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Geochemical Characterization and Thermal Maturation of Cerrejón

Formation: Implications for the Petroleum System in the Ranchería Sub-
Basin, Colombia
Article in Geosciences · July 2020

DOI: 10.3390/geosciences10070258
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geosciences
Article
Geochemical Characterization and Thermal
Maturation of Cerrejón Formation: Implications for
the Petroleum System in the Ranchería
Sub-Basin, Colombia
Luis Felipe Cruz-Ceballos 1,2, * , Mario García-González 1,3 , Luis Enrique Cruz-Guevara 1,3
and Gladys Marcela Avendaño-Sánchez 1,2
1 Geology School, Universidad Industrial de Santander (UIS), Carrera 27 Calle 9 Ciudad Universitaria,
Bucaramanga 680002, Colombia; mgarciag@uis.edu.co (M.G.-G.); lecruz@uis.edu.co (L.E.C.-G.);
gmavesan@correo.uis.edu.co (G.M.A.-S.)
2 Grupo de Investigación en Geología Básica y Aplicada (GIGBA), UIS Guatiguará,
Piedecuesta 681011, Colombia
3 Energy and Other Non-Renewable Resources Research Group (EONr3g), UIS Guatiguará,
Piedecuesta 681011, Colombia
* Correspondence: LUIS.CRUZ@correo.uis.edu.co

Received: 17 April 2020; Accepted: 19 June 2020; Published: 4 July 2020
Abstract: The Upper Paleocene Cerrejón Formation is a great source of coal in Colombia.
The northeastern part of the Ranchería Sub-Basin sees the most intense mining activity. As a
consequence, all geological studies have been concentrated on this region. Consequently, neither
the distribution of the Cerrejón Formation, nor the quality and quantity of organic matter in the
rest of the sub-basin is clear. In this study, we analyzed new geochemical data from Rock–Eval
pyrolysis analyses and vitrinite reflectance using core samples from the ANH-CAÑABOBA-1 and
ANH-CARRETALITO-1 wells. Based on this information, it was possible to classify the geochemical
characteristics of the Cerrejón Formation as a source rock, particularly in the central area of the
sub-basin, which had not been extensively studied before. Additionally, based on the interpretation
of seismic reflection data, the numerical burial history models were reconstructed using PetroMod
software, in order to understand the evolution of the petroleum system in the sub-basin. The models
were calibrated with the data of maximum pyrolysis temperature (Tmax), vitrinite reflectance (%Ro),
and bottom hole temperature (BHT). We infer the potential times of the generation and expulsion of
hydrocarbon from the source rock.
Keywords: Cerrejón Formation; Cesar–Ranchería Basin; Ranchería Sub-Basin; source rock

characterization; source rock modeling; coal; coal mining industry in Colombia
1. Introduction
Geochemical studies have been insufficient in relation to the Ranchería Sub-Basin [1]. Previous
works have focused on data acquired in the northern part of the sub-basin, where the Cerrejón Mine
is located (Figure 1). However, the southern part has only one well drilled and there are little data
regarding it [2], and the central part has not been explored/studied at all. This study provides new
geochemical data for the central part of the sub-basin. The Cerrejón Formation is an excellent source
of coal in Colombia, with a potential 3000 million tons [3]. The Cerrejón Formation in the Ranchería
Sub-Basin has an area distribution of 2500 km2 [4], with a net thickness of 360 ft (109.7 m) of coal,
ranging from bituminous to sub-bituminous, with a variation in vitrinite reflectance (%Ro) from 0.4 to
Geosciences 2020, 10, 258; doi:10.3390/geosciences10070258 www.mdpi.com/journal/geosciences

Geosciences 2020, 10, 258 2 of 18
Geosciences 2020, 10, x FOR PEER REVIEW 2 of 18
ranging from bituminous to sub-bituminous, with a variation in vitrinite reflectance (%Ro) from 0.4
0.8, which could potentially generate on-site gas reserves associated with more than six trillion cubic
to 0.8, which could potentially generate on-site gas reserves associated with more than six trillion
feet (TCF) of coal. The study of the evolution of the oil system in this sub-basin is under discussion
cubic feet (TCF) of coal. The study of the evolution of the oil system in this sub-basin is under
due to its high
discussion structural
due complexity
to its high [5] and the[5]
structural complexity lack
andofthe
data from
lack paleo
of data geothermometers
from (%Ro and
paleo geothermometers
maximum pyrolysis temperature (Tmax)). This is proven by the results obtained
(%Ro and maximum pyrolysis temperature (Tmax)). This is proven by the results obtained by [6,7],by [6,7], whose
proposals regarding the basin’s evolution are radically contrasting. The National
whose proposals regarding the basin’s evolution are radically contrasting. The National Hydrocarbon Agency
(ANH), a public Agency
Hydrocarbon institution whicha oversees
(ANH), the economic
public institution whichactivity of hydrocarbons
oversees the economicin activity
Colombia,
of is
interested in investigating this sub-basin in the short and long term in order to increase knowledge
hydrocarbons in Colombia, is interested in investigating this sub-basin in the short and long term in
about itstohydrocarbon
order production
increase knowledge aboutpotential.
its hydrocarbon production potential.
B
Lithology
Per iod
Epoch
Age Picks Thickness
(My) Era (My) (meters) Units Grain size
A
Sand Gravel
Clay Silt vf f m c vc gr pb cb bl
0 Q uat Pleis
H oloc 0.01
2.6
Plioc
5.3
Neogene
’’Conjunto
360 - 610 Conglomeratico’’
10
Miocene
11.6
16
20
23 ’’Conjunto
75 - 270
Oligoc e
calcareo’’
Cenozoic
28.4
30
33.9
Paleogene
37.2
40 Aguas Nuevas
Eocene
Fm.
48.6
50
55.8 Palmito Fm.
Paleoc.
58.7 100 - 1000 Tabaco Fm.
60 61.7
Cerrejon Fm.
150 - 200 Manantial Fm.
175 - 375 Hato Nuevo Fm.
65.5
70 70.6
500
Molino
Fm.
80
Late
83.5
85.8 40 - 120
La Luna
Fm.
90 89.3
93.5
Cretaceous
Aguas Blanca
235 - 280
100 99.6 Fm.
Lagunitas
110 260 - 350
Mesozoic
Fm.
112
Rio Negro
? Fm
120
Early
Venezuela
125
130 130
136
Colombia 140 140
145.5
Jurassic La Quinta
Fm.
201.6
Ecuador Brazil
Triassic
Peru
251
Paleozoic Basement
Coal Volcanic rock Continental mudstone

Chert Marine/littoral mudstone
Limestone Marine/littoral sandstone
Crystalline basement Continental conglomerate
Figure
Figure (A)
1. 1. (A)Map
Mapwith
withthe
thelocation
locationof ofthe
the Ranchería
Ranchería Basin, Colombia(yellow
Basin, Colombia (yellowarea).
area).Locations
Locations of of
thethe
Ranchería
Ranchería Sub-Basin
Sub-Basin(red
(redbold
boldlines),
lines),studied
studied wells ANH-CARRETALITO-1
ANH-CARRETALITO-1and andANH-CAÑABOBA-
ANH-CAÑABOBA-1
1 (red
(red dots),
dots), andand seismic
seismic lines
lines (bold
(bold bluelines)
blue lines)are
arepresent,
present, with the
the major
majorfault
faultsystem
systemandandthethe
Cerrejón
Cerrejón
mining
mining activityarea.
activity area. (B)
(B) The
Thegeneralized
generalized stratigraphic column
stratigraphic of theofRanchería
column Sub-Basin
the Ranchería is takenisfrom
Sub-Basin taken
Mesa
from andand
Mesa Rengifo [1]. [1].
Rengifo
This
This studypresents
study presentsnew
newgeochemical
geochemical data, including
includingthe theRock–Eval
Rock–Evalpyrolysis
pyrolysisof of
127127
samples,
samples,
thethe total
total organic
organic carbon
carbon (TOC)
(TOC) of of
58 58 samples,
samples, and
and thethe vitrinite
vitrinite reflectance
reflectance (%Ro)
(%Ro) of of
58 58 samples.
samples. The
The core
core samples were acquired from the ANH-CAÑABOBA-1 and
samples were acquired from the ANH-CAÑABOBA-1 and ANH-CARRETALITO-1 wells (Figures 1ANH-CARRETALITO-1 wells
and(Figures
2). This1 and
study2).aims
This to
study aims the
establish to establish the current
current maturity maturity
state and thestate and theforpotential
potential for
hydrocarbon
hydrocarbon
generation generation
(quality (quality and
and quantity) quantity)
of the of the
rocks in the rocks in the
Cerrejón Cerrejón Formation.
Formation. Furthermore,Furthermore,
we would
we would like to recreate the burial history scenario through numerical modeling
like to recreate the burial history scenario through numerical modeling with the PetroMod with the PetroMod
software.
software. The modeling is based on geochemical data, the stratigraphic/structural architecture as
The modeling is based on geochemical data, the stratigraphic/structural architecture as interpreted
interpreted by 2D seismic reflection data, and the several uplift events of the Perijá Range (PR) that
by 2D seismic reflection data, and the several uplift events of the Perijá Range (PR) that affected the
affected the burial history. It also provides insights which may help to understand the current state
burial history. It also provides insights which may help to understand the current state of maturity,
of maturity, as well as the organic transformation ratios (TR) of the cretaceous formations underneath
as well as the organic transformation ratios (TR) of the cretaceous formations underneath the Cerrejón
the Cerrejón Formation, which is fundamental for any understanding of the organic geochemical
Formation, which is fundamental for any understanding of the organic geochemical characteristics of
characteristics of the Cerrejón Formation, as well as how the basin was filled with sediments. It has
the Cerrejón Formation, as well as how the basin was filled with sediments. It has direct implications
regarding the maturation of organic matter of the units as well as the generation of hydrocarbons.
direct implications
Geosciences 2020, 10, 258 regarding the maturation of organic matter of the units as well as the generation
3 of 18
of hydrocarbons.
Figure 2.2. Interpreted

