Discovery of a large accumulation of natural hydrogen in

Bourakebougou (Mali)
Alain Prinzhofer1, Cheick Sidy Tahara CISSE2 and Aliou Boubacar Diallo3

1
Alain Prinzhofer – Corresponding author

GEO4U, Scientific Director

[email protected]

Rua Tavares Bastos 123

Catete

22221-030 Rio de Janeiro – Brazil

2
Cheick Sidy Tahara CISSE

PETROMA

[email protected]

3
Aliou Boubacar Diallo

PETROMA, President

[email protected]
Abstract
Recent exploratory wells in Mali (Bourabougou field) targeting natural hydrogen were a success and
provide a new understanding of a first test well exploited by PETROMA (Bougou-1), and a
comprehension of continental hydrogen functioning systems. Based on extensive gas data of a pioneer
well and preliminary geochemical data obtained from a dozen exploratory wells in the vicinity, it is
possible to confirm the presence of an extensive hydrogen field featuring at least five stacked reservoir
intervals containing significant hydrogen that cover an estimated area well superior to 8 kilometers in
diameter. Results underline the potential economic interest of future natural hydrogen exploitation in
continental onshore areas. A “hydrogen system” is presented with a kitchen of generation in the
cratonic basement. The relatively pure hydrogen reservoirs are associated with traces of methane,
nitrogen and helium. The geological stratigraphic accumulation of hydrogen is linked to the presence
of multi overlaid doleritic sills and aquifers that seem to play a role to disable upward gas migration
and leakage. The occurrence of a mixture of gas and water acting with an artesian activity confirms the
presence of over-pressured fluids. This results in a geyser-type eruptive diphasic surface fluid in many
of the wells. The “gas lift” system and the presence of traces of highly unstable carbon monoxide is
linked to a recent hydrogen gas charge to reservoirs from underground aquifers, erupting with
associated water. The Mali wells underscore the non-fossil source of hydrogen gas and presents
features of a sustainable energy. The current estimate of its exploitation price is much cheaper than
manufactured hydrogen, either from fossil fuels or from electrolysis.

Keywords: Natural Hydrogen, Mali, geology, geochemistry, sustainable resource exploration.

Introduction
Natural hydrogen seeping out as a gas from hydrothermal systems in mid-oceanic ridges has been
detected in the 1970’s (Whelan and Craig, 1979; Charlou et al., 2002; Marcaillou et al., 2011). Hydrogen
sourcing out has also been observed few years later in ophiolites (Neal and Stanger, 1983; Abrajano et
al., 1988; 1990) and in continents (Goebel et al., 1983; 1984; Angino et al., 1984; 1990; Coveney et al.,
1987). However, it is still mainly considered as a geological curiosity for the majority of researchers
and natural hydrogen has only recently been taken seriously as a potential clean source of energy for
humankind (Petersen, 1990). One advantage lies in combustion, as the end product is water, rendering
hydrogen technically a clear and sustainable source of energy. Manufactured hydrogen is abundantly
used in chemistry (Prinzhofer and Deville, 2015) and its role as an energy vector drives the energy
industrial sectors to massively invest in the use of hydrogen for electricity storage and production.
Recent developments of flux energies (eolian, photovoltaic) induces the use of hydrogen as a buffer of
electricity (through electrolysis and fuel cells) because of the non-continuous production of electricity
through these processes all the while associated to a clear difficulty to store electricity directly and in
large quantity.

The discovery of various natural hydrogen seeps combined with surface indices in continental areas,
i.e. near industrial centers have underlined a feasible industrial exploitation (Ikorsky et al., 1999;
Sherwood-Lollar et al., 2007; Newell et al., 2007; Larin et al., 2015; Zgonnik et al., 2015; Brière and
Jerzykiewicz, 2016; Guélard et al., 2017).

Recent published studies have discussed hydrogen associated with ophiolites (Oman: Sano et al., 1993;
Deville et al., 2010; 2011. New Caledonia: Deville and Prinzhofer, 2016. Turkey: Hosgörmez et al., 2007;
2008. Philippines: Vacquand et al., 2018). Other documented studies present hydrogen data from very
widely distributed continental areas: In Russia (Larin et al. 2015), in the United States/North Carolina
(Zgonnik et al. 2015) and in Brazil (Moretti et al. 2018).

