Marine and Petroleum Geology 137 (2022) 105491

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Marine and Petroleum Geology

journal homepage: www.elsevier.com/locate/marpetgeo

The Claromecó frontier Basin: Hydrocarbon source rock potential of the

Tunas Formation, southwestern Gondwana margin, Argentina
María Belén Febbo a, b, c, *, Guadalupe Arzadún a, d, Nora N. Cesaretti b, c, Renata N. Tomezzoli a, e,
Natalia B. Fortunatti b, c
a
Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Argentina
b
Dpto. de Geología, Universidad Nacional del Sur, Avenida Alem 1253, B8000ICP, Bahía Blanca, Argentina
c
Centro de Geología Aplicada y Medio Ambiente (CGAMA, CIC-UNS), Dpto. de Geología, Universidad Nacional del Sur, Bahía Blanca, Argentina
d
Laboratorio de Termocronología (La.Te Andes-CONICET), Las Moreras 310, A4401XBA, Vaqueros, Salta, Argentina
e
Laboratorio de Paleomagnetismo “Daniel A. Valencio”, Instituto de Geociencias Básicas, Aplicadas y Ambientales de Buenos Aires (IGEBA), Departamento de Ciencias
Geológicas, Facultad de Ciencias Exactas y Naturales (FCEyN), Universidad de Buenos Aires (UBA), Pabellón II 1428, CABA, Argentina

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

Keywords: Coal-bearing deposits of the Tunas Formation suggest the existence of potential gas-prone source rocks in the
Claromecó frontier Basin Claromecó Basin, south of Buenos Aires province, Argentina. Two wells, PANG 0001 and PANG 0003, containing
Permian Permian rocks assigned to the Tunas Formation were studied through core observation, X-Ray diffraction,
Coal-bearing deposits
petrographic description, geochemical analysis, and organic petrography to investigate the hydrocarbon po­
Source rock
Catagenesis
tential of the Claromecó Basin and define horizons with source rock potential. The analyzed sedimentary suc­
cessions are composed of medium- to fine-grained sandstones interbedded with tuffs, mudrocks, carbonaceous
mudrocks, and coal. Two main horizons with potential source rocks were determined: an upper horizon, at the
top of the succession (300–400 m) and a lower one, at the base (740–850 m). These layers are mainly composed
of mudrocks, carbonaceous mudrocks, and coal beds up to 4.50 m in cumulative thickness. Total organic carbon
(TOC%) content is high, with most samples ranging from 0.5 to 2% in organic-rich mudrocks, and from 26 to
53.9% in carbonaceous mudrocks and coals, characterizing the coal-bearing layers as good-quality source rocks.
The organic matter is of terrigenous origin as indicated by the abundance of woody plant debris. Predominant
organic matter constituents belong to vitrinite group (type III kerogen), with a low abundance of the inertinite
group macerals. Vitrinite reflectance (Ro) values in carbonaceous mudrocks and coals ranged from 1.3 to 1.6%
for the upper horizon to 1.9–2.4% at the lower one, reflecting a catagenesis to late catagenesis stage within the
wet to dry gas window. The organic matter quantity, type, and maturity in Tunas Formation coal-bearing de­
posits suggest that this unit has a good potential as gas-prone source rocks.

1. Introduction
Due to the growing demand for energy resources worldwide, hy­
drocarbon exploration in “frontier” basins and unexplored areas has
increased. The Claromecó Basin, located in southern Buenos Aires
province (Fig. 1a), Argentina, is considered a frontier basin (Lesta and
Sylwan, 2005), which has attracted considerable exploration interest
from the oil industry over the last decades. The basin extends from the
Sierras Australes fold and thrust belt towards the northeast and the
continental platform, covering about 65000 km2. Hydrocarbon explo­
ration in Buenos Aires province began in the 1990s, when gravimetric
studies, seismic data, and exploration wells found coal beds within the
Upper Paleozoic sedimentary record (Lesta and Sylwan, 2005). Seven oil
exploration wells were drilled onshore, some of which contain coal beds
in Piedra Azul and Tunas formations (Upper Carboniferous-Lower
Permian in age; Lesta and Sylwan, 2005). In the 2000s, the Rio Tinto
Mining company drilled cored boreholes to characterize and delimit
coal-bearing deposits. These wells, PANG 0001 (S37◦ 40.8′ 17.0′′ , W61◦
11.30′ 06′′ ) and PANG 0003 (S37◦ 34.0′ 44.24”, W61◦ 22.0′ 12.56′′ ),
located north-east of the Sierras Australes of Buenos Aires province
(Fig. 1a and b), penetrated several horizons with coals and carbonaceous
mudrocks, up to 11 m in thickness. Based on their age, lithology, and

* Corresponding author. Dpto. de Geología, Universidad Nacional del Sur, Avenida Alem 1253, B8000ICP, Bahía Blanca, Argentina.
E-mail address: belenfebbo@gmail.com (M.B. Febbo).

https://doi.org/10.1016/j.marpetgeo.2021.105491
Received 12 April 2021; Received in revised form 14 December 2021; Accepted 15 December 2021
Available online 21 December 2021
0264-8172/© 2021 Elsevier Ltd. All rights reserved.
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

fossiliferous content, the cores were assigned to the Tunas Formation

(Permian, Pillahuincó Group; Harrington, 1947).
Coal and coal-bearing deposits are of economic interest because they
can be considered gas-prone (Stahl, 1968; Barstenstein and Teichmüller,
1974; Lutz et al., 1975). The hydrocarbon generation potential of coals is
defined according to three basic parameters: coal grade (mineral matter
content versus organic matter content), coal type (macerals), and coal
rank (organic matter maturity) (O’Keefe et al., 2013). Thermogenic gas
generation begins at the high-volatile bituminous coal rank, with vitri­
nite reflectance values (Ro) between 0.6% and 0.8%, and reaches a
maximum at Ro ~ 1.2%, in the range of medium volatile bituminous
coal (Scott et al., 1994). Large volumes of gas can be retained on the
internal coal surfaces by adsorption (Thomas, 2002). Methane produced
from coal layers is an unconventional resource know as Coal Bed
Methane (CBM). CBM is economically produced in several coal basins in
the United States, Canada, China and Australia, and has become an
important exploration target in the Paraná Basin, Brazil (Kalkreuth
et al., 2006, 2010, 2013, 2020; Holz et al., 2010; Mussa et al., 2020,
2021). With increasing maturity, bituminous coals and anthracites will
continuously release generated hydrocarbons retaining only a small
portion in the porous coal system, whereas the rest migrates and may
eventually accumulate to form natural gas deposits (Meissner, 1984,
1987).
Permian coal beds in the southern part of Gondwana have been
mentioned by several authors (Hobday, 1986; Langford, 1992; Tankard
Fig. 2. Paleogeographic reconstruction of Gondwana during the Lower
et al., 1995; Jasper et al., 2008; Kalkreuth et al., 2006; Holz et al., 2010;
Permian and global distribution of coal beds in Permian basins, modified from
Mendonça Filho et al., 2013, among others). Carboniferous-Permian Arzadún et al. (2017).
coal deposits, characterized by Glossopteris flora, developed under
fluvial, deltaic, and paralic environments (Limarino et al., 2014 and
hydrocarbon exploration in Buenos Aires Province since potential source
references therein). The Upper Paleozoic stratigraphic succession of the
rocks have been identified in coal-bearing successions of the Permian
Claromecó Basin is correlated with Permian sequences of the Paraná
Rio Bonito Formation in the intra-cratonic Paraná Basin (Fig. 2; Kalk­
(Brazil) and Karoo (South Africa) Basins based on geological settings,
reuth et al., 2006; Holz et al., 2010; Mendonça Filho et al., 2013) and the
fossiliferous record, and geochronological ages obtained from detrital
Karoo Super-group in the Karoo foreland Basin (Fig. 2; Geel et al., 2015).
zircons in tuff beds (Fig. 2; Bangert et al., 1999; Tohver et al., 2012;
Hydrocarbon exploration in frontier basins involves identifying po­
Santos et al., 2006; Rocha-Campos et al., 2006, 2011; Alessandretti
tential source rocks and defining their characteristics, for example:
et al., 2013; López-Gamundi et al., 2013; Arzadún et al., 2018;
organic matter content, type, and thermal maturity (Tissot and Welte,
López-Gamundi and Rossello, 2021). This correlation encourages
1984; Hunt, 1996). The objectives of this study are two-fold: firstly, to

