Marine and Petroleum Geology 19 (2002) 711–725

www.elsevier.com/locate/marpetgeo

Petroleum generation and migration in the Putumayo Basin, Colombia:

insights from an organic geochemistry and basin modeling study
in the foothills
Félix T.T. Gonçalvesa,*, Cesar A. Moraa, Fabio Córdobab, Edgar C. Kairuzb, Blanca N. Giraldoa
a
ECOPETROL, Instituto Colombiano del Petróleo (ICP), km 7 Autopista Piedecuesta, Bucaramanga AA 4185, Colombia
b
ECOPETROL, Vicepresidencia Adjunta de Exploración (AEX), Calle 37 # 8-43, 88 Piso, Bogota, Colombia
Received 2 January 2002; received in revised form 21 May 2002; accepted 23 May 2002

Abstract
This paper discusses the results of 1D modeling and geochemical analyses of rock, oil and gas samples performed in the foothills of the
Putumayo Basin, Colombia. A multivariate statistical assessment of biomarker data points to the existence of three oil groups, two of the
them similar to oil families reported in previous studies and related to the Villeta Formation source rocks, and a novel one tentatively
associated with the Caballos Formation source rocks. Geochemical data of oil and gas samples points to a complex reservoir filling history in
the foothills, with at least two migration pulses with distinct maturity levels. Vitrinite reflectance data together with modeling results shows
that the source rock is practically immature in the Putumayo foothills, even in the footwall of large thrust faults. The thermal and burial
reconstruction of a pseudo well located in the present cordillera area suggests that the source rocks have started petroleum generation and
expulsion during the Late Oligocene/Miocene. The oil and gas expelled during such a period have migrated over 80 km, reaching the present
foreland area. Subsequent tectonic burial and/or higher heat flows related to the Late Miocene/Pliocene Andean Paroxysm is thought to
account for a second pulse of migration of thermally evolved hydrocarbons limited to the foothills area. q 2002 Elsevier Science Ltd. All
rights reserved.
Keywords: Putumayo basin; Villeta formation; Biomarker; Basin modeling

1. Introduction the characterization of oil families and potential source

The Putumayo Basin, with an approximate area of
30,000 km2, is located in southern Colombia and represents
the northward extension of the Oriente Basin in Ecuador
(Fig. 1). Both basins are part of the prolific sub-Andean
petroleum province that lies east of the Andean Cordillera.
Since the 1940s, the drilling of over 110 exploratory wells in
the Putumayo Basin resulted in the discovery of 27 oil
fields, with reserves of about 400 MMbbl of oil and 0.3TCF
of gas. The largest petroleum accumulation is the Orito field
(Fig. 1), located in the eastern limit of the foothills area and
with oil reserves of approximately 250 MMbbl.
Previous geochemical and petroleum system investi-
gations performed in the Putumayo Basin have emphasized
* Corresponding author. Fax: þ 57-7-644-5444.
E-mail address: fgoncalv@ecopetrol.com.co (F.T.T. Gonçalves).
0264-8172/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 6 4 - 8 1 7 2 ( 0 2 ) 0 0 0 3 4 - X
rocks (Córdoba et al., 1997; Kairuz, Córdoba, Moros,
Calderón, & Buchelli, 2000; Ramón, 1996). In this work,
new geochemical data of rock, oil and gas samples from
wells located in the Putumayo foothills are presented and
compared with previous results. Geochemical methods
included Rock-Eval pyrolysis, total organic carbon and
visual kerogen analyses of cuttings and core samples, GC
and GC –MS analyses of oils and organic extracts, and bulk
and isotopic analyses of natural gas samples. Two wells of
the foothills and a pseudo-well located in the present
Andean Cordillera area were submitted to thermal and
kinetic 1D modeling. The integration of geochemical
analyses and basin modeling results with available geologic
and geochemical data of the Putumayo and Oriente basins
provided basis for the discussion of petroleum generation
and migration history, and the timing of hydrocarbon charge
and trap formation in the Putumayo Basin.
712 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725

Fig. 1. Simplified map showing the tectonic framework of the Putumayo Basin and the location of the main oil fields of the Putumayo Basin (modified from
Córdoba et al., 1997). On the bottom, schematic W–E cross section displaying the structural style and stratigraphic succession in the foothills and foreland
areas.