Interpreted 2D2D seismic
seismic lines
lines in two-way
two-way time (TWT) with location of ANH-CARRETALITO-1
ANH-CARRETALITO-
1and
and ANH-CAÑABOBA-1
ANH-CAÑABOBA-1 wells.
wells. Seismic
Seismic lineslines (A) CV-1989–2200;
(A) CV-1989–2200; (B) CV-1989–1885;
(B) CV-1989–1885; and (C) CV-
and (C) CV-1959–1100.
Line locations
1959–1100. Lineare shown in
locations areFigure
shown1A. in Figure 1A.
2. Study
2. Study Area
Area
The Cerrejón
The Cerrejón Formation
Formation belongs
belongs to to the
the stratigraphic
stratigraphic section
section of of the
the Ranchería
Ranchería Sub-Basin
Sub-Basin [8].
[8].
Based on
Based on palynological
palynologicalanalysis,
analysis,it it
is dated to the
is dated LateLate
to the Paleocene, which
Paleocene, formed
which in a period
formed of 2 million
in a period of 2
years (my) [9]. The progression of the depositional system to the east during
million years (my) [9]. The progression of the depositional system to the east during the Late the Late Paleocene was
suggested by Bayona et al. [10]. Furthermore, Morón et al. [11] stated that the Cerrejón
Paleocene was suggested by Bayona et al. [10]. Furthermore, Morón et al. [11] stated that the Cerrejón Formation was
deposited inwas
Formation tectonic subsidence
deposited with constant
in tectonic subsidencesedimentation
with constant ratessedimentation
and a rhythmic variation
rates and ainrhythmic
the base
level of erosion, which generated repetitive and monotonous sedimentation
variation in the base level of erosion, which generated repetitive and monotonous sedimentation patterns. The Cerrejón
FormationThe
patterns. was Cerrejón
described Formation
by Ingeominas was[12] as a sequence
described with a predominance
by Ingeominas [12] as a of mudstones
sequence with
with a
some quartz-feldspar sandstones. Numerous coal layers distributed
predominance of mudstones with some quartz-feldspar sandstones. Numerous coal layers regularly throughout the entire
stratigraphicregularly
distributed column. The Cerrejón the
throughout Formation was depositedcolumn.
entire stratigraphic in a fluvial–estuarine
The Cerrejónenvironment
Formation was[13].
It was in a tropical
deposited lowland coastalenvironment
in a fluvial–estuarine humid forest[13]. basedIton fossil
was in amegaflora [14], which
tropical lowland had characteristics
coastal humid forest
of a multi-layered tropical forest environment in the Neotropics [15], with a mean annual
based on fossil megaflora [14], which had characteristics of a multi-layered tropical forest environment temperature
(MAT) of 32 to 33 ◦ C estimated from the 13-m size snake, Titanoboa cerrejonensis, recovered from the
in the Neotropics [15], with a mean annual temperature (MAT) of 32 to 33 °C estimated from the 13-m
Cerrejón
size snake, Mine [16]. Regarding
Titanoboa cerrejonensis,therecovered
Cerrejón Formation, Wilf et al.
from the Cerrejón Mine[17][16].
calculated the mean
Regarding annual
the Cerrejón
precipitation (MAP) as around 3240 mm (ranging from 2260 to 4640 mm) using correlations of the
Geosciences 2020, 10, 258 4 of 18
paleo-leaf size and the precipitation observed in live vegetation. The Cerrejón Formation presents
1000 m in total thickness and contains 80 layers of coal [11].
Bayona et al. [10] proposed that the presence of intercalation of siliciclastic materials in the Cerrejón
Formation, not only in the Maracaibo Basin (Diablo Mine), but also in the Ranchería Sub-Basin (Cerrejón
Mine), may have been due to significant uplift from the Perijá Range (PR) in the late Paleocene to Middle
Eocene, between 66 to 41 million years ago (mya). This fact is consistent with the lack of stratigraphic
records in the Eocene–Oligocene in the Ranchería Sub-Basin as mentioned by Mesa and Rengifo [1],
indicating several tectonic pulses during the Andean Orogeny. Some sediments assigned to this period
in the supergiant Maracaibo Basin were from alluvial fan and fluvial deposits (conglomerates and
sandstones) [18]. Hernandez and Jaramillo [19] studied the Apatite Fission-Track (AFT) on the Lower
Cretaceous rocks present in the PR, asserting that the last uplift event began in the Late Miocene (11
mya). These data were consistent with the studies carried out by Bermudez [20]: AFT established the
orogeny of the Andes de Mérida, which had a rapid cooling in the Miocene–Pliocene, indicating its
exhumation. This orogeny also occurred in the Merida Block which includes the PR [21].
Previous studies have determined the characteristics of the coal from the Cerrejón Mine to the
north of the Ranchería Sub-Basin. They established that the coal is bituminous, high in volatiles A and
B [22]. From the analysis of 196 samples of Cerrejón coals, Departamento Nacional de Planeacion [22]
obtained an average of 31.19 MJ/kg of calorific value and 37% volatile materials. The analysis by
Piñeres et al. [23] of the coal from the mine showed a calorific value of 23.75 MJ/kg with an average of
1.41% sulfur, and were high in volatiles, which were classified as a sub-bituminous B coal [24]. Rincon
et al. [25] presented data of 34% volatile material with values of 0.66% sulfur in the coal of the Cerrejón
Central Mine and 33.4% volatile material with 0.7% in the coal of the Cerrejón Norte Mine. According
to Henao [26], coals of the WRV-04752 and WRV-04774 wells were high in volatiles as well, between
34.09 to 37.2%, with sulfur values from 0.22 to 0.41%. Layton [27] analyzed 25 coal samples from the
WRV-04752 Well, establishing an average of 34.91% volatile material with an average of 0.56% sulfur
content. Layton [27] also analyzed 28 coal samples from the WRV-04774 Well, determining that volatile
material was on average 34.479%, with an average of 0.81% sulfur content.
3. Data and Methods

Geochemical analysis was used to establish the type and quality of organic carbon and
other geochemical properties of rocks, which contributed to evaluating the potential production
of conventional or unconventional hydrocarbons in a prospective play. Geochemical data were
obtained using core samples from the Cerrejón Formation of two wells, ANH-CARRETALITO-1 and
ANH-CAÑABOBA-1. Vertical sampling was not performed with symmetrical length values (Figure 3).
The selection criterion was based on the visible presence of organic matter using an ultraviolet lamp.
Geochemical analysis of Rock–Eval pyrolysis, TOC, and total sulfur (TS) were carried out for 108
samples of the ANH-CARRETALITO-1 Well and 19 samples of the ANH-CAÑABOBA-1 Well. Vitrinite
reflectance analyses on 58 samples were obtained through organic petrography. Additional geochemical
data used in this study were obtained from [2,28,29], and corresponded to 356 samples of the hydrogen
index (HI) and oxygen index (OI), and 332 samples of TOC belonging to lithological formation where
geochemical analyses were performed. The TOC analysis was carried out with the intention of
quantifying the amount of organic matter present in the sample using the Leco SC-144DR automated
analyzer. It also allowed us to calculate the TS as well as the carbonate content. Likewise, to evaluate
the quality of this organic matter, a Rock–Eval pyrolysis analysis was performed in each of the samples
with Rock–Eval 6 technology equipment. This technique presented by Barker [30] and Behar [31] uses
programmed heating of a small amount of rock (70 mg) or coal (30–50 mg) in an inert atmosphere
(helium or nitrogen) in order to determine the quantity of free hydrocarbons present in the sample
(S1 peak), as well as those that potentially can be released after maturation (S2 peak). This procedure
permitted us to know the Tmax and the current state of thermal maturation. The TOC had to be
determined along with the mineral carbon content (MinC), the volume of free hydrocarbon generated
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258x FOR PEER REVIEW 5 of518
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to be determined along with the mineral carbon content (MinC), the volume of free hydrocarbon
before pyrolysis
generated (S1),pyrolysis
before the amount of the
(S1), hydrocarbon
amount ofgenerated
hydrocarbonduring pyrolysisduring
generated (S2), the amount(S2),
pyrolysis of emitted
the
amount
carbon of emitted
dioxide carbon
(S3), the dioxide
hydrogen index the=hydrogen
(S3),(HI S2/TOC × index
100),(HI
the=index
S2/TOC × 100), the
of oxygen = S3/TOC
(OIindex × 100),
of oxygen
the(OI = S3/TOC yield
production the=production
× 100),(PY S1 + S2), and
yield (PY
the = S1 + S2), index
production and the = S1/(S1 +index
(PIproduction S2). (PI = S1/(S1 + S2).
ANH CARRETALITO -1 well ANH CAÑABOBA-1 well

Total Total
Geochemistry
Geochemistry
Type of analysis
Type of analysis
m Lithologies Sulfur organic
m Lithologies Sulfur organic
Fm. carbon Fm. carbon
content content
(TOC) (TOC)
0.01
0.01
0.10
1.00
10.0
0.10
1.00
10.0
0.10
1.00
10.0
0.10
1.00
10.0
100
100
0 0
Cuesta
100 100
200 200
Cuesta
300 300
Cerrejon
400 400
500 500
Cerrejon
600 600
700 700
Lithologies mudstone sandstone coal conglomerate limestone

