydrogen in the wells studied (Fang et al., concentrations (a probability of 0.8 was projected for an earthquake
2018). event). An earthquake of magnitude ≥5.6 was recorded close to the
It may be that hydrogen is too diffusive and too reactive to sig- observation site, and ≥7 for earthquakes located at some distance from
nificantly accumulate in geologic traps. However, during earthquakes the hydrogen monitoring location. The authors suggested that it should
hydrogen concentrations in fault zones have been shown to increase by be possible to predict the position of future epicenters by analyzing the
several orders of magnitude (Осика et al., 2002). Numerous articles start times of hydrogen impulses at different monitoring locations
discuss hydrogen as a good earthquake indicator and the possibility of (Firstov and Shirokov, 2005; Фирстов et al., 2006). In later studies, the
monitoring hydrogen for the prediction of seismic events. Hydrogen same investigators put in place a continuous monitoring system for
concentrations normally vary with time in soils and fractures, some- multiple parameters, including hydrogen, and reported the successful
times its variation could be up to several orders of magnitude. Hy- detection of pre-earthquake signals (Shirokov et al., 2011). It was
drogen concentrations respond to even very weak disturbances such as suggested that earthquake epicenters could be detected from hydrogen
tidal effects, as was described in the Section 2.4 Periodic variations in soil gas measurements. For example, the highest observed values for
concentration. However, hydrogen concentrations increase even more helium and hydrogen corresponded to the positions of the 1976 and
drastically during seismic events (Войтов and Осика, 1982). The main 1984 Gazli earthquakes in Uzbekistan, with 7–7.5 magnitudes, and
reason for this is that tectonic stress causes rocks to release absorbed hypocenters situated at a depth of 20–25 km (Перевозчиков, 2012).
and adsorbed hydrogen (Giardini et al., 1976; Fong-liang and Gui-ru, Another observation confirmed the release of hydrogen from earth-
1981). quakes with epicenters marked by a reduction in the ozone layer above
For example, during the Dagestan earthquake in 1970 (M=6.7), a them (Сывороткин, 2011) (for comments on this process, see the
20 fold increase in hydrogen concentrations was observed, and reached Section 5.3 Atmosphere). Other atmospheric phenomena which ac-
values which were 5–6 orders of magnitude higher than normal hy- company some earthquakes are the so-called “earthquake lights”. Some
drogen concentrations in the atmosphere (Осика, 1981). Spike-like researchers have suggested that combustible gases, such as hydrogen or
anomalies in hydrogen concentration were recorded in a 1000 m deep methane, are released and ignited during earthquakes. Other peculiar
hot water well in Beijing prior to the M=6.9 Ninghe earthquake in phenomena such as sharp flashes, fireballs and diffusive luminosity may
1976 (Fong-liang and Gui-ru, 1981). Increases of 3 orders of magnitude be due to a sudden release of large amounts of gas into the atmosphere
in H2 concentration after earthquakes were observed in the Zuramakent (Gold and Soter, 1980).
thermal springs in Dagestan (Войтов and Осика, 1982). Weekly mea- Taking into account the numerous observations of an abrupt in-
surements of hydrogen concentration in soil gas at five locations si- crease in hydrogen concentration during earthquakes, some researchers
tuated over the Atotsugava and Ushikubi faults north of Toyama city, have proposed that Earth degassing in general and hydrogen in parti-
Japan, documented outstanding discharges of hydrogen during the cular, plays an important role in the mechansms of earthquake
41
behaviour (Сывороткин, 2011; Gold and Soter, 1980). It has been exponentially as the samples locations decrease from 30 to 0 km from
suggested by some that deep earthquakes can be explained by an abrupt the oil field (Levshounova, 1991). Ground water close to petroleum
change in hydrogen concentration at depth (Гуфельд, 2012). The deposits has been reported to be richer in hydrogen than ground water
amount of energy which can be liberated by the degassing of 6 Tg/year close to natural gas deposits (Зингер, 1962). Another study shows that
of hydrogen is 2.16*1017 J/year. This is close to the global annual ground water samples from aquifers surrounding oil and gas fields,
earthquake energy total of 1017–1018 J/year. The authors see the Gu- contain dissolved hydrogen at concentrations higher than those in di-
