Llanos Basin Petroleum Composition - Garcia Et Al-2015 PDF

Controls on petroleum AUTHORS
composition in the Llanos Diego Fernando Garcia Bautista ∼

Ecopetrol International Exploration, Calle
basin, Colombia: Implications 37, #8-43, 7th Floor, Bogotá, Colombia;

diego.garcia@ecopetrol.com
for exploration Diego Fernando Garcia Bautista holds a B.Sc.

degree in geology from the National
University of Colombia. He received an
Diego Fernando Garcia Bautista, Eugenio Vaz dos M.Sc. degree in quantitative basin analysis
Santos Neto, and Henrique L. de B. Penteado from the School of Mines of Paris and a
D.Sc. in petroleum system analysis from the
Federal University of Rio de Janeiro. He has
worked for Ecopetrol since1998, and his
ABSTRACT research interests include fluid flow and
Physical and geochemical characteristics of produced petroleum petroleum migration.
from the central region of the Llanos basin, Colombia, were ana- Eugenio Vaz dos Santos Neto ∼ Petrobras
lyzed to understand the petroleum charge history and alteration R&D Center, Rio de Janeiro, Brazil;
processes. Petroleum properties in the study area are the result of eugenioneto@petrobras.com.br
the complex charge history of the oil fields. The amount of gas Eugenio Vaz dos Santos Neto is a geologist
in fluids is controlled by the migration distance from the late or, working for Petrobras since 1981. In 1983,
possibly, the current generation kitchen located beneath the foot- he joined geochemistry at Petrobras R&D
hill deformation zone. Gas influx decreases toward the foreland Center in Rio de Janeiro. He received his
M.S. degree in geology in 1993 from the
domain, as indicated by lower values of the gas–oil ratio and sat- Federal University of Rio de Janeiro and his
uration pressure. The API gravity of the oil samples is mainly con- Ph.D. in isotopic geochemistry in 1996 from
trolled by the intensity of biodegradation. Marine-sourced oils Indiana University. His current studies focus
accumulated in shallow reservoirs of the foreland prior to the mainly on gas geochemistry.
onset of Andean deformation. Those fluids were subjected to dif- Henrique L. de B. Penteado ∼ Petrobras
ferent levels of biodegradation, depending on the time they E&P Exploration, Av. República do Chile,
remained at reservoir temperatures lower than 80°C (176°F) and 330, Rio de Janeiro, Brazil; hpenteado@
before being buried to their maximum depth. petrobras.com.br
Geochemical data suggest multiple charge pulses from differ- Henrique L. de B. Penteado graduated in
ent source kitchens of two main types of source rocks, as well as geology from the University of São Paulo
different biodegradation levels. The proposed petroleum charge in 1985. He joined Petrobras in 1986 and
and alteration model allows prediction of the temperature history worked at the R&D Center in Rio de Janeiro
of a reservoir and the most likely physical properties of the petro- from 1990 to 2009, specializing in petroleum
geochemistry and petroleum systems
leum at a specific location. The model can be used as an explora- modeling. Henrique Penteado obtained his
tion tool to assess the risk of charge prior to drilling in unexplored Ph.D. from the University of Paris in 1999.
areas of the basin. He currently manages the Petroleum
Systems Modeling Group in Petrobras
Exploration.
ACKNOWLEDGEMENTS
Copyright ©2015. The American Association of Petroleum Geologists. All rights reserved. We are greatly indebted to Ecopetrol for
Manuscript received August 1, 2011; provisional acceptance October 11, 2012; revised manuscript permission to publish this work. We would
received July 22, 2013; revised manuscript provisional acceptance November 15, 2013; 2nd revised like to thank Jen Beall and Diego Sanabria
manuscript received February 28, 2014; 2nd revised manuscript provisional acceptance May 5, 2014; for review of the last version of this text.
3rd revised manuscript received June 19, 2014; final acceptance October 23, 2014. Special thanks are due to Yolima Blanco,
DOI: 10.1306/10231411111
AAPG Bulletin, v. 99, no. 8 (August 2015), pp. 1503–1535 1503

Leonardo Mogollón, and the geochemical INTRODUCTION
team of Ecopetrol for their help and
technical discussions. Petroleum behavior in reservoirs is a critical factor in
exploration, as well as in reservoir simulation and development
planning of oil fields. Petroleum properties depend mainly on
the composition of the liquid and gas phases, as well as the
gas–oil ratio (GOR) and the physical properties (density or API
gravity and viscosity) of the produced fluids (Pedersen
et al., 1989).
The composition of reservoir fluids can be predicted through
complex thermodynamic models of the mixed petroleum com-
pounds (Riazi et al., 2004). However, reliable results from those
models are difficult to achieve in the predrilling stage of explora-
tion, because complete fluid characterizations are not available
to supply appropriate input data for the simulations. In these
cases, it may be necessary to make estimates from a limited reser-
voir pressure, temperature, and API gravity measurements
(Elsharkawy et al., 1995).
This work combines interpretation of both geochemical and
physical properties of the fluids to propose a petroleum charge
history and unravel its effects on petroleum quality in the Llanos
basin, eastern Colombia (Figure 1). This study aims to enhance
understanding of processes that control petroleum composition
and thus provide guidelines to predict compositional characteris-
tics before drilling in unexplored areas.
Petroleum composition is the end product of a complex his-
tory that includes kerogene type in the source rock, geological
processes that control the kerogen to petroleum transformation,
and later changes in fluid composition during migration in the car-
rier beds and accumulation in reservoirs (Meulbroek and
MacLeod, 2002). Such factors include the following:
• composition of the organic matter in the source rock and its