This paper presents updated geochemical considerations based on a hydrogen site in Mali, Africa. The
area is located near the village of Bourakebougou about 50 km north of Bamako where an old water
well (drilled in 1987) was quickly plugged and temporarily abandoned because of an unexpected gas
explosion. In 2011, the oil and gas company PETROMA uncemented the well, in the objective of
acquiring exploration rights for the block 25 production (Figure 1). A pilot hydrogen production was
made for the first explored Bougou-1 well, which lasted about 5 years. Additional drilling of two
stratigraphic wells close to 100 km North of Bourakebougou by PETROMA was an incentive to initiate
a broader exploration campaign with a series of 18 shallow wells in the surrounding of the pioneer
Bougou-1 well. Main geological and geochemical information obtained from a dozen of the total
eighteen 2017-2018 wells will be discussed in this paper and put in a broader perspective. Detailed
geochemical data of cores and rock samples and gas samples collected during these drilling will follow
in an upcoming technical paper.
 25°
Reguibat
A Shield

20°

15°
Bloc 25
Bougou 1

10°
B
Ivory Coast
Shield
500 km
5°

NNW SSE
Tamboura Basin B
A
0

10 km
500 km

Cambro- Devonian
Mesoprot. Neoprot. Silurian
Ordovician Carbonif.

Mesozoic Orogenic Archean

Cenozoic belts basement

Figure 1: Geological map of the Taoudeni Basin and north-south cross-section showing the structural
style of the basin passing close to the wells of Bourakebougou (Mali). Figure from Villeneuve (2005)
and Albert-Villanueva et al. (2016). SGI, Supergroup I: a, Char Goup, b., Atar Group Carbonates, c, Atar
Group siliciclastics, d, Assabet el Hassiane Group, e, glacial deposits of Bakoye Group; SG2, Supergroup
2; SG3, Supergroup 3; SG4, supergroup 4.

Different objectives are proposed with natural hydrogen R&D. The first one is an understanding of the
mechanisms involved in a hydrogen system (generation process, T-P conditions of generation, flux of
generation versus time, migration, accumulation, natural leakage and oxidation of H2). A second
objective is to provide practical guidelines for hydrogen exploration, based on sound geology,
geophysics and geochemistry. This paper focusses on shallow hydrogen gas accumulations, with less
emphasis on deep generation kitchen pods.

Rock and fluid geochemistry issued from results of the latest exploratory wells in Mali carry paramount
scientific interest. However, as a reminder, it is not the first time that substantial hydrogen has been
accounted for, and documented from Mali (N. Africa, Brière and Jerzykiewicz, 2016) and Kansas (USA,
Goebel et al., 1983). Nonetheless, in both cases, wells were initially drilled for oil and gas or water and
the presence of hydrogen was fortuitous. The fact that a Malian company has specifically targeted a
hydrogen discovery with an extensive exploration campaign is a world’s first.

Geological setting
The initial Bourakebougou water well (“Bougou-1”) was drilled in Proterozoic sedimentary formations,
interlayered with dolerite sills of Triassic age. These formations are part of the Taoudeni Basin, large
sedimentary system present mainly in Algeria, Mauritania and Mali. The Paleozoic and Mesozoic upper
part of the basin (mainly in Algeria) is famous for its hydrocarbon potential (Craig et al., 2008). On the
other hand, the lower Proterozoic section is much poorer in organic matter content (less than 1
percent) and no significant hydrocarbon discovery has ever been made so far in this area. The studied
area is located in the Tamboura sub-basin, consisting in a graben filled with Neo-Proterozoic and lower
Paleozoic sediments (Figure 1).

A preliminary geochemical soil monitoring was performed in various areas of the block 25 in Mali prior
to the exploration of upcoming drilled wells. Results of soil enrichment in non-hydrocarbons showed
a surprising hydrogen concentration profile in 1-meter depth samplings. Maps displayed hydrogen
spiking around the structure in a full ring. This likely is resulting from regular upward hydrogen seeping.
In the center of the circular structure hydrogen gas exultations have also been recorded. Hydrogen
seeping out of circular depressions (figure 2), as is actually observed in various continental zones, is
perhaps a first indicator for hydrogen exploration (Larin et al., 2015; Zgonnik et al., 2015). This may be
significant as a first elementary guideline for enriched soils containing H2 and should be pursued and
validated at grand scale in different areas of Mali, or other parts of the world for that matter.