tenberg-Richter relation as an energy law, which requires a constant rect contact with the oil and gas fields (Стадник, 1970). These facts
supply of energy (Gilat and Vol, 2005; Gilat and Vol, 2012). In an at- suggest that hydrogen is reacting with carbon-containing material,
tempt to explain possible mechanisms for the action of hydrogen in the which explains why hydrogen concentrations decrease in the vicinity of
Earth’s crust, one researcher examined the geochemical and geological oil and gas deposits.
factors controlling the precursory processes of earthquakes and the If hydrogen is released from depth, it is unlikely that any portion of it
occurrence of low- and high-magnitude seismicity. In the list of leading will penetrate upward beyond the hydrocarbon thermogenic zone because
factors contributing to the occurrence of earthquakes, the author pro- the hydrogen will be taken up by reactions with carbon compounds (Apps
posed degassing of hydrogen (and helium to a lesser extent) and mutual and Van De Kamp, 1993). Laboratory experiments measuring hydrogen
displacements of lithospheric blocks. In the scenario proposed, seis- saturation in clastic and carbonate rocks show that rocks can adsorb very
motectonic processes are triggered by physicochemical reactions of large amounts of hydrogen compared to their initial content (24–57 times)
hydrogen with rocks which “lock” the boundaries of crustal blocks, thus and are able to retain this hydrogen over several days. The highest re-
changing their seismic regimes (Гуфельд, 2007; Gufeld, 2008). If hy- tained hydrogen concentrations were observed in limestones. It was sug-
drogen plays a major role in earthquakes, non-tectonically induced gested that while it is retained in sediments H2 promotes a more complete
variations in gas concentration should be recognized in the search for transformation of organic matter into hydrocarbons (Levshounova, 1991;
earthquake markers (King, 1986). Молчанов, 1981). This published research confirms the need to further
It was suggested, that the action of geologic hydrogen could have evaluate the hypothesis that hydrogen originating from deep in the Earth
contributed, or even have been a trigger for the Chornobyl catastrophe would play an important role in the genesis of hydrocarbons (Hawkes,
(Шестопалов et al., 2018; Шестопалов, 2016) (n.b. correct transli- 1972). And this idea is supported byconclusions from another study,
teration from Ukrainian). The Chornobyl region is covered with surface which proposes that observed increases in H/C ratio in hydrocarbons with
depressions, which have been shown to be releasing molecular hy- age and depth may be related to hydrogen influx at depth (Hawkes, 1980).
drogen. It was shown in other studies that soil in such areas may sub- Another study reported the observation that with depth, reduced forms of
side (Larin et al., 2015; Zgonnik et al., 2015; Шестопалов et al., 2018), carbon become more widespread (Войтов, 1986). Moreover, it has been
probably as a result of diagenetic action of hydrogen on rock. During proposed that it is possible that the organic matter in coal deposits also
the year of the Chornobyl catastrophe many small earthquakes were accepts hydrogen coming from depth, and only in zones of active meta-
recorded and one earthquake in particular was registered only 16 s morphism of organic matter is hydrogen produced from organic material
before the catastrophe. It was therefore proposed, that the quake re- (Молчанов, 1981). It has also been proposed that deep life forms may
sulted from a soil subsidence may have caused a resonance effect in the contribute to the generation of hydrocarbons at depth, where free hy-
building, which housed the reactor, and the resultant catastrophic ex- drogen and a source of carbon is available (Шевченко, 2017).
plosion (Шестопалов et al., 2018; Шестопалов, 2016). A more detailed analysis of the role of hydrogen in the formation of
Another process called hydrogen embrittlement may contribute to hydrocarbons is beyond the scope of this paper. The reader interested in
the weakening of structures. It is well known that some metals become the role of hydrogen in abiogenic theories for the origin of petroleum
brittle and fracture due to the introduction and subsequent diffusion of can find a lot of information in the next review (Glasby, 2006).
hydrogen into the metal. While this is actively studied for industrial The next several references show how hydrogen plotting can be
applications, no work has been done to draw attention to the possibility used in oil and gas exploration. Based on a study of hydrogen con-