Poorly consolidated mudstone Poorly consolidated sandstone Poorly consolidated conglomerate
Figure 3. Lithologies, sample site (+), and variation of sulfur content and total organic carbon
Figure 3. Lithologies, sample site (+), and variation of sulfur content and total organic carbon (TOC)
(TOC) of the rock samples of the Cerrejón Formation in the ANH-CARRETALITO-1 and ANH-
of the rock samples of the Cerrejón Formation in the ANH-CARRETALITO-1 and ANH-
CAÑABOBA-1
CAÑABOBA-1 wells.
wells.
The vitrinite reflectance (%Ro) was measured using Zeiss imager microscopy. Sample chips or
The vitrinite reflectance (%Ro) was measured using Zeiss imager microscopy. Sample chips or
sidewall core samples
sidewall core sampleswere
werecleaned
cleanedto
to remove
remove drilling mudor
drilling mud ormud
mudcake
cakeand
andthen
thencrushed
crushed using
using a a
mortar and pestle to a grain-size of less than 3 mm. These samples were mounted in cold-setting
resin and polished “as received”, so that whole-rock samples were examined, excluding concentrates
Geosciences 2020, 10, 258 6 of 18
of organic matter. The core samples were mounted and sectioned perpendicularly to the bedding.
Vitrinite reflectance measurements were made using immersion oil of refractive index 1.518 at 546 nm
at 23 ◦ C and at spinel and garnet standards of 0.42, 0.917, as well as 1.726% reflectance for calibration.
Fluorescence-mode observations were made on all samples, providing supplementary evidence
concerning organic matter type, exinite abundance, and maturity. For fluorescence-mode, a 3-mm
BG-3 excitation filter was used with a TK400 dichroic mirror and a K490 barrier filter.
Geochemical information was plotted to visualize its distribution on profiles using free software
PanPlot2 as described by Sieger and Grobe [32]. The 2D seismic lines in two-way time (TWT) used
in this research were CV-1989–2200, CV-1989–1885, and CV-1959–1100; the interpretation of the lines
was used for the purpose of defining the cutting relationships between lithological units present in
the basin. Additionally, they had the geographic and stratigraphic positions of the wells used for
this study.
One-dimensional modeling was carried out with the PetroMod software (2012 version) in order
to reconstruct the burial history and thermal maturation of the geological units present in the wells.
This modeling used the vitrinite thermal maturation model (EASY %Ro) proposed by Sweeney and
Burnham [33], based on the Arrhenius first-order parallel-reaction approach with a distribution of
activation energies. EASY %Ro were calibrated to a more rigorous model of vitrinite maturation
based on the chemical properties of coal vitrinite. Previous studies such as Mesa and Rengifo [1]
were also considered, which provided the deposition ages of each unit, and the maximum and
minimum thicknesses of those units. The eroded thickness input for the modeling was inferred
by the relation to the maximum thickness reported plus those found in the wells. The heat flow
evolution was established by Petromod software using the Mackenzie method, and based on the
sub-basin evolution proposed by Mesa and Rengifo [1]. Paleo-water depths were estimated with
biostratigraphic studies (e.g., [34]). Sediment water interface temperatures (SWIT) were estimated using
PetroMod software (e.g., [35]), which assumed that the current position of the study area is 11 degrees
north latitude in the northernmost part of South America. To determine the evolution of the source
rock units, the multiple kinetics were used; IES_TII_Toarcian_Shale_2C, IES_TIII_Tertiary_Coal_2C,
and IES_TII_Brown_Limestone_2C, based on lithologies.
4. Results and Discussion
4.1. TOC and Rock Eval Pyrolysis Results

The values of the S1 peak indicated the volume of hydrocarbon generated before the pyrolysis.
In this study, S1 values from the ANH-CARRETALITO-1 Well and ANH-CAÑABOBA-1 Well samples
varied from 0.05 to 4 and from 0.05 to 1.36 mg HC/g rock, respectively. S2 values, indicating the amount
of hydrocarbon generated during pyrolysis, showed variations from 0.13 to 166.96 and from 0.50 to
124.02 mg HC/g rock, respectively, and the S3 peak of the amount of carbon dioxide emission showed
variations from 0.10 to 19.61 and from 0.32 to 17.93 mg CO2 /g rock, respectively.
The accumulated thickness of coals in the Cerrejón Formation were: 63.94 m in the ANH-
CARRETALITO-1 Well samples and 9.63 m in the ANH-CAÑABOBA-1 Well samples. The accumulated
thicknesses of the mudstone were 291.19 and 107.60 m, respectively. The organic richness of the
Cerrejón Formation ranged from poor to excellent, according to Lewan [36]. The Cerrejón Formation
rocks (Paleocene age) showed variations in TOC from 0.3 to 72.5%, and from 0.74 to 65.46%, respectively.
The OI and HI were the most important parameters, of which the correlation indicated the kerogen
type of source rocks. The OI value, as calculated, varied from 7.68 to 64.18 mg CO2 /g TOC in the
ANH-CARRETALITO-1 Well, and from 19.59 to 52.22 in ANH-CAÑABOBA-1 Well. The HI value,
as calculated, varied from 10.53 to 330.64 and from 67.40 to 215.96 mg HC/g TOC, respectively.
Total sulfur (TS) is an important consideration in coal utilization. The TS obtained varied from
0.001 to 16.233% w/w of the coal in the ANH-CARRETALITO-1 Well samples (the last value being
the only one higher than 10%), and from 0.29 to 0.37% w/w of the coal in ANH-CAÑABOBA-1
Well samples.
Geosciences 2020, 10, 258 7 of 18
the only one higher than 10%), and from 0.29 to 0.37% w/w of the coal in ANH-CAÑABOBA-1 Well
samples.
The PY was the total amount of hydrocarbon generated/liberated under the pyrolysis S1 and S2
The PY was the total amount of hydrocarbon generated/liberated under the pyrolysis S1 and S2
curves [37]. This index helped to categorize the target horizon in terms of total petroleum-generation
curves [37]. This index helped to categorize the target horizon in terms of total petroleum-generation
potential [38]. The PY values, as calculated, varied from 0.2 to 168.6 mg HC/g rock and from 0.6 to
potential [38]. The PY values, as calculated, varied from 0.2 to 168.6 mg HC/g rock and from 0.6 to
124.9 mg HC/g rock in the ANH-CARRETALITO-1 and ANH-CAÑABOBA-1 wells, respectively.
124.9 mg HC/g rock in the ANH-CARRETALITO-1 and ANH-CAÑABOBA-1 wells, respectively.
The PI value was taken from a ratio between S1 and S2, which indicated the relationship between
The PI value was taken from a ratio between S1 and S2, which indicated the relationship between
the amounts of free hydrocarbon before pyrolysis with respect to the amount of hydrocarbon generated
the amounts of free hydrocarbon before pyrolysis with respect to the amount of hydrocarbon
during pyrolysis, similar to Rock–Eval and Tmax. PI was used as a maturity proxy [38]. The PI values,
generated during pyrolysis, similar to Rock–Eval and Tmax. PI was used as a maturity proxy [38].
calculated in ANH-CARRETALITO-1 Well, varied from 0.01 to 0.32 TOC. Only 13 data were higher
The PI values, calculated in ANH-CARRETALITO-1 Well, varied from 0.01 to 0.32 TOC. Only 13 data
than 0.1 and had an average of 1.1% TOC, indicating that the value could have been affected; while
were higher than 0.1 and had an average of 1.1% TOC, indicating that the value could have been
in the ANH-CAÑABOBA-1 Well, the calculated values ranged from 0.01 to 0.09 TOC. According to
affected; while in the ANH-CAÑABOBA-1 Well, the calculated values ranged from 0.01 to 0.09 TOC.
Peters [39], source
According rocks[39],
to Peters withsource
PI values of less
rocks withthan 0.1 are considered
PI values of less thanthermally immature, while
0.1 are considered those
thermally
from
immature, while those from 0.1 to 0.4 are considered thermally mature. According to Nuñez is
0.1 to 0.4 are considered thermally mature. According to Nuñez and Baceta [40], there andno
depletion in the values of these two pyrolysis peaks since the samples were taken
Baceta [40], there is no depletion in the values of these two pyrolysis peaks since the samples were from the core and
had notfrom
taken beentheexposed to weathering.
core and had not been exposed to weathering.
The Tmax values correspond
The Tmax values correspond to the
to maximum
the maximum hydrocarbon generation
hydrocarbon point during
generation point the pyrolysis
during the
(S2), which(S2),
pyrolysis is widely
whichused as a thermal
is widely used asmaturity
a thermalindicator
maturity[38]. According
indicator to Peters and
[38]. According Cassaand
to Peters [41],
any value
Cassa of Tmax
[41], that is
any value of less
Tmaxthan 435is◦less
that C is than
considered
435 °Cthermally immature.
is considered The immature.
thermally Tmax values Theobtained
Tmax
ranged from 414 to 440 ◦ C in the ANH-CARRETALITO-1 Well, with only two samples higher than
values obtained ranged from 414 to 440 °C in the ANH-CARRETALITO-1 Well, with only two
435 ◦ C (Figure 433 ◦ C
samples higher4).than
Likewise, in the ANH-CAÑABOBA-1
435 °C (Figure Well, the values ranged
4). Likewise, in the ANH-CAÑABOBA-1 Well, from 414 toranged
the values
(Figure
from 414 5).toThus,
433 °Cit(Figure
can be 5).concluded thatbethe
Thus, it can data showed
concluded thedata
that the Cerrejón
showed Formation
the Cerrejónin the wells is
Formation
thermally immature, bordering on the limit of 435 ◦ C.limit of 435 °C.
in the wells is thermally immature, bordering on the
Figure4.4.Results
Figure Resultsof
ofthe
thegeochemical
geochemical analyzes.
analyzes. Total organic
organic carbon
carbon (TOC),
(TOC), total
total carbon
carbon(TC),
(TC),total
total
sulfur(TS),
sulfur (TS),and
andRock–Eval
Rock–Eval pyrolysis
pyrolysis of
of the
the Cerrejón Formation
Formation rocks
rocks in
in the
the ANH-CARRETALITO-1
ANH-CARRETALITO-1
Well,see
Well, seeSupplementary
SupplementaryMaterials
MaterialsTable
TableS1.
S1.
Finally,
Finally,%Ro
%Roanalysis
analysisfunctioned
functioned as
as an
an indicator
indicator of level of organic maturity
maturity (LOM).
(LOM).Jarvie
Jarvieand
and
Pollastro
Pollastro[42] provided
[42] the thermal
provided maturity-profiling
the thermal states: Immature,
maturity-profiling oil-window
states: Immature, mature, condensate
oil-window mature,
wet-gas mature,
condensate dry-gas
wet-gas mature
mature, shales,
dry-gas withshales,
mature %Ro values of <0.55,
with %Ro 0.55–1.15,
values of <0.55, 1.15–1.40,
0.55–1.15, and >1.40,
1.15–1.40,
respectively. The average of %Ro values were from 0.45 to 0.57 in the ANH-CARRETALITO-1 Well, with
Geosciences 2020, 10, 258 8 of 18
and
and >1.40,
>1.40, respectively.
respectively. The
The average
average of of %Ro values were
%Ro values were from
from 0.450.45 to to 0.57
0.57 inin the
the ANH-
ANH-
CARRETALITO-1
CARRETALITO-1 Well, with a mean of 33.55 measurements per analysis (Figure 6), and from 0.37 toto
Well, with a mean of 33.55 measurements per analysis (Figure 6), and from 0.37
a mean
0.43 of 33.55 measurements per analysis (Figure 6), and frommeasurements
0.37 to 0.43 in the perANH-CAÑABOBA-1
0.43ininthe
theANH-CAÑABOBA-1
ANH-CAÑABOBA-1 Well, Well, with
with aa mean of 40.32
mean of 40.32 measurements per analysis(Figure
analysis (Figure7).
7).
Well, with
Vitrinite a mean
reflectanceof 40.32
could measurements
also be plotted per
with analysis
Tmax to(Figure
identify7).
theVitrinite
state of reflectance
thermal couldfor
maturity also
thebe
Vitrinite reflectance could also be plotted with Tmax to identify the state of thermal maturity for the
plotted
organic with Tmax to identify the state of thermal maturity for the organic matter [43]. The 8data
organicmatter
matter[43].
[43].The
Thedata
data correlation
correlation of
of the
the average %Ro versus
average %Ro versus Tmax
Tmax isispresented
presented inFigure
in Figure 8 toto
correlation
show
showthe
of the
thechange
changein
average %Ro
inthermal
versus
thermal maturity
maturity of
Tmax
of the
is presented
the Cerrejón
in Figure
Formation in
Cerrejón Formation
8
in the to show the change
the ANH-CARRETALITO-1
ANH-CARRETALITO-1and in thermal
and
maturity of the
ANH-CAÑABOBA-1 Cerrejón
ANH-CAÑABOBA-1 wells. Formation
wells. in the ANH-CARRETALITO-1 and ANH-CAÑABOBA-1 wells.
Figure
Figure
Figure 5.5.5. Results
Results
Results of
ofof geochemicalanalyses.
geochemical
geochemical analyses. Total
analyses. Total organic
Total organic carbon
carbon(TOC),
carbon (TOC),total
(TOC), totalcarbon
total carbon(TC),
carbon total
(TC),
(TC), sulfur
total
total sulfur
sulfur
(TS),
(TS), and
(TS),and Rock–Eval
andRock–Eval pyrolysis
Rock–Eval pyrolysis of the
ofthe
pyrolysis of Cerrejón
theCerrejón Formation
CerrejónFormation
Formationrocks in
rocks
rocks the ANH-CAÑABOBA-1
in the
in the ANH-CAÑABOBA-1
ANH-CAÑABOBA-1 Well,
Well,see
Well,
see
seeSupplementary
Supplementary
Supplementary Materials
Materials
Materials Table S2.
Table
Table S2.S2.
Standard
Standard
deviation
deviation
Figure 6. Graphic distribution of vitrinite reflectance analysis (%Ro), total organic carbon (TOC), total
sulfur (TS), and hydrogen index (HI) of the Cerrejón Formation in the ANH-CARRETALITO-1 Well,
see Supplementary Materials Table S3.
Figure 2020,
Geosciences 6. Graphic distribution
10, x FOR PEER REVIEWof vitrinite reflectance analysis (%Ro), total organic carbon (TOC), total
9 of 18
sulfur (TS), and hydrogen index (HI) of the Cerrejón Formation in the ANH-CARRETALITO-1 Well,
seeFigure 6. Graphic distribution
Supplementary of vitrinite
Materials Table S3. reflectance analysis (%Ro), total organic carbon (TOC), total
sulfur
Geosciences 2020,(TS), and hydrogen index (HI) of the Cerrejón Formation in the ANH-CARRETALITO-1 Well, 9 of 18
10, 258
see Supplementary Materials Table S3. Standard
deviation
Standard
deviation
Figure 7.
Figure 7. Graphic
Graphic distribution
distribution of
of vitrinite
vitrinite reflectance analysis (%Ro),
reflectance analysis (%Ro), total
total organic
organic carbon
carbon (TOC),
(TOC), total
total
Figure 7.
sulfur (TS), Graphic
(TS), and distribution
and hydrogen
hydrogen index of vitrinite
index (HI)
(HI) of
of thereflectance
the Cerrejón analysis (%Ro),
Formation in total
in the organic carbon (TOC), total
sulfur Cerrejón Formation the ANH-CAÑABOBA-1
ANH-CAÑABOBA-1 Well, see
Well, see
sulfur (TS), and hydrogen index (HI) of the Cerrejón Formation in the ANH-CAÑABOBA-1 Well, see
Supplementary
Supplementary Materials Table
Materials Table S4.
S4.
Supplementary Materials Table S4.
480
480
470
470
460
460
Thermal Mature
Thermal Mature
450 (Oil Window)
Tmax (°C)
450 (Oil Window)