thermal history (Schenk and Dieckmann, 2004; di Primio
and Horsfield, 2006);
• charge history of the reservoirs, especially when later light
charge is added to previous accumulations, whether contain-
ing biodegraded oil or not;
• extent of biodegradation of the oils (Larter et al., 2003;
Larter and di Primio 2005); and
• in-reservoir alteration as gravity segregation (Ganjavar et al.,
1998), oil deasphalting (nondegraded accumulations), and
water washing, among other processes (de Hemptinne et al.,
2001).
Petroleum expelled from source rocks containing types I or II

organic matter is characterized by low gas content and significant
quantities of high molecular weight compounds. With increasing
1504 Controls on Petroleum Composition

Figure 1. Location of the study area
in the Llanos basin showing the main
structural features.
input of terrigenous organic matter (type III), gener- saturated hydrocarbons range from 5% to more than
ated gas becomes more abundant, leading to higher 80%, whereas polar (nitrogen-sulfur-oxygen, or
saturation pressures (Psat) and greater formation vol- NSO) compounds vary from 10% to 50% by weight.
ume factors (Bo ) (England et al., 1987; England and As a result of these chemical differences, oil density
Mackenzie, 1989). In the same way, Düppenbecker ranges from 45° API in the lighter samples to less
and Horsfield (1990) proposed that source-rock orga- than 10° API in the heavy oils produced from the
nofacies dominantly control the physical properties of southern part of the basin.
the generated fluids. Previous geochemical studies have sought to
Higher values of saturation pressure and forma- understand the origin, evolution, and alteration of oils
tion volume factor have been observed to correlate in the Llanos basin based mainly on their geochemical
with increasing maturity of oils generated from the properties. These studies propose that petroleum origi-
same kitchen area (di Primio et al., 1998). nated from at least two different source-rock intervals:
In the Llanos basin, large variations in fluid com- the Upper Cretaceous marine black shales and marine-
position have been observed, which are closely linked to-continental facies of the Lower Paleogene (Palmer
to oilfield location and specific reservoir conditions, and Russell, 1988; Tegelaar et al., 1996; Rangel et al.,
such as pressure, temperature, and stratigraphic inter- 2000, 2003; Ramon et al., 2001; Garcia, 2008; Cortes
vals (Garcia, 2008). For instance, concentrations of et al., 2010). Earlier studies also highlighted the
GARCIA ET AL. 1505

dominant role of biodegradation (Dzou et al., 1999; Formations, all of which are considered to have excel-
Person et al., 2012) and mixing of oils of different ther- lent source-rock potential (Macellari and de Vries,
mal maturity (Springer et al., 2010) on the final com- 1987; Villamil, 1999).
position and geochemical signature of the oils. Tectonics associated with the Guaicaramo fault
The present study integrates, for the first time in system and the development of the modern Llanos
the basin, an extensive data set of fluid pressure/ basin are the result of a series of deformational events
volume/temperature (PVT) properties (physical prop- that occurred since the Early Paleogene. During this
erties) for 130 samples and geochemical characteris- time interval, northernmost South America underwent
tics of oils and gases (e.g., biomarkers, stable carbon substantial compression, Cretaceous sedimentary
isotopes of individual compounds, and diamondoids) basins were inverted, and the Eastern Cordillera was
to improve understanding of the petroleum charge uplifted (Cooper et al., 1995; Sarmiento, 2001). This
history in the central portion of the Llanos basin. produced eastward convergent thrusting along the
eastern boundary of the ancient rift (Hebrard, 1985;
REGIONAL GEOLOGICAL SETTING AND Fabre, 1987; Cooper et al., 1995). Structural inversion
PETROLEUM HABITAT of the basin began during the Late Cretaceous to early
Paleocene (Bayona et al., 2008), possibly because the
The Colombian Andes consist of three mountain final accretion of the Western Cordillera (McCourt
ranges formed as a result of the Neogene tectonic et al., 1984). Loading associated with the formation
evolution of northern South America (e.g., of the Central Cordillera led to the development of a
Mora et al., 2010). The Llanos basin is bounded to foreland basin and a marked change from marine to
the west by the easternmost range, the Eastern continental sedimentation (Cooper et al., 1995).
Cordillera (Figure 1) and is located at the northern In the Llanos foothills, petroleum is produced
end of a series of sub-Andean basins that extend from from three main reservoirs: (1) the Guadalupe, (2)
Argentina to Venezuela. Most of the ca. 207; 600 km2 Barco, and (3) Mirador Formations (Figure 2), which
(128; 996 mi2 ) of the Llanos basin lie within behave as a single pay zone in the Cusiana and
Colombia, with a small portion in southwestern Cupiagua oil fields. Traps occur mainly in hanging-
Venezuela. wall anticlines associated with west-dipping thrust
The Llanos basin is separated from the Eastern faults. The regional top seal is the lower muddy inter-
Cordillera by the Guaicaramo fault system (Figure 1). val of the Carbonera Formation. However, other shale
Within this system, the Yopal fault divides the basin and mudstone intervals within the Los Cuervos and
into two areas: the Llanos foothills to the west and Upper Guadalupe Formation are locally considered
the Llanos foreland to the east (Cooper et al., 1995; effective seals as well (Cooper et al., 1995).
Martinez, 2006). The foothills are represented by a In the area of study in the foothills, the northern
northeast–southwest-oriented fold-and-thrust belt, sector underwent more intense thin-skinned tectonic
whereas the foreland basin is genetically related to deformation that triggered the formation of stacked
Neogene flexural subsidence and molasse sedimenta- anticlines and duplex structures beneath a wide roof
tion (Van Houten, 1976). syncline (Figure 3). Toward the south, deformation
Prior to the onset of Early Paleogene tectonic defor- is dominated by the inversion of deep faults, which
mation and uplift of the Eastern and Central Cordilleras, involve the basement (thick-skinned), with the devel-
the Llanos basin was part of an extensional basin, with opment of subtle but wide structural closures (Mora
sedimentation driven primarily by subsidence and et al., 2010).
changes in eustatic sea level (Fabre, 1987; Villamil, Oil fields in the foreland occur mainly in the foot-
1999; Sarmiento, 2001). During the early Cenomanian wall of normal east-dipping faults. Toward the foot-
to Turonian, global sea level rise and widespread anoxic hills, both the reservoirs and the gross sedimentary
conditions on the sea bottom led to deposition of a suc- interval become thicker and oil is trapped mainly in
cession of interbedded marine shales, including the sandstones of the Barco and Mirador Formations.
Upper Cretaceous La Luna, Gachetá, and Chipaque Eastward, these formations and the regional seal

