Journal of Petroleum Science and Engineering 213 (2022) 110410

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Journal of Petroleum Science and Engineering

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Geochemical evaluation of sedimentary rocks and hydrocarbon fluids in the

Amistad offshore field, Progreso Basin Province, Southwest Ecuador
M.A. Guzmán a, G. Márquez a, *, C. Boente a, C. Witt b, A. Morato c, R. Tocco d
a
Center for Research in Sustainable Chemistry (CIQSO), University of Huelva, 21006, Huelva, Spain
b
Laboratoire D’Océanologie et de Géosciences, University of Lille, CNRS, F59000, Lille, France
c
School of Engineering Sciences, State University Santa Elena Peninsula, 240204, La Libertad, Ecuador
d
Independent Petroleum Geochemistry Consultant, Madrid, 28410, Spain

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

Keywords: This study contains a thorough isotopic and molecular characterization of a series of thirteen (13) gas samples
Gas geochemistry and six (6) liquid hydrocarbons produced from late Miocene reservoirs in the offshore Progreso Basin (SW
C1–C4 alkanes Ecuador), along with Rock-Eval and petrographic analyses of sixty-two (62) rock samples from the area. The
CSIA-D
principal aim of this research work is to investigate the geochemistry of hydrocarbon fluids and sedimentary
Reservoir compartments
Amistad field
rocks in the area of the Amistad field to determine the origin of the studied wet gases. Potential source rocks in
the Amistad stratigraphic section are immature and have no oil-generating capability, except for the early
Miocene Dos Bocas Formation. Studied low-boiling condensates have similar gas chromatographic fingerprints
while their compound-specific isotopic analyses of lower diamondoids (CSIA-D) indicate an oil-source correla­
tion between them and Dos Bocas extracts. Sampled gases are mainly methane of biogenic origin except for that
from the Delfín B-17X well, which might represent the thermogenic end-member gas signature of the Amistad
gases. Results suggest a complex hydrocarbon filling history with multiple charges of thermogenic gas and hy­
drocarbons generated from the distal deltaic Dos Bocas source rocks followed by biodegradation, leakage and
partial displacement by biogenic methane due to the uplifting of the Amistad structure. The Amistad gases form
three homogeneous groups located in the southern, central and northern parts of the Progreso reservoir, although
the geological segmentation of it into compartments cannot be clearly identified.

CRediT author statement
Gonzalo Márquez: Conceptualization, Writing - Original Draft,
Formal Analysis, Supervision, Data Curation. Carlos Boente: Software,
Data Curation, Visualization, Methodology. Marco Antonio Guzmán:
Investigation, Methodology. César Witt: Writing - Review & Editing,
Formal Analysis. Antonio Morato: Funding acquisition, Validation,
Formal Analysis. Rafael Tocco: Visualization, Supervision.
1. Introduction
The Progreso Basin Province includes the Santa Elena Block and the
Gulf of Guayaquil-Tumbes Basin (Higley, 2004), which comprises the
Esperanza, Tumbes and Jambelí sub-basins (Witt et al., 2006; Aizprua
et al., 2019). This region has been defined as an oil petroliferous prov­
ince because of the presence of source rock intervals, trapping
mechanisms as well as an abnormally high temperature gradient (Hig­
ley, 2004). The evolution of the Gulf of Guayaquil-Tumbes Basin is
linked with extensional and strike-slip processes resulting from the
tectonic escape of the North Andean Block (or North Andean Sliver),
mostly a crustal fragment accreted to the continent from Late Cretaceous
times (e.g. Jaillard et al., 1999). The locus of the Gulf of
Guayaquil-Tumbes Basin being related with the trailing-tail of the
microplate in a complex interaction with weaknesses zones resulting
from the accretional processes (Aizprua, 2021).
Hydrocarbon exploration in the southern coastal Ecuador was
encouraged by the presence of several oil seeps and the Ancón field
discovery in 1915 (Sheppard, 1937). During the 1940s a branch of
Exxon attempted to extend this oilfield southward along the Santa Elena
Peninsula, encountering numerous oil and gas shows (Stainforth, 1948).
Exploration efforts by subsidiaries of Chevron and Tenneco in the 1950s
and 1960s, respectively, did not report important hydrocarbon

* Corresponding author.
E-mail address: gonzalo.marquez@diq.uhu.es (G. Márquez).