Tmax (°C)
440
440
430
430
420
420
Thermal Immature
Immature
410
410
0.2
0.2 0.4
0.4 0.6
0.6 0.8 1.0
1.0 1.2
1.2 1.4
1.4
Vitrinite Reﬂectance
Vitrinite Reﬂectance (Ro%)
(Ro%)
Carretalito well
Carretalito well data
data Cañaboba
Cañabobawell
welldata
data
Figure
Figure 8. 8.Data
8. Datacorrelation
correlationofofmaximum
maximum pyrolysis
pyrolysis temperature
temperature (Tmax)
(Tmax)versus
versusvitrinite
vitrinitereflectance
vitrinite reflectance
reflectance
(%Ro) average
(%Ro) average to indicate
average totoindicate source
indicatesource
source rock
rock
rock thermal maturity
thermal
thermal in
maturity
maturity the Cerrejón
in Cerrejón
in the Formation
the Cerrejón of the
Formation
Formation of theANH-
of the
ANH-
CARRETALITO-1
ANH-CARRETALITO-1 and ANH-CAÑABOBA-1
and ANH-CAÑABOBA-1
CARRETALITO-1 and ANH-CAÑABOBA-1 wells.
wells.wells.
4.2.4.2.
Quality of of
Quality Organic
OrganicMatter
Matter
4.2. Quality of Organic Matter
The
The cross
cross plot
plot of of
S1S1 versus
versus TOC
TOC (Figure9)9)was
(Figure wasused
usedtotoevaluate
evaluatethe
theorigin
originof
ofthe
thehydrocarbons
hydrocarbons in
The cross plot of S1 versus TOC (Figure 9) was used to evaluate the origin of the hydrocarbons
theinCerrejón
the Cerrejón Formation
Formation atRanchería
at the the Ranchería Sub-Basin,
Sub-Basin, using
using samples
samples of the
of the ANH-CARRETALITO-1
ANH-CARRETALITO-1 and
in the Cerrejón Formation at the Ranchería Sub-Basin, using samples of the ANH-CARRETALITO-1
and ANH-CAÑABOBA-1 wells, based on the methodology of Fakhri et al. [44].
ANH-CAÑABOBA-1 wells, based on the methodology of Fakhri et al. [44]. It was established that the It was established
and ANH-CAÑABOBA-1 wells, based on the methodology of Fakhri et al. [44]. It was established
that theFormation
Cerrejón Cerrejón Formation was not contaminated
was not contaminated with hydrocarbon.
with migrated migrated hydrocarbon. The hydrocarbon
The hydrocarbon generation
that the Cerrejón
generation Formation was not contaminated with migrated hydrocarbon. The hydrocarbon
potential was potential was proven
proven using using
the cross plotthe cross
of PY plot TOC
versus of PY(Figure
versus 10),
TOCbased
(Figure
on10),
the based on theby
proposition
generation
propositionpotential
by was
Ghori andproven
Hainesusing
[45]. the
It cross plotthat
concludes of PY
the versus
coals of TOC
this (Figure
formation 10),
hadbased on the
excellent
Ghori and Haines [45]. It concludes that the coals of this formation had excellent potential, while the
proposition by Ghori and Haines [45]. It concludes that the coals of this formation
potential, while the mudstones had a wide spectrum of potential that ranged from poor to excellent. had excellent
mudstones had a wide spectrum of potential that ranged from poor to excellent.
potential, while the mudstones had a wide spectrum of potential that ranged from poor to excellent.
1000 1000
Paleocene Paleocene
Mudstone Mudstone
Paleocene Paleocene
100 Coal 100 Coal
Contaminated Contaminated
S1 (mg HC/g roca)
S1 (mg HC/g roca)

10 10
Geosciences 2020, 10, 258 10 of 18
1 1
1000 1000
1000 Paleocene 1000 Paleocene
Mudstone
Paleocene Mudstone
Paleocene
0.1 Mudstone 0.1 Mudstone
Paleocene Paleocene
A Uncontaminated
B Uncontaminated
100 Coal
Paleocene 100 Coal
Paleocene
100 Coal 100 Coal
Contaminated Contaminated
0.01
0.1
Contaminated
1 10 100
0.01
0.1
Contaminated
1 10 100
roca)
roca)
10 10
roca)
roca)
10 TOC (wt.%) 10 TOC (wt.%)
HC/g
HC/g
HC/g
HC/g
Figure 9. Cross plot of S1 versus TOC to indicate the origin of hydrocarbon in the Cerrejón Formation
(mg
(mg
1 1
(mg
(mg
1 1
S1S1
S1S1
of the (A) ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1 wells.
0.1 0.1
0.1 0.1
0.01
1000
A
A
Paleocene
Mudstone
Uncontaminated
Uncontaminated
Excellent
1000
0.01
B
B
Paleocene
Mudstone
Uncontaminated
Uncontaminated
Excellent
0.010.1 Paleocene 1 10 100 0.010.1 Paleocene 1 10 100
0.1 Coal 1 10 100 0.1 Coal 1 10 100
TOC (wt.%) TOC (wt.%)
100 TOC (wt.%) 100 TOC (wt.%)
Figure 9. Cross plot of S1 versus TOC to indicate the origin of hydrocarbon in the Cerrejón Formation
Production yield
Production yield
Figure Cross plot
9. Cross plot of
of S1
S1 versus
versus TOC
TOC to
to indicate
indicate the
the origin
origin of
of hydrocarbon
hydrocarbon in the Cerrejón Formation
Very good Very good
of
of the (A) ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1
10 the (A) ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1 10
wells.
wells.
ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1 wells.
Good Good
1000 Fair 1000 Fair