Fig. 1. a) Location of the Claromecó Basin, PANG 0001 and PANG 0003 wells, and Gonzales Chaves locality (G. Chaves), located at the basin center. Basin limits
defined by Kostadinoff and Reartes, (1993), Ramos and Kostadinoff (2005) and Pángaro and Ramos (2015). b) Location of PANG 0001 and PANG 0003 wells, located
at the northeastern of the Sierras Australes, modified from Suero (1972).

2
M.B. Febbo et al.
characterize coal-bearing deposits from the Tunas Formation through
core observation, X-Ray diffraction, petrographic description,
geochemical analysis, and organic petrography; and secondly, to
investigate the hydrocarbon potential of the Claromecó Basin and define
potential source rock horizons. The results of this study can help to
decrease uncertainties in the exploration of potential conventional
and/or unconventional (CBM) gas resources in southern Buenos Aires
province.
2. Geological setting
The Claromecó Basin, extending between ~37◦ and 39◦ S and
61◦ –63◦ W (Fig. 1a), belonged to the southwestern Gondwana margin
during the Late Paleozoic (Fig. 2; Keidel, 1916; Du Toit, 1927; Har­
rington, 1947). It has been interpreted as a foreland basin during the
Carboniferous–Permian (López-Gamundi and Rossello, 1992; Ramos,
2008; Tomezzoli, 2012). The Paleozoic Claromecó Basin limits extend
from the Sierras Australes to the east-northeast area, close to the Tan­
dilia System (Fig. 1a). The basin extends to the south, toward the
Fig. 3. Stratigraphic column of the Paleozoic sedimentary succession of the Claromecó Basin, modified from Ramos et al. (2014). U–Pb zircon ages from tuff layers of
the Tunas Formation were obtained by Tohver et al. (2008); Alessandretti et al. (2013); López-Gamundi et al. (2013) and Arzadún et al. (2018).
3
Marine and Petroleum Geology 137 (2022) 105491
Argentinian platform, constituting the basement of the Mesozoic Colo­
rado Basin (Fryklund et al., 1996). Pángaro et al. (2015) interpreted the
Claromecó Basin as a part of the Hespérides Basin, which laterally
continues in the Kalahari-Karoo Basin (Africa) in the east and in the
Chaco-Paraná Basin (South America) to the northwest. The sedimentary
infill reaches a maximum thickness of 9–10.5 km (Kostadinoff and
Prozzi, 1998; Introcaso, 1982; Kostadinoff, 2007). Seismic data and
offshore exploration wells confirm the extension of the basin southward,
towards the Argentinian continental platform (Lesta and Sylwan, 2005;
Pángaro and Ramos, 2012).
The Claromecó Basin can be divided into two different geological
parts: the exhumed basin, in its southwestern portion, including the
highly deformed successions outcropping in the Sierras Australes fold
and thrust belt, and the subsurface basin, in the northeastern portion,
showing weak deformation (Von Gosen et al., 1989). Paleomagnetic and
anisotropy of magnetic susceptibility (AMS) studies from the Tunas
Formation (Tomezzoli, 2001; Arzadún et al., 2016b; Febbo et al., 2021)
confirm a decrease in the magnitude of deformation during the Permian
toward the foreland basin. The tectonic evolution of the Claromecó
M.B. Febbo et al.
Basin is linked to the collision of the Patagonia terrain with the south­
western Gondwana margin during the Late Paleozoic (Ramos, 2008;
Tomezzoli, 2001; Pángaro and Ramos, 2012; Ramos and Naipauer,
2014). Ramos and Kostadinoff (2005) proposed the development of the
basin in three stages: a rifting phase during the Early Paleozoic followed
by a passive margin period from the Ordovician to the Devonian and,
lastly, the development of a foreland basin, from the Carboniferous to
the Early Permian (Fig. 3). During the Mesozoic, several rifting events
affected the southern part of this area resulting in the formation of the
Colorado Basin, at the Argentinian continental platform (Lovecchio
et al., 2018; Arzadún et al., 2020).
The Upper Paleozoic succession of the Claromecó Basin comprises
the lithostratigraphic units known as Pillahuincó Group, subdivided into
four formations: Sauce Grande, Piedra Azul, Bonete, and Tunas (Har­
rington, 1947, Fig. 3). These units are exposed along the eastern portion
of the Sierras Australes (Fig. 1b) and continue toward the east, covered
by Cenozoic deposits, with a maximum thickness of 2800 m (Harrington,
1970, Fig. 3). The Late Carboniferous (Pennsylvanian-Cisuralian) Sauce
Grande Formation has a maximum thickness of 1100 m and consists of
diamictites, sandstones, and mudrocks of glacimarine origin (Andreis
et al., 1989; di Pasquo et al., 2008). Glacial conditions were progres­
sively replaced by fine-grained sandstones and mudrocks of the Piedra
Azul Formation, deposited in a shallow marine environment (Harring­
ton, 1947). The Early Permian Bonete Formation (Harrington, 1947)
conformably overlies the Piedra Azul Formation and is composed of
shallow marine arkosic-sandstones and mudrocks with Eurydesma fauna
and Glossopteris flora (Archangelsky and Cúneo, 1984).
The Tunas Formation is the youngest unit of the Pillahuincó Group
(Harrington, 1947, Fig. 3) and represents the last stage of the Paleozoic
basin filling. This unit is exposed from the north of Sierras de las Tunas
to the south of Sierra de Pillahuincó (Fig. 1b), with small isolated out­
crops near Gonzales Chavez locality (Fig. 1a; Monteverde, 1937; Furque,
1965; Harrington, 1970; Febbo et al., 2018a). There are many un­
certainties about its thickness due to the absence of marker horizons,
homogeneous lithology, and tectonic complexity. The exposed thickness
ranges from 600 to 2400 m (Harrington, 1970; Suero, 1972; Andreis and
Japas, 1991; Prezzi et al., 2018; Vazquez Lucero et al., 2020). In the
subsurface, this unit reaches 700 m in thickness (Lesta and Sylwan,
2005; Arzadún et al., 2017). In outcrops, Tunas Formation deposits