Figure 2. Stratigraphic
scheme for the Llanos
basin. Significant lateral
variations are observed in
most of the sedimentary
units. For example,
Turonian source rock
changes from proximal
facies (Gachetá
Formation) to distal facies
(Chipaque Formation)
from east to west.
(the C8 interval of the Carbonera Formation) pinch part of the foreland, however, reservoirs are shal-
out (Figure 2), allowing oil to reach the upper sandy lower (1.5–3.5 km [0.93–2.17 mi] depth) and their
intervals of the Carbonera Formation (Person et al., temperatures range between 80° and 140°C (176°
2012), as well as reservoirs in underlying and 284°F) (Figure 4).
Cretaceous sequences (e.g., sandstone intervals in
the Gachetá and Une Formations). SAMPLES AND METHODS
Reservoirs in the foothills area and the western
foreland have depths ranging between 3.5 and The PVT fluid properties from 23 oil fields located in
5.0 km (2.17 and 3 mi). Their current temperatures the central portion of the Llanos basin were compiled
are above 110°C (230°F). In the central and eastern from both the foothills and the foreland sectors
GARCIA ET AL. 1507

1508
Controls on Petroleum Composition
Figure 3. Structural cross sections across the Llanos foothills. BB′ shows the northern zone with stacked anticlines beneath a roof syncline (thin-skin deformation). AA′ shows the
transition to a less deformed southern zone where structural shortening is absorbed mainly by inversion (thick-skin deformation) of a normal fault (Guaicaramo Fault). H = horizontal;
V = vertical.
Figure 4. Formation tempera-
ture as a function of depth of the
reservoirs in the study area,
Llanos basin. The study area was
divided into nine sectors: three
in the foothills (FH-S = southern
foothills; FH-C = central foot-
hills; and FH-N = northern foot-
hills) and six in the foreland area
(FW-S = western foreland
south; FW-N = western foreland
north; FC-S = central foreland
south; FC-N = central foreland
north; FE-S = eastern foreland
south; FE-N = eastern foreland
north).
(Figure 5). The data set contains measured values of to 590°F) at 6°C/min (42.8°F/min) and held for
Psat at reservoir temperature, Bo at bubble point, 19 min. Saturated hydrocarbon fractions were analyzed
GOR, and API gravity. For more details on the petro- by GC-MS (mass spectrometer) using an Agilent
leum properties, the reader is referred to Pedersen Technologies 6890 N gas chromatograph equipped
et al. (1989). with a DB-5 capillary column coupled to an Agilent
Twenty-three samples of oil and gas were sub- Technologies 5973 mass selective detector. Samples
jected to a broad spectrum of geochemical analyses. were analyzed in selected ion mode. Regular steranes
We obtained information on molar compositions were monitored using m∕z 217 and m∕z 218 mass
and stable carbon isotopic ratios of the gases. For chromatograms, whereas the terpanes (e.g., hopanes)
the liquid phase (oil and condensate), geochemical were examined using ions m∕z 191 and m∕z 177.
data include composition of saturate, aromatic, To facilitate data interpretation, the study area
resin, and asphaltene fractions, stable carbon iso- was divided into two geologic regions, the foothills
topic ratios of the whole oils, distribution of normal (FH) and the foreland (F). The foothills were further
paraffins, isoprenoids and other compounds in the subdivided into three sectors (Figure 5) on the basis
whole-oil gas chromatogram (GC), and the relative of the structural style. In the northern sector (FH-N),
abundance of regular steranes (m∕z 217, m∕z 259, oil fields are in stacked anticlines of duplex struc-
and m∕z 218 mass chromatograms) and terpanes tures. The intensity of deformation decreases toward
(m∕z 191 mass chromatograms) in the saturated the south in the central foothills (FH-C); and, in the
fraction of the oils. southern foothills (FH-S), oil fields are wide struc-
Prior to analysis, crude oil samples were fraction- tures associated with faults involving the basement
ated over activated silica gel. Saturated hydrocarbon (Mora et al., 2010).
fractions were eluted with hexane, aromatic hydrocar- The foreland region was further divided into
bons were eluted using hexane:dicloromethane (8:2) three areas (Figure 5), according to the depth and
and NSO compounds were eluted using diclorome- age of the reservoirs. The western foreland (FW)
thane:methanol (8:2). Whole-oil analyses were carried comprises oil fields in deeper and older reservoirs.
out by GC-FID (flame ionization detection) using a Both age and depth (Figure 4) of reservoirs decrease
Hewlett-Packard 5890 equipped with DB-5 capillary toward the east in the central foreland (FC), reaching
column (30 m × 0.25 mm i.d., film thickness the shallowest positions in the eastern foreland (FE).
0.25 μm). Hydrogen was used as a carrier gas and oven Based on the distribution of API values, an addi-
temperature was programmed from 40° to 310°C (104° tional division of the study area was made. Each
GARCIA ET AL. 1509