Paleocene Paleocene
1000 1000
1 Mudstone
Paleocene Excellent 1 Mudstone
Paleocene Excellent
Poor Poor
Mudstone Excellent Mudstone Excellent
Paleocene Paleocene
Coal Coal
A B
Paleocene Paleocene
100 Coal 100 Coal
100 100
0.1 0.1
0.1 1 10 100 0.1 1 10 100
yield
yield
TOC (wt.%) TOC (wt.%)

yield
yield
Very good Very good

Production
Production
10 Very good 10 Very good

Production
Production
10 10 Good
Figure 10. Cross plot of production yield versus TOC to exhibit the generating potential of the
Good
Good
Good
Fair
Cerrejón Formation in the (A) ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1 wells. Fair
Fair Fair
1 Poor 1 Poor
1 Poor 1 Poor
of organic
0.1 matter (Figure
A
The diagram of S2 versus TOC proposed by Langford and Blanc [46] was used to classify the type
A
11). It was10 established that the
0.1 hydrocarbons of the Cerrejón Formation were
B
B
0.10.1 1 100 0.1 0.1 1 10 100
mainly0.1the type III kerogen, 1 TOC (wt.%)
which
TOC (wt.%)
10
is conducive to100
gas 0.1
generation. 1
However, TOC (wt.%)
TOCthey
10
(wt.%) were present in small
100
quantities,
Figureshowing
Figure 10. Crossthat
10. Cross plot this
plotof formation
production
of production also
yield contained
versus
yield versus TOCTOC totype toII/III
exhibit thekerogen,
generating
exhibit which canpotential
potential
the generating produce ofa mixture
of the Cerrejón
the
Figure 10. Cross plot of production yield versus TOC to exhibit the generating potential of the
of oilFormation
and gas. in the (A) ANH-CARRETALITO-1 and
Cerrejón Formation in the (A) ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1 wells. (B) ANH-CAÑABOBA-1 wells.
Cerrejón Formation in the (A) ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1 wells.
To assess the maturity and kerogen type, the obtained data were plotted on an HI versus Tmax
diagramThe
The diagram
(e.g.,
diagram of
of S2
S2 versus
[41,47,48]) (Figure
versus TOC
TOC proposed
12). by
by Langford
This concluded
proposed Langford that and Blanc
Blanc [46]
the Cerrejón
and was
was used
[46]Formation used toin classify
to the
the type
the central
classify area
type
of The diagram
organic matter of S2 versus
(Figure 11). TOC
It was proposed
established bythat Langford
the and Blanc [46]
hydrocarbons of wasCerrejón
the used to classify
Formation thewere type
of the Ranchería
organic matterSub-Basin
(Figure 11). has It not
wasreached the oil
established that generation
the hydrocarbons window,ofbut theitCerrejón
would have the capacity
Formation were
of organic
mainly thematter
type (Figure
III kerogen,11). It was established
which that the hydrocarbons of the Cerrejón Formation were
to generate
mainly the mainly
type III gas-type
kerogen, which is is
hydrocarbons conducive
conducivedue to togasto
its gas
organicgeneration.
generation. matter However,
type
However, IIIthey they
werewere
kerogen. present
Additionally,
present in small in
it
mainly
small the type
quantities, III kerogen,
showing which
that thisis conducive
formation alsoto gas generation.
contained type However,
II/III they
kerogen, were
which present
can in
produce smalla
may also have
quantities, showing the capacity
that this to generatealso
formation oil-type
contained hydrocarbons to a lesserwhich
type II/III kerogen, quantity due to its
can produce organic
a mixture
quantities,
mixture showing
ofgas.
oil that
andkerogen.
gas. this formation also contained type II/III kerogen, which can produce a mixture
matter
of oil and type II/III
of oil and gas.
To assess the maturity and kerogen type, the obtained data were plotted on an HI versus Tmax
300To assess the maturity and kerogen type, the obtained 300 data were plotted on an HI versus Tmax
A B
Paleocene
diagram (e.g., Mudstone
[41,47,48]) (Figure 12). This concluded thatPaleocene the Cerrejón Formation in the central area
Mudstone
diagram (e.g., [41,47,48]) (Figure 12). This concluded that the Cerrejón Formation in the central area
of the
250 Ranchería
Paleocene Sub-Basin has Type IInot reached the oil generation 250 window, but it would
Paleocene
Type II have the capacity
of the Ranchería Coal Sub-Basin has not reached
Oil prone the oil generation
Type II/III
window, but it Oilwould
Coal
prone have the capacity
Type II/III
to generate mainly gas-type hydrocarbonsMixed due to its organic matter type III kerogen. Additionally, Mixed it
to generate
200 mainly gas-type hydrocarbons due to its organic
200 Type I matter type III kerogen. Additionally, it
S2 (mg HC/g rock)
S2 (mg HC/g rock)
may alsoOilType haveI

prone
the capacity to generate oil-type hydrocarbons Oil prone to a lesser quantity due to its organic
may also have the capacity to generate oil-type hydrocarbons to a lesser quantity due to its organic
matter
150 type II/III kerogen. 150
matter type II/III kerogen.
Type III Type III
300
100 Gas prone 300
100 Gas prone
A B
A B
Paleocene
Mudstone Paleocene
Mudstone
Mudstone Mudstone
50 Coal
Paleocene Type II 50 Coal
Paleocene Type II
250 Oil prone
Type II 250 Oil prone
Type II
Coal Type II/III Coal Type II/III
Oil prone Dry gas prone
Type II/III Oil prone Dry gas prone
Type II/III
Mixed Mixed
200 Mixed 200 Type I Mixed
0 0
rock)
rock)
Type I Type
Oil I
prone
200 0 20 40 60 80 100 200 0 20 40 60 80 100
rock)
rock)
Oil prone
Type I Oil prone
Oil prone
HC/g
HC/g
TOC(wt.%) TOC(wt.%)
150 150
HC/g
HC/g
150 150
(mg
(mg
Figure 11. Cross plot of S2 versus total organic

Type III carbon (TOC) to exhibit the generating potentialType
of the
(mg
(mg
III
S2S2
S2S2
100 Gas prone

Type III 100 Gas prone
Type III
100 Gas prone 100 Gas prone
50 50
50 50
To assess the maturity and kerogen type,
Dry gas prone the obtained data were plotted on an HI Dry versus
gas prone Tmax
Dry gas prone Dry gas prone
diagram
0
0 0
(e.g., [41,47,48])
20 40
(Figure6012). This80
concluded 100
that
0
0 0
the Cerrejón
20
Formation
40
in the central
60 80
area
100
of
0 20 40
the Ranchería Sub-Basin has not60reached80the oil generation
TOC(wt.%)
100 0 20
window, but40it TOC(wt.%)
would60have the80 capacity 100
to
TOC(wt.%) TOC(wt.%)
Geosciences 2020, 10, 258 11 of 18

generate mainly gas-type hydrocarbons due to its organic matter type III kerogen. Additionally, it may
also have the capacity to generate oil-type hydrocarbons to a lesser quantity due to its organic matter
Figure 11. Cross plot of S2 versus total organic carbon (TOC) to exhibit the generating potential of the
type II/III kerogen.
1000 1000
Condensate Wetgas Zone
Condensate Wetgas Zone

Immature Mature Post Mature Immature Mature Post Mature
Type I Type I
900 900
Oil Prone Oil Prone
800 800
700 700
Hydrogen Index (mg HC/g TOC)
Hydrogen Index (mg HC/g TOC)

Type II Type II
Oil Prone Oil Prone
600 600
500 500
400 Type II-III 400 Type II-III

Oil/Gas Oil/Gas
Prone Prone
300 300
Paleocene Paleocene
Mudstone Mudstone
Paleocene Paleocene
200 Coal
200 Coal
Type III
Gas
A B
Type III
100 Gas 100 Prone
Prone
0 0
400 425 450 475 500 400 425 450 475 500
Tmax (ºC) Tmax (ºC)
Figure 12. Cross