The presence of substantial hydrogen gas in all the wells located in the vicinity of the Bourakebougou
structure implies the existence of a large natural hydrogen system. As a reminder, hydrogen gas is a
low molecular weight compound and, as such, has a high mobility allowing hydrogen to migrate large
vertical distances from a potentially deep kitchen pod of generation to a shallow
accumulation/reservoir.
 600
500

H2 (ppm)
400
North 300
200
100
0

Figure 2: Surface geochemistry of a circular structure located East of the block 25 of PETROMA and
close to the village of Gassola. A profile of the hydrogen concentrations (in ppm) is also presented. The
coordinates of the center of the structure are a latitude of 13.194605° and a longitude of -6.242527°.

The Bourakebougou Pioneer well (1987)

The Bourakebougou water well, Bougou-1, was cemented after a gas explosion occurred during drilling
operations. The incident occurred when a measured drilled depth of 112 meters was reached. Bougou-
1 well was unplugged in 2011 in order to use it as a pilot well for a local hydrogen production. A
production of a gas predominantly composed at 98% of hydrogen, 1% of nitrogen and 1% of methane
was reported at that time. Hydrogen was then produced as an energy resource to supply local
electricity through an engine with internal combustion to the nearby village. The project proved to be
a success for the nearby town and has lasted for years now.

Rock geochemistry

Geochemical rock analyses were performed on 29 cuttings from two stratigraphic wells (F1 and F2
wells, depths of 2067m and 2339m respectively) 100 km North of Bourakebougou (in the area of 13.84°
of latitude and -8.12 of longitude), following the Bougou-1 well, in order to study the petroleum
potential, the carbon content and various indices important for the determination of petroleum
potential of the Malian part of the Taoudeni basin. Figure 3 presents pyrolysis data (Rock Eval-6)
obtained from the neo-Proterozoic sediments sampled at depths from 100 to 2000m. Carbon content
measured in cuttings presented low Total Organic Carbon content (TOC) which seems to refute the
presence of potential hydrocarbon source-rocks in this part of the basin (average of 0.28%, with
minimum and maximum values from 0.02 to 0.94% (Figure 3). Moreover, plotted in a modified Van
Krevelen diagram with Hydrogen Index (HI) versus oxygen Index (OI) (Figure 3a), the hydrogen indices
are very low whereas the oxygen indexes are extremely high, indicative of a severe oxidation of organic
matter traces. Geochemical data also underline an absence of any petroleum potential due to low
Hydrogen Index between 1.9 and 150 mg HC/g Rock (average of 29 mg HC/g Rock). Figures 3c and 3d
show that the two pyrolysis derived parameters HI and OI have decreasing values with the % TOC. It
can be inferred that those rock samples which are less depleted in organic matter have in fact lowest
petroleum potential. This leads to the conclusion that there is an absence of hydrocarbon prone source
rocks and therefore little hydrocarbon potential in this area of the Taoudeni Basin.

a) 1000 Type I kerogen

b) 0,14
0,12
800
0,1
S1 (mg/g)
HI (mg/g)

600
0,08
Type II kerogen
0,06
400

0,04
200
Type III kerogen 0,02

0 0
0 1000 2000 3000 4000 5000 6000 7000 8000 0 0,2 0,4 0,6 0,8 1
OI (mg/g) TOC (%)
1000

c) d) 7000
8000

800

6000
HI (mg/g)

600
5000
OI (mg/g)

400 4000

3000
200
2000

1000
0
0 0,2 0,4 0,6 0,8 1 0
TOC (%) 0 0,2 0,4 0,6 0,8 1
TOC (%)

Figure 3: RockEval data of some rocks with organic matter of the neo-Proterozoic Tamboura graben.
a) Hydrogen Index (HI) versus Oxygen Index (OI). b) Free hydrocarbons (S1 peak) versus Total Organic
Carbon (TOC). c) Hydrogen Index (HI) versus Total Organic Carbon (TOC). d) Oxygen Index (OI) versus
Total Organic Carbon (TOC).

Chemical gas composition

It was mentioned that Bougou-1 pioneer well contained predominantly hydrogen with traces of
nitrogen and methane. Bougou-1 gas composition presents different chemical features as compared
to other case studies, where the gases associated to hydrogen are present in widely different
proportions. Figure 4 presents different chemical compositions of natural hydrogen gas occurrence
from different geological settings. Plotted data are from gas samples originating either from sampled
drilled wells (Kansas and Bougou-1) or gases collected in surface macro-seeps (Oman, Turkey, New
Caledonia, Philippines). In the Bougou-1 well shown in red on the ternary plot, the gas content appears
the richest in hydrogen proportion, whereas other onshore gases from different areas always have
presented higher proportions of methane and nitrogen.