Figure 5. Location of studied oil fields in the Llanos basin. In the foreland, reservoir depths increase toward the west. The 30° API isoline
was used to separate the southern and northern sectors of the foreland area. Lighter oils are found in the foothills and northern foreland.
FH-N = northern foothills; FW-N = western foreland north; FC-N = central foreland north; FE-N = eastern foreland north; FE-S = eastern
foreland south; FC-S = central foreland south; FW-S = western foreland south; FH-S = southern foothills; FH-C = central foothills.
foreland sector was divided into two portions sepa- PVT analyses on samples from drill stem test (DST)
rated by the 30° API isoline, with the highest values or modular formation dynamics tester (MDT). The
lying in the northern part. Thus, the oil fields in the petroleum fluids in the study area range from black
study area were ultimately divided into a total of nine oil to gas condensate. Reservoir depths below the sur-
sectors (Figure 5) for the geochemical interpretation. face range from 1500 to 5700 m (4921 to 18,700 ft).
The API gravities vary from 16° to 46°, GORs from
RESULTS less than 1 to 4700 m3 ∕m3 , and consequently forma-
tion volume factors cover a large range (from around
Physical Properties 1 to more than 8 m3 ∕m3 ½26 ft3 ∕ft3 ).
As mentioned above, petroleum accumulations in
Physical and PVT properties of the petroleum in the the foothills are in general deeper than those in the
reservoirs (Table 1) consist of API gravity, the foreland. In the foreland, API gravities range from
GOR, the Psat, and the Bo . Di Primio (2002) pro- 16° to 42°, and the fluids are black oils with Bo usu-
posed that an initial interpretation of genetic relation- ally less than 2.0 m3 ∕m3 . In contrast, oil from foot-
ships among petroleum samples, relative maturity, hills reservoirs tend to have higher API gravities,
and likely source-rock organofacies could be per- GOR, and Bo , ranging from 27° to 46°, 160 to
formed using cross plots of these properties. 4700 m3 ∕m3 ð524 to 15419 ft3 ∕ft3 Þ, and 1.1 up to
Diagrams showing the physical properties of the 8.5 m3 ∕m3 ð3.6 to 27.8 ft3 ∕ft3 Þ, respectively. Thus,
fluids were plotted using a set of compiled data from fluids in the foothills comprise black oil, volatile oil,