2. Geologic background (Córdoba et al., 1997). The Cretaceous – Paleocene

2.1. Stratigraphic and tectonic summary
The sedimentary infill of the Putumayo Basin comprises
three major sedimentary sequences separated by regional
unconformities (Fig. 2). The Triassic –Jurassic sequence
(Motema Formation) is considered as the economic base-
ment and is composed of volcanic deposits (tuffs and lava)
and shallow marine to continental siltstones and sandstones
sequence encompasses the coastal to shallow marine
sandstones and shales of the Caballos Formation, the marine
limestones, shales and sandstones of the Villeta Formation,
and the shallow marine to continental siliciclastic sediments
of the Rumiyaco Formation (Fig. 2). The Eocene – Miocene
sequence comprises the fluvial/alluvial conglomerates of the
Pepino Formation, the lacustrine/fluvial shales, siltstones
and sandstones of the Orteguaza Formation, and the
continental to transitional shales, conglomerates and
 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725
Fig. 2. Generalized stratigraphic column of the Putumayo Basin (after
Córdoba et al., 1997).
sandstones with minor gypsum and coal layers of the Orito-
Belén Group and the Ospina Formation. The Pliocene to
Quaternary coarse siliciclastic deposits of the Guamués and
Caimán formations cover the older sequences. Igneous
intrusions of inferred post-Oligocene age locally affect
the sedimentary section (Córdoba et al., 1997).
The highly complex tectonic-sedimentary evolution of the
Putumayo reflects the multiphase geological history of the
northwest corner of South America (Casero, Salel, & Rossato,
1997; Cooper et al., 1995; Dengo & Covey, 1993). From Late
Triassic to Jurassic times, the siliciclastic and volcanic
deposits of the Motema Formation filled grabens formed in a
back-arc setting (Casero et al., 1997). During Aptian to
Maastrichtian times, the sedimentation of the Caballos and
Villeta formations took place over a broad and relatively
shallow pericratonic depression that extended throughout
most of northwest South America. During this phase, relative
sea-level changes and paleoceanographic events exerted a
primary control on sedimentation (Villamil & Pindell, 1998).
713
The final accretion of the Western Cordillera during the
Maastrichtian/Early Paleocene caused the inversion of
ancient normal faults (Cooper et al., 1995), uplift of the
Central Cordillera and a marked change of sedimentation
conditions from marine (Villeta Fm.) to continental
(Rumiyaco Fm.). Subsequently (Early Paleocene/Middle
Eocene), the increase in convergence rates between the
Nazca and South America plates continued inverting normal
faults, leading to the development of thrust and back-thrust
structures, erosion and deposition of the coarse siliciclastics
of the Pepino Formation (Casero et al., 1997; Córdoba et al.,
1997). The enhanced uplift of the Central Cordillera during
Middle Eocene to Middle Miocene times (Cooper et al.,
1995) induced a flexural subsidence and the deposition of
the Orito-Belén Group and the Ospina Formation. Finally,
the intense compression related to the Andean Orogeny
(Late Miocene to Recent) induced the uplift and inversion of
back-arc basin depocenters, which resulted in the formation
of the Eastern Andean Cordillera and the development of
the sub-Andean foreland basins (Casero et al., 1997;
Coletta, Hebrard, Letouzey, Werner, & Rudkiewicz, 1990;
Cooper et al., 1995).
As well as in other sub-Andean basins, two major
structural compartments can be recognized in the Putumayo
Basin: foothills and foreland (Fig. 1). The foreland (or
platform) compartment covers most of the basin area, being
characterized by a regional monocline that dips to the west,
locally affected by subtle anticlines, reverse and normal
faults. The foothills compartment encompasses two distinct
domains: to the east, (1) a thick-skin tectonics domain that
displays large NE –SW high angle thrust faults associated
with small back-thrusts; and to the west, (2) a folded-belt
domain that shows typical thin-skin tectonic features
involving the Upper Cretaceous/Tertiary section and large
thrust faults that put the Pre-Cretaceous sequence over the
Cenozoic sequence (Córdoba et al., 1997).
2.2. Petroleum systems
The marine calcareous shales and marls of the Villeta
Formation are considered the main petroleum source rocks
of the Putumayo Basin (Córdoba et al., 1997; Giraldo &
Ramón, 1997; Kairuz et al., 2000; Ramón, 1996; Rangel,
Giraldo, & Córdoba, 1997). Such rocks display high total
organic carbon contents (TOC up to 10%), fair to good
hydrocarbon source potential (S2 of about 10 mgHC/gRock)
and hydrogen indices (HI around 300– 400 mgHC/gTOC),
and dominance of amorphous organic matter. Coeval source
rocks are found within the Napo Formation to the south, in
the Oriente Basin (Dashwood & Abbotts, 1990; Mello,
Koutsoukos, & Erazo 1995).
Two major oil families have been recognized the
Putumayo Basin (Córdoba et al., 1997; Ramón, 1996;
Rangel et al., 1997). The so-called marine carbonate oil
family, pooled within sandstone reservoirs of the Pepino and
upper Villeta (informal unit N) formations (Fig. 2), is
714 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725