Bougou 1
0 100
H2
H2
10 90

20 80

30 70
Oman 1
40 60

50 Philippines Kansas 50

60 40

70 30

New Caledonia
80 20

Turkey
90 10

100 0
0 10 20 30 40 50 60 70 80 90 100

CH4
CH4 N2
N2

Figure 4: Ternary diagram with the relative proportions of hydrogen, methane and nitrogen, for various
gas samples containing natural hydrogen. Oman and Philippines: macro gas seeps, from Vacquand et
al., 2018. New Caledonia, macro gas seeps, from Deville and Prinzhofer, 2016. Turkey, macro gas seeps,
from Hosgörmez et al., 2007. Kansas, gas well, production test from Guélard et al., 2017.

The Bougou-1 gas sample is associated with traces of hydrocarbon gases (methane, ethane, propane,
iso- and normal-butane, neo-, iso- and normal-pentane), helium and carbon dioxide. The chemical
composition is presented in Table 1, as well as the carbon and hydrogen isotopic ratios of different
measured species.
 Concentration Concentration
Compound  13C D
% (TCD) ppm (FID)

He 4,90E-02
H2 9,74E+01 -702
CO2 4,00E-02
N2 1,20E+00
O2 0,00E+00
C1 1,30E+04 -40,4 -249
C2 2,16E+02 -32,1 -165
C3 2,72E+01 -31,0
iC4 3,83E+00 -26,1
C4 5,00E+00 -38,1
neoC5 5,20E-01 -32,6
iC5 1,18E+00 -20,5
C5 4,10E-01 -49,7

Table 1: chemical composition (hydrocarbon and non-hydrocarbon compounds) and isotopic analyses
(carbon and hydrogen stable isotopes) of Bougou-1 gas, Bourakebougou Village (Mali). The carbon
isotopic ratios are presented in 13C unit, variation in per mil compared to the PDB (Peedee Belemnite)
international standard, and hydrogen isotopic ratios in D unit, variation in per mil compared to the
SMOW (Standard Mean Oceanic Water) international standard

Based on published data from Sherwood-Lollar et al. (2008), the proportions of C2-C5 linear
hydrocarbons clearly show an abiotic origin for these hydrocarbons (Figure 5). Abiotic hydrocarbon gas
compounds are generated through a hydrogenation of mineral carbon and have a different genetic
origin than the more usual thermogenic gases (thermal cracking of organic matter) or biological gas
(biological activity of methanogens producing mainly methane). Bougou-1 gas is therefore assumed of
abiotic origin from this interpretation. Moreover, this is consistent with the Tambura basin
sedimentary rocks which have been characterized as organic matter-lean rocks and would limit the
probability of any potential for thermogenic hydrocarbon generation. One plausible explanation on
the origin of methane in this well is a hydrogenation mechanism where carbon dioxide CO2 is
hydrogenated into CH4. The reduction of CO2 may occur either from a bacterial activity or a catalytically
driven chemical reaction. On the other end, the generation of heavier hydrocarbons is likely to proceed
through a Fisher-Tropsch process type chemical reaction (degenerated polymerization), at relatively
high temperature and without any biological associated process. Considering that the kitchen of
generation of the various gas compounds of the well may be in the continental basement, the
pressure/temperature conditions may be compatible with a Fisher-Tropsch process. Taking in
consideration the actual setting and results, it can be tentatively assumed that the Bougou-1
hydrocarbon gas compounds have mainly an abiotic origin.
 0
Purely KC 8558
abiotic gas KC 8428
Archean KC 8282
Log (mole fraction) -1 KC 8402
basement
KC 8539

-2

-3

-4
1 2 3 4 5
Carbon number

Figure 5: relative proportions of normal-paraffin hydrocarbon gas compounds, with carbon numbers
from 1 (methane) to 5 (normal-pentane), taken from Sherwood-Lollar et al., 2008. Comparison of the
pattern of the Bougou-1 well with Archean gases analyses by Sherwood-Lollar et al. (2008) and
interpreted as generated through an abiotic process.