Table 1. Physical Property Data*
Sample Depth Reservoir Saturation Oil Gravity

Sample Name (m MD) Temperature (°C) Pressure (Bar) GOR ðm ∕m Þ
3 3
Bo ðm ∕m Þ
3 3
at 60°F
F_C_1_1 2591 91.1 14.8 5.7 1 40.4
F_C_1_2 2883 104.4 21.3 8.3 1.1 31.7
F_C_1_3 2589 93.3 26.7 9.5 1 41.7
F_C_1_4 2910 103.9 16.5 6.2 1.1 36.7
F_C_2_1 3134 110.3 24.7 7.8 1 38.8
F_C_2_2 3020 107.2 15.7 4.5 1 35.8
F_C_3_1 3207 116.1 84.9 55.5 1.2 21.5
F_C_4_1 2914 106.7 7.9 2.5 1 34
F_C_5_1 1603 78.9 4 1.8 1 21.7
F_C_6_1 2620 99.7 12.3 0.3 n.a. n.a.
F_C_7_1 2749 100 39.7 53.6 1.3 39.1
F_C_8_1 2949 104.4 9.2 2.1 1.1 18.2
F_C_8_2 2908 108.3 11.7 3 1.2 30.5
F_C_8_3 2910 106.1 11.5 3.4 1.1 22
F_C_8_4 2906 104.4 9 1.4 1.1 22.1
F_C_8_5 2947 112.8 7.8 2 1 19.4
F_C_8_6 2910 112.8 8.1 2.3 1 22.1
F_C_8_7 2920 105.6 6.7 2.5 1.1 19.2
F_C_8_8 2913 107.2 10 2.1 1.1 29
F_E_10_1 1734 91.1 13.9 8.4 1.1 41
F_E_10_2 1613 85 6.3 2.8 1.1 31.8
F_E_11_1 1824 86.7 4.8 1.2 1.1 28
F_E_11_2 1824 95 5.6 0.7 1.1 26
F_E_14_1 1837 87.2 2.4 0.5 1.1 26.3
F_E_15_1 1524 85.6 5 1.1 1.1 36
F_E_2_1 1505 75 11.4 5.5 1.1 39.8
F_E_2_2 1476 77.8 2.4 1.6 1.1 38.2
F_E_3_1 1793 95.6 17 3.9 1.1 34.2
F_E_4_1 1857 85 4.1 1.5 1.1 29.8
F_E_4_2 1857 86.7 2.3 0.5 1.1 28.6
F_E_5_1 1800 86.7 4.6 2 1 23.9
F_E_7_1 1837 83.3 11 0.2 n.a. n.a.
F_E_8_1 1758 98.9 n.a. n.a. n.a. n.a.
F_E_8_2 1756 98.9 32.5 7.6 1.1 33.7
F_W_1_1 4208 123.3 n.a. 1658.1 n.a. n.a.
F_W_13_1 3911 111.1 272.6 97.4 1.4 17
F_W_13_2 3910 118.3 342.5 168.2 1.4 16.4
F_W_13_3 3897 118.9 401.8 144 n.a. n.a.
F_W_13_4 3916 117.2 369.2 192.4 n.a. n.a.
F_W_13_5 3911 118.9 359.4 166.2 1.4 17.1
F_W_18_1 4301 122.8 112.9 61.8 1.3 30.9
F_W_2_1 4010 121.1 365.6 178.9 1.5 24
F_W_2_2 4344 121.7 246.9 182.2 1.5 32.7
F_W_2_3 4376 125 312.5 411.6 2.5 38
F_W_2_4 4386 122.8 303.9 370.3 2.1 n.a.
(continued )
GARCIA ET AL. 1511

Table 1. Continued

Sample Name (m MD) Temperature (°C) Pressure (Bar) GOR ðm3 ∕m3 Þ Bo ðm3 ∕m3 Þ at 60°F
F_W_6_1 3856 116.7 244.4 73.5 1.2 18.4
F_W_6_2 4214 121.1 297.9 481 1.3 16.9
F_W_6_3 3867 113.9 324.9 273.1 1.7 16.7
F_W_6_4 3856 115.6 327.9 189.2 1.5 16.9
F_W_6_5 4226 124.4 175.1 54.1 1.2 18.4
F_W_6_6 3816 116.7 237.1 75.5 1.1 17.2
F_W_6_7 4171 124.4 193.7 56 n.a. 16.9
FH_C_1_1 4441 120.6 397.8 751.5 n.a. n.a.
FH_C_1_2 4441 120.6 397.8 565.2 n.a. n.a.
FH_C_1_3 3917 116.1 352.7 763.7 3.5 40.2
FH_C_1_4 72 116.7 366.8 601.8 n.a. n.a.
FH_C_1_5 3915 117.8 389.6 563.4 n.a. n.a.
FH_C_1_6 3825 116.7 386.1 n.a. n.a. n.a.
FH_C_1_7 3825 116.7 384.4 898.4 3.9 43.8
FH_C_2_1 5061 140.6 366.5 645.5 3 34.1
FH_C_3_1 87 132.2 n.a. 631.9 n.a. n.a.
FH_C_4_1 4446 119.4 366.9 585.6 2.7 42.7
FH_C_5_1 4730 130.6 372.7 587.4 2.9 39.9
FH_C_6_2 4866 128.3 349.5 424.4 2.4 36.9
FH_C_6_3 5116 124.4 186.3 n.a. n.a. n.a.
FH_C_6_1 5116 133.3 339.7 354.5 2.3 37.1
FH_N_1_1 5358 127.2 425.8 572.8 2.7 38.9
FH_N_2_1 4311 108.9 386.2 691.1 3.8 41.2
FH_N_2_2 4256 108.9 371.4 589 2.8 41.6
FH_N_2_3 4197 108.9 404 917.4 3.9 43.7
FH_N_3_1 4875 117.8 287.2 333.1 2.1 41.7
FH_N_6_1 4601 122.2 442.5 1265.8 5.1 46.1
FH_N_6-2 4602 126.7 461.3 3703.8 4.1 41.3
FH_N_8_1 5672 143.3 426.4 n.a. n.a. 34.1
FH_N_9_1 5720 141.7 446.9 4719.9 n.a. 40.7
FH_N_9_2 4600 141.7 427.6 2184.1 8.5 42.3
FH_S_1_1 4368 126.7 340.5 231.2 n.a. n.a.
FH_S_1_2 4369 124.4 392.4 n.a. n.a. n.a.
FH_S_1_3 4438 126.7 340.5 242 1.1 34.9
FH_S_1_4 4583 131.7 352.6 163.1 1.5 41.7
FH_S_1_5 4363 123.3 390.6 1241.2 1.2 39.7
FH_S_2_1 4478 126.7 391.1 231.1 1.7 31
FH_S_2_2 4260 123.9 403 1131.6 n.a. n.a.
FH_S_2_3 4260 123.9 403 1131.6 n.a. n.a.
FH_S_2_4 4107 122.2 430.9 n.a. n.a. n.a.
FH_S_2_5 4022 120.6 384.4 n.a. n.a. n.a.
FH_S_3_1 4107 122.2 399.5 1547.8 6.2 42.6
FH_S_4_1 4668 129.4 339.9 218.1 1.8 34.4
FH_S_4_2 4642 124.4 323 230.9 1.8 36.1
FH_S_5_1 2215 113.3 395.8 1200.1 n.a. n.a.
(continued )