https://doi.org/10.1016/j.petrol.2022.110410
Received 26 October 2021; Received in revised form 9 January 2022; Accepted 15 March 2022
Available online 17 March 2022
0920-4105/© 2022 Elsevier B.V. All rights reserved.
M.A. Guzmán et al.
accumulations in the region (Marchant, 1965). During the early 1970s, a
Phillips consortium carried out extensive exploration in the Gulf of
Guayaquil. This resulted in the discovery of the Amistad gas field
(located 65 km northwest of the city of Machala; Fig. 1a), in which, after
a drilling program in 1969, gas was found at some wells from the
Miocene Progreso Formation. This offshore field is an anticlinal struc­
ture: the presence of natural gas is reported on both sides of a large
NE-SW trending fault zone, which deepens to the east. The size of the
reservoir is approximately 25 km2 and the pay zone can be as thick as 85
m (Bristow, 1975). Also in the 1970s, Tenneco drilled several explora­
tion wells in the Peruvian sector of the Gulf of Guayaquil, which led to
the discovery of the Albacora oilfield (Evans and Whittaker, 1982).
Exploratory efforts in the Progreso Basin Province for following decades
reported no economic results (Higley, 2004).
Fig. 1. a) Location of the B-17X gas well, boreholes, and fields in the Progreso Basin Province; b) map showing the situation of wells and compartmentalization in the
Amistad gas field.
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Journal of Petroleum Science and Engineering 213 (2022) 110410
Since exploration begun, around 8 billion m3 of natural gas have
been produced from southern coastal Ecuador, with Amistad field hav­
ing an average annual gas production of about 40 million of ft3 and
recoverable gas reserves estimated to be in the order of one trillion ft3
(Evangelista, 2019). A previous work (Encalada, 2017) studied gas
composition and reported abundances of ca. 97% of methane in some
Amistad offshore wells but to date, no thorough gas analyses have been
reported from the Amistad field so the origin of these gases, along with
their potential source rocks, remain unknown.
The molecular composition of natural gas depends on a series of
geological and geochemical factors, such as source kerogen type,
maturity, thermal cracking, biodegradation, migration, and/or mixing
(Behar et al., 1992; Pallasser, 2000; Gürgey et al., 2005; Tian et al.,
2009). Generally, carbon and hydrogen isotope signatures of C1–C4
M.A. Guzmán et al.
gaseous hydrocarbons can be used to identify the genetic types of nat­
ural gas (e.g., Jenden et al., 1993; Patience, 2003; Wang et al., 2018; El
Diasty et al., 2020) and to assess gas maturity within each genetic type
(Clayton, 1991; Dai et al., 2005; among others).
In this study, carbon and hydrogen isotopic analyses and C1–C4 gas
compositions are complemented with analyses of C5–C7 light hydro­
carbons and lower diamondoids from condensate samples of two
offshore areas located in the southern Gulf of Guayaquil in order to
generate a comprehensive geochemical investigation of the sources and
origin of the natural gases from both areas. Also, the organic matter
throughout the stratigraphic section of the Amistad structure is exam­
ined. Integration of geochemical data (i.e. C1–C4 compositions, molec­
ular nitrogen concentration, isotopic signatures in gas samples) allowed
elucidating reservoir continuity in the Amistad field. This all informa­
tion can be used to assist in guiding future drilling programs in the
Amistad field.
2. Geological setting
2.1. Tectonic evolution and structural geology
The early evolution of the southernmost Ecuadorian forearc is out­
lined by several plate-scale processes that mainly include the accretion
of oceanic terranes of the Caribbean Large Igneous Province and the
modern tectonic escape of the North Andean Block, which includes such
oceanic terranes and others of the South American Plate (Alvarado et al.,
2016; Aizprua et al., 2019). The Gulf of Guayaquil-Tumbes Basin is part
of a series of Plio-Pleistocene forearc basins related to the northward
tectonic escape of the North Andean Sliver and shows a complex ar­
chitecture made up of three main depocenters: the Esperanza, Jambelí
and Tumbes sub-basins (Egbue and Kellogg, 2010). Sub-basins are
separated by structural highs most-likely resulting from transpression
linked to strain-partitioning along a major weakness zone inherited from
the accretionary processes (Witt and Bourgois, 2010; Aizprua et al.,
2019), a structural style which seems to continue towards the
Peru-Ecuador border (latitude 3◦ 23′ 34′′ S; Fig. 1a). The subsidence
related to the drift of the North Andean Sliver started as early as
Oligocene, in the early to middle Pleistocene subsidence took place in
the Esperanza and Jambelí sub-basins (at least 6 km thick in the
Esperanza basin) representing one of the most significant subsidence
through the entire North Andean forearc area. A proto Amistad structure
separated the Miocene depocenters of the Jambelí and Esperanza Basins.
A major reaccommodation of basin depocenters occurred during the
Pleistocene implied the migration of the main depocenter from the
southern part of the Jambelí sub-basin towards the Esperanza sub-basin;
a process accompanied by a change in the tectonic signature of the
Amistad structure (Deniaud et al., 1999; Witt et al., 2006).
The Posorja and Jambelí detachment systems are also important
tectonic features of the Progreso Basin Province, both representing half-
grabens with oppositely dipping detachments. The NE-SW trending
Puna-Amistad transfer fault system bounds the Esperanza and Jambelí
sub-basins, denoting that the evolution of they both is tightly controlled
by the two above-mentioned detachments at depth (Witt and Bourgois,
2010). N–S trending tensional stresses characterize the Pleistocene times
throughout. The westernmost N–S trending Domito fault system marks
the limit of the Esperanza sub-basin (Calahorrano et al., 2008). From
late Pleistocene to recent times, tectonic activity is restricted along the
normal faults bounding the Esperanza sub-basin (Witt et al., 2006).
The Amistad structure, of N–S orientation, is most-likely related to
strain partitioning along the major weakness zone produced during
oceanic accretions (i.e. transform boundary). It consists of a large anti­
cline of flower structure, extensively faulted and compartmentalized
(Kraemer et al., 2001). The Amistad gas field is situated on the down
thrown east side of the main fault zone (see Fig. 1a; Aizprua, 2021).
Lateral trapping mechanisms are the NE-SW trending fault zone in the
NW part of the structure, and simple dip closure in all other directions. It
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Journal of Petroleum Science and Engineering 213 (2022) 110410
is not clear whether connectivity exists through the fault zone or later­
ally in the southern part of the structure where the fault zone terminates
within the closing contour indicative of the hydrocarbon/water contact,
and if local faulting has affected the reservoir connectivity and has
caused reservoir separation into smaller compartments (Barzallo and
Bemúdez, 2016).
2.2. Stratigraphic framework
The stratigraphic column that is representative of the Jambelí sub-
basin comprises sedimentary rocks of Oligocene and Neogene ages
(Fig. 2; after Benítez, 1995). The Delfín wells crosses the early Miocene
to Pleistocene sequences including, base to top, the Heath, Zorritos,
Cardalitos, Tumbes, Mal Pelo, La Cruz, and Tablazo formations (Fig. 2).
The basement (Early Cretaceous Piñón Formation) is more than 1000 m
thick and consists of pillow lavas, wehrlites, tholeiitic basalt-andesite
porphyry flows associated with hyaloclastic breccias, and cumulate
gabbros intruded by massive dolerites forming a dense network of sills
and dykes (Luzieux et al., 2006).
The Oligocene Zapotal Formation (maximum thickness of 3200 m)
consists of a sequence of imbricated conglomerates, pebbly sandstones
with marine fossils, tuffs and coaly shales or thin coal beds deposited by
alluvial fans near the shoreline (Bristow and Hoffstetter, 1977; Benítez,
1995; Jaillard et al., 1995; among others). It has not been reached by any
of the wells of the Gulf of Guayaquil-Tumbes Basin. Reworked tuffs and
volcaniclastic deposits yielded two U–Pb zircons ages in the Progreso
Basin Province between 32 and 30 Ma (Witt et al., 2019). The fauna
association reported near Zapotal village is very similar to that reported
in the Mancora Formation in Perú (Olsson, 1931).
The Miocene Dos Bocas and Villingota formations have been only
observed in outcrops. The former comprises a sequence of dark-gray,
endurated, foraminifera- and diatom-rich shales intercalated with
sandstones and conglomerates deposited in inner to mid-shelf environ­
ments, with relatively restricted oceanic circulation (Benítez, 1995). The
Villingota Formation mainly consists of slightly tuffaceous, diatoma­
ceous shales deposited in outer shelf to slope environments during
coastal upwelling and seems to be a lateral equivalent facies of the Dos
Bocas Formation, both correlate with the Peruvian Heath Formation
(Benítez, 1995). Upward in the stratigraphic record, the Subibaja For­
mation is a sequence of calcite-cemented sandstones, siltstones and
shales (Bristow and Hoffstetter, 1977) observed in the deepest parts of
the Gulf of Guayaquil-1 and Domito-1 wells (south of the tip of the
Amistad structure and western border of the basin, respectively). This
transitional marine unit represents the progradation of sand-rich lobes
onto a muddy shelf during a regressive cycle (Benítez, 1995). The shales
of the Villingota, Dos Bocas and Subibaja formations act as top seals for
interbedded sandy reservoirs (Higley, 2004; Deckelman et al., 2008).
Provenance models based mostly on U–Pb radiometric dating (Witt
et al., 2017, 2019) suggest that the Miocene sedimentary series in the
Amistad structure (Amistad-10 well) show affinities that may allow to
rely them to the Tumbes sub-basin, instead of the Esperanza sub-basin.
The affinity is mostly based on the ratios between zircons derived for the
modern arc (very significant in SW Ecuador) and those derived from the
continental basement (very significant in NW Peru and in the Amistad
structure).
The Progreso Formation has been reached in all wells of the Gulf of
Guayaquil-Tumbes Basin with the exception of the Esperanza-1
exploratory well that reached only Pliocene sediments. The Progreso
Formation (maximum thickness of 1400 m) consists of shales inter­
bedded with silty sandstones. The base of the Progreso Formation was
deposited in a shallow marine environment, while the top of which
(known as the Cerro Mala Member) represents fluvio-deltaic sedimen­
tation (Benítez, 1995). To the south, in the Amistad field, the Progreso
Formation contains relatively thick shales, which may behave as
important pressure seals (Higley, 2004), and gas-producing sandstones
with porosity and permeability of up to 30% and 20 mD (Deckelman
M.A. Guzmán et al. Journal of Petroleum Science and Engineering 213 (2022) 110410

Fig. 2. Stratigraphic columns in the southern Gulf of Guayaquil. Note: source rocks (black circle) and reservoir rocks (black square). Hatched areas show non-
depositional periods and dotted lines separate members of the same formation.

et al., 2008). A dated deposit in the Progreso Basin Province yielded an
age of ~10 Ma (Witt et al., 2019). The Puna Formation (maximum
thickness of 1000 m) represents shallow shelf sedimentation and, to­
wards the bottom, is a sequence of transitional sandstones intercalated
with conglomerates and massive silty rocks (Benítez, 1995). By contrast,
this unit mainly comprises soft, arkosic and indurated sandstones
interbedded with massive siltstones and volcanic tuffs (Placer Member)
and, on top, gray and green siltstones with lenses of sandstones (Lechuza
Member; Bristow and Hoffstetter, 1977). These latter two members were
deposited in deltaic and estuarine environments with significant input of