consist of fine- to medium-grained greenish and yellowish sandstones
with cross-stratification, interbedded with laminated purple and green
siltstones, claystones and thin pyroclastic beds (Harrington, 1947, 1970;
Andreis et al., 1989; López-Gamundi, 1996, 2006). In the subsurface,
these deposits consist of medium to fine-grained sandstones, inter­
bedded with black organic rich mudrocks, heterolites, greenish
mudrocks, tuff layers, carbonaceous mudrocks, and coals (Lesta and
Sylwan, 2005; Arzadún et al., 2016a, 2017; Zavala et al., 2019; Febbo
et al., 2021). The Glossopteris flora indicates an Early Permian age
(Sakmarian-Artinskian; Harrington, 1947; 1970; Archangelsky and
Cúneo, 1984; Cúneo, 1996), consistent with U–Pb ages of 280–291 Ma
obtained from pyroclastic layers (Tohver et al., 2008; López-Gamundi
et al., 2013; Alessandretti et al., 2013; Arzadún et al., 2018, Fig. 3).
Arzadún et al. (2018) obtained SHRIMP U–Pb zircon ages of 295.5 ± 8.0
Ma (Asselian – Sakmarian) from tuff layers at ~700 m of PANG 0001
well (Fig. 4).
The Tunas Formation was deposited in deltaic to fluvial environ­
ments (Andreis et al., 1989; López-Gamundi et al., 1995, 2013; Andreis
and Japas, 1991; Zavala et al., 2019; Ballivián Justiniano et al., 2020),
representing the culmination of a regressive cycle after shallow marine
conditions (Piedra Azul and Bonete formations). Toward the foreland
basin, subsurface facies of Tunas Formation (PANG 0001 and PANG
0003) are interpreted as a river-dominated deltaic environment, where
coal beds developed on floodplains and interdistributary swamps
(Zavala et al., 2019).
Regarding the diagenetic history of the Tunas Formation, studies of
illite crystallinity from outcrops indicate a mesogenetic to very low-
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Marine and Petroleum Geology 137 (2022) 105491
grade metamorphic stage (Buggisch, 1987; Von Gosen et al., 1989). In
addition, mineralogical associations of laumontite-albite from PANG
0003 well samples, located at medium and basal layers, indicate a
mesogenetic stage (Febbo et al., 2018b). Preliminary studies in Tunas
Formation sandstone facies from the subsurface (PANG 0001; Febbo
et al., 2018b) and outcrops (Rossello, 2016; López-Gamundi and Ros­
sello, 2021) suggest naturally fractured sandstone beds have potential as
hydrocarbon reservoir rocks.
3. Methodology
PANG 0001 and PANG 0003 wells, located in the center of
Claromecó Basin (Fig. 1), contain the Tunas Formation record (Figs. 4
and 5) reaching depths of 958 and 900 m below wellhead (mbw),
respectively. The top of the succession is overlain by Cenozoic deposits
with a thickness of 190 and 170 m in PANG 0001 and PANG 0003 wells,
respectively. The lithology of the cores is described in detail with
particular emphasis on rock color, grain size, bedding contacts, sedi­
mentary structures, and bioturbation (Figs. 4 and 5). The bioturbation
index (BI) based on Reineck (1963) and Taylor and Goldring (1993) was
used to analyze bioturbation intensity.
Representative samples from fine-grained lithologies were collected
for petrographic analyses. Samples were analyzed with a Nikon Eclipse
50i POL microscope. X-Ray diffraction (XRD) analyses were done using a
Rigaku D-Max III-C diffractometer, Kα of Cu radiation, with a voltage of
30 kV, current of 15 mA, and scan of 2◦ per minute. Petrography and
XRD analyses were performed at Departamento de Geología, Uni­
versidad Nacional del Sur (Bahía Blanca, Argentina).
Geochemical analyses were performed to define the hydrocarbon
generation potential of the Tunas Formation. Core samples were
collected along the entire successions with particular emphasis on upper
(300–400 m) and lower (700–900 m) beds, where carbonaceous li­
thologies are located (Figs. 4 and 5). Sampling criteria are based on
lithological features, such as fine grain sizes, dark color, absence of
bioturbation, and presence of thin coal layers and pyrite.
Total carbon (TC%), total inorganic carbon (TIC%), total organic
carbon (TOC%), and total sulfur (TS%) were determined for 65 samples
(n = 24 from well PANG 0001 and n = 41 from well PANG 0003; Figs. 4
and 5) using a LECO® analyzer at the LABSPA-CERZOS-CONICET lab­
oratory, Departamento de Agronomía, Universidad Nacional del Sur.
Crushed samples (~100 mg) were heated to 1000 ◦ C in an induction
furnace after carbonate removal with hydrochloric acid (HCl) to deter­
mine these parameters.
Macroscopic samples and thin sections were examined to charac­
terize organic matter type. The results obtained were combined with
organic petrography and vitrinite reflectance (Ro) studies performed by
Arzadún et al. (2017) at Instituto de Geología Económica Aplicada
(IGEA, Universidad de Concepción, Chile), on seven samples from PANG
0001 coals and carbonaceous mudrocks from different stratigraphic
positions (Fig. 4). Organic matter quantity, quality and maturity were
used to determine the hydrocarbon potential of coal-bearing layers (e.g.,
Teichmüller, 1974; Teichmüller and Wolf, 1977; Taylor et al., 1998;
Tissot and Welte, 1984; Hunt, 1996; Vandenbroucke and Largeau, 2007;
Suárez-Ruiz et al., 2012).
4. Results
4.1. Lithology of the Tunas Formation
The analyzed successions (PANG 0001 and PANG 003 wells, Figs. 4
and 5) comprise more than 700 m sedimentary rocks of the Tunas For­
mation (Early Permian). The lower parts of both sections consist of thin
medium- to fine-grained sandstones with irregular bases, followed by
thick packages of carbonaceous mudrocks and coal beds with cumula­
tive thickness of up to 25 m, delimited by planar bases, with abundant
pyrite nodules, plant remains and Glossopteris imprints. The PANG 0003
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