Table 1. Continued

Sample Name (m MD) Temperature (°C) Pressure (Bar) GOR ðm3 ∕m3 Þ Bo ðm3 ∕m3 Þ at 60°F
FH_S_5_2 4339 116.7 399.2 n.a. n.a. n.a.
FH_S_6_1 4810 131.1 342.5 218.8 1.9 34.9
FH_S_7_1 4579 123.9 310.3 222.9 1.8 37.1
FH_S_8_1 4542 128.3 267 202.9 1.7 27.7
FH_S_8_2 4466 126.7 303 n.a. n.a. n.a.
*n.a. = data not available.
and gas condensate. It is worth mentioning that in (di Primio et al., 1998). Because Psat and Bo can be
black oils from the foreland areas having low API affected by alteration processes, such as mixing,
gravities, GOR and Bo are mostly undersaturated, that phase separation, or biodegradation, this diagram
is, pore pressures far exceed saturation pressures should be used with caution when determining
(bubble points). Conversely, accumulations in the genetic relationships in altered black oils (di Primio,
foothills, especially the gas condensates in the 2002). In the study area, samples plot along two dif-
northern foothills, are closer to their saturation ferent trends on the Psat–Bo diagram (Figure 6).
pressures. Samples from the three foreland areas and from the
Another interesting observation is the difference southern foothills are characterized by low Bo (rang-
in GOR and Bo between oils from the eastern and ing from 1.0 to 2.0 m3 ∕m3 ½3.2 to 6.5 ft3 ∕ft3 ), with
central foreland regions and those in the western fore- saturation pressures increasing significantly from less
land. Although API gravities cover a similar range than 50 bar in the eastern and central foreland oil
throughout the foreland areas (16°–42°), fluids in fields, to up to 400 bar in the southern foothills accu-
the western foreland are consistently richer in gas mulations (Table 1). This group of samples defines a
(higher GOR). near-vertical trend in the diagram, which is inter-
A Psat–Bo diagram can be used as a complemen- preted as an expression of genetically related fluids
tary tool to determine genetic petroleum families sourced by a type II source rock.
Figure 6. Plot of satu-

ration pressure (Psat) as a
function of formation vol-
ume factor (Bo ). Note the
pronounced increase of
Bo , with Psat >350 bar in
oil samples from the
foothill sectors.
GARCIA ET AL. 1513

A second trend is observed in samples from the The usual trend of increasing Psat and GOR as a
foothills (Figure 6). Saturation pressure and Bo dras- function of reservoir depth was observed. In addi-
tically increase toward the north, indicating a high tion, saturation pressure and GOR increase drasti-
proportion of gas in the fluids of the northern reser- cally in the deeper reservoirs of the western
voirs. Higher gas contents in the foothills reservoirs, foreland and foothills (Figure 7), especially toward
as compared to the foreland oilfield fluids, could be the north of the study area, where petroleum is pro-
related to either a nearby source kitchen with more duced from intervals deeper than 5 km (16,404 ft).
terrigenous organic matter (type III kerogen) or to Larger variations of GOR and Psat in the 3000–
a higher maturity type II-bearing source rock 5000-m (9842–16,404-ft) depth range are also worth
or both. noting.
Figure 7. (A) Gas–oil

ratio (GOR) versus depth
and (B) saturation
pressures versus depth
diagrams. Although much
scatter occurs within spe-
cific depth intervals, these
variables generally follow
the expected trend of
greater values with
increasing depth.