characterized by low to moderate gravity (, 308 API),

relatively high sulfur contents (around 1.5%), pristane/
phytane ratios around one, low Ts/Tm ratios, high relative
proportion of C35 homohopanes when compared to their C34
counterparts, and low diasteranes/regular steranes ratios.
The marine siliciclastic oil family, pooled within sandstone
reservoirs of the Caballos and lower Villeta (informal units
T and U) formations (Fig. 2), is marked by higher API
gravity values (up to 408), lower sulfur contents (, 0.75%),
pristane/phytane ratios ranging between 1 and 2, high Ts/Tm,
higher relative abundance of C34 homopanes, and higher
diasteranes/regular steranes ratios.
Biomarker-based oil– source rock correlations (Córdoba
et al., 1997; Ramón, 1996; Rangel et al., 1997) suggest that
the marine carbonate oils were sourced by Cenomanian –
Turonian shales and marls of A and M2 informal units
(upper part of the Villeta Formation, Fig. 2), while the
marine silicilastic oils are related to the Albian B and T
shales (lower part of the Villeta Formation). Based on such
correlations, Córdoba et al. (1997) and Kairuz et al. (2000)
defined two distinct petroleum systems: Upper Villeta–
Pepino and Lower Villeta–Caballos, with the later comprising
about 65% of the discovered reserves in the Putumayo Basin.
Visual kerogen analyses and pyrolysis data indicate that
the organic-rich deposits of the Villeta and Napo formations
range from immature to early mature throughout the
Putumayo and Oriente basins (Córdoba et al., 1997;
Dashwood & Abbotts, 1990; Mello et al., 1995). According
to previous basin modeling studies, the main phase of oil
generation and expulsion was reached prior to the Andean
Paroxysm in both basins (Córdoba et al., 1997; Dashwood &
Abbotts, 1990; Tegelaar, Zaugg, Hegre, & Rangel, 1995).
3. Organic geochemistry results
3.1. Source rock characterization
Total organic carbon, Rock-Eval pyrolysis and visual
kerogen analyses (see Appendix A for analytical pro-
cedures) were performed on about 200 samples (cuttings
and core) from two wells of the foothills area: Orito-3 and
Unicornio-1 (Fig. 1). The results of bulk analyses of both
wells are in accordance with data from previous studies. In
the Orito-3 well (not shown in this paper), the Villeta
Formation displays high TOC contents (up to 9%) and S2
values (up to 40 mgHC/gRock), hydrogen indices between
200 and 500 mgHC/gTOC), and a dominance (. 80%) of
amorphous organic matter. The Caballos Formation pre-
sents TOC contents ranging from 1 to 3%, fair to good
hydrocarbon source potential (S2 up to 11 mgHC/gRock)
and hydrogen indices between 120 and 350 mgHC/gTOC,
reflecting the higher proportion of woody material (between
25 and 85%). Vitrinite reflectance and Tmax values reaches
0.6% and 435 8C in the Caballos Formation, which indicates
that the potential source rocks are immature in this well.
Fig. 3. Geochemical profile of the Unicornio-1 well (for location see Fig. 1),
showing the variation of total organic carbon content (TOC), hydrogen
index (HI) and vitrinite reflectance (%Ro) as a function of depth.
The Unicornio-1 well went through a large thrust fault
(Fig. 3), finding the Villeta and Caballos formations
repeated both in the upthrown and downthrown blocks.
Oil shows were found only in the hanging wall, within the
Caballos Formation sandstones. The calcareous shales and
marls of the Villeta Formation show fair to high TOC
contents (mostly from 1 to 3%), fair hydrocarbon source
potential (S2 up to 9 mgHC/gRock), hydrogen indices from
100 to 300 mgHC/gTOC, and a dominance of amorphous
organic matter (over 90%). In the calcareous shales of the
Caballos Formation, TOC contents locally reach up to 5%,
but hydrogen indices are generally lower than 200 mgHC/
gTOC, which is in accordance with the higher proportion of
woody organic matter (up to 70%). Vitrinite reflectance
measurements around 0.55 – 0.60% and Tmax values lower
than 435– 440 8C indicate that the Villeta Formation is
immature to early mature both in the upthrown and
downthrown blocks of the fault (Fig. 3). The tectonic burial
related to the thrusting event has apparently not affected the
thermal evolution of the footwall source rocks.
3.2. Oil characterization and oil– source rock correlation
Saturates fraction of 48 samples were submitted to gas
chromatography (GC) and gas chromatography – mass
spectrometry analyses (GC – MS; see Appendix A for
procedures). Analyzed samples comprised 14 organic
extracts from organic-rich calcareous shales and marls of
the Villeta and Caballos formations in the Orito-3 and
Unicornio-1 wells, 21 crude oils produced from reservoirs
of the Pepino, Villeta and Caballos formations of several
wells of the Orito field, and 13 oils extracted (see Appendix
A for procedures) from core samples of reservoir rocks of
 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725 715

the Caballos Formation in the Orito-3 and Unicornio-1
wells.
Besides a visual inspection of GC and GC – MS (m/z 191
and 217) fingerprints, a multivariate statistical approach was
used to differentiate and correlate the analyzed oils and
organic extracts. Primarily source-dependent biomarker
ratios, such as pristane/phytane, C24 tetracyclic/C26 tricyclic
terpanes, Ts/Tm, C35/C34 homohopanes, hopanes/steranes,
diasteranes/regular steranes and C30/C29 steranes (Peters &
Moldowan, 1993), were calculated and compared using the
hierarchical cluster analysis technique available in the
commercial software program DATADESK 6.0. Since source
rock samples are immature to early mature (around
0.6%Ro) and oils have not exceeded the peak generation
stage of thermal evolution (C29 steranes abb/aaa þ abb
and aaa S/S þ R ratios lower than 0.65 and 0.48,
respectively), oil – oil and oil – source rock correlations
were likely unaffected by maturity. By using the multi-
variate statistical approach, three broad clusters are clearly
identified in the resulting dendrogram (Fig. 4).
The cluster labeled A comprises lower Villeta Formation
(informal units B and T) organic extracts of the Orito-3 and
Unicornio-1 wells and a number of oils produced from the
Caballos Formation in several wells of the Orito field
(Fig. 4). These samples are characterized by Pristane/
Phytane . 1, dominance of low molecular weight n-
alkanes, high relative abundance of tricyclic terpanes, Ts/Tm
around 1, moderate abundance of C29 norhopane, C35/C34