Fig. 4. Sedimentary profile of the Tunas Formation in PANG 0001 well, Claromecó Basin, modified from Arzadún et al. (2017). Stratigraphic positions of samples are
represented with different symbols: red circles for TOC; blue stars for organic petrography and Ro; and orange stars for petrographic analyses.

5
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

Fig. 5. Sedimentary profile of the Tunas Formation in PANG 0003 well, Claromecó Basin. Stratigraphic positions of samples are represented with different symbols:
red circles for TOC; violet stars for XDR; orange stars for petrographic analyses; and light-blue stars for macroscopic core samples.

6
M.B. Febbo et al.
succession has thicker carbonaceous beds than the PANG 0001 well
(Figs. 4 and 5).
Toward the top of the sections, coal strata become thinner and
gradually disappear, replaced by thick packages (~20 m) of medium- to
fine-grained sandstones, with irregular bases and abundant plant re­
mains interbedded with grayish laminated mudrocks and thin tuff
layers.
The upper parts of the successions are characterized by greenish
massive mudrocks and medium to fine-grained sandstones, interbedded
with intensely bioturbated mudrocks, heterolites, fine-grained sand­
stones, and thin carbonaceous beds. Sedimentary profiles end with
greenish massive mudrocks and heterolites packages, with up to 15 m
cumulative thickness, and thin layers of medium- to fine-grained
sandstones.
Twelve main lithologies were identified based on sedimentary
features:
− Laminated tuffs (Tl): Laminated fine-grained greenish tuffs, up to 5
m in thickness, with planar bases. Presence of associated thin coal
beds (0.5–1 cm) and calcite and pyrite in fractures (Fig. 6a).
− Massive mudrocks (Mm): Massive to laminated greenish mudrocks,
range from 1 to 10 m in thickness, planar bases, abundant clay clasts,
carbonate nodules, and disseminated pyrite (Fig. 6b).
− Laminated mudrocks (Ml): Laminated greyish mudrocks, 2–20 m
thick, with planar bases. Presence of plant remains, weak bio­
turbation (BI: 2), abundant pyrite nodules, and calcite veins (Fig. 6c).
− Bioturbated mudrocks (Mb): Bioturbated greyish mudrocks, up to 2
m in thickness, with planar bases, weakly laminated, and intense
bioturbation (BI: 4) (Fig. 6d).
Fig. 6. Photos of a) Laminated tuffs (Tl) with pyrite in fractures (py). b) Massive mudrocks (Mm) with clay clasts and pyrite (py). c) Laminated mudrocks (Ml) with
abundant plant remains and pyrite nodules. d) Bioturbated mudrocks (Mb). e) Carbonaceous mudrocks (Mc) with thin coal beds interbedded and calcite veins. f) Coal
(C) with plant imprints, plant remains and pyrite (py). The sample numbers are marked on each photo, for location of samples see Fig. 5.
7
Marine and Petroleum Geology 137 (2022) 105491
− Carbonaceous mudrocks (Mc): Massive to laminated black
mudrocks, 0.5–7 m thick, planar to transitional bases, interlayered
with thin coal beds (1–5 cm). Presence of plant imprints, abundant
plant remains, calcite veins, and pyrite, occurring in nodules and
fractures. (Fig. 6e).
− Coal (C): Coal beds, range from 0.5 to 4.5 m in thickness. Presence of
pyrite, plant imprints, and calcite veins (Fig. 6f).
− Heterolites (H): Greyish heterolites, 1–20 m thick, with planar to
transitional bases, composed of fine-grained sandstones and lami­
nated mudrocks. Sandstones vary in thickness between 3 and 5 cm,
with wavy bedding structure, while mudrocks have a thickness of
1–3 cm. Heterolites present thin coal beds, abundant plant remains
and weak to moderate bioturbation (BI: 2–3) (Fig. 7a).
− Medium sandstones (Sm): Greyish to greenish medium- to fine-
grained sandstones with cumulative thickness up to 7 m, irregular
sharp bases, cross-bedding to massive stratification, and abundant
plant remains (Fig. 7b).
− Fine sandstones (Sf): Greyish fine- to very fine-grained sandstones,
with variable thickness of 1–15 m, planar and irregular bases, ripple
cross-lamination structure, abundant plant remains, and pyrite
(Fig. 7c).
− Very fine sandstones (Svf): Dark fine- to very fine-grained sand­
stones, up to 5 m in thickness, planar bases, weakly laminated to
massive stratification, and thin coal beds (up to 0.5 cm). Presence of
weak bioturbation (BI: 2), abundant plant remains, coal clasts, and
pyrite nodules (Fig. 7d).
− Carbonatic sandstones (Sc): Greyish fine- to very fine-grained
sandstones, with cumulative thickness up to 5 m, planar to
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

Fig. 7. Photos of a) Heterolites (H) with bioturbation, plant remains, and thin coal beds. b) Medium-grained sandstones (Sm) with plant remains. c) Fine-grained
sandstones (Sf) with plant remains. d) Very fine-grained sandstones (Svf) with plant remains, pyrite (py), and thin coal beds. e) Carbonatic sandstones (Sc). f)
Bioturbated sandstones (Sb) with intense bioturbation. The sample numbers are marked on each photo, for location of samples see Fig. 5.

transitional bases, weakly laminated to massive stratification, and
carbonate cement and nodules (Fig. 7e).
− Bioturbated sandstones (Sb): Greyish fine- to very fine-grained
sandstones, up to 2 m in thickness, planar to transitional bases,
massive stratification, plant remains, and intense bioturbation (BI:
3–4) (Fig. 7f).
f). In addition, there are four horizons located at the base of the
sequence, composed of interbedded mudrocks and coal beds, with a
cumulative thickness of 4.50 m (Fig. 5). The upper horizon, between 282
and 320 m in depth (Fig. 5), consists of very fine-grained sandstones
with abundant plant remains, interbedded with laminated mudrocks,
bioturbated mudrocks, heterolites, and abundant thin coal beds (5 cm
thick) (Fig. 6a, d and 7a).

4.2. Organic-rich horizons in Tunas Formation

4.3. XDR and petrographic analyses
Two main intervals composed of organic-rich fine-grained lithologies
Whole-rock XDR analyses were performed on mudrocks and carbo­
were observed in the Tunas Formation cores: a lower horizon at the base
naceous mudrocks to determine their mineralogical composition. The
of the succession and an upper one at the top (Figs. 4 and 5). These layers
samples have a homogenous mineral composition. Quartz, feldspars,
could be correlated between both wells based on stratigraphic position,
and phyllosilicates (mica/illite, chlorite/smectite) were identified in
lithology, fossiliferous record (Glossopteris imprints), and TOC content
mudrocks (Fig. 8a), while quartz, feldspars, phyllosilicates (mica/illite),
(Table 1).
and pyrite were observed in carbonaceous mudrocks (Fig. 8b).
The lower interval of the PANG 0001 well, between 836 and 850 m
From petrographic analyses, mudrocks and carbonaceous mudrocks
(Fig. 4), consists of carbonaceous mudrocks and coals interbedded with
were classified as claystones and argillaceous siltstones according to
laminated mudrocks. Coal layers have a maximum thickness of 1.50 m.
their grain size. Their mineral composition consists of quartz, feldspar,
Plant imprints and pyrite are common in carbonaceous mudrocks and
and phyllosilicates (muscovite, biotite, chlorite, and clay minerals)
coal beds (Fig. 6e and f). The upper horizon, between 390 and 412 m
(Fig. 9 a-d). Organic matter and framboidal pyrite are common in
(Fig. 4), is characterized by very fine-grained sandstones with abundant
mudrocks (Fig. 9 b-d) and very fine-grained sandstones (Fig. 10 a-d).
plant remains interbedded with laminated mudrocks, carbonaceous
Carbonaceous mudrocks show dispersed organic matter and carbonate
mudrocks, and tuffs. Thin coal beds are 3 cm thick. Plant remains and
veins (Fig. 9 c-d).
pyrite are common in laminated mudrocks and very fine-grained sand­
stones (Figs. 6b and 7d).
The lower interval of the PANG 0003 well, between 787 and 823 m in 4.4. Organic matter analysis
depth (Fig. 5), consists of laminated mudrocks, carbonaceous mudrocks,
and coal beds with a maximum thickness of 3.50 m. Plant imprints and 4.4.1. Total organic carbon
pyrite are common in carbonaceous mudrocks and coal beds (Fig. 6e and Organic matter content was evaluated by TOC measurements from

8
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

Table 1
Geochemical results from PANG 0001 and PANG 0003 wells. TC %, total carbon; TIC %, total inorganic carbon; TOC %, total organic carbon; total S %, total sulfur.
Well Samples Depth (m) Lithologies TC (%) TIC (%) TOC (%) total S %