Stable carbon isotopes

The geochemical stable carbon isotopes measured by GC-C-IRMS (Gas Chromatography Combustion
Isotopic Ratios Mass Spectrometer) and represented as 13C ratios for each linear hydrocarbon present
unusual trends which are hardly compatible with purely thermogenic, biological or abiotic sourced
(Figure 6). The very light isotopic signatures, highlighted with 13C of normal-butane and normal-
pentane for example, in this case, can be explained by an abiotic polymerization process. However,
the heavier isotopic signatures of iso-alkanes isomers (iso-butane, neo- and iso-pentane) can be better
explained if they are assumed to have a thermogenic origin. This has been shown to occur and it is
known that a polymerization process favors mainly the paraffinic, linear hydrocarbons (Szatmari,
1989). In view of the present data, it can be tentatively concluded that there is a mixed mechanism
between an abiotic process and trace of thermal cracking of organic matter. As the total hydrocarbon
proportion of the gas is around 1%, each of these processes remains however quite marginal.
 -20

-25
13C (o/oo PDB)

-30

-35

-40

-45

-50

-55
C1 C2 C3 iC4 nC4 neoC5 iC5 nC5

Figure 6: Carbon isotopic ratios pattern for the gas of Bougou-1 expressed in per mil versus PDB. The
complex pattern is interpreted as a mixture between an abiotic gas containing without any isoprenoid
molecule, and a thermogenic dry gas, containing all the compounds. The grey dashed lines represent
standard values of 13C for a purely and a purely abiotic gas. The black line represents the Bougou-1
composition, fitted with a mixture of the two thermogenic and abiotic endmembers, as the chemical
proportions are very different for each endmember.

Noble gas isotopes

Noble gas isotope studies are well adapted to trace physical processes affecting crustal or mantle
fluids, as well as quantifying the origins of the fluids from superficial, crustal or mantellic origin
(Prinzhofer, 2013). Their chemically inert property renders them conservative when exchanging
between different geological reservoirs, whereas some radiogenic isotopes (4He, 40Ar, …) may be used
for chronological and source-characterizing purposes.

Noble gas concentrations (He, Ne, Ar, Kr and Xe) and respective isotopic ratios were analyzed and are
reported in Table 2. Data show no air contamination in the analyses (Figure 7a) of 20Ne, 36Ar and 84Kr,
while there is a signature due to the Air Saturated Water reservoir (ASW, i.e. noble gases solubilized in
aquifers through the recharge zones). The fractionation that can be accounted for, independent of the
ASW signature cannot be due to a mixture, because no other endmember is known to have such
signature on Earth. Therefore, it is suggested to represent a fractionation process due to migration.
The enrichment of light isotopes (20Ne versus 36Ar and 36Ar versus 84Kr) may explain the observed
signatures, as they may be relatively enriched during a migration process (Prinzhofer et al., 2000).
Helium and argon have a large radiogenic component, indicating a deep source from metasediments
or from the basement (Figure 7b). As the isotopic ratios of mantle helium (1.12 10-5) and mantle argon
(3 104) are very different from the measured ones from the Bougou-1 gas, it may be concluded that no
trace of any mantle contribution has been evidenced.
 0,045 1,2

ASW
0,04
ASW
1
0,035 Air
Wellhead
0,03 Separator 0,8
84Kr/36Ar

R/Ra
0,025
84Kr/36Ar

0,6

R/Ra
0,02 Air

0,015 0,4
y = -9,84x + 1

0,01
0,2
0,005
Separator
Wellhead
0 0
0,000 0,100 0,200 0,300 0,400 0,500 0,600 0,700 0 0,02 0,04 0,06 0,08 0,1 0,12
a) 20Ne/36Ar
20Ne/36Ar
b) 40Ar*/4He
40Ar*/4He

Figure 7: ratios between different noble gas isotopes. a) Fossil isotopic ratios 84Kr/36Ar versus 20Ne/36Ar.
b) radiogenic isotopes R/Ra (equivalent to 3He/4He normalized with the atmospheric ratio of 1.6 10-6)
versus the radiogenic proportion of 40Ar (40Ar*) over the radiogenic 4He.

Concentrations Separator Wellhead

4
He (ppm) 547 552
20
Ne (ppm) 0,244 0,381
36
Ar (ppm) 0,516 0,586
84
Kr (ppb) 16,7 18,3
129
Xe (ppb) 0,91 1,39
Isotopic ratios
40
Ar/ 36Ar 400 384
3
He/4He 6,1E-08 8,2E-08

Table 2: Helium concentrations and fossil noble gas isotope concentrations (20Ne, 36Ar, 84Kr and 129Xe in
ppm) and isotopic ratios of argon (40Ar/36Ar) and helium (3He/4He)