4
M.A. Guzmán et al.
siliciclastic sediments by meandering rivers. Finally, the Pleistocene
Tablazo Formation mainly consists of shallow marine calcareous sands
(Benítez, 1995).
3. Samples and methods
Eleven produced gases were sampled from the Amistad field, along
with one gaseous sample from a well (B-17X) in the nearby Delfín field,
using sealed glass bottles by means of metal separators connected to two
sealed cylinders in parallel in the well-head. Geochemical gas data from
the currently non-producing Amistad-9 (A-9) well has also been used.
Regarding low-boiling condensates (also called “distillates”), together
with one sample (B-17X) from the Zorritos unit, five samples (labeled A-
3, A-6, A-7, A-8A, and A-12) were taken from the Progreso reservoir.
Sixty-two core samples from several of the aforementioned wells were
also studied. Among them, fifty-one were analysed for vitrinite reflec­
tance maturity, of which sixteen selected samples from the Neogene
sequence were analysed for maceral characterization (visual kerogen
analysis). Lastly, two representative Dos Bocas rock samples from the
Amistad Sur borehole (total depth of 4506 m) were collected for fluid-
source correlation purposes. Fig. 1b shows the sampled wells in the
study area.
Optical microscopy analyses were carried out on grain pellets ground
to 1 mm following ISO 7404–2:2009 for sample preparation, ISO
7404–5:2009 for vitrinite reflectance measurements, and ISO
7404–3:2009 for maceral analysis; the latter being performed at a
maceral level for liptinite and a maceral group level for vitrinite and
inertinite using white light complemented with fluorescence observa­
tions. Rock-Eval/TOC analyses were performed using a Rock Eval II Plus
TOC module apparatus, Delsi-Nermag instruments, according to
Espitalié et al. (1977).
Analyses of the components in gaseous samples were performed,
following the procedures provided by Márquez et al. (2013), through an
Agilent 6890 series gas chromatograph (GC) with electronic pneumatic
control. Relative standard deviations were below 0.8%. Carbon and
hydrogen isotope analyses of individual compounds in the gaseous
samples were measured by gas chromatography-isotope ratio mass
spectrometry through a GC/C III interface connected through a com­
bustion reactor to a Finningan MAT Delta plus XL mass spectrometer
(conditions as described in Márquez et al., 2013). The 13C/12C, D/H and
15
N/14N ratios are reported in “δ” notation. δ13C, δD and δ15N values
refer to V-PDB, SMOW and N-SVEC standards for carbon, hydrogen and
nitrogen stable isotope measurements. Reproducibility of the measure­
ments of δ13C, δ15N and δD were better than ±0.3‰, ±0.5‰ and ±5‰,
respectively.
Core samples were softly disaggregated, air-dried for 24 h, and
manually grounded. Previous artificial maturation, in which potential
source-rock samples are heated for 6 days at 330 ◦ C (Lijmbach et al.,
1983), subsamples were extracted with a mixture of dichloromethane:
methanol (3:1, v/v) in a Soxtherm system (Gerhardt). The extracts were
concentrated by rotary evaporation at 40 ◦ C, then filtered (0.45 μm), and
finally dissolved in dichloromethane. Later, an aliquot of each rock
extract was fractioned into saturated and aromatic hydrocarbons, and
polar compounds. Asphaltene fraction was precipitated with n-heptane
in a 1:40 v/v ratio according to the method outlined by Speight (2007).
Then, saturates were separated from aromatic and resin fractions by
liquid chromatography. The columns were filled with silica gel and
alumina. The saturated hydrocarbons were eluted with hexane, the ar­
omatics with a mixture of dichloromethane:hexane (4:1 v/v) and,
finally, the resins were eluted with methanol.
Whole oil gas chromatographic analyses of light hydrocarbons in
condensate samples were carried out using a J&W Agilent PONA GC
column (50 m × 0.2 mm i. d.; film thickness 0.25 μm; helium was the
carrier gas) in a Delta Chrom Series 9980 instrument with flame ioni­
zation detection. The following operating conditions were used for the
gas chromatograph: temperature maintained at 35 ◦ C for 15 min;
5
Journal of Petroleum Science and Engineering 213 (2022) 110410
increased from 35 ◦ C to 320 ◦ C at a rate of 2 ◦ C/min; and maintained at
320 ◦ C for 30 min. Additionally, gas chromatographic-mass spectro­
metric (GC-MS) and compound-specific isotope (CSIA) analyses of lower
diamondoids were done on distillates and saturate fractions of rock
extracts. For these two analyses, which were performed on a TRACE™
gas chromatograph coupled to a Thermo Scientific ISQ EC mass spec­
trometer and a Delta V Advantage mass spectrometer with GC-isolink
interphase, respectively (Esquinas et al., 2018), the saturate frac­
tions/distillates were priorly treated with ZSM-5 zeolite to remove
n-alkanes (He et al., 2012). Absolute concentrations were measured by
adding two deuterated-labeled compounds (1-methyladamantane-d3
and 1-methyldiamantane-d3) as internal standards to hydrocarbon liq­
uids before performing analysis by GC-MS (Dahl et al., 1999).
4. Results and discussion
4.1. Potential hydrocarbon source rocks
4.1.1. Total organic carbon and Rock-Eval data
Table 1 shows total organic carbon (TOC) values for selected rock
samples throughout the stratigraphic section penetrated by the A-8A,
− 11, − 12, and Amistad-Sur wells. TOC is quite low in most analysed
samples (0.11–0.79%; averaging 0.42%), except for the rock samples
from the Amistad Sur well sampling the Subibaja and Dos Bocas for­
mations. These rock samples have TOC values between 0.98 and 2.16%
(1.45% on average), with good S2 pyrolysis peaks. As for the hydrogen
indices (HI; Table 1), the Progreso and younger formations exhibit
values lower than 200 mg HC/g TOC and S2/S3 below 3, indicatives of
Type III-IV precursor organic matter with little natural gas and no oil-
generating capability (Peters, 1986). Similarly, the samples from the
Subibaja Formation (HI and S2/S3 data below 100 mg HC/g TOC and 3)
are only capable of generating limited amounts of natural gas. Only the
two deepest Dos Bocas samples have Rock Eval data which can rated as
good in source quality (HI values of 244 and 256 mg HC/g TOC, with
S2/S3 exceeding 3), denoting a Type II-III kerogen and gaseous/liquid
hydrocarbon generation attributes, because this type of kerogen gener­
ates mixtures of gas and secondarily oil, in contrast to Type I-II and Type
III-IV kerogens as they tend to be oil-prone and gas-prone, respectively
(Tissot and Welte, 1984). These results are corroborated by the HI versus
OI diagram (Fig. 3a) and the plot of HI versus Tmax (Fig. 3b). This latter
eludes any variability related to the oxygen index (Cornford et al.,
1998).
Tmax data (values below 430 ◦ C; Table 1) indicate that the entire
section analysed is thermally immature for petroleum generation even if
good quality source rocks are present. That is, the Dos Bocas and Sub­
ibaja formations have not reached here sufficient levels of maturity to
generate hydrocarbons. All samples from the Amistad field (with the
exception of those from the Amistad Sur well), apart from being ther­
mally immature, contain only small quantities of terrigenous organic
matter that cannot generate sufficient petroleum to form producible
deposits. Therefore, the thermal wet gas and low-boiling condensate
must have migrated from deeper mature source rocks. Within this
stratigraphic section, only a very slight maturity increase with depth is
observed. This is not usual (Dow, 1977) and should be explained by a
very short thermal exposure time due to uplift, by a low
paleo-geothermal gradient, or the combination of both. If the section
was rapidly buried and then promptly uplifted, there may not have
enough heating time to mature the organic material in the rocks: this
could be what happened on the Amistad structure, which has repre­
sented a structural high at least since the middle Miocene to the present,
coeval with the onset of the Jambelí sub-basin depocenter, and where
recent activity has been observed in high-resolution seismic character­
ization (Reynaud et al., 2018). Depth-projection of the maturity profile
(%Rc) suggests that if source horizons are present, petroleum generation
in the study area might have occurred at 6000 m depth or deeper (in
concordance with Evangelista, 2019).
M.A. Guzmán et al. Journal of Petroleum Science and Engineering 213 (2022) 110410

Table 1
Measured and calculated vitrinite reflectances (Ro and Rc), TOC values, depths, and Rock-Eval data for the sampled rocks.
Sample Depth Rock unit Lithology TOC Tmax Rr Rc S1 S2 S3 HI OI

Amistad-8D/01 2436–2450 Cerro Mala Sandy claystone 0.31 417 – 0.35% 0.02 0.30 0.45 97 145
Amistad-8A/02 2520–2534 Progreso s.s. Silty claystone 0.39 418 0.30% 0.36% 0.02 0.18 0.28 46 72
Amistad-8A/03 2646–2660 Progreso s.s. Sandy claystone 0.39 419 0.30% 0.38% 0.01 0.14 0.17 36 44
Amistad-8A/04 2688–2702 Progreso s.s. Silty claystone 0.31 418 0.29% 0.37% 0.01 0.12 0.02 39 6
Amistad-8A/05 2772–2786 Progreso s.s. Silty shale 0.52 419 0.30% 0.38% 0.03 0.28 0.32 54 62
Amistad-8A/06 2856–2870 Progreso s.s. Silty shale 0.52 420 0.31% 0.39% 0.04 0.28 0.34 54 65
Amistad-8A/07 2940–2954 Progreso s.s. Silty claystone 0.58 419 0.32% 0.39% 0.05 0.32 0.16 55 28
Amistad-8A/08 3024–3038 Progreso s.s. Silty claystone 0.79 420 0.31% 0.40% 0.03 0.41 0.23 52 29
Amistad-8A/09 3108–3122 Progreso s.s. Sandy claystone 0.58 419 0.31% 0.39% 0.02 0.25 0.16 43 28
Amistad-8A/10 3192–3206 Progreso s.s. Sandy shale 0.37 419 0.31% 0.39% 0.01 0.16 0.09 43 24
Amistad-8A/11 3262–3276 Progreso s.s. Sandy shale 0.18 420 0.32% 0.40% 0.00 0.04 0.09 22 50
Amistad-8A/12 3346–3360 Progreso s.s. Sandy shale 0.41 420 0.31% 0.40% 0.02 0.17 0.17 41 41
Amistad-8A/13 3388–3402 Progreso s.s. Sandy shale 0.51 421 0.30% 0.41% 0.02 0.22 0.14 43 27
Amistad-8A/14 3430–3444 Progreso s.s. Sandy claystone 0.37 421 0.31% 0.41% 0.15 0.33 0.60 89 162

Amistad-11/01 876–960 Lechuza Shaly sandstone 0.22 – 0.37% – 0.02 0.08 0.14 36 64
Amistad-11/02 1212–1296 Lechuza Shaly sandstone 0.57 421 0.39% 0.41% 0.03 0.32 0.38 56 67
Amistad-11/03 1380–1464 Placer Shaly claystone 0.28 421 0.39% 0.41% 0.01 0.11 0.06 39 21
Amistad-11/04 1548–1632 Placer Clayey shale 0.22 421 0.39% 0.42% 0.03 0.31 0.14 141 64
Amistad-11/05 1800–1884 Puná s.s. Claystone 0.73 421 0.38% 0.41% 0.11 1.42 0.62 195 85
Amistad-11/06 2069–2153 Puná s.s. Claystone 0.22 422 0.39% 0.42% 0.01 0.17 0.11 77 50
Amistad-11/07 2237–2321 Cerro Mala Silty claystone 0.41 420 0.38% 0.40% 0.02 0.28 0.10 68 24
Amistad-11/08 2405–2489 Progreso s.s. Shale 0.67 421 0.38% 0.41% 0.03 0.37 0.35 55 52
Amistad-11/09 2489–2573 Progreso s.s. Shale 0.47 421 – 0.41% 0.02 0.37 0.21 79 45
Amistad-11/10 2574–2618 Progreso s.s. Shale 0.69 422 0.38% 0.42% 0.01 0.55 0.23 80 33
Amistad-11/11 2632–2646 Progreso s.s. Shale 0.60 422 0.38% 0.42% 0.01 0.49 0.14 82 23
Amistad-11/12 2716–2730 Progreso s.s. Sandy shale 0.25 421 0.38% 0.41% 0.01 0.10 0.13 40 52
Amistad-11/13 2814–2828 Progreso s.s. Sandy shale 0.25 420 0.37% 0.40% 0.01 0.13 0.13 52 52
Amistad-11/14 2884–2898 Progreso s.s. Shale 0.49 422 0.40% 0.42% 0.01 0.26 0.22 53 45
Amistad-11/15 2954–2968 Progreso s.s. Sandy shale 0.23 422 0.39% 0.42% 0.01 0.23 0.05 100 22