Fig. 4. Hierarchical cluster analysis dendrogram showing the differentiation of three source-related families (A, B and C). Each sample is identified by the well
name, formation and type (organic extracts from source rocks, oils from production wells and oils extracted from reservoir cores).
716 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725

homopanes ratios generally lower than 1, high diasteranes/
steranes ratios, dominance of C27 steranes over their C28 and
C29 counterparts and moderate to high C30/C29 steranes ratio
(Fig. 5(a)).
The cluster labeled as B embraces upper Villeta
Formation (informal units A and M2) organic extracts of
the Orito-3 and Unicornio-1 wells, oils produced from the
Upper Villeta and Pepino reservoirs in a number of wells of
the Orito field and oils extracted from sandstone core
samples of the Caballos Formation in the Orito-3 well
(Fig. 4). All such samples are characterized by Pristane/
Phytane equal or lower than one, dominance of low
molecular weight n-alkanes, high relative abundance of
tricyclic terpanes, Ts/Tm , 1, moderate abundance of C29
norhopane, C35/C34 homopanes ratios equal or higher than
1, moderate to low diasteranes/steranes ratios, dominance of
C27 steranes over their C28 and C29 counterparts and high
C30/C29 steranes ratio (Fig. 5(b)).
The biomarker characteristics of cluster A samples are
indicative of a relatively proximal/shallow marine deposi-
tional environment with a significant siliciclastic input
(Mello, Gaglianone, Brassel, & Maxwell, 1988; Mello et al.,
1995), while the molecular features of cluster B samples
point to a more distal/deeper marine carbonate dysoxic–
anoxic environment (Mello et al., 1988; Mello et al., 1995;
Palacas, Anders, & King, 1984; Zumberge, 1984). Geo-
chemical characteristics of clusters A and B oils display a
good correlation with features reported by former authors
respectively for the so-called marine siliciclastic and marine
carbonate oil families (Kairuz et al., 2000; Ramón, 1996;
Rangel et al., 1997). The distribution of the organic extracts
between these clusters (Fig. 4) is also in accordance with
such previous work, confirming that the marine siliciclastic
oil family was probably generated by the lower Villeta
Formation (informal units B and T), while the marine
carbonate oils are related to the upper part of the same
formation (informal units A and M2). Different from the
previous studies however, marine carbonate oils were found
also in the reservoirs of the Caballos Formation in the Orito-
3 well (Fig. 4), indicating that the upper and lower Villeta
formations petroleum systems are not completely isolated as
previously proposed by Ramón (1996). The confirmation of

Fig. 5. Gas chromatograms (GC) and m/z 191 and 217 mass chromatograms of representative oils of clusters A, B and C from Fig. 4. Peaks identification:
1 ¼ n-C15, 2 ¼ Pristane, 3 ¼ Phytane, 4 ¼ n-C25, 5 ¼ C23 tricyclic terpane, 6 ¼ C24 tetracyclic terpane, 7 ¼ C27 18a(H) Trisnorhopane (Ts), 8 ¼ C27 17a(H)
Trisnorhopane (Tm), X ¼ unknown terpane, 9 ¼ C29 17a(H), 21b(H) norhopane, 10 ¼ C30 17a(H) diahopane, 11 ¼ C30 17a(H), 21b(H) hopane, 12 ¼ C31
17a(H), 21b(H) homohopane 22S, 13 ¼ C27 ba diasterane 20S, 14 ¼ C27 abb sterane 20R þ C29 ba diasterane 20S, 15 ¼ C29 abb sterane 20R.
 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725 717

the lack of marine siliciclastic oils (derived from Lower
Villeta source rocks) in the Late Cretaceous and Tertiary
reservoirs of the Orito Field suggests that the Orito Fault
behaved as a seal for petroleum migration.
The cluster labeled C encompasses organic extracts of
organic-rich shales from the Caballos Formation in the
Orito-3 and Unicornio-1 well and an oil extracted from a
core sample of the Caballos Formation in the Unicornio-1
well (Fig. 4). Such samples are characterized by a strong
dominance of pristane over phytane (Pr/Ph . 3), high
proportion of high molecular weight n-alkanes (. n-C23)
with odd over even preference, low relative proportion of
tricyclic terpanes, Tm higher than Ts, presence of an
unknown terpane (X) that elutes just before the Tm,
significant abundance of C30 diahopane, high relative
proportion of C29 norhopane, very low C35/C34 homopanes
ratios, moderate to low diasteranes/steranes ratios, domin-
ance of C29 steranes over their C27 and C28 counterparts and
low C30/C29 steranes ratio (Fig. 5(c)). These features are
notably distinct from the characteristics displayed by
samples from previous clusters and points to a nearshore
(transitional) marine environment with a strong input of
terrestrial plants (Abdullah, Murchinson, Jones, Telnaes, &
Gjelberg, 1988; Isaksen, 1995; Philp & Gilbert, 1986). The
presence of organic extracts of the Caballos Formation from
both Unicornio and Orito areas together with the oil in
cluster C (Fig. 4) suggests that the organic-rich shales of this
unit are the source rocks. Such results provide support to a
proposition of a new speculative petroleum system
designated Caballos, which is subject to confirmation by
further analyses.
The GC traces of the studied oil samples point to the
existence of different histories of petroleum migration and
alteration in the Putumayo foothills. Oils produced from the
reservoirs of the Caballos Formation in the Orito field
display a normal distribution of n-alkanes (Fig. 6(a)) and a
lack of demethylated hopanes, while oils extracted from
cores taken from the water zone of the same reservoir are
characterized by the depletion of n-paraffins and a
pronounced unresolved complex mixture (‘hump’) that
rises above GC baseline (Fig. 6(b)). Such results indicate
that the Orito petroleum accumulation was not biodegraded
in the past (Peters & Moldowan, 1993) but alteration
processes are currently affecting the base of the oil column.
Conversely, the saturates fraction of oils extracted from core
samples of the Caballos Formation (hanging wall) in the
Unicornio-1 well presents a depletion of high molecular
weight n-alkanes, baseline hump and high proportion of
pristane and phytane associated with a significant abun-
dance of low weight n-alkanes (Fig. 6(c)). Such association
points to a complex reservoir filling history, possibly
comprised by an early oil migration pulse, a subsequent
biodegradation event that accounts for the removal of the n-
paraffins, and a late migration pulse of lighter oil. The
absence of demethylated hopanes in such extracted oils
indicates that the paleobiodegradation event was not
intense.
3.3. Natural gas characterization
Bulk and isotopic composition of seven gas samples from
wells of the foothills and four gas samples from wells of the