PANG 0001 571 231.70 Heterolite 5.416 0.021 5.395 0.078

553 248.90 Laminated mudrock 0.723 0.041 0.682 0.030
475 344.45 Laminated mudrock 0.654 0.038 0.616 0.528
471 350.70 Carbonaceous mudrock 0.552 0.036 0.516 0.073
467 355.78 Laminated mudrock 1.439 0.862 0.577 0.040
464 358.44 Carbonaceous mudrock 1.817 0.359 1.458 0.059
457 365.62 Laminated mudrock 2.606 0.864 1.742 0.053
452 371.70 Laminated mudrock 0.359 0.021 0.338 0.022
449 374.54 Laminated mudrock 3.088 0.709 2.379 0.032
432 397.90 Laminated mudrock 0.402 0.012 0.390 0.012
426 403.44 Laminated mudrock 0.988 0.017 0.971 0.013
400 441.60 Laminated mudrock 2.535 0.026 2.509 0.058
382 466.02 Laminated mudrock 0.191 0.028 0.163 0.012
370 484.75 Laminated mudrock 0.223 0.023 0.200 0.019
312 563.20 Massive mudrock 1.448 0.362 1.086 0.021
301 574.90 Massive mudrock 0.642 0.052 0.590 0.028
269 603.86 Laminated mudrock 0.930 0.039 0.891 0.015
230 650.28 Laminated mudrock 4.706 0.454 4.252 0.070
212 679.72 Bioturbated mudrock 0.513 0.019 0.494 0.023
149 769.80 Laminated mudrock 1.360 0.043 1.317 0.054
129 792.92 Carbonaceous mudrock 26.390 0.292 26.098 0.599
76 858.03 Laminated mudrock 3.342 0.092 3.250 0.071
101 925.00 Laminated mudrock 2.851 0.921 1.930 0.065
21 939.81 Laminated mudrock 4.867 0.086 4.781 0.048
PANG 0003 383 176.60 Massive mudrock 0.296 0.138 0.158 0.037
348 245.85 Massive mudrock 0.101 0.008 0.093 0.021
342 255.95 Massive mudrock 0.018 <0.001 0.018 0.020
324 292.60 Laminated mudrock 0.794 0.322 0.472 0.054
320 299.95 Heterolite 1.541 0.003 1.538 0.026
313 312.70 Heterolite 6.204 <0.001 6.204 0.071
310 324.10 Laminated mudrock 1.179 <0.001 1.179 0.036
308 348 Laminated mudrock 0.045 <0.001 0.045 0.009
299 382.70 Massive mudrock 0.114 0.004 0.11 0.020
265 486 Massive mudrock 0.227 <0,001 0.227 0.087
254 505.95 Laminated mudrock 0.213 0.007 0.206 0.004
242 531.25 Carbonaceous mudrock 2.426 0.004 2.422 0.101
231 547.60 Laminated mudrock 0.359 <0,001 0.359 0.024
230 550.65 Laminated mudrock 0.581 0.008 0.573 0.030
222 566.85 Carbonaceous mudrock 1.221 0.153 1.068 0.239
215 588.30 Laminated mudrock 0.789 <0,001 0.789 0.013
213 595.40 Laminated mudrock 0.084 <0,001 0.084 0.015
209 606.70 Heterolite 0.802 <0,001 0.802 0.033
204 618.55 Laminated mudrock 0.552 0.004 0.548 0.025
196 634.20 Laminated mudrock 6.829 0.204 6.625 0.051
193 638.60 Laminated mudrock 0.171 0.007 0.164 0.040
167 693.08 Carbonaceous mudrock 1.185 0.666 0.519 0.053
152 709.75 Laminated mudrock 0.376 <0,001 0.376 0.016
149 714.53 Carbonaceous mudrock 34.474 <0.001 34.474 1.787
127 743.86 Laminated mudrock 0.626 <0.001 0.626 0.017
125 746.30 Laminated mudrock 0.169 <0.001 0.169 0.035
120 753 Carbonaceous mudrock 1.481 0.087 1.394 0.046
112 769 Carbonaceous mudrock 1.619 0.109 1.51 0.054
103 778.53 Carbonaceous mudrock 0.639 <0.001 0.639 0.034
97 786.25 Coal 57.472 3.486 53.986 1.767
85 799.40 Carbonaceous mudrock 1.164 <0.001 1.164 0.011
80 807.15 Coal 49.78 <0.001 49.78 1.724
61 829.47 Laminated mudrock 0.346 <0.001 0.346 0.043
58 832.30 Carbonaceous mudrock 2.348 0.0669 2.2811 0.045
49 842.40 Coal 50.912 <0.001 50.912 1.509
42 851 Laminated mudrock 1.215 0.004 1.211 0.045
39 853.60 Coal 29.973 <0.001 29.973 1.937
31 867.20 Laminated mudrock 2.062 <0.001 2.062 0.075
13 888.40 Carbonaceous mudrock 4.214 <0.001 4.214 0.173
6 896.55 Carbonaceous mudrock 0.992 0.011 0.981 0.064
2 900.78 Laminated mudrock 1.693 0.977 0.716 0.041

different stratigraphic positions of the PANG 0001 and PANG 0003 wells
(Figs. 4 and 5). Total carbon (TC%), total organic carbon (TOC%), total
inorganic carbon (TIC%) and total sulfur (TS%) of all samples are pre­
sented in Table 1. TOC shows large variations, ranging from 0.01 to
53.9%, with most of the samples showing contents of 0.5–2% (Fig. 11).
Outliers obtained from coal and carbonaceous mudrocks (TOC:
26–53.9%) were excluded for the calculation of mean TOC values, as
they are limited to some intervals and are not characteristic of the whole
formation. TOC values from the PANG 0001 samples range from 0.16%
to 5.39%, with an average of 2.73% (Fig. 11). Results from the PANG
0003 samples range from 0.01% to 6.62%, with an average of 2.64%
(Fig. 11). TIC shows values between 0.001 and 0.9%, with an average of
0.05% (Table 1; Fig. 11). TS values range from 0.01 to 1.93%, with a
mean value of 1% (Table 1; Fig. 11). The maximum sulfur

9
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

Fig. 8. XRD diagram showing peaks corresponding to quartz (Qtz), feldspars (Fsp), muscovite/illite (Ms/ill), chlorite/smectite (Chl/Sm), and pyrite (Py) for a)
mudrocks (sample 127; Fig. 5) and b) carbonaceous mudrocks (sample 58; Fig. 5).

Fig. 9. Photomicrographs under transmitted light of mudrocks (a-b, sample 49; Fig. 5) and carbonaceous mudrocks (c-d, sample 92; Fig. 5) composed of quartz (Qtz),
feldspar (Fsp), biotite (Bt), and muscovite (Ms). Carbonaceous mudrocks show dispersed organic matter (OM) and carbonate veins (Ca Vn).

concentrations (>0.5%) are related to high TOC values, recorded in 5. Discussion

carbonaceous mudrocks and coals (Table 1; Fig. 11).
4.4.2. Organic matter type
Core observation and petrography revealed the terrestrial origin of
the organic matter, composed of plant remains and woody tissues. The
organic matter is dispersed in fine-grained lithologies (i.e., mudrocks
and heterolites; Figs. 6c, 7a and 9a, b), fine-grained sandstones (Fig. 7c
and d and 10), carbonaceous mudrocks (Figs. 6e and 9c, d), and forms
coals (Fig. 6f). Analyzed coal and carbonaceous samples also contain a
considerable amount of minerals (Figs. 9 and 10; Table 2).
Effective source rocks result from deposition and good preservation
of organic matter in fine-grained sediments, followed by thermal
maturation, usually due to burial (Tissot and Welte, 1984). The main
requirements for characterizing a potential source rock are as follows: i)
amount of organic matter in the rock; ii) quality and type (different types
of organic matter have different hydrocarbon potentials) of organic
matter capable of yielding hydrocarbons; iii) maturity of organic matter.
In this contribution, published data and new results will be discussed
and integrated to define potential hydrocarbon source rocks at the
Claromecó Basin.
The Tunas Formation constitutes a siliciclastic succession alternating
with organic-rich deposits composed of terrestrial material, recorded at

10
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

Fig. 10. Photomicrographs of fine-grained sandstones (samples 411 and 458; Fig. 4) under transmitted (a–c) and reflected light (d) with dispersed organic matter
(OM), quartz (Qtz), biotite (Bt), and framboidal pyrite (py).