Amistad-12/01 448–532 Tablazo Sandy siltstone 0.33 414 0.28% 0.29% 0.05 0.13 0.37 39 112
Amistad-12/02 700–784 Lechuza Shaly sandstone 0.26 415 0.29% 0.30% 0.05 0.09 0.14 35 54
Amistad-12/03 952–1036 Lechuza Shaly sandstone 0.32 415 – 0.31% 0.01 0.06 0.15 19 47
Amistad-12/04 1204–1288 Placer Shaly claystone 0.27 415 0.30% 0.32% 0.03 0.15 0.72 56 267
Amistad-12/05 1456–1540 Placer Clayey shale 0.57 416 0.31% 0.32% 0.02 0.30 0.19 53 33
Amistad-12/06 1624–1708 Placer Clayey shale 0.46 416 0.31% 0.32% 0.04 0.37 0.18 80 39
Amistad-12/07 1792–1876 Puná s.s. Claystone 0.46 416 0.32% 0.32% 0.03 0.24 0.20 52 43
Amistad-12/08 2044–2128 Puná s.s. Claystone 0.37 416 0.32% 0.32% 0.03 0.28 0.14 76 38
Amistad-12/09 2296–2380 Cerro Mala Silty claystone 0.34 417 0.32% 0.33% 0.03 0.23 0.10 68 29
Amistad-12/10 2464–2478 Progreso s.s. Sandy claystone 0.47 417 0.32% 0.33% 0.02 0.22 0.13 47 28
Amistad-12/11 2534–2548 Progreso s.s. Silty claystone 0.24 416 0.32% 0.32% 0.02 0.11 0.16 46 67
Amistad-12/12 2590–2604 Progreso s.s. Sandy claystone 0.54 417 – 0.33% 0.02 0.27 0.18 50 33
Amistad-12/13 2646–2660 Progreso s.s. Silty claystone 0.71 418 0.31% 0.35% 0.02 0.30 0.18 42 25
Amistad-12/14 2702–2716 Progreso s.s. Silty shale 0.78 418 0.32% 0.35% 0.02 0.48 0.32 62 41
Amistad-12/15 2744–2758 Progreso s.s. Silty shale 0.56 417 0.32% 0.33% 0.01 0.32 0.09 57 16
Amistad-12/16 2800–2814 Progreso s.s. Shale 0.12 – 0.33% – 0.01 0.03 0.07 25 58
Amistad-12/17 2856–2870 Progreso s.s. Shale 0.30 417 0.32% 0.33% 0.01 0.12 0.10 40 33
Amistad-12/18 2912–2926 Progreso s.s. Sandy shale 0.70 417 0.32% 0.34% 0.02 0.38 0.19 54 27
Amistad-12/19 2982–2996 Progreso s.s. Sandy shale 0.50 418 0.33% 0.35% 0.02 0.24 0.26 48 52
Amistad-12/20 3108–3122 Progreso s.s. Sandy shale 0.11 – 0.32% – 0.01 0.03 0.10 27 91
Amistad-12/21 3122–3136 Progreso s.s. Sandy shale 0.14 417 0.32% 0.34% 0.01 0.02 0.18 14 127
Amistad-12/22 3136–3150 Progreso s.s. Sandy shale 0.29 417 0.33% 0.34% 0.83 0.27 0.16 92 67

Amistad-Sur/01 4144–4150 Subibaja Claystone 1.77 425 0.40% 0.49% 0.07 0.95 3.84 54 217
Amistad-Sur/02 4161–4167 Subibaja Claystone 1.69 425 – 0.49% 0.05 0.88 2.79 52 165
Amistad-Sur/03 4183–4189 Subibaja Claystone 1.18 425 – 0.49% 0.25 0.65 2.54 55 215
Amistad-Sur/04 4239–4245 Subibaja Claystone 1.12 426 0.41% 0.50% 0.16 1.12 1.26 95 112
Amistad-Sur/05 4250–4256 Subibaja Claystone 2.16 425 – 0.49% 0.22 1.55 4.13 72 191
Amistad-Sur/06 4317–4323 Dos Bocas Sandy Claystone 1.17 427 – 0.51% 0.07 0.61 3.88 52 332
Amistad-Sur/07 4342–4348 Dos Bocas Sandy Claystone 0.98 427 0.42% 0.52% 0.04 0.32 1.63 33 166
Amistad-Sur/08 4384–4390 Dos Bocas Sandy Claystone 0.98 428 – 0.53% 0.08 0.49 2.95 50 301
Amistad-Sur/09 4429–4435 Dos Bocas Sandy Claystone 1.18 428 – 0.53% 0.07 1.11 2.44 94 207
Amistad-Sur/10 4452–4458 Dos Bocas Sandy Claystone 1.70 428 – 0.53% 0.08 4.34 1.20 256 71
Amistad-Sur/11 4474–4480 Dos Bocas Sandy Claystone 2.03 429 0.43% 0.54% 0.08 4.95 1.39 244 69

Notes: TOC data in wt.%; S1and S2 in mg HC/g rock, while S3 in mg CO2/g rock; HI–
– S2/TOC; OI–
–S3/TOC; HI in mg HC/g TOC; depth in m; Tmax in ◦ C; IO in mg CO2/
g TOC. %Rc = 0.018⋅Tmax-7.16 (Jarvie et al., 2001).

4.1.2. Kerogen composition and maturity measurements
All the selected cutting samples for petrographic studies from the A-
8A, A-11, A-12, and Amistad Sur wells consist mainly of vitrinite/
huminite (58–80%) with minor quantities of inertinite (2–10%) and
exinites not exceeding 10% (Table 2); although some amorphous
organic material is also observed, it is difficult to identify as algal or
humic debris. Herbaceous plant debris including traces of possible oil-
prone sporinite (Mukhopadhyay et al., 1991) and resinite are also
observed in the deepest Dos Bocas rock samples. Based on petroleum
potential, exinite and vitrinite macerals are light oil/condensate- and
mostly gas-prone, respectively, while inertinite macerals only have a
little gas potential (Stach et al., 1982). With exception of the probable

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M.A. Guzmán et al. Journal of Petroleum Science and Engineering 213 (2022) 110410

Fig. 3. a) and b), respectively, HI versus OI diagram and plot of HI against Tmax for rock samples.

Table 2
Petrographic composition (vol%) for the some rock samples.
Sample Depth Rock unit Vitrinite/huminite Dark vitrinite Amorphous Exinite Inertinite

Amistad-8A/03 2646–2660 Progreso s.s. 80% 65% 10% 4% 6%

Amistad-8A/08 3024–3038 Progreso s.s. 75% 60% 15% 5% 5%
Amistad-8A/13 3388–3402 Progreso s.s. 80% 65% 10% 5% 5%

Amistad-11/02 1212–1296 Lechuza 70% 60% 20% 4% 6%

Amistad-11/05 1800–1884 Puná s.s. 58% 40% 35% 2% 5%
Amistad-11/08 2405–2489 Progreso s.s. 50% 40% 40% 5% 5%
Amistad-11/11 2632–2646 Progreso s.s. 65% 45% 20% 6% 9%
Amistad-11/14 2884–2898 Progreso s.s. 70% 65% 15% 9% 6%

Amistad-12/05 1456–1540 Placer 65% 10% 25% 5% 5%

Amistad-12/10 2296–2380 Cerro Mala 60% 10% 30% 8% 2%
Amistad-12/14 2702–2716 Progreso s.s. 65% 35% 25% 7% 3%
Amistad-12/18 2912–2926 Progreso s.s. 70% 40% 20% 5% 5%

Amistad-Sur/01 4144–4150 Subibaja 70% 55% 15% 9% 6%

Amistad-Sur/04 4239–4245 Subibaja 70% 55% 10% 10% 10%
Amistad-Sur/07 4342–4348 Dos Bocas 55% 40% 30% 10% 5%
Amistad-Sur/11 4474–4480 Dos Bocas 60% 45% 25% 10% 5%

Notes: Petrographic data expressed in a mineral-matter-free basis. Terminology according to ICCP in 2001.