Fig. 6. Whole oil gas chromatogram of an oil produced from the Caballos Formation reservoir in the Orito-35 at 1975 m depth (a), and gas chromatograms of
the saturate fraction of oils extracted from core samples of the Caballos Formation reservoir in the water zone of the Orito-3 at 2016 m depth (b) and in the
upthrow block of the Unicornio-1 at 1306 m depth (c). For peak identification see Fig. 5.
718 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725
foreland area were used to assess gas generation and
migration history in the Putumayo Basin. All analyzed
samples present high contents (up to 90 vol.%, Fig. 7) of
carbon dioxide with carbon isotopic ratios ranging from
2 1.3 to 2 7.1‰. Such high contents of relatively light CO2
have been considered the result of the thermal breakdown of
carbonate rocks of the Villeta Formation by the heat effect
of the Tertiary igneous intrusions (Kairuz, 1993). Concern-
ing the hydrocarbons, foothills samples are in general dryer,
displaying higher relative abundances of methane when
compared gases from the foreland wells (Fig. 7). The
application of the interpretative approach proposed by
Prinzhofer, Mello, Freitas, and Takaki (2000) and Prinzhofer
and Pernaton (1997) suggests that bulk composition and
isotopic signature of hydrocarbon gases were primarily
controlled by the degree of thermal evolution, without
significant influences of other phenomena such as segrega-
tive migration (Fig. 8(a)) or biodegradation (Fig. 8(b)).
Since secondary phenomena appear to have not sub-
stantially affected gas composition, a model that describes
the isotopic evolution of methane and ethane generated by
types I and II kerogens as a function of maturity (Whiticar,
1994) was used to assess the degree of thermal evolution of
the analyzed samples. By applying such model, two groups
of gases with distinct characteristics may be recognized
(Fig. 9). The foreland samples present a co-genetic behavior
with isotopic ratios indicative of a moderate degree of
thermal evolution (oil window). On the other hand, most of
the foothills samples display an association of isotopically
heavy methane indicative of a high degree of maturity (gas
window) with a relatively light ethane that is more
compatible with the oil window. Such association points
to the mixing of gases from at least two migration phases,
being one composed of mature gases and the other
Fig. 7. Compositional variation of the 11 analyzed gas samples taken the foothills and foreland areas of the Putumayo Basin. The graph displays the proportion
in volume of carbon dioxide (CO2), methane (C1) and hydrocarbon gases heavier than ethane (C2þ).
comprised by over mature gases enriched in isotopically
heavy methane.
4. Basin modeling
To better understand the thermal evolution of the source
rocks in the Putumayo foothills, the Orito-3 and Unicornio-1
wells (Fig. 1) were submitted to one-dimensional thermal
and kinetic modeling using the software GENEX 3.3.0. The
structural complexity of the Unicornio-1 well required the
use of the GenTect module.
Burial reconstruction took into account measured thick-
ness of formations drilled in the wells and erosion estimates
based on regional stratigraphic correlations (Casero et al.,
1997; Córdoba et al., 1997). Absolute ages of depositional
and erosional events were defined using the chronostrati-
graphic framework of the basin (Fig. 2) and the geologic
time scale proposed by Harland et al. (1989). Compaction
history was described through a porosity– depth law in
which porosity is a function of depth. An average porosity–
depth curve was automatically calculated by the program
for each formation by weighing the porosity law of each
pure lithology (sandstone, shale, limestone, etc.) according
to its relative proportion in the formation. Paleo-water
depths were not incorporated to the model due to the lack of
reliable estimates. This simplification probably will have
little impact over the burial reconstructions, since the
studied sedimentary succession was deposited under con-
tinental to relatively shallow marine environments (Córdoba
et al., 1997). The resulting geohistory plots (e.g. Orito-3
well, Fig. 10) shows two major subsidence phases (Late
Cretaceous/Paleocene and Late Eocene/Miocene) and uplift
events (Early/Middle Eocene and Late Miocene/Pliocene).
According to the burial reconstruction of the modeled wells,
 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725
Fig. 8. Geochemical diagrams used to characterized the gases from the
Putumayo Basin (after Prinzhofer & Pernaton, 1997; Prinzhofer et al.,
2000). The d 13C1 versus C2/C1 cross plot (a) shows a dominance of the
maturity trend over the segregative migration trend, while the C2/C3 versus
C2/iC4 cross plot (b) indicates that the gases were not affected by
biodegradation.
the base of the Villeta Formation reached its maximum
depth (about 3000 m) during the Late Miocene.
The assessment of corrected bottom-hole temperatures
(BHT) of over 100 wells indicates that mean geothermal
gradients vary between 18 and 25 8C/km across the
Putumayo Basin. In the Orito-3 and Unicornio-1 wells,
Fig. 9. Ethane (d 13C2) versus methane (d 13C1) carbon isotopic ratios
crossplot for foothills and foreland gases of the Putumayo Basin. The
diagram also displays the maturity trend with vitrinite reflectance