that hydrogen present in the sufficient quantities to cause embrittle- centrations along a transect across the Lost Hills Oil field in California
ment of man-made structures. However, some Nuclear Power Plants in (Jones and Pirkle, 1981) the statement was made that H2 shows a
the Russian Federation have already started to monitor for H2 in soil strong correlation with hydrocarbon anomalies and can be used as a
(Шестопалов, 2016). Also, in a recent study, hydrogen mapping was petroleum predictor. Hydrogen concentrations in soil gas were studied
successfully used as a tool to predict rockslides around oil and gas pi- above the Ostashkovich oil field in Belarus (Voitov and Rudakov, 2000;
pelines and storage facilities (Аксютин et al., 2010). Войтов et al., 1997). Hydrogen concentrations were higher where the
sampling profile crossed clearly visible fault zones and zones corre-
5.5. Oil, gas and minerals sponding to the oil-water contact. Similar results were obtained for
Yuzhno-Aleksandrovskoe oil field (Войтов et al., 2000) and the Pripyat
This review summarizing the occurrence of hydrogen in nature basin in Belarus (Voitov and Rudakov, 2000). High concentrations of
shows that hydrogen degassing is likely to be widespread phenomenon hydrogen, up to 95.2%, were observed in the discovery well for the Elsk
in both space and time. In the light of these facts, the claims of some field in Belarus (Шорохов, 1960). Anomalously high hydrogen con-
authors, that hydrogen plays a major role in the formation of hydro- centrations were found in the Gazli gas field, Uzbekistan
carbons should be taken more seriously (Войтов and Осика, 1982; (Перевозчиков, 2011; Перевозчиков, 2012). The authors concluded
Levshounova, 1991; Маракушев and Маракушев, 2008a; Маракушев that hydrogen could be used as a marker in the search for new oil fields
and Маракушев, 2008b). In the presence of carbon-containing com- (Войтов et al., 1997).
pounds, hydrogen will reduce and convert them into hydrocarbons In the Sections 2.1 Hydrogen as a free gas and 2.4 Hydrogen in
(Glasby, 2006). Indeed, it has been reported that measured hydrogen inclusions many examples are given of hydrogen being detected in gas
concentrations in gas reservoirs are 25 times less than hydrogen con- from of orebodies and mines. Some authors even state that high con-
centrations measured beyond reservoir boundaries (Rodgers and centrations of explosive gases, especially hydrogen, is one of the par-
Tyrone-Mt, 1984). This would be consistent with a model which attri- ticular properties of orebodies and mines (Малышев and Айруни,
butes the consumption of H2 by reactions with carbon-containing ma- 2005). H2 was reported to be present along with other explosive gases
terial. In other studies, it was also reported that concentrations of hy- in metal mines (Harrington and Denny, 1931) and to be one of the main
drogen are inversely related to the concentrations of hydrocarbon in oil constituents of gas in gold mines (Eschenburg, 1980). The presence of
fields (Левшунов, 1972). Another study indicates that the hydrogen hydrogen is a safety issue for miners. There have been attempts to
content of the strata of a known hydrocarbon pool decreases predict the presence of combustible gases in mines through the
42
sampling and analysis for hydrogen in occluded rocks but it was shown While examples such as those cited above may appear rare, it is ne-
to be a poor predictor of spontaneous hydrogen releases (Nivin, 2009). cessary to mention that these were accidental discoveries. With an inten-
The many instances of the detection of hydrogen associated with or- tional search for hydrogen at locations likely to be optimal for the oc-
ebodies and mines has stimulated researchers to examine whether there is a currence and production of hydrogen, the chance of finding similar and
causal link between hydrogen and mineral ore. For example, in the next even greater quantities will be greatly increased. The vast majority of wells
cited study the authors compare gold-bearing zones with hydrogen-rich worldwide have been drilled in sedimentary basins. But hydrogen is
zones and suggest that there is a relationship (Letnikov and Narseev, 1991). probably too diffusive and too reactive to be trapped in geologic traps for
They observed an increase in hydrogen concentration with depth and any length of time. Its discovery in significant quantities has shown that it
proposed that it can be used as search marker for new mineral veins. By is likely to be more concentrated at depth, with the largest accumulations