Dos Bocas source rock organofacies corresponding to a prodeltaic
depositional environment, under oxygen-deficient conditions
(Montenegro and Benítez, 1991), these kerogen assemblages indicate
deposition under relatively oxic conditions, and could be characteristic
of transitional-fluvial settings (Stach et al., 1982). The maceral analyses
also showed that there are two kinds of vitrinite, a dark and a light
variety, in the cutting samples. Most samples comprise predominately
lipid-rich vitrinite in dark gray-black color: the vitrinitic fraction ap­
pears to be predominantly normal at the shallower samples from Cerro
Mala to younger strata, and then changes to a mixture of light and
mostly dark vitrinite at deeper samples from the A-12 well (Table 2). The
existence of a dark and light vitrinite in terrigenous organic facies is
relatively common at low maturity levels, probably resulting in sup­
pressed reflectance (Kalkreuth, 1982). Even though coexistence with
liptinite, whose bituminous substances can permeate through the vitri­
nite, could often explain the presence of dark (perhydrous) vitrinite
(Iglesias et al., 2000), in this case this option is unlikely given the low
exinite content of most samples, excepting the deepest cuttings.
Palaeo-desiccation of woody components at the time of deposition under
specific conditions might be another explanation for dark vitrinite
occurrence in cutting samples (Taylor et al., 1989), but these processes
are generally related to environments with contrasted seasons and a
high inertinite content (Diessel, 2010). Alternately, associated to tissues
and resinous fillings, the vitrinite can become darker (Suarez-Ruiz et al.,

7
M.A. Guzmán et al. Journal of Petroleum Science and Engineering 213 (2022) 110410

1994). A last scenario requires that a distinct density of plants gener­ amounts of higher hydrocarbons; whereas thermogenic gas is suggested
ating dark vitrinites or different chemistry in the vitrinites may explain by methane/ethane ratios typically below 100 (Jackson et al., 2014).
the darker appearance (Petersen and Rosenberg, 1998). Gas dryness usually increases with increasing gas maturation
As shown in Table 1, vitrinite reflectance values (%Rr) near or below (Prinzhofer et al., 2000), and it is considered that values exceeding 0.95
0.4% confirm that maturity is low throughout the Neogene sequence generally indicate microbial processes (Dai, 1992). Thus, bacteriogenic
analysed. Noteworthy is also an appreciable difference between %Rc hydrocarbons have a dominant contribution to gaseous samples A-4,
and %Rr values (Table 1). This feature might be partially caused by the A-6, A-7, A-11, and A-12 with C1/C2 gas ratios clearly above 100; while
problem of reflectance suppression, which in turn can be attributed to the other Amistad gases, with C1/C2 ratios near o below 100, have an
various reasons such as overpressure in sedimentary basins and/or the appreciable thermogenic gas input. The B-17X gas contains small, but
fact that Tmax could evolve differently for Types II and III organic significant contents of ethane and other paraffins, which might reflect
matter at low maturities (Espitalié et al., 1985; Carr, 2000); in this associated oil accumulations (Dai, 1992).
context, the most reliable explanation would be given by the occurrence The molecular C1/C2 and C2/C3 ratios can be used to distinguish
of low-reflecting vitrinite. between kerogen- and oil-cracking gases by using in the ln (C1/C2)
against ln (C2/C3) graph, since the first/second ratio increases notably/
remains constant during primary cracking and vice versa during sec­
4.2. Geochemical characteristics of petroleum samples
ondary cracking (Prinzhofer and Huc, 1995). None of the Amistad gases
plot along the evolution lines of Type-II (sapropelic) or Type-III (humic)
4.2.1. Natural gas components
kerogen. Instead, the Delfín gas plotts near the evolution line of Type-II
Molecular concentrations of methane, ethane, propane, n-butane,
kerogen (Fig. 4a), with lower C1/C2 values, which are typical of primary
iso-butane, n-pentane, and iso-pentane for the natural gases throughout
cracking processes.
the studied area are shown in Table 3. Methane is the main component
Based on the ratios of iso-butane to n-butane (i-C4/n-C4) and ethane
of the sampled gases, ranging from 96.36 to 99.54%. Several groups of
to propane (C2/C3) it is possible to determine the extent of biodegra­
samples can be defined based on these results. First, the samples with
dation (as opposed to migration and other secondary processes) in the
highest molar concentrations of methane (around 99.5%) are A-4, A-6,
gas samples (e.g., Márquez et al., 2013). Relatively high values
A-7, A-11, and A-12, which also show the lowest molar concentrations of
(approaching or exceeding 3) of both ratios are observed in all the gases
heavier alkanes (Table 3). Second, samples A-1, A-5, A-8A, and A-9 have
produced from the Progreso reservoir, while the A-8D and B-17X gases
similar C1–C3 alkanes patters, with average contents of methane and
show the lowest C2/C3 and i-C4/n-C4 values (Table 4 and Fig. 4b). Since
ethane approaching 98% and 1%. Third, A-2 and A-3 samples, nearly
propane is preferentially attacked by microbes (James and Burns, 1984)
identical, have slightly lower and higher values of methane (96.94% on
and n-butane is selectively biodegraded relative to its isomeric
average) and ethane (averaging 1.611%) contents, respectively, than the
iso-alkane (Katz et al., 2002; Larter and di Primio, 2005), it is likely that
two previous groups of Amistad gaseous samples. Four, the lowest
all the analysed gases (except A-8D and B-17X) can be affected by
abundance of methane (96.39%) and highest concentration of heavier
slightly biodegradation rather than migration.
alkanes (Table 3) are noticed in the B-17X gaseous sample, excluding the
Non-hydrocarbon components are also present in most analysed
A-8D sampled gas. This latter natural gas from the Cerro Mala interval
natural gases. In the Amistad samples, CO2 and N2 range from 0.010 to
exhibited an abnormal low molar concentration of methane (68.34%),
0.033% and 0.14%–0.32%, respectively (Table 3). Delfín B-17X natural
which would suggest air contamination during sampling and/or the fact
gas (sampling the Zorritos interval) has CO2 and N2 contents of
that vertical composition is not equilibrated along the study strati­
approximately 0.2%. A-8D gaseous sample from the Cerro Mala reser­
graphic section because of barriers to molecular diffusion, as discussed
voir has 0.27% of CO2 and 30.38% of N2, values notably higher than
below.
those in the other reservoirs (see Table 3). In particular, the excep­
The gas dryness (defined as C1/ΣC1-5, which evaluates the proportion
tionally high molar nitrogen content in the A-8D gas, up to almost three
of hydrocarbon compounds in the samples) lies in the 0.963–0.998
hundred times higher than those from the other wells, seems to reflect
range for the studied samples (Table 4), averaging 0.988, with A-8D gas
air contamination during sampling, which would be supported by N2/Ar
having a value of 0.993. The molar concentration of methane in gaseous
of 90 and δ15N of 0‰ (Zhu et al., 2000); however, molecular oxygen
samples (excluding A-8D) increases with gas dryness (Pearson’s coeffi­
would have been almost consumed by reaction with the steel cylinder or
cient of about 0.99). Methane abundance in natural gas can be governed
by other feasible means (Jenden et al., 1988).
by numerous and complex factors including genetic type, gas maturity,
and geochromatography during secondary migration, among others
4.2.2. Isotopic compositions of gas hydrocarbons
(Tissot and Welte, 1984; Behar et al., 1992; Chen et al., 2000). For
The carbon isotopic compositions of the C1–C4 n-alkanes and
instance, biogenic gas is mostly methane, with no or very scarce

Table 3
Average aliphatic hydrocarbons (C1–C6+), CO2, and N2 for the gases from Amistad field and Delfín B-17X well.
Well Reservoir Latitude Longitude CH4 C2H6 C3H8 n-C4 i-C4 n-C5 i-C5 C6+ CO2 N2

Amistad-1 Progreso 3◦ 15′ 41′′ S 80◦ 27′ 36′′ W 98.50 0.708 0.218 0.028 0.089 0.006 0.030 0.046 0.030 0.32
Amistad-2 Progreso 3◦ 13′ 47′′ S 80◦ 27′ 00′′ W 97.97 0.835 0.270 0.023 0.065 0.006 0.020 0.056 0.011 0.30
Amistad-3 Progreso 3◦ 14′ 33′′ S 80◦ 28′ 06′′ W 97.83 0.842 0.271 0.022 0.063 0.006 0.021 0.053 0.010 0.31
Amistad-4 Progreso 3◦ 17′ 36′′ S 80◦ 28′ 21′′ W 99.47 0.205 0.058 0.006 0.022 0.001 0.006 0.030 0.016 0.16
Amistad-5 Progreso 3◦ 16′ 09′′ S 80◦ 28′ 20′′ W 98.53 0.700 0.212 0.028 0.088 0.006 0.027 0.044 0.033 0.31
Amistad-6 Progreso 3◦ 16′ 42′′ S 80◦ 28′ 19′′ W 99.54 0.193 0.056 0.006 0.020 0.001 0.006 0.021 0.015 0.14
Amistad-7 Progreso 3◦ 16′ 53′′ S 80◦ 27′ 55′′ W 99.51 0.202 0.059 0.006 0.021 0.001 0.006 0.028 0.012 0.15
Amistad-8D Cerro Mala 3◦ 15′ 26′′ S 80◦ 27′ 25′′ W 68.34 0.235 0.106 0.035 0.044 0.026 0.050 0.102 0.270 30.38
Amistad-8A Progreso 3◦ 15′ 36′′ S 80◦ 27′ 32′′ W 98.60 0.696 0.215 0.028 0.089 0.006 0.025 0.045 0.032 0.31
Amistad-9 Progreso 3◦ 16′ 16′′ S 80◦ 27′ 49′′ W 98.62 0.698 0.216 0.027 0.087 0.007 0.025 0.046 0.032 0.31
Amistad-11 Progreso 3◦ 17′ 00′′ S 80◦ 28′ 17′′ W 99.49 0.200 0.060 0.007 0.022 0.001 0.005 0.029 0.010 0.14
Amistad-12 Progreso 3◦ 17′ 48′′ S 80◦ 28′ 34′′ W 99.48 0.199 0.057 0.006 0.021 0.001 0.006 0.031 0.015 0.16
Delfín B-17X Zorritos 3◦ 36′ 50′′ S 80◦ 48′ 30′′ W 96.06 1.955 1.116 0.217 0.142 0.091 0.080 0.105 0.110 0.12
Amistad Sur – 3◦ 18′ 40′′ S 80◦ 28′ 19′′ W – – – – – – – – – –

Note: all data in molar percentages.