Figure 12. Cross plot
plot between hydrogen index
between hydrogen index (HI)
(HI) (mgHC/g
(mgHC/g TOC)
TOC) versus
versus maximum
maximumpyrolysis
pyrolysis
temperature
temperature (Tmax) to indicate source rock maturity in the Cerrejón Formation of the (A) the
(Tmax) to indicate source rock maturity in the Cerrejón Formation of ANH-(A)
ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1
CARRETALITO-1 and (B) ANH-CAÑABOBA-1 wells. wells.
The
The organic
organic matter
matter values
values from
from the
the mudstones
mudstones and the coals
and the coals were
were fairly
fairly high.
high. They
Theydid didnot
not
present
presentanan HI
HI higher
higher than 300, and
than 300, andthethecharacterization
characterizationofofthe the kerogen
kerogen waswas mainly
mainly typetypeIII, III, which
which is
isclosely
closely related to terrestrial plant remains, with average TS values for
related to terrestrial plant remains, with average TS values for coals of 0.60% in the ANH- coals of 0.60% in the
ANH-CARRETALITO-1
CARRETALITO-1 Well Well and 1.11%
and 1.11% in ANH-CAÑABOBA-1
in ANH-CAÑABOBA-1 Well.Well.
TheseThese findings
findings correlate
correlate with with
the
the
paleontological findings of [14,16,49], and with the analysis of organic geochemistry carried out inin
paleontological findings of [14,16,49], and with the analysis of organic geochemistry carried out
the
theCerrejón
CerrejónFormation
Formation at the Cerrejón
at the Mine,Mine,
Cerrejón similar to Piñeres
similar et al. [23],
to Piñeres et which
al. [23],presents
whicha presents
distribution a
of 77.3% vitrinite,
distribution 15.7%
of 77.3% inertinite,
vitrinite, 15.7%and 6.9% liptinite
inertinite, and 6.9% onliptinite
average onfor the different
average sizes of particles
for the different sizes of
percentages, using a petrographic
particles percentages, analysis free
using a petrographic of mineral
analysis free ofmaterial. This study
mineral material. Thisconcurs with those
study concurs withby
Layton [27], giving the distribution as 80% vitrinite, 12.5% inertinite, 7.5% liptinite
those by Layton [27], giving the distribution as 80% vitrinite, 12.5% inertinite, 7.5% liptinite for the for the WRV-04752
Well, and 77%Well,
WRV-04752 vitrinite for the
and 77% WRV-04774
vitrinite Well, as wellWell,
for the WRV-04774 as 15% inertinite
as well as 15%and 8% liptinite.
inertinite and 8% liptinite.
The ◦ C) with respect to the PI proposed by Katz [3] was used to
Thediagram
diagram cross
cross plot
plot of
of Tmax
Tmax ((°C) with respect to the PI proposed by Katz [3] was used to
assess
assessthe
thematuration
maturation condition
condition of the
of Cerrejón Formation
the Cerrejón (Figure
Formation 13). It 13).
(Figure can be It seen
can bethatseen
the mudstone
that the
and coal samples
mudstone and coaloccupy
samples the occupy
immature thearea, whicharea,
immature reinforce
which the immaturity
reinforce of the rocksofofthe
the immaturity therocks
basin;
aofcondition
the basin;also found when
a condition comparing
also found whenTmax versusTmax
comparing %Ro.versus
Three%Ro.examples
Threeofexamples
mudstone of did not fall
mudstone
indid
thenot
immaturity
fall in the area, one of area,
immaturity themonewasofinthem
the area
was ofin inert coal,ofthe
the area other
inert coal,inthe
theother
area in of the
indigenous
area of
indigenous hydrocarbon
hydrocarbon generation, and generation,
the lastandonethe lastmigrated
in the one in thehydrocarbon
migrated hydrocarbon
field. These field.
threeThese
datathree
were
data were inconclusive
inconclusive and corresponded
and corresponded to samplesto samples
with low TOCwithvalues.
low TOC values.
Tmax data versus depth (Figure 14) as done by Peters and Cassa [41], showed that there was no
repetition of the sedimentary sequences in the wells and that there was no presence of displacement
due to geological faults; a situation confirmed with the information obtained from the seismic
interpretation, as well as from the drilling report.
Based on the data, the Cerrejón formation is immature in the central zone of the Ranchería Sub-
Basin. However, as determined by organic petrography [50], the thermal maturation of the coals and
shales of the Cerrejón Formation in the Cerrejón Mine established that the Cerrejón Formation is in
the oil generation window. Arango and Blandon [51] also established that the appearance of different
forms of inertinite present in these coals may be due to hydrocarbon expulsion processes at moderate
pressures and temperatures. This information coincides with the study carried out by Martinez [52],
which 2020,
Geosciences determined
10, 258 by chromatography the existence of gases such as methane, hexane, and heptane,
12 of 18
associated with coal mantles in the Cerrejón mine area.
the oil generation window. Arango and Blandon [51] also established that the appearance of different
forms490of inertinite present in these coals may be due to
Paleocene
490 hydrocarbon expulsion processes at moderate
Paleocene
Mudstone Mudstone
pressures
480 and temperatures. This information coincides
Paleocene
480 with the study carried out by Martinez
Paleocene
[52],
Inert Carbon Post mature Coal Inert Carbon Post mature Coal
which470
determined by chromatography the existence of
470
gases such as methane, hexane, and heptane,
associated
460
with coal mantles in the Cerrejón mine area.
460
Tmax (°C)
Tmax (°C)
490450 Hydrocarbon 490
450 Hydrocarbon
generation Paleocene generation Paleocene
(Indigenous) Mudstone (Indigenous) Mudstone
480440 440
480
Non-Indigenous Paleocene Non-Indigenous Paleocene
Inert Carbon Post mature
Hydrocarbon Coal Inert Carbon Post mature
Hydrocarbon Coal
470430 430
470
460420
A B
Immature 420
460 Immature
Tmax (°C)
Tmax (°C)
410 Hydrocarbon 410 Hydrocarbon
450 0 0.2 0.4 0.6 0.8 1 4500 0.2 0.4 0.6 0.8 1
generation generation
(Indigenous) Production Index (PI) (Indigenous)
Production Index (PI)
440 440
Non-Indigenous Non-Indigenous
Figure Hydrocarbon Hydrocarbon
430
Figure 13.13. Cross
Cross plot
plot of of production
production index
index (PI)
(PI) versus
versus Tmax
Tmax
430
(℃)totoidentify
(°C) identifysource
sourcerock
rockmaturity
maturityininthe
the Cerrejón
Cerrejón Formation
Formation of theof(A)
theANH-CARRETALITO-1
(A) ANH-CARRETALITO-1 andand (B) ANH-CAÑABOBA-1
(B) ANH-CAÑABOBA-1 wells.
wells.
A B
420 Immature 420 Immature
0 0
A and that there was no presence of displacement

B due
Tmax data versus depth (Figure 14) as done by Peters and Cassa [41], showed that there was no
410 410
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
repetition of the sedimentary sequences in the wells Production Index (PI) Production Index (PI)
Condensate Condensate
to geological
100 faults; a situation
Immature Oil window confirmed
gas window with the information
100 obtained Oil
Immature from the seismic
window interpretation,
Figure 13. Cross plot of production index (PI) versus Tmax (℃) to identify sourcegasrock
window
maturity in
as well as from the drilling report.
the Cerrejón Formation of the (A) ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1 wells.
200 200
0 0
A B
Depth (meters)
Depth (meters)
300 300
Condensate Condensate
100 Immature Oil window gas window 100 Immature Oil window gas window
400 400
200 200
500 500 Paleocene

Paleocene
Mudstone
Depth (meters)
Depth (meters)
300 Mudstone 300

Paleocene Paleocene
Coal
Coal
600 600
400 400
700 700
410 420 430 440 450 460 470 480 490 410 420 430 440 450 460 470 480 490
Tmax (ºC) Tmax (ºC)
500 500 Paleocene
Paleocene
Mudstone
Mudstone
Figure 14. Cross plot of Tmax (℃) versus depths (m) to demonstrate the distribution of the parameter
Paleocene
Paleocene
Coal
with increasing depth in the Cerrejón Formation
Coal of the (A) ANH-CARRETALITO-1 and (B) ANH-
600 600
CAÑABOBA-1 wells.
4.3.
700 Geochemical Modeling 700
410 420 430
450 460 440
470 480 490 410 420 430 440 450 460 470 480 490
A Tmax
one-dimensional (ºC)
model was performed in theTmax
of burial history (ºC)
location of the ANH-
CARRETALITO-1
Figure
Figure 14. Cross
14. Cross and
plot of ANH-CAÑABOBA-1
plot of Tmax
Tmax (℃) (°C)
versus versus
depths wells,
depths using
(m) to (m) the information
to demonstrate
demonstrate obtained
the distribution
the distribution from
of thethe
of the parameter
interpretation
parameter of
with the seismic
increasing lines
depth in
in time,
the the
Cerrejónboundary
Formation conditions
of the (A)heat flow, the
ANH-CARRETALITO-1
with increasing depth in the Cerrejón Formation of the (A) ANH-CARRETALITO-1 and (B) ANH-
paleo-water anddepth,
(B)
theANH-CAÑABOBA-1
SWIT (Figure 15),
CAÑABOBA-1 wells.wells.
and the bottom hole temperature (BHT) of the wells (Figure 16, right side). The
heat flow, considering the sin-rift stage and the post-rift stage in this sub-basin, was established from
200
4.3. to 116on
Based mya
Geochemical theand from
data,
Modeling 116Cerrejón
the to 20 mya, respectively.
formation The paleo-water
is immature in the depth
centralused
zone forofthe simulation
the Ranchería
Sub-Basin. However, as determined by organic petrography [50], the thermal maturation of the coals
A one-dimensional
and shales model of in
of the Cerrejón Formation burial historyMine
the Cerrejón was established
performedthat in the
the Cerrejón
locationFormation
of the ANH- is in
CARRETALITO-1 and ANH-CAÑABOBA-1 wells, using the information
the oil generation window. Arango and Blandon [51] also established that the appearance of different obtained from the
interpretation of the seismic lines in time, the boundary conditions heat flow,
forms of inertinite present in these coals may be due to hydrocarbon expulsion processes at moderate the paleo-water depth,
the SWIT and
pressures (Figure 15), and theThis
temperatures. bottom hole temperature
information coincides(BHT)
with theof the wells
study (Figure
carried out16,byright side).[52],
Martinez The
heat flow, considering the sin-rift stage and the post-rift stage in this sub-basin,
which determined by chromatography the existence of gases such as methane, hexane, and heptane, was established from
200 to 116 with
associated mya and
coal from
mantles116intothe
20 Cerrejón
mya, respectively.
mine area.The paleo-water depth used for the simulation
Geosciences 2020, 10, 258 13 of 18
4.3. Geochemical Modeling