Higher gas concentrations in deeper reservoirs of with API gravities between 16° and 25°) have GOR
the foothills and western foreland areas, as well as the below 10 m3 ∕m3 ð32 ft3 ∕ft3 Þ in the relatively shallow
geochemical properties of the gases (further dis- accumulations in the eastern and central foreland,
cussed below), support the hypothesis of a late influx whereas oils with a similar API range have GOR
of gas condensates and volatile oils from deep sourc- between 50 and 480 m3 ∕m3 ð164 and 1574 ft3 ∕ft3 Þ in
es located beneath the deformation zone of the foot- the deeper reservoirs of the western foreland. Even
hills. It appears that only small proportions of these when only one area is considered, such as the western
light fluids reached the shallower reservoirs in the foreland, heavier biodegraded oils (16°–25° API)
eastern part of the basin. within a quite narrow depth range (3800–4200 m
Petroleum biodegradation must be taken into [12467–13779 ft]) might have GOR as low as 50 or
account when analyzing physical data. Because gases as high as 480 m3 ∕m3 ð1574 ft3 ∕ft3 Þ (the higher values
(particularly methane) are the final product of bacte- associated with nearly gas-saturated oils), suggesting
rial activity, biodegradation of both oil and wet gas that late gas charge affected previously biodegraded
can increase the gas content of the fluid (Larter and accumulations.
di Primio, 2005) and substantially affect reservoir Variations in the petroleum physical and PVT
engineering properties, such as saturation pressure, properties in the study area lead us to suggest two
GOR, and Bo . Conversely, increasingly biodegraded preliminary working hypotheses.
oils become enriched in the heavier polar compound
classes that are less capable of dissolving hydrocar- 1. The markedly different gas content of reservoirs in
bon gases, leading to lower GOR. the foothills and foreland areas is related to two
Evidence of gas biodegradation has not been rec- different source rocks with different organofacies.
ognized in the gas geochemical data (see discussion The foreland oil fields may have been charged
on gas composition below). Thus, from the stand- from a type II source rock, whereas the foothills
point of molar gas composition, changes in the received lighter, gas-enriched fluids from more
mature and/or terrigenous (type III) source rocks.
behavior of fluids likely reflect the mixing of high-
2. Lower API values for oils from the southern por-
maturity gas with gas previously dissolved in accu-
tion of the study area suggest that they underwent
mulated oils rather than gas biodegradation. biodegradation. This alteration does not seem to
In contrast, the available API gravity data, ranging be directly controlled by the present-day depth
from 16° to 45° (Figure 5), indicate wide variations in and temperature of the reservoirs.
the current composition of the liquid phase. Liquids
with higher API values (>30°) are clustered in the Geochemical information for the oil and gas sam-
foothills, whereas lower values (<20°) are found in ples was therefore used to test these preliminary
the southwestern part of the foreland. Geochemical hypotheses.
properties of the liquids confirm the effects of biodeg-
radation on petroleum properties, as discussed below.
Neither the present-day temperatures of the reser- Geochemical Characterization of the
voirs nor their current depth seem to be the main con- Petroleum Samples
trol on the distribution of oil API gravity. Reservoirs
at similar depths and temperatures contain oils that vary One interpretation of the physical properties was that
by more than 20° API (Table 1). Thus, the current API two different oil kitchens supplied petroleum to the
gravities of the oils appear to result from the complex oilfields in the study area. Differences between those
and widely different charge histories for each sector. pods could be related mainly to source-rock types,
Similarly, the relationships among reservoir depth as well as the maturity of the expelled fluids.
(or alternatively pore pressure), API gravity, and GOR Because petroleum behavior is strongly affected by
are not straightforward. The variation of API gravity changes in the gas content of the fluids (as suggested
and GOR as a function of reservoir depth was by the GOR, Psat, and Bo values), we analyzed the
discussed above. Biodegraded oils (i.e., those geochemical characteristics of the gas phase in order
GARCIA ET AL. 1515

Table 2. Geochemical Data for the Gas Phase*
1516
Gas Composition (mol%) Gas Isotopic Ratio (δ13 C, in ‰)
Gas Sample ID C1 C2 C3 iC4 nC4 C4 iC5 nC5 C5 C6+ C1 C2 C3 iC4 nC4 C4 iC5 nC5 C5
F_C_1_1 86.29 1.79 2.04 2.63 2.11 4.74 n.d. n.d. n.d. n.d. −52.43 −29.47 −28.35 −30.16 −28.69 n.d. n.d. n.d. n.d.
F_C_1_2 89.3 1.54 1.01 0.71 0.49 1.2 n.d. n.d. n.d. n.d. −53.76 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
F_C_3_1 31.1 2.67 1.2 0.2 0.32 0.52 n.d. n.d. n.d. n.d. −36.48 −29 – n.d. n.d. n.d. n.d. n.d. n.d.
F_C_8_1 54.08 4.82 2.42 0.93 1.26 2.19 n.d. n.d. n.d. n.d. −39.12 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
F_C_8_2 54.1 4.47 2.78 0.86 1.23 2.09 n.d. n.d. n.d. n.d. −35.3 −28.1 – n.d. n.d. n.d. n.d. n.d. n.d.