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M.A. Guzmán et al. Journal of Petroleum Science and Engineering 213 (2022) 110410

Table 4
δD (‰) in methane, δ13C values (‰) in carbon dioxide and C1–C4 alkanes, as well as light hydrocarbon parameters for the gaseous samples.
Well Net pay Depth C1/ΣC1-5 i-C4/n-C4 C1/C2-3 C2/C3 C1/C2 C2/C1 δ13C1 δ13C2 δ13C3 δ13nC4 δ13iC4 δD1 δ13CCO2

A-1 3145–3215 4777 0.990 3.18 106.37 3.25 139.12 0.007 − 56.30 − 32.42 − 27.32 − 27.41 − 28.35 − 203.9 –
A-2 2585–2850 3164 0.984 2.81 88.66 3.09 117.33 0.008 − 56.26 − 31.56 − 27.48 − 27.56 − 28.44 − 205.6 − 16.45
A-3 2296–2324 2475 0.984 2.85 87.89 3.10 116.20 0.008 − 56.24 − 31.33 − 27.41 − 27.45 − 28.29 − 205.8 –
A-4 2492–2525 2944 0.997 3.66 378.21 3.53 485.22 0.002 − 61.68 − 43.34 − 30.55 − 27.29 − 28.14 − 207.0 − 18.65
A-5 2520–2530 2994 0.989 3.14 108.03 3.30 141.44 0.007 − 56.18 − 32.91 − 27.54 − 27.55 − 28.38 − 204.7 − 18.08
A-6 2492–2567 2919 0.998 3.33 399.75 3.44 515.75 0.002 − 61.39 − 43.27 − 30.45 − 27.46 − 28.43 − 210.9 − 16.96
A-7 2836–2916 3498 0.997 3.50 381.26 3.42 492.62 0.002 − 61.62 − 43.78 − 30.71 − 27.29 − 28.12 − 209.3 − 19.22
A-8D 2178–2294 2952 0.993 1.26 200.41 2.22 290.81 0.004 − 59.47 − 36.62 − 27.59 − 27.51 − 28.38 − 208.1 –
A-8A 3327–3376 4024 0.990 3.18 108.23 3.24 141.41 0.007 − 56.10 − 32.67 − 27.43 − 27.50 − 28.41 − 206.1 − 17.34
A-9 2873 3330 0.990 3.22 107.89 3.23 141.61 0.007 – – – – – – –
A-11 2733–2799 3232 0.998 3.14 382.65 3.33 497.45 0.002 − 61.37 − 43.91 − 30.80 − 27.33 − 28.17 − 211.3 –
A-12 3001–3032 3428 0.997 3.50 388.59 3.49 499.89 0.002 − 61.76 − 43.45 − 30.12 − 27.38 − 28.30 − 210.1 − 17.87
B-17X 1756 2634 0.963 0.65 31.27 1.74 49.13 0.020 − 38.45 − 30.48 − 27.96 − 27.22 − 28.09 − 180.1 –

Note: Net pay data and depths in meters.

hydrogen signature of methane for the gaseous samples are shown in
Table 4. Biogenic gas can be identified by methane-based carbon iso­
topic signatures (δ13C1) below − 55‰; while δ13C1 values of thermo­
genic gas usually range from − 20 to − 55‰ (Dai, 1992). As for
depositional environment and organic matter type, it is considered that
δD values for methane (δD1) up to around − 190‰ are typical of
humic-type natural gases (Schoell, 1980), along with δ13C2 and δ13C3
exceeding − 27.5‰ and − 25.5‰; instead, δ13C2 and δ13C3 values below
− 29‰ and − 27‰ are typical of sapropelic-type gases, while gaseous
samples with δ13C2 and δ13C3 between aforementioned values are either
mixtures of the two end-member types or generated from type II-III
kerogen (Dai et al., 2005). Also, δD1 values from − 190‰ to − 180‰
correspond to paralic brackish environment range (Liu et al., 2008). The
δ13C1 and δD1 values in Amistad gaseous samples range from − 57.26‰
to − 60.7‰ and − 203.5‰ to − 211.3‰ (Fig. 5a), thus indicating mixed
biogenic-thermogenic origin and mostly humic-type precursor material
for these gaseous samples. By contrast, δ13C1, δ13C2, δ13C3 and δD1
values for the Delfín B-17X gas (Table 4 and Fig. 5a) suggest a ther­
mogenic input probably generated from mostly marine source rocks
deposited in paralic brackish settings.
Fig. 5b shows a plot of the C1/C2+3 ratio versus methane carbon
isotopic composition (also known as Bernard diagram), a useful tool to
differentiate the genetic type of gas (Bernard et al., 1978; Galimov,
2006). In this diagram, two groups of Amistad samples are recognised: a
first group (A-4, A-6, A-7, A-11, and A-12) is characterised by a domi­
nantly bacteriogenic gas contribution, with minor thermogenic gas
input; the other Amistad gases (A-1, A-5, A-8A, and A-8D) plot in the
“mixing” zone (Fig. 5b), but with a less dominant bacteriogenic input.
The B-17X natural gas sample has δ13C1 < − 40‰ and C1/C2+3 about 30
(Table 4), which denotes a thermogenic origin. The modified
δ13C1-δ13C2-δ13C3 plot diagram (Fig. 6) corroborates a dominantly
biogenic origin for Amistad gaseous samples and
thermogenic-sapropelic origin for B-17X gas (Dai et al., 2014). Delfín
B-17X gaseous sample show a near-linear negative correlation between
δ13C values for individual C1–C4 n-alkanes and reciprocal carbon num­
ber, as opposed to Amistad gases as their δ13C1 values are depleted,
thereby supporting the aforementioned outcomes (Dai, 1992). Among
other factors accounting for this latter feature (e.g., biodegradation), a
substantial biogenic signature to the Amistad gases might have added
enough bacteriogenic ethane to shift the thermogenic C2 isotopic char­
acter of these samples to lighter values.
The carbon isotopic series of C1–C4 n-alkanes of the primary biotic
gases usually follows a positive trend (δ13C1<δ13C2<δ13C3<δ13C4;
Boreham and Edwards, 2008). However, partial reversals of the δ13C gas
series can be caused by various processes such as mixing (e.g., Fuex,
1977; Cai et al., 2001; Hao et al., 2008; Yang et al., 2008), biodegra­
dation (Zumberge et al., 2009; Xia et al., 2013), overmaturity (Zum­
berge et al., 2012; Gao et al., 2015) and/or thermochemical sulfate
reduction (Hao et al., 2008). Delfín B-17X follows a positive trend
(Table 4), which is consistent with a kerogen cracking origin of this
gaseous sample. In Amistad, some samples also follow a positive trend
whilst samples A-1, A-2, A-3, A-5, and A-8A show a partial reversal of the
δ13C series: δ13C1<δ13C2<δ13C3>δ13C4 (see Table 4). Although the
higher carbon isotopic values of propane compared to n-butane might be
explained by mixing of gases (Tao et al., 2016), biodegradation seems to
be the more probable explanation alongside other evidences, so that C3
molecules composed of the light isotope 12C are preferentially metabo­
lized by microbes with respect to 13C-containing C3 molecules (Strąpoć
et al., 2010) and, as a result, the residual propane becomes richer in 13C
(Strąpoć et al., 2007).
The Lorant et al. (1998) diagram, C2/C3 versus δ13C2-δ13C3, can be
used to distinguish between primary cracking gases (those generated
directly from kerogen) and secondary cracking gases (those derived
from oil/wet gas) and to characterize oil-cracking gases of different
maturity stages (e.g., Tissot and Welte, 1984; Prinzhofer et al., 2010). In
the particular case of the thermogenic gas from Delfín B-17X well, re­
sults suggest primary cracking and thermal maturity within the oil
window. Lastly, it is possible to determine the maturity level of
sapropelic-type gases through the methane carbon isotopic ratio (Dai,
1992): δ13C1 from − 40.2 to − 37.4‰, from − 45 to − 40.2‰, higher than
− 37.4‰, and lower than − 45‰ usually indicate highly maturity,
normal maturity, overmaturity, and immaturity to low maturity stages,
respectively. Following this, the B-17X thermogenic gas (δ13C1 =
− 38.45‰) would be very mature.
4.2.3. Light hydrocarbons in condensates
Light hydrocarbon compositions of distillates, which can be used to
indicate source and maturity of natural gases (Thompson, 1983; Mango,
1990), are shown for the study samples in Table 5. The condensates from
the Amistad Field are very similar among them and have API gravities of
a ca. 60◦ . In the ternary diagram of methylcyclohexane (MCH), n-heptane,
and dimethylcyclopentanes (ΣDMCP), which derive mainly from
land-plant, algal-bacterial, and aquatic sources, respectively (Hu et al.,
2007, 2010; Thompson, 1979), all the analysed condensates plot in the
“sapropelic” zone (Fig. 7a), where hydrocarbon liquids usually show
n-C7>30% and MCH<70% (Hu et al., 1990). The Amistad distillate
samples are also characterised by low n-C7/MCH ratios (paraffinicity)
and isoheptane values (Table 5), generally related to biodegradation
(Thompson, 1987). The ternary diagram of the C5–C7 normal alkanes,
isoparaffins, and cyclanes is also used here for constraining the source of
the study samples (Cao et al., 2012; Chen et al., 2014). B-17X sample
plots clearly in the “sapropelic” zonation. Instead, all the Amistad
condensate samples plot close to the separation line between the “sap­
ropelic” and “humic” zones (Fig. 7b) and are characterised by abundant
cyclic alkanes, which is a feature consistent with biodegradation
processes.
Heptane and isoheptane values are typically used to denote gas
maturity (e.g., Chen et al., 1987). Based on the heptane value, it is