Absolute concentrations of fossil noble gases may be further used to calculate an estimation of the
Gas/Water ratio at physical equilibrium (Prinzhofer, 2013). It is considered that the fossil isotopes
(20Ne, 36Ar, 84Kr and 129Xe) present concentrations in aquifers controlled by the atmospheric
concentrations (which did not change in the last billion years) and the solubility of these compounds
in water at the recharge zones of the aquifers. When a vapor phase (here hydrogen gas) enters in
contact with aquifer water, these fossil isotopes equilibrate between the water and the vapor phase,
with concentrations depending on the solubilities and the relative proportions of vapor and water,
allowing to calculate a gas/water ratio. The estimated Gas/Water ratio calculated for Bougou-1 gas, is
approximately 1m3/1m3. Such a value indicates that Bougou-1 gas has been equilibrated with the same
volume of water (at STP conditions).
2018 exploratory wells
The wells are located within a radius of 8 km and the total depths for the different wells ranges from
105 meters to 1807.4 meters. The total length of core drillings reaches 5.4 km. A map of the well
positions is presented Figure 8.

BOU19

BOU8
BOU9
BOU18 BOU7
BOU14 BOU3

Bougou 1
BOU4
BOU6 BOU5
BOU5A
BOU20

BOU13

0 1 2 km

Figure 8: GoogleEarth satellite image of the Bourakebougou area (Mali). The well numbers and
positions are shown with circles.

The recently drilled wells in Mali seem to confirm the hydrogen influx in this area. These wells bring a
large dataset of rock and fluid samples that undoubtedly will help constrain and characterize the
hydrogen system. At this time however, many high-resolution analyses are underway and only scarce
geochemical results are available.

The Neo-Proterozoic sediments are characterized by sandstones, marls, silts, pelites and limestones
formations. Lithofacies show that carbonates rocks are constituted of calcite, dolomite and siderite.
Their texture may appear at times as marble as well as karstified carbonates. Sandstones bodies
present variable porosities and are described as closed porosity to coarse grained and highly porous.
Grain dissolution and other diagenetic process are evidenced, because of the presence of karst and
geods. Horizons of coarse breccias have also been noted by the well geologist. Basement has been
reached in only one well (Well Bougou-6). The basement rocks are characterized as plutonic rocks
composed of granite, granodiorite, diorite, syenite and aplite.
The mineralogy is also described as composed of iron containing minerals, present at different
oxidation state, like magnetite, hematite, pyrite, chalcopyrite.

Based on field description made during the actual drilling phase, wells show numerous sills and
intrusions of dolerite. The texture of magmatic rocks is aphanitic close to the sill walls, giving clues that
these magmatic rocks have intruded themselves in relatively “cold” formations, inducing chilled
margins of the intrusions. The magmatism of this area is dated around 200 million years (Sebai et al.,
1991) and emitted in a very narrow time interval.

Continuous gas detection and recording of fluids was made while drilling in exploratory wells. The
resulting reported geochemical gas compositions show a predominance of hydrogen gas (H2), with
variable proportions of methane in all the wells. The H2/CH4 ratios range between values of 10 to 500
(for the Bougou-1 gas, the ratio is of 98). Traces of H2S and CO (both above 1000 ppm concentrations)
were identified in few wells.

The origin of the H2S gas compound has been suggested to be related to the interaction between sulfur
and other compounds (H2, H2O) which could be generated through a shallow biologic activity. This
situation is somewhat expected in anoxic sediments. The other health hazardous gas encountered in
some wells is carbon monoxide, very often at concentrations above 1000 ppm. This gas is never
observed in natural sedimentary sequences, but occasionally detected with extensive drilling bit
metamorphism. Carbon monoxide is a reactive gas, whose geological residence time is very short.
Concentrations above 1000 ppm cannot be interpreted solely on artificial bit metamorphism during
drilling and a more plausible explanation is linked to some active geochemical processes undergoing
in subsurface fluids.

When discussing hydrocarbon geochemical signatures, it was mentioned that some of the hydrocarbon
compounds were likely associated with abiotic processes and CO2 reduction following the Sabatier’s
chemical reaction and/or Fisher-Tropsch polymerization. In these reactions, carbon monoxide is as a
matter of fact found to be an essential intermediate compound during these processes. Therefore, its
presence in relatively high concentration during drilling may indicate a steady-state concentration
associated with its generation and destruction during the chain of chemical reactions involved with
hydrocarbon generation. The presence of carbon monoxide thus can reinforce the notion of recent
and sustainable geological generation of natural hydrogen in this area.