equivalent values for co-genetic ethane and methane according to Whiticar
(1994).
719
Fig. 10. Burial curves of the Orito-3 well, Putumayo foothills (see location
on Fig. 1).
geothermal gradients are about 20 – 21 8C/km. Thermal
conductivity of the sedimentary column was automatically
calculated by the program taking into account the
lithological composition, porosity decay and temperature
of each formation. Due to the lack of measured data, thermal
conductivity values available in GENEX for pure litholo-
gies were used in the calculations. The radiogenic heat
contribution from the basement and the sediments was also
included in the modeling by using default values of
radiogenic heat production for pure lithologies available
in the modeling program. After a number of trial-and-error
simulations, the best fit between measured and calculated
temperatures (Fig. 11) was obtained by using heat flow
values of about 36 mW/m2 in the Orito-3 and 38 mW/m2 in
the Unicornio-1 well.
The highly complex tectonic evolution of the Putumayo
Basin hampers the reconstruction of its heat flow history.
Diverse paleoheat flow scenarios were simulated, such as
(1) a constant reduced heat flow through time, (2) a higher
heat flow during the Early Cretaceous rifting event, and (3) a
heat effect associated with the Tertiary igneous episode.
Nevertheless, despite the tectonic complexity, a constant
reduced heat flow equal to the present was the thermal
history scenario that best accounted for the measured
vitrinite reflectance values in both wells (Fig. 12).
Apparently, the thermal influence of mentioned tectonic
events on source rock maturity in the Putumayo Basin was
practically insignificant. Such results contrast with the ones
obtained for other Colombian basins (Mora & Santos Neto,
2000), where a strong thermal anomaly associated to the rift
phase is required to account for the present degree of
maturity of the source rocks.
Kinetic determinations performed on a selected imma-
ture sample of the Villeta Formation source rocks revealed
activation energy distributions and frequency factors
representative of Type II kerogens (Fig. 13), with frequency
720 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725
Fig. 11. Calibration of the present thermal regime in the Orito-3 (a) and
Unicornio-1 (b) wells, Putumayo foothills (see location on Fig. 1). Notice
the good correlation between measured (squares) and calculated tempera-
ture (thick dashed lines).
factor of 1.0 £ 1014 s21 and principal activation energy of
53 kcal/mol. Using these measured kinetic parameters and
the calibrated thermal model, kerogen transformation ratios
calculated for the Villeta Formation in the studied wells are
lower than 10% (Fig. 14), confirming that the source rocks
are practically immature in the foothills. Besides, the small
differences found between transformation ratios calculated
above and below the thrust-fault in the Unicornio-1 well
indicates that, at least in this area, the tectonic burial was not
enough to enhance substantially the conversion of kerogen
into petroleum.
Since mature source rocks have not been found in the
platform and foothills, the hypothesis of the existence of an
ancient oil-kitchen in the area of the present Cordillera was
tested through the simulation of a pseudo-well located
Fig. 12. Calibration of thermal and maturity modeling in the Orito-3 (a) and
Unicornio-1 (b) wells, Putumayo foothills (see location on Fig. 1). Notice
the good correlation between measured (squares) and calculated vitrinite
reflectance (thick dashed lines).
approximately 80 km to the northwest of the Unicornio-1
well (Fig. 1). The poor knowledge of the structural
configuration in the Cordillera and the lack of seismic
data hamper the definition of the present stratigraphic
succession in the selected location. By assuming that the
Cretaceous to Oligocene units succession was little
disturbed by pre-Miocene tectonic events, burial history of
such units was reconstructed based on the extrapolation of
sediment isopachs from the platform and foothills areas
(Córdoba et al., 1997) to the selected location. Lithologies,
as well as their petrophysical and thermophysical
parameters were based on the composition of each
formation in the foothills. Likewise, the constant reduced
 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725
Fig. 13. Activation energies distribution and frequency factor of a representative sample of the Villeta Formation from a well located in the foreland area.
heat flow history calibrated with temperature and vitrinite
reflectance data in the Unicornio-1 well was used in the
pseudo-well.
According to the geohistory plot obtained for the pseudo-
well (Fig. 15), the base of the Villeta Formation might have
reached about 6000 m depth by the beginning of the
Miocene. Due to the lack of geologic data to constrain the
Miocene to Present burial and deformation histories, neither
additional stratigraphic/tectonic burial nor uplift events
were included in the model during this period. Hence,
results of burial and thermal modeling of the last 10 My are
disregarded. Modeling of kerogen conversion using the
measured kinetic parameters indicates that Villeta For-
mation source rocks possibly started to generate petroleum