9
M.A. Guzmán et al.
Fig. 4. a) Molecular ratios C2/C3 against C1/C2 (in natural logarithmic scales) for kerogen- and mixed sampled gases analysed; b) plot of C2/C3 versus C2/iC4 for
gaseous samples denoting biodegradation and other secondary processes.
possible to define the level of gas maturity and if biodegradation
occurred: percentages exceeding 30%, 18–30%, 12–18%, and
approaching 0% suggest highly mature, normally mature, low mature,
and biodegraded hydrocarbons, respectively (Thompson, 1983). The
Amistad condensates have heptane values of approximately 2%
(Table 5), which might indicate biodegradation processes. As whole oil
gas chromatograms of the Amistad condensates, these show a relative
high abundance of n-C5 to n-C7 hydrocarbons (Fig. 8a), non-typical of
biodegraded oils, this could indicate that at least one late oil charge
would have occurred and mixed with the original altered oil. The Delfín
B-17X distillate (value of ~21%) would be normally mature and this
does not necessarily contradict previously discussed δ13C1 data, as
generally maturity derived from light hydrocarbons is slightly lower
than that derived from methane carbon isotopes (Sun et al., 2016); also
since maturity levels inferred from carbon isotopic data and light
10
Journal of Petroleum Science and Engineering 213 (2022) 110410
hydrocarbons reflect thermal maturation of light and heavy gas frac­
tions, respectively, disparity between both data does not preclude
multi-stage gas accumulation (Chen et al., 2010).
4.3. Oil-oil and oil-source rock correlation
Previous information from some boreholes drilled in the offshore
Amistad field suggested that only the Dos Bocas Formation has gaseous/
liquid hydrocarbon source potential in the study area (Evangelista,
2019). Therefore, a geochemical evaluation was carried out to correlate
the analysed condensates with the probable Dos Bocas source rocks. As
shown in Table 5, Amistad and Delfín B-17X distillate samples show
pristane-to-phytane ratios of about 2, also similar to the potentially
parent Dos Bocas extracts, suggesting suboxic/dysoxic bottom-water
conditions during deposition. Moreover, the ratios of pristane and
M.A. Guzmán et al.
Fig. 5. a) Whiticar diagram for the elucidation genesis mechanisms of sampled gases; b) Bernard diagram for the gaseous samples analysed, indicating genetic types
of the sampled gases.
phytane to their adjacent normal alkanes, n-C17 and n-C18 (Table 5),
would indicate that the unaltered B-17X low-boiling condensate was
derived from a Type II/III kerogen (Peters et al., 2005), suggesting a
possible correlation between this sample and the Dos Bocas rock extract
with similar Pr/n-C17 and Ph/n-C18 values (1.15 and 0.79).
Additionally, as the lower diamondoids are highly thermally stable
and relatively recalcitrant, they can be successfully applied in oil-oil and
oil-source correlation in low-boiling condensates and other liquids
where the classical biomarkers are very scarce or absent (Schulz et al.,
2001; Wei et al., 2007). Despite the fact that diamondoid-based source
and maturity ratios should be used with caution when evaporative
fractionation occurs (Chakhmakhchev et al., 2017), the condensate
samples and the Dos Bocas extracts show similar values (around 75%
and 22%) of dimethyl diamantane index 1 (ratio of 3,4-DMD to 4,9-DMD
plus 3,4-DMD) and methyl diamantane parameter (ratio between 4-MD
11
Journal of Petroleum Science and Engineering 213 (2022) 110410
and the sum of 1-, 3- and 4-MD), suggesting a type II-III precursor
organic material (Schulz et al., 2001) and a maturity level close to peak
oil-generation (Chen et al., 1996). Moreover, these non-cracked liquid
samples exhibit similar absolute concentrations of 3- and 4-methyldia­
mantane (diamondoid baseline of about 4.7 ppm), which could indi­
cate a common source. As expected, the evaporative fractionated
Amistad hydrocarbon liquids show lower values (approximately 25) of
the ratio between 1- plus 2-methyladamantane versus 3- plus 4-methyl­
diamantane (Moldowan et al., 2015) when compared to the B-17X
sample and Dos Bocas extracts (around 30). The compound-specific
isotopic signatures of the lower diamondoids (CSIA-D) provide a use­
ful tool for oil-oil and oil-source correlation in this case: the study
condensates match almost perfectly with one another and with the Dos
Bocas extracts (Fig. 8b), indicating that Amistad distillates probably
derive from the early Miocene Dos Bocas source rocks. Previous 1D
M.A. Guzmán et al. Journal of Petroleum Science and Engineering 213 (2022) 110410

Fig. 6. Plot of δ13C2-δ13C2-δ13C3 diagram for the gaseous samples analysed, suggesting genetic types of the sampled gases. Notes: I (sapropelic-type gas), II (mixed-
type), III (humic-type gas), and IV (biogenic).

mainly biogenic methane with minor quantities of thermally generated

Table 5
gas and hydrocarbon liquid. Presence of biogenic gas at great depths is
Main light hydrocarbon parameters of representative condensates in the Amis­
usually a result of rapid trap closure in actively subsiding basins (Pieri,
tad and Delfín fields.
2001). When combined δ13C1 with δD1 data (Whiticar diagram; Fig. 5a),
Parameter A-3 A-6 A-7 A-12 A-8A B-17X isotopic compositions of methane from some Amistad gases suggest that
%n-C7 2.13 2.32 2.36 2.44 2.21 25.50 the bacterial source generation mechanism followed a CO2 reduction
%MCH 45.11 44.49 42.96 43.93 43.25 37.13 pathway and not a fermentation pathway (the latest restricted to
%ΣDMCP 52.76 53.19 54.40 53.86 54.59 37.37
shallow sediments and the prior extending up to 2000 m below sediment
i-Heptane value 0.08 0.08 0.09 0.09 0.08 0.92
n-Heptane value (%) 2.05 2.12 2.15 2.18 2.07 20.66 surface; Whiticar, 1999). Some gas samples exhibit carbon isotopic
Tol/n-C7 4.12 3.41 3.33 3.77 3.90 0.59 signatures of CO2 from − 16.45‰ to − 19.22‰ (Table 4), which are
n-C7/MCH 0.05 0.05 0.05 0.05 0.05 0.68 consistent with gases formed by organic genesis (Dai et al., 1996). The
n-C6/n-C7 0.56 0.67 0.69 0.71 0.62 1.02 C2/C1 versus δ13C1 graph can be used to estimate the isotopic value of
%C5-7 n-Alkanes 4.23 3.68 4.19 3.92 3.50 29.04
%C5-7 i-Alkanes 4.98 4.73 5.13 4.99 4.26 30.46
the biogenic gas end-member: biogenic gases have extremely small or no
%C5-7 Cycloalkanes 90.79 91.59 90.68 91.09 92.24 40.50 amounts of ethane, and thus, among the studied samples, A-7, A-8D and
Pristane/Phytane 2.15 2.29 2.27 1.97 2.04 1.87 A-8A allow to extrapolate the δ13C1 value (near − 64‰; see Fig. 9a) of
Pristane/n-C17 8.66 8.22 9.14 8.73 9.46 1.22 such biogenic end-member.
Phytane/n-C18 3.23 3.56 3.56 3.19 3.45 0.78
Regarding the Delfín B-17X gas, assuming that the carbon isotope
value of the Dos Bocas kerogen is nearly − 23‰ (Montenegro and
geochemical modeling approach in the exploratory well Amistad Sur, Benítez, 1991) and using the model reported by Chung et al. (1988), the
which reported vitrinite reflectance data and penetrated the whole plot of reciprocal carbon number (1/n) versus δ13Cn (r2 > 0.999) in
sequence, suggested that the Dos Bocas Formation reached the main Fig. 9b confirms that this gaseous sample appears completely or almost
phase of oil generation during the Neogene and can still be within the oil entirely to have a thermogenic origin (Rangel et al., 2003). In the C2/C1
window in the southern Progreso Basin (Evangelista, 2019). versus δ13C1 graph (Fig. 9a), where all the gaseous samples plot
approximately along a straight line, the sample B-17X would represent
the thermogenic end-member gas signature of the Amistad gases. On the
4.4. Origin and accumulation of hydrocarbons in the study area basis of methane isotopic data and according to Schoell (1984), the A-7,
A-8D, and A-8A gases reveal predominantly bacteriogenic methane
Producible hydrocarbons in reservoir sands of the Amistad field are