the top and the base of the sequence. Variations of lithology and organic
matter content and type were controlled by the paleo depositional
environment, chemical conditions during deposition, such as fluid cir­
culation, oxidation potential (Eh), hydrogen ion concentration (pH), and
biological activity (Berner, 1980; Berner and Canfield, 1989; Bralower
and Thierstein, 1984; Burdige, 2007; Tyson, 2001), and subsequent
burial that protect the organic matter from surface processes. By
contrast, the degree of organic matter maturity is a function of sedi­
mentation and the resulting burial as well as the thermal and tectonic
scenarios throughout geologic history (Suárez-Ruiz et al., 2012 and
references therein). The thermal stress experienced by the organic
matter is controlled by temperature rise during burial, geothermal
gradient, and tectonic processes.
5.1. Depositional conditions and organic matter preservation
The paleoenvironmental, paleogeographic, and paleotectonic setting
during Tunas Formation sedimentation favored the generation, accu­
mulation, and preservation of the organic matter that formed carbona­
ceous deposits in the Claromecó Basin. The analyzed sedimentary
profiles of PANG 0001 and PANG 0003 wells (Figs. 4 and 5) show a great
lithological heterogeneity that evidences chemical and physical changes
in the paleoenvironment during sedimentation, such as flow rate, sedi­
mentary input, oxygen content (anoxic/oxic conditions) and bacterial
activity. The depositional paleoenvironment of Tunas Formation facies
(PANG G0001 and PANG 0003 well) has been interpreted by Zavala
et al. (2019) as a fluvial-dominated deltaic system. These authors
defined transgressive-regressive cycles represented by lower delta-plain
deposits at the lower part of the successions, defined by carbonaceous
facies. The coal-bearing deposits progressively changed toward the
upper section to delta front and shelf deposits, characterized by sandy
and heterolites facies respectively.
The base of the Tunas Formation sedimentary record is composed of
carbonaceous mudrocks and coals, interbedded with medium- to fine-
grained sandstones (Sm and Sf; Figs. 4 and 5), deposited in floodplains
and interdistributary swamp environments (Zavala et al., 2019).
Coal-bearing deposits with high TOC (5–54%), TS (>1.5%), and pyrite
content (Table 2; Fig. 10c and d, 11 and 12b, d, f) are indicative of low
energy and reducing conditions, which established a favorable
environment for the accumulation and preservation of organic matter
and pyrite precipitation (Berner, 1980; Canfield and Berner, 1987). In
addition, high sediment input contributed to a rapid burial, and,
consequently, to the preservation of organic matter.
Towards the top of the succession, carbonaceous mudrocks and coal
beds become thinner and rare, replaced by fine- to medium-grained
sandstones (Sm and Sf) interbedded with thin mudrocks and tuff
layers (Figs. 4 and 5), which mark a gradual transition from delta plain
to delta front deposits (Zavala et al., 2019). Sandy facies reveal
high-energy conditions of the paleoenvironment, leading to dilution of
organic material, as evidenced by numerous preserved plant remains
(Fig. 7b and c; Fig. 10 a-d). The decrease in organic matter content in
fine-grained lithologies (TOC between 0.1 and 6%) and the absence of
carbonaceous layers in this portion of the succession could indicate the
prevalence of a sub-oxic environment.
The sedimentary record culminates with intensely bioturbated
mudrocks, fine to very fine-grained sandstones (Sf and Svf), heterolites,
mudrocks (Mm and Ml), and thin coal beds (Figs. 4 and 5) deposited in a
prodelta and shelf environment (Zavala et al., 2019). These deposits are
related to oscillations in the water column and oxygen level concen­
trations, which affected the organic matter preservation/oxidation.
Bioturbated mudrocks reflect an increase in oxygen content and bacte­
rial activity which degraded the organic matter by oxidation (Figs. 6d
and 7f). Additionally, the increasing sediment input could have
contributed to the dilution of organic matter by siliciclastic components,
promoting the deposition of very fine-grained sandstones and heterolites
with abundant plant remains (Fig. 7a and d). Low-energy episodes and
reducing conditions, together with increased bacterial activity, could
have favored short periods of anoxia documented by organic-rich
mudrocks and thin coal layers with high TOC (0.5–6%) and pyrite
content.
The deltaic depositional environment gave rise to coal-bearing de­
posits composed of thick carbonaceous mudrock with a significant
amount of mineral matter content (sometimes >50%, Table 2, Arzadún
et al., 2017, Figs. 8 and 9) alternating with organic-rich layers. This
results in coal grade variations between medium grade (<20% mineral
matter; Table 2, Arzadún et al., 2017) and very low grade (30–50%;
Table 2, Arzadún et al., 2017). Siliceous mineral matter predominates
(quartz and clays, Figs. 8 and 9), while carbonate content is low

11
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

Fig. 11. Lithostratigraphic logs of the PANG 0001 and PANG 0003 wells plotted against geochemical data (TOC, TIC, TS). Values of TOC >30%, TIC >0.75%, and TS
> 1.5 are represented out of scale. In addition, variations of macerals (Vitrinite, Inertinite), mineral matter, pyrite content, and Ro values from carbonaceous
mudrocks and coals of the PANG 00001 well obtained by Arzadún et al. (2017) are presented.

12
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

Table 2 (Table 1). Oscillation in the water column, resulting from

Maceral (Vitrinite and Inertinite), mineral matter, and pyrite content from transgressive-regressive cycles, and high siliciclastic input, conditioned
carbonaceous mudrocks and coal samples from the Tunas Formation, belonging coal bed thickness and favored deposition of sandstones and heterolites
to PANG 0001 well, based on Arzadún et al. (2017). (Figs. 4 and 5).
Well Sample Depth Vitrinite Inertinite Mineral Pyrite The development of carbonaceous deposits could be further favored
(m) (%) (%) matter (%) by the paleogeographic position of the Claromecó Basin during the Early
(%)
Permian (Fig. 2; Tomezzoli, 2009; Arzadún et al., 2017; Tomezzoli et al.,
PANG 433 396.18 46.63 12.15 40.32 0.90 2018) and paleoclimatic conditions. Carboniferous-Permian coal de­
0001 420 412.65 55.20 24.17 17.74 2.89 posits in southwestern Gondwana basins (e.g., Karoo Basin, southern
111 813.10 56.77 28.52 14.70 0
C 842.00 0.83 1.05 98.03 0.09
Africa, and Paraná Basin, Brazil; Holz et al., 2002; Holz et al., 2010;
A 842.00 58.26 0 30.30 11.44 Mendonça Filho et al., 2013; Langford, 1992) reveal an improvement in
83 850.33 64.91 2.11 30.82 2.16 climate conditions during the Late Paleozoic, resulting from the Gond­
79 856.87 54.02 13 31.72 1.26 wana supercontinent drift across the South Pole towards high paleo­
latitudes (Limarino et al., 2014; Tomezzoli et al., 2018; Gallo et al.,
2020, Fig. 2). Glacial conditions during the Devonian–Early Carbonif­
erous gave way to a cold and humid climate, which allowed

Fig. 12. Photomicrographs with reflected light from carbonaceous mudrocks and coals from the PANG 0001 well, where different components (macerals, mineral
matter, and pyrite) are observed, modified from Arzadún et al. (2017). a) Collotelinite (Col) and fragment of fusinite (Fu). b) Collotelinite (Col) interbedded with
fusinite (Fu) and pyrite (Py) filling the structure gaps. c) Fusinite (Fu) where the plant structure is observed. d) Collotelinite (Col) with pyrite (Py) associated. e)
Collotelinite (Col) interbedded with mineral matter (Mi) and fusinite (Fu). f) Gelinite (Ge) interbedded with mineral matter (Mi) and framboidal pyrite (Py). Analyzed
samples correspond to the lower horizon of the PANG 0001 well: samples 111 (a–c) and 83 (d–f) (see Fig. 4 for samples location).