mapping hydrogen concentrations in the Trans-Challis fault system of Idaho being found in Precambrian basement, which is seldom targeted during
and the Carlin trend in Nevada, researchers concluded that anomalous drilling for conventional oil and gas. Moreover, because of preconceptions
concentrations of hydrogen can be useful in the identification of mineral as to the significance and origin of hydrogen, it is rarely measured by gas
deposits covered by overburden (McCarthy and Kiilsgaard, 2001; McCarthy analyses. These factors in combination with the fact that hydrogen is
and McGuire, 1998). Other studies mention that hydrogen concentrations colorless, odourless and non-toxic may explain why hydrogen seepages
increase with depth in uranium and rare earth orebodies (Поцелуев, 2010). have not been recognized earlier.
A hydrogen anomaly was reported to have been detected over the Uch- It has been shown in this review that hydrogen on the Earth’s sur-
kuduk uranium deposit in Uzbekistan (Перевозчиков, 2011). Some work face has as yet been insufficiently studied. Some studies on hydrogen
has been done to suggest that hydrogen may have been active in the for- only selectively take into consideration just a part from a complex of
mation of certain uranium deposits for which no other reducing agents have processes, which are generating and simultaneously oxidizing and re-
been found (Перевозчиков, 2011; Levinson, 1977). It was suggested that ducing chemical species in the geosphere. These are studies on radi-
hydrogen plays an important role in the formation of native elements and olysis and water interaction with fresh mineral surfaces. It is not ac-
their alloys (Яценко et al., 2012a; Dekov and Damyanov, 1997; Лукин, curate from a chemical point of view to consider only that part of a
2006). Other work has been done which proposes that orogenesis could be reaction where hydrogen is generated and ignore the oxygen side of the
related to ascending hydridic fluids acting as vectors for mineral systems equation. Reffering to biological process of hydrogen production is used
(Walshe, 2006; Walshe et al., 2005; Larin, 1993). often to explain the source of hydrogen. However, it has been shown in
Earlier in this article it was shown that high volume releases of this review that hydrogen is an essential energy source for many simple
hydrogen were discovered in kimberlite pipes (Table 7). Some work has forms of life, therefore in nature it is mostly consumed rather than
been done to suggest a primary role for hydrogen in the formation of produced. The only well-examined process for the occurrence and
kimberlites (Портнов, 1999), and also in the formation of diamonds genesis of hydrogen is serpentinization. Because of this, serpentiniza-
(Larin, 1993). Indeed, it should be noted that it has been shown ex- tion is, in this author's opinion, mistakenly considered as the main (and
perimentally that diamonds can be grown from methane-hydrogen gas sometimes the only) mechanism for the natural generation of hydrogen.
mixtures (Matsumoto et al., 1982). More detailed experiments have However, serpentinization is only a small part of a much larger picture
shown that diamonds form in the presence of hydrogen-rich fluids in which includes a complex hydrogen cycle as part of the many cycles
carbon-containing silicates and sulfides at pressures of 50–60 Kbar. In which make-up a dynamic Earth. From a chemical point of view, ser-
the absence of hydrogen-rich fluid, the P-T conditions necessary for the pentinization is a redox process between the oxidized surface and a
formation of diamonds are too high for the P-T conditions estimated for slightly reduced subsurface. Whereas, with increasing depth the redox
their formation depths derived from other indicators (Федоров, 2001). state of matter becomes more and more reduced and numerous studies
In a recent work the analysis of growth zones in diamonds and con- propose that the interior of the planet cold be hydrogen-rich.
centration of hydrogen in them has been documented. The authors The behaviour and habitat of hydrogen at depth remains almost an
concluded that hydrogen plays a crucial role in the formation of dia- unknown subject and researchers should give specific attention to a
monds (Vasilev and Kozlov, 2018). deep-seated source for hydrogen. Many studies have already demon-
strated that the Earth’s core and mantle could contain significant
6. Conclusions quantities of hydrogen stored in the form of hydrides, most likely since
the formation of the planet. The progressive decomposition of these
This review clearly shows that molecular hydrogen is present in every hydrides could sustain the observed near surface occurrence of hy-