A one-dimensional model of burial history was performed in the location of the ANH-
CARRETALITO-1 and ANH-CAÑABOBA-1 wells, using the information obtained from the
interpretation of the seismic lines in time, the boundary conditions heat flow, the paleo-water
depth, the SWIT (Figure 15), and the bottom hole temperature (BHT) of the wells (Figure 16, right
side). The heat flow, considering the sin-rift stage and the post-rift stage in this sub-basin, was
established
Geosciences
Geosciences from
2020, x 200
10, 10,
2020, FOR to
PEER
x FOR 116REVIEW
PEER mya and from 116 to 20 mya, respectively. The paleo-water depth
REVIEW ofused
1313 of
1818
for the simulation was proposed by [34], 50 m from 126 to 103 mya, subsequently, increasing to 200
was
m in proposed
was92 proposed
mya and byby [34], 5050
[34],
gradually mm from
from126
126toto103
decreasing 103mya,
100 m insubsequently,
mya, subsequently,
79 increasing
increasing
mya, then 15 m in 70 toto200
mya,200and,
mminin9292mya
mya
finally, 0and
mandto
gradually
thegradually
present. decreasing
decreasing to to
100 mminin7979mya,
100 mya,then
then15
15m
min
in 70
70 mya,
mya, and, finally,
finally,00mmtotothe
thepresent.
present.
80 80 32
32 0 0
Paleo water depth (m)

Heat flow (mW/m^2)
Paleo water depth (m)

Heat flow (mW/m^2)
30
Temperature (°C)
30
Temperature (°C)
60 100
60 100
28
28
40 200
40 200
Heat flow Paleo water depth
Heat flow 26 Paleo water depth
SWI-Temperature
26 SWI-Temperature
20 300
20 200 150 100 50 100 50 300
200 150 Time (Ma)
100 50 100 Time (Ma) 50
Time (Ma) Time (Ma)
Figure 15. Boundary conditions used for 1D modeling of burial history of the lithological units in the
Figure 15.
Figure Boundary conditions used for 1D modeling of burial history of the lithological units in the
15. Boundary
ANH-CARRETALITO-1 and ANH-CAÑABOBA-1 wells.
ANH-CARRETALITO-1
ANH-CARRETALITO-1 and and ANH-CAÑABOBA-1
ANH-CAÑABOBA-1 wells. wells.
A
Burial history with %Ro variations, ANH-CARRETALITO-1 well Modeled temperature
ANH-CARRETALITO-1 well
A
Burial Cretaceous
history with %Ro variations, ANH-CARRETALITO-1
Paleogene wellNeogene Modeled temperature well
vs BHT ANH-CARRETALITO-1
ANH-CARRETALITO-1 well
Lwr Cretaceous Upper Cretaceous Plc. Eocene Oligocene Miocene 40 60 80 100 120
0 Cretaceous Paleogene Neogene vs BHT ANH-CARRETALITO-1 well
Conjunto Conglomeratico 0
Lwr Cretaceous Upper Cretaceous Plc. Eocene Oligocene Miocene Cerrejon Fm
40 60 80 100 120
0
Conjunto Conglomeratico 0
Manantial Fm
1000 Cerrejon
Molino FmFm 500
Manantial
La Luna FmFm
1000 Aguas
MolinoBlancas
Fm Fm 500
Lagunitas Fm
La Luna Fm
2000
Rio Negro
Aguas Fm Fm 1000
Blancas
Depth [m]
Sweeney and Burnham La Quinta Fm

(1990) Easy %Ro: Lagunitas Fm
2000
Rio Negro Fm 1000
Depth [m]
3000 Immature
Sweeney and (0.25
Burnham - 0.55) La Quinta Fm
EarlyEasy
(1990) Oil (0.55
%Ro-:0.7) 1500
Main Oil (0.7 - 1.0)
3000 Immature (0.25
Late Oil -(1.0
0.55)
- 1.3)
Early Oil
Wet(0.55 - 0.7)- 2.0)
gas (1.3 1500
4000 Main Oil
Dry(0.7
gas-(2.01.0)- 4.0)
Late OilOvermature
(1.0 - 1.3) > 4 2000
Wet gas (1.3 - 2.0)
4000 Dry gas (2.0 - 4.0)
5000 Overmature > 4 2000
BHT ANH-CARRETALITO-1WELL (°C)

5000 100 50 0 Modeled Temperature (°C)
Time [Ma]
BHT ANH-CARRETALITO-1WELL (°C)
B 100 Burial history with %Ro variations,50ANH-CAÑABOBA-1 well 0 Modeled temperature

Modeled Temperature (°C)
Time [Ma] ANH-CAÑABOBA-1 well
Cretaceous Paleogene Neogene vs BHT ANH-CAÑABOBA-1 well
B
Burial history
Lwr Cretaceous with %Ro
Upper Cretaceous variations,
Plc. ANH-CAÑABOBA-1
Eocene OligocenewellMiocene 20 40 Modeled
60 temperature
80 100 120
0 0 ANH-CAÑABOBA-1 well
Paleogene Neogene Conjunto Conglomeratico vs BHT ANH-CAÑABOBA-1 well
Cretaceous
Lwr Cretaceous Upper Cretaceous Plc. Eocene Oligocene Miocene Cuervos Fm 20 40 60 80 100 120
0 1000 0
Manantial Fm 500
Conjunto Conglomeratico
Molino Fm
Cuervos
La Luna FmFm
1000 2000 Aguas Blancas Fm
Manantial Fm 500
1000
Lagunitas Fm
Depth [m]
Sweeney and Burnham Molino Fm

(1990) Easy %Ro: Rio Negro Fm
La Quinta
La Luna FmFm
Immature (0.25 - 0.55) Aguas Blancas Fm
2000 3000 Early Oil (0.55 - 0.7)
Lagunitas Fm 1000
1500
Depth [m]
SweeneyMain OilBurnham
and (0.7 - 1.0)
LateEasy
(1990) Oil (1.0
%Ro - 1.3)
: Rio Negro Fm
Wet gas (1.3 - 2.0) La Quinta Fm
3000 4000 ImmatureDry(0.25 - 0.55)
gas (2.0 - 4.0)
Early OilOvermature
(0.55 - 0.7)> 4 2000
1500
Main Oil (0.7 - 1.0)
Late Oil (1.0 - 1.3)
5000 Wet gas (1.3 - 2.0)
4000 Dry gas (2.0 - 4.0) 2500
2000
Overmature > 4 BHT ANH-CAÑABOBA-1WELL (°C)
100 50 0 Modeled Temperature (°C)
Time [Ma]
5000
2500
BHT ANH-CAÑABOBA-1WELL (°C)
Figure Burial
16. 16.
Figure history
100Burial using
history modeled
using 50 temperature
modeled variation
temperature for
variation (A)
0 for ANH-CARRETALITO-1
(A) ANH-CARRETALITO-1 andand(B)
Modeled Temperature (°C)
Time [Ma]
ANH-CAÑABOBA-1 wells.
Figure 16. Burial history using modeled temperature variation for (A) ANH-CARRETALITO-1 and
(B) The model of burial history
ANH-CAÑABOBA-1 wells. (Figure 16), with overlapping values and the different hydrocarbon
generation windows were colored as proposed by Sweeney and Burnham [33]. The current
temperature
The modelmodel washistory
of burial calibrated with 16),
(Figure BHT.with
Likewise, it was possible
overlapping values to calibrate
and the model
the different of EASY
hydrocarbon
%Ro with paleo-geothermometer data (%Ro) from samples from the Cerrejón
generation windows were colored as proposed by Sweeney and Burnham [33]. The current Formation (Figure 17).
The resulting model predicts that the Upper Cretaceous formations, Molino
temperature model was calibrated with BHT. Likewise, it was possible to calibrate the model of EASYand La Luna,
%Roentered in the early oil window
with paleo-geothermometer at (%Ro)
data the Late
fromPaleocene, beforethe
samples from theCerrejón
Middle Formation
Eocene uplift event.
(Figure 17).
Likewise, the Lower Cretaceous formations would be in the main oil window
The resulting model predicts that the Upper Cretaceous formations, Molino and La Luna, since the Late
Paleocene; after this time, it is expected that its thermal maturation did not progress any further, and
entered in the early oil window at the Late Paleocene, before the Middle Eocene uplift event.
Geosciences 2020, 10, 258 14 of 18
The model of burial history (Figure 16), with overlapping values and the different hydrocarbon
generation windows were colored as proposed by Sweeney and Burnham [33]. The current temperature
model was calibrated with BHT. Likewise, it was possible to calibrate the model of EASY %Ro with
Geosciences 2020, 10, x FOR PEER
paleo-geothermometer dataREVIEW
(%Ro) from samples from the Cerrejón Formation (Figure 17). 14 of 18
A 0.20 0.40 0.60 0.80 1.00 Ro(%)

B 0.20 0.40 0.60 0.80 1.00 Ro(%)
0 Quaternary 0 Quaternary
Conjunto
conglomeratico
200 200
Conjunto
conglomeratico
Depth (m)
Depth (m)
400 Cerrejon Fm 400
600 600
Cerrejon Fm
Manantial Fm
800 800
Measured %Ro Measured %Ro