12
M.A. Guzmán et al.
Fig. 7. a) and b), respectively, ternary diagrams of C7 and C5-7 light hydrocarbons in sampled gases from Amistad field and Delfín B-17X well.
associated with a minor thermogenic input (<10%, ~17% and ~30%,
respectively), assuming that the δ13C1 value for each sample is equal to
the weighted average between the δ13C1 signatures of biogenic (− 64‰)
and thermogenic (− 38.45‰) end-members.
Amistad condensate samples have a series of light hydrocarbons in
the n-C5 to n-C7 range showing a distribution with disproportionate
amounts of toluene (Tol/n-C7 or aromaticity exceeding 3; Table 5),
which would be indicative of partial vaporization. This feature is
coherent with variations in the volatile-sensitive n-C6/n-C7 ratio (note
that in B-17X distillate the ratio is about one as opposed to Amistad
13
Journal of Petroleum Science and Engineering 213 (2022) 110410
Fig. 8. a) example of whole-oil gas chromatogram for
a representative gas condensate sample; b) CSIA-D for
oil-oil and oil-source correlations between represen­
tative condensate samples and with an extract ob­
tained from Dos Bocas source rocks. Note the
identification of the lower diamondoids 1 to 12 in the
order given: adamantane; 1-methyladamantane; 1,3-
dimethyladamantane; 1,3,5-trimethyladamantane; 2-
methyladamantane; cis-1,4-dimethyladamantane;
trans-1,4-dimethyladamantane; 1,3,6-trimethylada­
mantane; 1,2-dimethyladamantane; cis-1,3,4-trime­
thyladamantane; trans-1,3,4-trimethyladamantane,
and 1,2,5,7-tetramethyladamantane.
condensates with ratios markedly below one), also indicative of partial
vaporization (Mango, 1997). Based on geochemical data and oil-source
rock correlations, the Delfín B-17X thermogenic gas and liquid could be
associated with normally mature oil, which originated from the deeply
buried distal/deltaic Dos Bocas source rocks and possibly migrated
vertically along faults.
A probable hydrocarbon filling scenario for the Amistad structure
implies that thermal gas and liquid hydrocarbons might be related to a
light crude oil, which nowadays could be present in reservoirs below the
current pay zones to depths of up to about 6000 m (Evangelista, 2019).
M.A. Guzmán et al. Journal of Petroleum Science and Engineering 213 (2022) 110410

Fig. 9. a) Plot of methane carbon isotope ratio versus C2/C1 molecular ratio for sampled gases. This plot is used to estimate the characteristic isotopic value that may
be assigned to the locally sourced bacterial gas end-member present in the Amistad region. Data from this plot may be also used to accurately determine the bacterial
and thermogenic inputs into Amistad gaseous samples; b) plot of δ13C versus the inverse C number of individual C1–C4 n-alkanes.

Later, much of the original thermogenic hydrocarbons may have been
lost and/or phase-separated prior to in-reservoir biodegradation and
biogenic gas charge. Dry gas of biogenic origin may have partitioned
into an oil and gas phases. Thus, only residual quantities of altered hy­
drocarbon liquid and thermal gas in the Amistad reservoirs escaped
leakage and biogenic gas displacement. The effect of this mixing would
be that the thermogenic component of the resultant gas phase is diluted
to such an extent that the Amistad gases appear completely to have a
bacteriogenic origin. The Amistad field has a complex history of fault­
ing, burial, uplift and erosion, therefore multiple charges of thermogenic
hydrocarbons may have taken place, probably at different time intervals
in the geologic past due to their distinct levels of maturity. Also, sedi­
ment reburial may have caused most of the biogenic gas to go into water
solution and subsequent overburden removal resulting in fizz gas.
4.5. Compartmentalization in Amistad structure
Comparison of chemical and isotopic data for Amistad gas samples
was made to allow delineation of reservoir compartmentalization in the
Amistad Field. For this, natural gas data from the Amistad structure is
studied with Gastar-diagrams (Márquez et al., 2013). A series of 11
normalized parameters (C1/C2, C2/C3, iC4/nC4, δ13C1, δ13C2, δ13C3,
δ13iC4, δ13nC4, δ13C3-δ13C2, δ13nC4-δ13iC4, and δ13C2-δ13C1) were
examined following the method proposed by Prinzhofer et al. (2000).
These parameters are related with the main processes that affect the
chemical and isotopic compositions of natural gases: maturity (all of
them), efficiency of accumulation (the three isotopic ratios differences),
segregative migration (those involving methane) and biodegradation
(C2/C3 and iC4/nC4). Fig. 10 shows the mentioned-above data plotted in
four Gastar-diagrams.
The A-8D gas from the Cerro Mala reservoir exhibits a markedly
different Gastar-diagram (Fig. 10a). In spite of contamination of this
sample during collecting, as discussed above, the significant variations
in C1–C4 alkane chemical and isotopic data between this gaseous sample
and the other Amistad gases would indicate a lack of vertical commu­
nication between the Progreso and Cerro Mala reservoirs. As for the
remaining gases from the Amistad field, although the Gastar diagrams in
Figs. 10b and c do not reveal large compositional differences between
the group of gases from the southern part of the Progreso reservoir (A-4,
A-6, A-7, A-11, and A-12) and those from the central part (A-1, A-5, and
A-8A), the E-W normal F1 fault could act as a intra-reservoir barrier
between at least two separate reservoir bodies with partial or no con­
nectivity between them (Fig. 1b), which would be in agreement with
prior literature (Barzallo and Bemúdez, 2016). In addition, even though
the differences between the studied gases in each group are close to
analytical accuracy, baffles and barriers to diffusion within the central
and southern parts of the Progreso reservoir cannot be completely
dismissed.
The small differences of A-1, A-5, and A-8A gaseous samples with
respect to A-2 and A-3 gases (Fig. 10c and d) apparently discard the
notion of compartmentalization in the north-central area in the Amistad
field, where the E-W normal F2 fault might act as a partial seal (Fig. 1b).
However, minimal differences between the latter two gaseous samples
were within experimental error range, suggesting that both can be
grouped, representing a separate compartment or sub-compartment in
the northern part of the Progreso reservoir. The relatively low C1/C2
values for A-2 and A-3 gases indicate that they might be slightly affected
by the preferential loss of methane by cap rock leakage. This feature is
consistent with previous results by Barzallo and Bemúdez (2016).
5. Conclusions
Organic richness and thermal maturity are low in most rock samples
throughout the Neogene sequence in the Amistad area. Only several Dos
Bocas rock samples contain enough organic matter to be considered as
potential source rocks, but even in these latter samples thermal matu­
ration is low. The vitrinite/huminite in most rock samples depicts
slightly suppressed reflectance. All the analysed condensates show
similar gas chromatographic fingerprints. Molecular data and
compound-specific isotopic analyses of lower diamondoids (CSIA-D)
indicate oil-source correlation between such hydrocarbon liquids and
the Dos Bocas rock extracts.

14
M.A. Guzmán et al.
Fig. 10. a), b), c) and d), four normalized Gastar diagrams for the groups of Amistad gaseous samples coming from the studied reservoirs. The scales are the same for
all 11 axes of each diagram.
Producible gases in reservoir sands on the Amistad structure and
Delfín B-17X well are mainly composed of hydrocarbons dominated by
biogenic and thermogenic methane, respectively. The latter gas might
represent the thermogenic end-member gas signature of the Amistad
gases. Results, combined with geological data available for the study
area, lead to the conclusion that the Amistad area has experienced a
complex geological history in which liquid thermal hydrocarbons and
gas were generated in deeply buried distal/deltaic Dos Bocas source
rocks and migrated along deep faults to late Miocene reservoir sands;
later, thermal petroleum were leaked out and partially displaced by
subsequent biogenic methane during uplift events. Therefore, petroleum
could be present in deeper reservoirs and consideration should be given
to the drilling of the bore of an exploratory well to test the petroleum
potential below the current pay zones in the Amistad structure.
Analytical results also denote that Amistad hydrocarbons show
biodegradation and partial vaporization. Finally, the heterogeneities
identified in Gastar diagrams are not decidedly indicative of three lateral
compartments being connected by the F1 and F2 normal faults. In turn, a
reasonable communication within the southern, central and northern
parts of the Progreso reservoir in the Amistad gas field could be inferred
from the C1–C4 alkane analyses, though it is impossible to conclude
complete fluid homogenization in each of them.
15
Journal of Petroleum Science and Engineering 213 (2022) 110410
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
Authors are grateful to Professors Galo Montenegro (ESPOL) and
Marcos Escobar†(LUZ) for access to samples and scientific assistance.
Carlos Boente obtained a post-doctoral contract within the program
PAIDI 2020 (Ref 707 DOC 01097), co-financed by the Junta de Anda­
lucía (Spain) and the EU.
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