type of environment on Earth and often plays an important role in many drogen, which can impact many processes such as volcanism, the
natural processes. However, its role is underestimated, misunderstood and genesis of ores and hydrocarbons, the addition of water to the oceans,
neglected, which has been the author's primary incentive for this review. A microbial life, atmospheric and climatic events, integrity of the ozone
good illustration of the current perception of natural H2 is the Wikipedia layer and much more. Some researchers have suggested that most of the
article on hydrogen fuel, stating that “pure hydrogen does not occur naturally H2 is seeping from the mantle, but its high chemical activity makes it
on Earth in large quantities”. This is clearly not true based on the docu- difficult to clearly determine its' origin. Therefore, it is often mistakenly
mented evidence from wells flowing hydrogen with the rate of up to attributed to other processes (Моисеенко and Сахно, 1982). We should
100,000 m3 per day in East Siberia or the first producing wells in West agree that an understanding of the extent and nature of hydrogen as a
Africa, where extraction of natural hydrogen has been recorded since 2012 constituent of the planet is a key to an understanding of the structure,
without any apparent decrease in production. The hydrogen flow rate in evolution and dynamic state not only of the deep interior of the Earth,
that West African gas well is high enough to run a generator that produces but ultimately of the crust, as well of the hydrosphere and biosphere
all the needed electricity for a local village. It is the first case of commercial (Williams and Hemley, 2001). Moreover, deep-seated hydrogen could
exploration for natural hydrogen. In 2018, there were 18 exploratory wells represent an inexhaustible source of energy.
drilled in search of hydrogen (Prinzhofer et al., 2018). The first drilling Hydrogen is the most energy-rich of gases and is currently considered
project for natural hydrogen in the USA by Natural Hydrogen Energy LLC to be a good candidate to replace fossil fuels. A recent comprehensive
successfully ended in the early 2019. Other small and large companies are study has reviewed methods for hydrogen production (Nikolaidis and
starting to explore for natural hydrogen in different countries and to test Poullikkas, 2017) and shows that all of the current methods are as yet too
their gas wells for the presence of H2. Note that scientists who have re- expensive to compete with fossil fuels. Therefore, the discovery of sub-
viewed the data and literature on natural hydrogen in the past have stated stantial sources of natural hydrogen gas would provide a cost-effective
that “in the future the extraction and refining of gases containing hydrogen will boost to a hydrogen economy. Moreover, hydrogen becomes a source of
become a separate branch of industry” (Shcherbakov and Kozlova, 1986). energy, and not its vector, like it is seen currently (Moretti, 2019). At the
43
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Declaration of Competing Interest Batenburg, A.M., Walter, S., Pieterse, G., Levin, I., Schmidt, M., Jordan, A., et al., 2011.
Temporal and spatial variability of the stable isotopic composition of atmospheric
molecular hydrogen: observations at six EUROHYDROS stations. Atmos. Chem. Phys.
The author declares no competing interests. 11, 6985–6999. https://doi.org/10.5194/acp-11-6985-2011.
Batsanov, S.S., 1999. Van der Waals Radii of hydrogen in gas-phase and condensed
Acknowledgments molecules. Struct. Chem. 10, 395–400. https://doi.org/10.1023/A:1022495220338.
Berkner, L.V., Marshall, L.C., 1966. Limitation on oxygen concentration in a primitive
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Hodorov for their help in acquiring copies of paper documents from Bertrami, R., Buonasorte, G., Ceccarelli, A., Lombardi, S., Pieri, S., Scandiffio, G., 1990.
Soil gases in geothermal prospecting: two case histories (Sabatini Volcanoes and
libraries, Nikolay Larin for his advice on geological questions, and Alban Hills, Latium, Central Italy). J. Geophys. Res. 95, 21475. https://doi.org/10.
Alexander Caruana, last but not least, for his valuable help in proof- 1029/JB095iB13p21475.
reading the manuscript. Bindi, L., Cámara, F., Griffin, W.L., Huang, J.-X., Gain, S.E.M., Toledo, V., et al., 2019.
Discovery of the first natural hydride. Am. Mineral. 104, 611–614. https://doi.org/
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Earth-Science Reviews 203 (2020) 103140