during the Late Oligocene and that they attained a
transformation ratio of over 80% and a maturity degree of
about 0.9%Ro before the Andean Paroxysm (Figs. 16 and
17). Such a degree of thermal evolution is consistent with
Fig. 14. Modeled evolution of kerogen transformation ratio of the middle
part of the Villeta Formation in the Orito-3 and Unicornio-1 wells,
Putumayo foothills (see location on Fig. 1).
721
the maturity of most of the oils and gases of the Putumayo
Basin, but it is lower than the maturity level of the light oils
and over mature gases attributed to a later migration pulse in
the foothills. Therefore, a higher heat flow and/or additional
burial would be required to lead the source rock to a higher
stage of thermal evolution.
5. Petroleum generation and migration: summary and
discussion
Pyrolysis and visual kerogen analyses performed in this
study reasserts the results of previous works that found that
the Villeta Formation source rocks have not reached the
main phase of petroleum generation and expulsion in the
foothills of the Putumayo Basin. Since the source rocks are
Fig. 15. Burial curves of a pseudo-well located in the present cordillera area
of the Putumayo Basin (see location on Fig. 1). Burial history was
reconstructed only until the Late Miocene (10 Ma).
722 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725
Fig. 16. Modeled evolution of kerogen transformation ratio of the middle
Villeta Formation until the Late Miocene (10 Ma) in a pseudo-well located
in the present cordillera area of the Putumayo Basin (see location on Fig. 1).
also immature in the foreland, the likely oil kitchen for the
petroleum accumulations must have been located to the
west, in the deeper parts of the foothills and the present
cordillera. To the south, Dashwood and Abbotts (1990)
report that the Napo Formation (equivalent to the Villeta
Formation) is also immature to early mature throughout the
Oriente Basin, indicating that effective source areas are
located to the west.
Faults have probably exerted a minor role as conduits for
petroleum migration as evidenced by the lack of oils
generated by the Lower Villeta Formation within the Pepino
Formation reservoirs in the Orito field, and by the relative
isolation between the two main petroleum systems through-
out the basin (Córdoba et al., 1997; Ramón, 1996), despite
the local presence of oils generated by the Upper Villeta
Formation source rocks in the Caballos Formation reser-
voirs of the Orito-3 well reported in the present study. Since
migration appears to have been dominantly horizontal,
hydrocarbon accumulations located in the foreland must
have formed before the development of the major thrust
fault that separates the foothills from the foreland during the
Andean Paroxysm (Late Miocene/Pliocene) and caused the
disruption of potential horizontal carrier beds (Fig. 1).
Therefore, the existence of pre-Andean traps is required to
account for the formation of these accumulations. In the
Fig. 17. Modeled reconstruction of the maturity evolution of the middle part
of the Villeta Formation in terms of vitrinite reflectance (%Ro) until the
Late Miocene. Notice that before the Andean Paroxysm (about 10 Ma) the
source rocks have reached around 0.9%Ro, which is compatible with the
degree of thermal evolution of the oils and gases attributed to the early
migration pulse, but is not in accordance with the maturity level estimated
for the highly evolved gas and light oil probably related to a later pulse (see
text for explanation).
Oriente Basin, Dashwood and Abbotts (1990) report that the
productive structures show evidence of Cretaceous to
Oligocene growth.
Geochemical data of oil and gas samples point to a
complex hydrocarbon charge history, with at least two
pulses of petroleum migration. The GC fingerprint of the oil
extracted from a core sample of the Unicornio-1 well
(Fig. 6(c)) points to a possible mixing of a biodegraded oil
with a lighter and probably more mature oil from a later
pulse. Likewise, whole-oil chromatograms of petroleum
accumulations of the Oriente Basin foothills (e.g. Oglan
field; Dashwood & Abbotts, 1990) also point to the mixing
of biodegraded oil from an early pulse with a more mature
oil. While hydrocarbon gases from the Putumayo foreland
share a moderate level of thermal evolution (oil window),
most of the gases from the foothills appear to comprise a
mixture of gases generated within the oil window with gases
from the (late) gas window. The integration of such
geochemical information with the geological data suggests
that the less mature oils and gases are related to an early pulse
of migration that has probably preceded the main phase of the
Andean Paroxysm, since it has charged traps located both in
the foothills and the foreland. Conversely, the more mature
oils and gases, apparently restricted to the foothills, probably
correspond to a later pulse of migration that followed this
Andean Paroxysm, whose migration was limited by the
large thrust faults that disrupted the main carrier beds.
The maturity modeling of the pseudo-well located in the
present cordillera area (Fig. 1) indicates that the Villeta
source rocks might have reached the peak of oil generation
before the Andean Paroxysm due to an inferred westward
 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725 723