13
M.B. Febbo et al. Marine and Petroleum Geology 137 (2022) 105491

peat-forming vegetation to accumulate in the Upper Carbon­
iferous–Early Permian (Limarino et al., 2013 and references therein).
During the Upper Permian–Lower Triassic, the continents continued
moving towards high latitudes to form Pangea, which contributed to the
increase in global temperature and semiarid or arid conditions (Limar­
ino et al., 2014; Gallo et al., 2020). In addition, the paleotectonic
configuration of the basin, acting as an active foreland basin with a high
continental input during the Late Paleozoic (Ramos, 1984;
López-Gamundi and Rossello, 1992; Tomezzoli, 2012) could have
influenced the rate of subsidence and accumulation of sediments and,
therefore, the thickness of the carbonaceous layers.
5.2. Organic matter content
documented in the sedimentary record of southern Gondwana Basins,
attributed to peat fires (Scott and Jones, 1994; Scott, 2000, 2010;
Mendonça Filho et al., 2013; Jasper et al., 2008, 2011, 2012, 2013;
Degani-Schmidt et al., 2015; Kauffmann et al., 2016; Arzadún et al.,
2017; Benício et al., 2019). The presence of inertinite in low quantities
in coal samples from basal horizons (Fig. 11), and more predominant in
samples from the upper section (Fig. 11), reflects drier and more
oxidizing environmental conditions (Taylor et al., 1989; Scott, 2000,
2002) toward the top of the succession. This is in agreement with
paleoenvironmental interpretations made by other authors (Arzadún
et al., 2017; Zavala et al., 2019), confirming water column oscillations,
resulting from transgressive-regressive cycles with varying preserva­
tion/oxidation conditions for organic matter.

Based on their organic matter content, source rocks are classified as

good with a TOC content of 2% for shale-type and 0.6% for carbonate-
type source rocks (Magoon and Dow, 1994; Cornford, 2004).
Geochemical analyses of organic matter quantity in the analyzed sam­
ples indicate that source rocks from the Tunas Formation classify as good
to very good (Cornford, 2004), with an average TOC of 2.68% (Table 1).
Lithostratigraphic logs plotted against TOC, TIC, and TS were used to
compare and correlate geochemical data variations with lithologies
changes (Fig. 11). The TOC content decreases from the bottom to the top
of the sedimentary succession due to thinning of coal-bearing beds
(Fig. 11). The highest TOC values were recorded in limited intervals,
mainly situated at the base of the successions, belonging to carbona­
ceous mudrocks (TOC: 0.5–34.4%; Table 1) and coals (TOC:
29.9–53.9%; Table 1). The upper sections are mainly composed of
organic-rich mudrocks with TOC values of 0.01–6%, (average 3.8%;
Table 1). In these horizons, heterolites (TOC: 0.8–6.2%; Table 1) and
laminated mudrocks (TOC: 0.04–6.6%; Table 1) show the highest TOC
values, while the lowest values were recorded in massive mudrocks
(TOC: 0.01–0.3%; Table 1).
The TIC is low and mostly stable throughout the entire sequences
(Fig. 11). The highest values were recorded in carbonaceous mudrocks
and coals, which could be related with the presence of carbonate veins
that are frequent in these lithologies.
The TS curves show a similar trend as the TOC curves, except for a
few samples located at the upper section of the PANG 0001 well
(Fig. 11). The sulfur content also decreases toward upper horizons, with
maximum values recorded in carbonaceous mudrocks (0.5–1.7%;
Table 1) and coals (1.5–1.9%; Table 1). The high sulfur content is related
to the occurrence of iron sulfides (e.g., pyrite) which are usually
accompanied by well-preserved organic matter due to reducing condi­
tions throughout sedimentation and diagenesis (Berner, 1980).
5.3. Kerogen type
Organic matter in the analyzed samples from the Tunas Formation is
mainly terrestrial, composed of plant remains and woody tissues
(Fig. 10), defining it as type III kerogen. Terrigenous components are
mostly present in carbonaceous mudrocks, coals, and mudrocks (Fig. 9)
and can also be preserved in fine-grained sandstones and heterolites
(Fig. 10). Organic petrographic analyses previously performed by
Arzadún et al. (2017) in mudrocks and humic coals from different
stratigraphic positions of PANG 0001 well (Fig. 4) confirm that the
dominant maceral group observed is vitrinite (collotelinite and gelinite,
Fig. 12 a-b and d-f; Table 2), followed by inertinite (fusinite, Fig. 12 a-c
5.4. Thermal maturity of organic matter and burial depth of the Tunas
Formation
According to measured vitrinite reflectance (Arzadún et al., 2017,
Table 3), coals are classified as medium to low volatile bituminous to
semi-anthracitic (Teichmüller, 1974; Teichmüller and Wolf, 1977; Hunt,
1996; Taylor et al., 1998). Semi-anthracitic coals located in the bottom
part of the succession, with Ro values from 1.9% to 2.4% (average
2.07%; Arzadún et al., 2017), lie within the dry gas window (Table 3;
Fig. 11). Medium to low volatile bituminous coals located in the upper
part of the sequence, with Ro values from 1.3% to 1.6% (average 1.48%;
Arzadún et al., 2017), fall within the wet gas window (Table 3; Fig. 11).
These results confirm that carbonaceous rocks from Tunas Formation
are thermally mature for dry (methane) gas generation (Table 3;
Teichmüller, 1974; Teichmüller and Wolf, 1977; Tissot and Welte, 1984;
Hunt, 1996; Arzadún et al., 2017). Vitrinite reflectance can be used as an
indirect method to determine the burial depth of the sequence as a
function of the maximum paleotemperatures reached during the thermal
maturation of the organic matter (Montero Serrano et al., 2010). In this
sense, it is important to consider the geothermal gradient to relate total
burial depth to Ro measurements. Ro values obtained for Tunas For­
mation allow estimating maximum paleotemperatures from 120 ◦ C to
190 ◦ C, based on Hunt (1996), coinciding with those calculated by
Arzadún et al. (2017) from 145 to 187 ◦ C. Mineralogical associations
from PANG 0003 samples (laumontite-albite; Febbo et al., 2018b),
which can be used as geothermometer, yielded paleotemperatures from
140 to 200 ◦ C. Besides, preliminary fluid inclusion studies from sub­
surface and outcrops (Arzadún et al., 2013, 2020) reported paleo­
temperatures between 130 ◦ C and 200 ◦ C, confirming a mesogenetic
stage within the inorganic diagenesis. These paleotemperatures could
have occurred at burial depths greater than 4 km, on the assumption of a
stable geothermal gradient of 25 ◦ C/km (Lee and Uyeda, 1965).
Currently, no data about the paleogeothermal gradient of the Claromecó
Basin are available; however, based on studies from
Carboniferous-Permian synorogenic foreland basins of Gondwana,
Table 3
Mean values of vitrinite reflectance (Ro) measured in samples from the Tunas
Formation, belonging to PANG 0001 well, obtained by Arzadún et al. (2017).
Coal rank and hydrocarbon generation zones from mean Ro based on Teich­
müller (1974), Hunt (1996) and Taylor et al. (1998).
Well Sample Depth mean Ro Coal Rank Oil
(m) (%) window

and e; Table 2). PANG 433 396.18 1.36 Medium volatile Wet gas
The concentration of TOC, ranging from 0.5% to 6.2% in mudrocks, 0001 bituminous
420 412.65 1.60 Low volatile Wet gas
to 29.9–53.9% in carbonaceous mudrocks and coals respectively, along
bituminous
with type III kerogen, suggest a good to very good hydrocarbon gener­ 111 813.10 2.38 Semi-anthracitic Dry gas
ation potential as gas source (Tissot and Welte, 1984; Magoon and Dow, C 842.00 2.02 Semi-anthracitic Dry gas
1994). The fusinite maceral is common in carbonaceous mudrocks and A 842.00 1.98 Semi-anthracitic Wet gas
coals, belonging to the inertinite group, interpreted as charcoal (Arzadún 83 850.33 2.07 Semi-anthracitic Dry gas
79 856.87 1.94 Semi-anthracitic Wet gas
et al., 2017, Fig. 12 a-c and d; Table 2). Permian charcoals have been