(min, mean,max) (min, mean,max)
Modelled %Ro Modelled %Ro
Figure 17. Calibration

Figure 17. Calibrationof
ofvitrinite
vitrinitereflectance
reflectance(%Ro) with
(%Ro) depth
with forfor
depth thethe
(A) (A)
ANH-CARRETALITO-1 and
ANH-CARRETALITO-1
(B)
andANH-CAÑABOBA-1
wells.
The
The resulting
thermal stress modelcan predicts that the by
be measured Upper takingCretaceous
into account formations,
the Tmax Molino
and %Roand La Luna,which
values, enteredis
in the early oil window at the Late Paleocene, before the Middle
necessary to evaluate the amount of organic matter that has been transformed into hydrocarbon [53]. Eocene uplift event. Likewise,
the
ThisLower Cretaceous
is the reason formations
for the variationwould be in the main rates
in the transformation oil window
(TR) insince
Figure the18.Late
As aPaleocene;
result, TRafterwas
this time, it is expected that its thermal maturation did
not expected in the study area for Cenozoic formations. The TR estimated for the Cretaceousnot progress any further, and the Cerrejón
Formation
Lagunitas, is immature
Aguas in both
Blancas, La Luna, wells.and TheMolino
higherformations
maturationinlevels might have reached for Well
the ANH-CARRETALITO-1 the other
had
source rock of Cretaceous formations in the ANH-CARRETALITO-1
values of 90, 85, 67, and 29%, respectively. The TR expected for the Cretaceous Lagunitas, Aguas Well.
The La
Blancas, thermal
Luna,stress can be measured
and Molino formations byintaking into account the Tmax
the ANH-CAÑABOBA-1 anddid
Well %Ro values,
not seem whichto be ofis
necessary to evaluate the amount of organic matter that has been
greater importance, as evidenced in Figure 18B. The TR occurred mainly in the Paleocene and Early transformed into hydrocarbon [53].
This is the
Eocene, reason
with for the
values variation
of 70, 45, 26, in and the8%,
transformation
respectively.rates (TR) in
It should beFigure
noted18. thatAsthe a result, TR was
Cretaceous not
units
expected in the study area for Cenozoic formations. The
reached their maximum TR value in the Middle Eocene. However, only in the ANH-CARRETALITO- TR estimated for the Cretaceous Lagunitas,
Aguas
1 Well Blancas,
did the La LowerLuna, and Molino
Cretaceous formationshave
formations in the ANH-CARRETALITO-1
a greater advance in their Well TR at had
thevalues
end ofofthe
90,
85, 67, and 29%,
Paleocene, whilerespectively. The TR expected
the Upper Cretaceous units for hadthe Cretaceous
almost Lagunitas,
all their increaseAguas in their Blancas,
TR during La Luna,
the
and Molino formations in the ANH-CAÑABOBA-1 Well did
Eocene. This establishes two pulses of hydrocarbon generation in the Paleocene and the Eocene, not seem to be of greater importance,
as evidenced in Figure 18B. The TR occurred mainly in the Paleocene and Early Eocene, with values of
respectively.
70, 45, 26, and 8%, respectively. It should be noted that the Cretaceous units reached their maximum
TR value in the Middle Eocene. Cretaceous However, only in the Paleogene ANH-CARRETALITO-1Neogene Well did the Lower
Upper Cretaceous Paleocene Eocene Oligocene Miocene Plio.
100.0
Cretaceous formations have a greater advance in their TR at the end of the Paleocene, while the Upper
TR-ALL at Middle of Cerrejon Fm.
Cretaceous units hadTR-ALL almost
at Middleall their
of Molino Fm. increase in their TR during the Eocene. This establishes two
TR-ALL at Middle of La Luna Fm.
pulses of hydrocarbon generation in the Paleocene and the Eocene, respectively.
TR-ALL at Middle of Aguas Blancas Fm.
Fraction[%]
This shows thatTR-ALL theatCerrejón Formation

Middle of Lagunitas Fm. in the study area is not in the oil window. A trend
50.0
of higher levels of thermal maturation towards the north of the Ranchería Sub-Basin is expected,
as corroborated by Sanchez and Mann [6], who proposed that in general the thermal maturation of the
A
generating units is increasing towards the northeast of the sub-basin. This is caused by the increase in
sedimentary coverage and does not coincide with the study by Martinez et al. [7], which suggested
0.0
that there are thermal
100 maturation bands generated by 50 the uplift of PR. These bands are oriented 0 in
Time [Ma]
parallel to the reverse faultCretaceous trace of Cerrejón-Villanueva,Paleogene where the displacement Neogene of the PR developed,
Upper Cretaceous
whereas the100.0 areas of greater maturation arePaleocene those close to the PR. Oligocene
Eocene Miocene Plio.

TR-ALL at Middle of Molino Fm.
Fraction[%]
TR-ALL at Middle of Lagunitas Fm.

50.0
B
0.0
100 50 0
Eocene, with values of 70, 45, 26, and 8%, respectively. It should be noted that the Cretaceous units
reached their maximum TR value in the Middle Eocene. However, only in the ANH-CARRETALITO-
1 Well did the Lower Cretaceous formations have a greater advance in their TR at the end of the
Paleocene, while the Upper Cretaceous units had almost all their increase in their TR during the
Eocene. This
Geosciences establishes
2020, 10, 258 two pulses of hydrocarbon generation in the Paleocene and the Eocene,
15 of 18
respectively.
Cretaceous Paleogene Neogene

100.0
Fraction[%]

50.0
A
0.0
100 50 0
Time [Ma]
Cretaceous Paleogene Neogene
100.0
Fraction[%]

50.0
B
0.0
100 50 0
Time [Ma]
Figure 18. Hydrocarbon middle-component and transformation ratios (TR) for the Cretaceous and
Paleogene formations in the (A) ANH-CARRETALITO-1 and (B) ANH-CAÑABOBA-1 wells.
5. Conclusions
• The mudstones of the Cerrejón Formation showed 10.68% TOC value on average, which indicated
the presence of organic matter consisting of mixed type II/III kerogen. It supported a good source
rock potential to produce oil/gas type hydrocarbons.
• The coals of the Cerrejón Formation presented ~64% TOC value and the presence of organic
matter consisting of mixed type III kerogen. Evidence of excellent gas-generating hydrocarbon
were indicated in the intervals.
• The Cerrejón Formation in the central area of the Ranchería Sub-Basin is in the immature stage,
but close to the oil window.
• The high values of Tmax and %Ro obtained in the rocks of the Cerrejón Formation revealed
a possible great tectonic event in the Middle Eocene as the cause of the highest loss of the
stratigraphic record in the Ranchería Sub-Basin.
• Based on the burial history diagrams calibrated with %Ro data, the loss of sedimentary coverage
in the Middle Eocene was estimated as 2600 m in the ANH-CARRETALITO-1 Well and 500 m in
the ANH-CAÑABOBA-1 Well.
• Two peaks of increase in the organic matter transformation were recognized in the Paleocene and
Middle Eocene intervals. They showed distinct characteristics in hydrocarbon generation and
migration patterns. This corresponded better to the northern part of the sub-basin.
Supplementary Materials: The following are available online at http://www.mdpi.com/2076-3263/10/7/258/s1,

Table S1: ANH-Carretalito-1 Well, Rock Eval pyrolysis data. Table S2: ANH-Cañaboba-1 Well, Rock Eval pyrolysis
data. Table S3: ANH-Carretalito-1 Well, vitrinite reflectance data. Table S4: ANH-Cañaboba-1 Well, vitrinite
reflectance data.
Author Contributions: Conceptualization, L.F.C.-C., M.G.-G., L.E.C.-G., G.M.A.-S.; investigation, L.F.C.-C.,
G.M.A.-S.; writing—original draft preparation, L.F.C.-C., G.M.A.-S.; writing—review and editing, L.F.C.-C.,
M.G.-G., L.E.C.-G., G.M.A.-S.; visualization, L.F.C.-C.; supervision, M.G.-G., L.E.C.-G. All authors have read and
agreed to the published version of the manuscript.
Geosciences 2020, 10, 258 16 of 18
Funding: We would like to thank the Agencia Nacional de Hidrocarburos (ANH) for financing the project entitled:
“Thermal and geochemical modeling under subsidence and thrust of the Perijá Range, Ranchería Sub-Basin,
Colombia, South America” (project carried out under the contract No FP44842-454-2017). The Universidad
Industrial de Santander (UIS) provided lab and computing facilities.
Acknowledgments: Special thanks to the Agencia Nacional de Hidrocarburos (ANH), and the Departamento
Administrativo de Ciencia, Tecnología e Innovación (COLCIENCIAS), which allowed access to the information
published in this article. The geochemical analysis was performed by personnel of the Laboratorio de Geología
del Petróleo (LGP) at the headquarters of Guatiguará-UIS. Thanks to the style-writer corrector, German
Morales. We thank the anonymous reviewers for their valuable contributions, allowing the document to
improve substantially.
Conflicts of Interest: The authors declare no conflict of interest.
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Geochemical Characterization and Thermal Maturation of Cerrejón

Article in Geosciences · July 2020

Luis Felipe Cruz Mario Garcia-Gonzalez

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Luis Enrique Cruz

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Keywords: Cerrejón Formation; Cesar–Ranchería Basin; Ranchería Sub-Basin; source rock

Geosciences 2020, 10, 258; doi:10.3390/geosciences10070258 www.mdpi.com/journal/geosciences

Colombia 140 140

Coal Volcanic rock Continental mudstone

Figure 2.2. Interpreted

3. Data and Methods

ANH CARRETALITO -1 well ANH CAÑABOBA-1 well

Lithologies mudstone sandstone coal conglomerate limestone

4. Results and Discussion

4.1. TOC and Rock Eval Pyrolysis Results

450 (Oil Window)

S1 (mg HC/g roca)

S1 (mg HC/g roca)

1000 Fair 1000 Fair

TOC (wt.%) TOC (wt.%)

Very good Very good

10 Very good 10 Very good

S2 (mg HC/g rock)

may alsoOilType haveI

Figure 11. Cross plot of S2 versus total organic

100 Gas prone

Geosciences 2020, 10, x FOR PEER REVIEW 11 of 18

Condensate Wetgas Zone

Condensate Wetgas Zone

Hydrogen Index (mg HC/g TOC)

400 Type II-III 400 Type II-III

Figure 12. Cross

A and that there was no presence of displacement

500 500 Paleocene

300 Mudstone 300

4.3. Geochemical Modeling

Paleo water depth (m)

Paleo water depth (m)

Sweeney and Burnham La Quinta Fm

BHT ANH-CARRETALITO-1WELL (°C)

B 100 Burial history with %Ro variations,50ANH-CAÑABOBA-1 well 0 Modeled temperature

Sweeney and Burnham Molino Fm

A 0.20 0.40 0.60 0.80 1.00 Ro(%)

Measured %Ro Measured %Ro

Figure 17. Calibration

This shows thatTR-ALL theatCerrejón Formation

TR-ALL at Middle of Cerrejon Fm.

TR-ALL at Middle of Lagunitas Fm.

Cretaceous Paleogene Neogene

TR-ALL at Middle of Lagunitas Fm.

TR-ALL at Middle of Lagunitas Fm.

Supplementary Materials: The following are available online at http://www.mdpi.com/2076-3263/10/7/258/s1,

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