thickening of the sedimentary overburden (Figs. 15– 17).
Inasmuch as such a degree of thermal evolution does not
account for the over mature gases and oils attributed to the
later migration pulse, an additional burial and/or a higher
heat flow beyond those assumed for the pseudo-well would
be required in the same region to enhance source rock
maturity. The additional burial could have been provided by
the tectonic overburden associated with the development of
the Andean Cordillera. Such a hypothesis implies the
existence of a pod of source rock bellow the present
cordillera, as well as a possible presence of highly evolved
hydrocarbon accumulations. Due to the final uplift and
erosion of the Andes, such a pod of source rock must be
presently inactive. Alternatively, a different thermal regime
could also be invoked to account for the formation of the
highly mature hydrocarbons. However, since maturity and
temperature data point to the prevalence of relatively low
paleoheat flows throughout the entire Putumayo Basin, any
thermal event capable of providing additional heat flow
should be restricted to the area of the present cordillera. The
schematic diagram of Fig. 18 integrates and summarizes the
proposed model of hydrocarbon generation and migration in
the Putumayo Basin.
6. Conclusions
Results of bulk and visual kerogen analyses confirm that

Fig. 18. Diagram summarizing the proposed model of petroleum generation and migration in the Putumayo Basin. This simplified scheme is not to scale and
does not display the structural shortening.
724 F.T.T. Gonçalves et al. / Marine and Petroleum Geology 19 (2002) 711–725
the organic-rich deposits of the Villeta Formation are the
main potential source rocks of the Putumayo Basin. Such
deposits have not reached the oil window in the foothills,
even in the footwall of large thrust faults. A multivariate
assessment of biomarker data of a set of oils and organic
extracts points to the existence of three oil families: A, B
and C. The former two correspond to the marine siliciclastic
and marine carbonate oil families described in previous
works, respectively generated by the source rocks of the
lower (B and T units) and upper (A and M2 units) Villeta.
The new so-called transitional marine (C) oil family is
provisionally related to the potential source rocks of the
Caballos Formation. Geochemical data from oil and gas
samples points to the existence of mixing of hydrocarbon
derived from at least two pulses of petroleum migration with
distinct degrees of thermal maturity.
The integration of geochemical data, 1D basin modeling
results and geologic evidence provide support to the
proposal of a tentative two-phase model of hydrocarbon
charge for the Putumayo Basin. During the first phase (Late
Oligocene/Miocene), the Villeta Formation source rocks
have reached the peak of oil generation. Oils and gases
expelled in this phase migrated over 80 km, filling pre-
Andean structures both in the foothills and foreland areas.
During the second phase the later, concomitant and/or
subsequent to the Andean Paroxysm (Late Miocene/Plio-
cene), additional tectonic burial and/or heat flow gave rise to
the high maturity hydrocarbons whose migration was
restricted to the foothills by the major faults that separates
this area from the foreland.
Acknowledgments
The authors extend their appreciation to Ecopetrol for
permitting the publication of the results of this study, to the
laboratory personnel from the Geochemistry Group of the
Colombian Petroleum Institute (ICP) for the analytical
support, and to Antonio Rangel, Diego Garcı́a, Anthony
Tankard and two anonymous reviewers for their thoughtful
reviews and comments.
Appendix A. Analytical methods
A.1. Total organic carbon, Rock-Eval pyrolysis and visual
kerogen analyses
After being examined with a binocular microscope to
eliminate caved material, and drilling mud contaminants,
rock samples were washed using fresh water, dried and wet-
sieved with a 10 mesh top sieve and a 16 mesh bottom sieve
and powdered. For the determination of organic carbon
contents (TOC), a small fraction of each sample was
decalcified with HCl (50%) and analyzed using a LECO
WR-12 apparatus. Pyrolysis analyses were performed with a
Rock-Eval II apparatus following the method described by
Espitalié, Deroo, and Marquis (1985). For the visual
kerogen investigation, rock samples were demineralized
with HCl and HF. The isolated kerogen samples were
mounted on strewn slides and plugs to be analyzed in
transmitted (white light and fluorescence) and reflected
microscopy with Zeiss standard microscopes.
A.2. Extraction, GC and GC –MS analyses
Powdered source rock samples were submitted to
Soxhlet extraction for 24 h using dichloromethane. Reser-
voir rock samples were washed for 2 h also using the same
solvent. Saturate, aromatic and NSO compounds fractions
of the recovered oils and organic extracts were eluted from a
silica-gel column using n-hexane, n-hexane þ toluene and
toluene þ methanol, respectively. The saturates fractions
were analyzed in a Hewlett –Packard 5890-A gas chro-
matograph (splitless injector and 30 m SPB-TM-1 column),
with hydrogen as carrier gas and column temperature
programmed from 120 to 310 8C at 6 8C/min. The same
fractions were analyzed using a HP 5972A mass selective
detector coupled to a HP 5890A gas chromatograph (on-
column injector and 30 m HP-5MS column) with helium as
carrier gas and column temperature programmed from 70 to
170 8C at 20 8C/min and from 170 to 310 8C at 2 8C/min.
The above geochemical analyses were carried out in the
laboratories of the Colombian Petroleum Institute (ICP).
Whole-oil gas chromatography analyses of oils from
production wells were performed by Biomarker Technol-
ogy, kinetic analyses of source rock samples by Corelab/
Lab Instruments and gas analyses by DGSI and CENPES.
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