Permeability fluid barriers in Mali wells

A schematic cross-section joining several wells is presented Figure 9. It appears that 5 different
reservoirs may be defined, separated by dolerite sills.
 BOU-13 BOU-5 BOU-6 BOU-4 BOU-14 BOU-19 BOU-20
0m
Soil
100 m

200 m
Depth

Dolerite
300 m
Reservoir 2

400 m
Dolerite

500 m Reservoir 3

Dolerite Reservoir 4

Dolerite
Reservoir 5
Basement

Figure 9: schematic cross-section of the Bourakebougou gas field, passing through several wells
described in this work

Water was noted to gush out of some of the wells as observed with two artesian wells, propping up to
the surface with gas bubbles. This observation is important in trying to understand the buildup and
release of hydrogen at the surface when hydrogen mobilizes through shallow sediments. A possible
interpretation is that water is surging upwards because of pressure buildup with associated dissolved
gas at the surface, with a seemingly geyser dynamic.

A similar sedimentological model seems to be repeating itself in nearby wells which have at least five
defined stacked hydrogen-rich reservoirs. The most superficial accumulation is found at a shallow
depth near 100 meters which stratigraphically corresponds to the unique shallow Bougou-1 reservoir.
The effective permeability fluid barrier is considered to be superficial dolerites, outcropping in the
whole area near Bourakebougou. The fact that this 100-meter-deep accumulation is observed in all
newly drilled wells shows with little doubt that the regional extension is quite large (~ 8 km estimated)
and may well underline that the hydrogen system at play in this part of Mali is generating a substantial
volume of gas.

If the presence of different dolerite levels has been identified on the geochemical logging reports of
all these new wells, it is interesting to note that new additional details have emerged for example from
the deeper intervals of the Bougou-6 well (Fig. 10). Indeed, in this well, the seals may apparently be
other than solely dolerite sills. The presence of breccias noted by the field geologist in fact could play
a role and behaving as impermeable seals, even though they are highly porous.
 a) ppm b) (%)
10 100 1000 10000 100000 20 40 60 80 100
0

100

200

300

400

500

600 Well Bougou 6

Depth (m)

700

800

900

1000

1100

1200

1300

1400

1500 CH4
1600 H2
1700 Dolerites
1800 Carbonate (%)

Figure 10: Simplified gas-log (a) and mineralogical-log (b) of the deepest well drilled in this study
(Bougou-6). The concentrations of methane (dark grey in figure 10a) and hydrogen (light grey in figure
10a) are represented versus depth, as well as the dolerite sills (light grey in figure 10b) and the
proportion of carbonates (dark grey in figure 10b).

This is technically possible if one considers the very low solubility of hydrogen in water (twice smaller
than methane, and 50 times smaller than CO2). In that case, it can be suggested that water itself
behaves as an impermeable media as it is present in breccias and other possible porous rocks. The fact
that we observe the “gas lift” process during sediment penetration indicates that water acts physically
in the hydrogen migration and entrapment process, as it is located above the hydrogen phase.

It should be reminded that water, taking the role of a fluid barrier at shallow depths, is in opposition
to the conventional scheme of petroleum systems: as water is denser, it is mostly always positioned
below oil and gas traps. The exceptions being shallow aquifers above cap rocks. One explanation to
understand the physical mechanism associated with the pseudo geyser (composed of mostly water
and bubbling gas) is that a gas recharge is in place below shallow water aquifers. The latter do not have
time to equilibrate through buoyancy above the water table because of a slow migration through the
sedimentary rocks. When the well penetrates sediments, a gas phase is liberated and carries up water
by depressurization.

Ultimately, this indicates that hydrogen gas has charged sediments very recently in the structures,
without any equilibrium time to move through the water at respective densities. The relative recent
charge of hydrogen to these depths reiterates the notion of some sort of sustainable source of energy
and not a fossil one.

Discussion
Main reservoir rocks in this area of Mali, where hydrogen has been observed to occur, are
characterized as carbonates despite indices of hydrogen shows also present in sandstones and other
detritic rocks.

At the reservoir scale, the accumulations of hydrogen and methane present shifted maxima which
oscillate in intensity with depth (Figure 11). The “caprocks” seem to be of different mineral nature for
methane and hydrogen. In this example, both gases do not appear to be trapped simultaneously at
equivalent depths. Moreover, marble layers do not seem to retain hydrogen while methane appears
to be accumulated below thick carbonate sedimentary bodies.