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The occurrence and geoscience of natural hydrogen: A comprehensive T

ARTICLE INFO ABSTRACT

groups: H2-rich, N2-rich and mixed N2-H2-CH4 or H2-CH4. These dif-

H2, % Comments Country Name of placemark Reference

(Cruikshank et al., 1973). Gases sampled from the Icelandic volcano

(Angino et al., 1984; Bogdanowicz, 1934; Заварицкий,

Abrupt increases in H2 concentrations in the surface air were recorded a

seismic and volcanic events, H2 concentrations were observed to have

carried out at the Sabatini volcanoes in Italy, showed generally low

levels were a function of high permeability at depth (Bertrami et al.,

caldera, Canary Islands, identified anomalous hydrogen concentrations

curred. The distribution pattern was shown to be associated with vol-

canic tectonic lineaments (Hernández et al., 2000).

Table 6 lists examples of hydrogen observed in geysers and hydro-

canoes in Azerbaijan. In Iceland, it was reported that hydrogen is one of

studied based on δD measurements (ratio of deuterium to protium, two

reported that hydrogen-rich hydrothermal systems such as those in

Hydrogen discoveries in kimberlite pipes have been reported in only

highest reported flow of natural hydrogen. Well #42 in the Udachnaya

10% (Фомичев, 2008). Hydrogen measurements were also taken from

bar. Proposed origin: mixed, mostly inorganic.

reported values of H2 of up to 6% at depths of 550 to 1300 m

(Сороченко and Дроздов, 2010).

(seeping from the fractures), occluded (stored in closed pores), and

diffusively-dispersed (intermediate between the two previous types

(diffusively dispersed gases refer to gas stored in micropores, mostly in

(Войтов and Осика, 1982; Соколов, 1971; Войтов, 1986;

Фомичев, 2008; Дроздов, 2011)

from (Фридман, 1970).

special conditions are required for it to accumulate and reach high

concentrations (Молчанов, 1981).

concentrations of hydrogen in salt deposits can be explained by the fact

2.2. Diffusive flow

concentrations were observed in soils sampled in Kansas. The area with

mapped over a variety of sites in Ukraine (165 in total), mostly in oil

ecological research and prospecting (Багрій et al., 2019).

used to identify zones of high fluid conductivity on the East-European

H2, % Comments Depth, m Country Name of placemark Reference

H2, % Comments Depth, m Country Name of placemark Reference

6–10 In oilfield gases Russian Federation Lenno-Viluisk, 10 (Гресов et al., 2010)

4.2–10.7 Gas discovered in 1906 Russian Novo-Usensk, 10.7 (Rogers, 1921)

(Wiersberg and Erzinger, 2008)

(Ware et al., 1985)

sorption-desorption (Хитаров and Войтов, 1982).

the Russian Federation. The first measurements were started in the

in the Khibiny gas seeps. These variations demonstrated a 14 days

periodic trend corresponding to lunar tides with a correlation coeffi-

hydrogen to hydrocarbons changes periodically with time and pro-

nounced peaks at 2 weeks and 6 months were observed (Кривцов et al.,

Khibiny massif showed evidence of tidal effects (Хитаров et al., 1979).

clude that the most important factors controlling the dynamics of H2

to tidal influences. A correlation coefficient of 0.6–0.75 confirmed at-

tides of the Earth. The highest amplitudes in concentration variations

were observed at locations situated on faults. These variations were

of soil porosity by frost. A single instance of a sharp increase in H2

of Obninsk in the Russian Federation, pointed to higher H2 content

during summer months and a decrease during autumn (Войтов et al.,