14
M.B. Febbo et al.
geothermal gradient values of up to 50 ◦ C could be assume for this area
(Tissot and Welte, 1984; Macdonald et al., 2003; Fernandes et al., 2015).
Considering these geothermal values, paleotemperatures reached by the
Tunas Formation, between 120 and 200 ◦ C, could have occurred at
burial depths of at least 3 km. Several studies performed in SW Gond­
wana basins confirm that this region was affected by high heat flow and
steep thermal gradients associated with tectono-metamorphic over­
printing during the Gondwanide Orogeny (Upper Paleozoic; Keidel,
1916) and, subsequently, with extensive magmatism occurred along the
South Atlantic during the Mesozoic rift stage (Macdonald et al., 2003).
As a result, organic-rich rocks deposited during the Permian were
rapidly matured by increased pressure and temperature during foreland
deformation and volcanic intrusions as documented in the Karoo (Fer­
nandes et al., 2015; Geel et al., 2015; Nengovhela et al., 2021) and
Paraná basins (Santos et al., 2009; Bicca et al., 2020; Martins et al.,
2020). In the Claromecó Basin, the sedimentary burial and high
geothermal gradient could have been the factors responsible for the
maturation of organic matter. However, since this basin has been
scarcely explored to date, further studies should be performed to un­
derstand the thermal and subsidence history of this area.
Given the present-day depth of the studied Tunas Formation
sequence in the Claromecó Basin subsurface (~900m, this work, Arza­
dún et al., 2017, 2020), estimated paleotemperatures suggest that at
least 2–3 km of the sedimentary column have been uplifted and eroded,
as supported by low-temperature thermochronological studies per­
formed by Arzadún et al. (2020). Maximum burial depths may have
occurred during the Late Paleozoic-Early Mesozoic foreland basin stage,
when rapid sedimentation took place in connection with the tectonic
deformation and uplift of the Sierras Australes fold and thrust belt
(Ramos, 1984, 2008; López-Gamundi and Rossello, 1992; Ramos et al.,
2014; Tomezzoli, 2012). During the Mesozoic, several rifting events
affected the SW Gondwana margin as a consequence of the break-up of
the Gondwana supercontinent, associated with different generations of
faults and depocenter formation (Lovecchio et al., 2018, 2020). Recent
apatite and zircon fission-track data published by Arzadún et al. (2020)
postulate that the uplift and erosion of the sedimentary column occurred
during the late Early Cretaceous (Barremian-Aptian, 125.8 ± 10.6 Ma),
as this area acted as a northern flank of the Mesozoic Colorado Basin.
This fact could explain the unconformity observed in the Claromecó
Basin, which separates Permian deposits of the Tunas Formation from
Cenozoic deposits, since this area would have been exposed during this
period. The upper Paleozoic infill of the Claromecó Basin extended to­
ward the Argentinian continental platform, constituting the basement of
the Mesozoic Colorado Basin (Fryklund et al., 1996; Lesta and Sylwan,
2005; Pángaro et al., 2015).
In summary, the maturity of organic matter was achieved by burial
during the Permian–Early Mesozoic, when the sedimentary sequence
may have reached maximum burial depths of at least 3 km. Moreover,
this process probably has been accelerated by an additional heat source
given by an abnormal temperature gradient that acted in the region,
resulting in a high maturity range at shallower depths. During the late
Mesozoic, an inversion of the basin occurred, due to several rifting
events that affected the area, resulting in a stage of uplift, erosion, and
non-deposition of the basin (Lovecchio et al., 2018; Arzadún et al.,
2020).
6. Conclusions
The Tunas Formation presents two main horizons with good hy­
drocarbon source potential, located in the upper (300–400 m) and lower
section (740–850 m) of the analyzed successions, with significant dif­
ferences in lithology, organic richness, and maturity. The upper interval
is composed of fine-grained sandstones, organic-rich mudrocks, and
heterolites, interbedded with thin coal beds (from 1 to 5 cm), with TOC
values ranging from 0.1% to 6.2% (average 2.48%). The lowermost
horizon is characterized by carbonaceous mudrocks and coal beds, up to
15
Marine and Petroleum Geology 137 (2022) 105491
4.50 m in thickness, with TOC values from 0.5% to 6.3% (average 2.9%),
recording the highest TOC values at limited intervals belonging to
carbonaceous mudrocks (TOC: 0.5–34.4%) and coals (TOC:
29.9–53.9%). High TOC content (>2%) characterizes coal-bearing
layers as high-quality source rocks. The organic matter is of terrige­
nous origin, as indicated by the abundance of woody plant debris. Vit­
rinite (kerogen type III) is the dominant maceral, which is gas-prone.
Vitrinite reflectance values from 1.3% to 1.6% for the upper horizon,
and from 1.9% to 2.4% for the lower one indicate a catagenesis to late
catagenesis range of organic matter maturity within the wet to dry gas
window. High TOC content, together with type III kerogen and vitrinite
reflectance values, indicates that coal-bearing deposits of the Tunas
Formation has a good potential for dry (methane) gas generation. The
results obtained in this work allow us to characterize the hydrocarbon
potential of a scarcely explored area and improve the knowledge about
the Claromecó Basin, currently considered a frontier basin. Further
studies are needed to better understand the thermal and subsidence
history of this area, which will be important to determine the timing of
hydrocarbon generation and, on this basis, define the gas potential of the
basin.
Author statement
Miss María Belén Febbo: Data collection, Methodology, Formal
analysis, Investigation, Writing the original draft. PhD. Guadalupe
Arzadún: Data collection, Methodology, Investigation, writing-
reviewing the original draft. PhD. Nora N. Cesaretti: writing-reviewing
the original draft, funding acquisition. PhD. Renata N. Tomezzoli:
reviewing and editing the original draft, funding acquisition. PhD.
Natalia B. Fortunatti: reviewing and editing the original draft.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors thank the “Departamento de Geología” of the Uni­
versidad Nacional del Sur, Bahía Blanca and “Instituto de Geología
Económica Aplicada” (IGEA, Universidad de Concepción, Chile), for
providing the equipment and personnel to carry out sample analysis.
The cores were donated to Universidad Nacional del Sur (UNS, Bahía
Blanca, Argentina) by Rio Tinto Mining Exploring Company. We are
grateful to the associate editor, Dr. Robert Ondrak, and two anonymous
reviewers for their valuable suggestions and careful corrections of the
manuscript, which have improved it considerably. Special thanks to Dr.
Robert Ondrak for his valuable help in the reconstruction of the subsi­
dence history of the Basin.
This work was funded by Comisión de Investigaciones Científicas
(CIC - PIT-AP-BA 2016/17/18) and Secretaría de Ciencia y Tecnología,
Universidad Nacional del Sur, (SECYT-UNS - PGI24/H128) projects.
Also, this research was supported by doctoral research fellowships
awarded by “Comisión de Investigaciones Científicas (CIC)” and Consejo
Nacional de Investigaciones Científicas y Técnicas (CONICET).
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