Bougou-13 Well Bougou-19 Well

0 1000 2000 3000 4000 0 5000 10000 15000 20000 25000
20 90

Shales Metapelite
30

100
40 Breccia
H2 (ppm) Dolerite
50
110 H2 (ppm)
60

70 120 Marble
Marl
80

Marble 130
90
CH4 (ppm) 10 x CH4 (ppm)
100 Marl
140

110 Dolerite
Dolerite
150
Figure 11: Details of the gas logging of the wells Bougou-13 and Bougou-19. The gas concentrations of
hydrogen (black line) and methane (grey line) are represented versus depth (meters). A simplified
mineralogical log is also presented.

Concerning the apparent differential sealing efficiency for methane and hydrogen, it is not well defined
at this time and clearly deserves more investigation, in particular by studying and modeling gas-water-
rock interactions. Chemical models which take into account physical parameters controlling gas
migration (water solubility, mineral adsorption, advection and diffusion parameters, etc.) would be
necessary.

Conclusions
Recently drilled wells in Mali show significant hydrogen discoveries in the vicinity of Bourakebougou,
at a distance of 50 km north of Bamako, and present unique geochemical and geological features of
an active hydrogen system. This opens new perspectives of a future industrial exploitation of hydrogen.

The hydrogen natural system is a recent science. As a comparison, oil and gas exploration began in the
middle of the 19th century with an immediate success, and little knowledge about the petroleum
system, generation, source rocks and migration of hydrocarbons. Much later, in the 1930’s, advances
in analytical chemistry allowed to understand and link the organic origin of petroleum. The full
understanding of the functioning of a petroleum system (generation, migration, accumulation,
alteration and leakage) came only in the 1960’s.

Hydrogen accumulation in sediments might well be a technical challenge to understand its mechanism
and may follow a similar fate before the “Hydrogen System” be fully understood. However, as for oil
production, we may consider already that natural hydrogen accumulations have been clearly
demonstrated in Mali, opening a pathway to an industrial exploitation. The cost associated with the
exploitation of 1kg of natural hydrogen may be estimated to be 2 to 10 times smaller than the cost of
manufactured hydrogen, rendering this new source of energy quite attractive for the future of our
energy consumption.

Scientific and practical features of a natural hydrogen system as seen in Mali have been outlined and
can be summarized:

- From a scientific point of view, natural hydrogen in Mali is associated with neo-Proterozoic
sediments. This geological time is characterized by cold temperatures on Earth and a reduction
of the oxygen proportion in the atmosphere, inducing reducing conditions in the sedimentary
rocks.
- It appears that natural hydrogen accumulations are not limited to the vicinity of
Bourakebougou, but present additional sites extending regionally up to a minimum of 8 km.
Surface geochemistry indicates that the occurrence of hydrogen seeps extends up to 150 km.
- Apart from the relatively shallow gas accumulation of Bougou-1 well, known from the first
drilled well in 1987 at around 100 meters depth, four additional sedimentary layers enriched
in hydrogen have been encountered in deeper horizons (down to 1800 m) from a dozen newly
drilled wells in this area.
 - Hydrogen generation is suggested to occur deeper than present reservoir depths and most
probably issued from the basement, as demonstrated with the occurrence of large amounts
of radiogenic helium and argon, associated with deep nitrogen.
- The associated hydrocarbon gas compounds are generated through a reduction of CO2 with
H2. This reduction is likely to be a chemical reaction which takes place at relatively high
temperature, although a biological generation cannot be excluded.
- The present Mali hydrogen accumulations can be explained because of the presence of
numerous sills of dolerites that act as fluid barriers. Water levels however also seem to play a
role as permeability barriers, easily understood as H2 is practically insoluble in water at shallow
depths.
- Some of the recent wells present an “artesian” water flow mechanism, enriched in hydrogen
gas. This “geyser” dynamic may be due to a “gas lift” not so well understood process, and/or
to overpressures in the fluids of the subsurface. This would be in favor of a recent gas charge,
making the natural hydrogen kitchen a sustainable source of energy, in opposition with
hydrocarbon accumulations associated with residence times of million years, far from our
human time of consumption.
- Sustainable renewed hydrogen accumulations are emphasized with the presence of carbon
monoxide, a highly reactive gas compound which cannot be fossil in the subsurface.

Acknowledgements

We thank Isabelle Moretti and Joao Batista Françolin for reviewing the first draft of the manuscript.
Thanks also to Caroline Magnier for fruitful discussions and proof reading.

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