F_E_1_1 92.73 1.7 0.64 0.28 0.17 0.45 n.d. n.d. n.d. n.d. −58.96 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
F_E_3_1 80.87 1.72 0.76 0.4 0.25 0.65 n.d. n.d. n.d. n.d. −57.46 −33.05 −32.09 −31.52 −30.46 n.d. n.d. n.d. n.d.
F_W_1_1 80.5 9.79 4.29 0.62 0.57 1.19 n.d. n.d. n.d. n.d. −39.22 −31.48 −30.2 n.d. n.d. n.d. n.d. n.d. n.d.
F_W_1_2 82.52 10.47 5.15 0.88 0.97 1.85 n.d. n.d. n.d. n.d. −37.52 −30.26 −28.56 −29.13 −27.74 n.d. n.d. n.d. n.d.
F_W_2_1 76.77 10.16 5.32 1.12 1.27 2.39 n.d. n.d. n.d. n.d. −37.26 −29.67 −27.86 −27.8 −26.65 n.d. n.d. n.d. n.d.
FH_C_1_1 77.66 10.45 4.726 1.055 1.178 2.233 0.428 0.254 0.682 0.471 −37.78 −28.9 −27.2 n.d. n.d. −27.14 n.d. n.d. n.d.
FH_C_1_2 77.58 10.48 4.742 1.061 1.184 2.245 0.432 0.258 0.69 0.48 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
FH_C_1_3 79.07 10.23 4.171 0.852 0.911 1.763 0.304 0.173 0.477 0.31 −38.37 −29.09 −27.56 n.d. n.d. −27.81 n.d. n.d. n.d.
FH_C_10_1 69.71 2.493 0.313 0 0.015 0.015 0.007 0.006 0.013 0.074 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
FH_C_10_3 71.86 11.83 6.555 1.562 1.831 3.393 0.589 0.359 0.948 0.562 −34.38 −28.7 −27.32 n.d. n.d. −26.68 n.d. n.d. n.d.
FH_C_10_5 76.19 10.25 4.906 0.979 1.033 2.012 0.292 0.167 0.459 0.235 −37.58 −29.08 −27.69 n.d. n.d. −27.09 n.d. n.d. n.d.
FH_C_12_1 68.36 11.26 6.078 1.552 1.587 3.138 3.787 0.124 3.911 0.02 −37.27 −29.15 −27.66 −27.13 −27.05 −27.08955 −26.34 −25.78 −26.322
FH_C_12_2 69.12 8.853 3.542 0.81 0.449 1.258 0.079 0.012 0.091 0.003 −35.99 −27.12 −25.32 −25.26 −24.07 −24.83574 −21.39 −25.62 −21.949
(continued )
Table 2. Continued
FH_C_13_1 73.9 11.93 5.413 1.18 1.314 2.494 0.447 0.271 0.718 0.419 −37.31 −29.17 −27.57 −27.65 −27.12 −27.37076 −27.78 −28.88 −28.195
FH_C_13_2 73.9 11.93 5.413 1.18 1.314 2.494 0.447 0.271 0.718 0.419 −37.33 −29.13 −27.55 −27.74 −27.13 −27.41861 lost −28.81 n.d.
FH_C_13_3 73.9 11.93 5.413 1.18 1.314 2.494 0.447 0.271 0.718 0.419 −37.32 −29.15 −27.56 −27.7 −27.13 −27.39969 −27.78 −28.85 −28.184
FH_C_13_4 75.03 11.25 5.1 1.114 1.255 2.369 0.438 0.266 0.704 0.463 −37.82 −29.16 −27.55 −27.51 −27.36 −27.43054 −27.18 lost n.d.
FH_C_13_5 75.03 11.25 5.1 1.114 1.255 2.369 0.438 0.266 0.704 0.463 −37.72 −29.09 −27.48 −27.49 −27.26 −27.36816 −27.16 −28.45 −27.647
FH_C_13_6 75.03 11.25 5.1 1.114 1.255 2.369 0.438 0.266 0.704 0.463 −37.77 −29.13 −27.52 −27.5 −27.31 −27.39935 −27.17 −28.45 −27.654
FH_C_14_1 82.23 10.31 4.298 0.912 0.99 1.902 0.323 0.184 0.507 0.486 −37.88 −29.33 −27.7 −27.4 −26.99 −27.18663 −27.41 −27.65 −27.497
FH_C_14_2 82.23 10.31 4.298 0.912 0.99 1.902 0.323 0.184 0.507 0.486 −37.52 −29.24 −27.82 −27.27 −26.88 −27.06704 n.d. n.d. n.d.
FH_C_14_3 82.23 10.31 4.298 0.912 0.99 1.902 0.323 0.184 0.507 0.486 −37.7 −29.29 −27.76 −27.34 −26.94 −27.13184 −27.41 −27.65 −27.497
FH_C_14_4 76.16 9.343 3.921 0.89 0.946 1.836 0.319 0.171 0.489 0.179 −37.73 −29.35 −27.27 −26.23 −27.11 −26.6832 −26.16 −26.11 −26.143
FH_C_14_5 76.16 9.343 3.921 0.89 0.946 1.836 0.319 0.171 0.489 0.179 −37.82 −29.34 −27.19 −26.17 −27.09 −26.6438 −26.43 −26.14 −26.329
FH_C_14_6 76.16 9.343 3.921 0.89 0.946 1.836 0.319 0.171 0.489 0.179 −37.78 −29.35 −27.23 −26.2 −27.1 −26.6635 −26.3 −26.13 −26.241
FH_C_15_1 79.73 9.784 4.087 0.836 0.914 1.75 0.321 0.196 0.517 0.44 −37.1 −29.2 −27.17 −26.63 −25.96 −26.28007 −26.74 −26.36 −26.596
FH_C_16_1 72.72 12.45 5.649 1.204 1.345 2.549 0.452 0.271 0.723 0.437 −37.95 −29.41 −27.77 −28.18 −27.42 −27.77898 −27.68 −27.31 −27.541
FH_C_16_2 73.31 12.27 5.555 1.176 1.306 2.482 0.429 0.253 0.682 0.376 −37.95 −29.32 −27.73 −28.95 −27.94 −28.41855 n.d. n.d. n.d.
FH_C_17_1 74.89 11.32 4.701 0.874 1.016 1.89 0.316 0.215 0.531 0.438 −39.25 −29.34 −27.62 −28.61 −27.57 −28.05093 −27.95 −28.4 −28.132
FH_C_18_1 72.92 12.4 5.663 1.201 1.342 2.543 0.445 0.266 0.711 0.435 −38.47 −29.33 −27.78 −28.4 −27.4 −27.87228 −27.77 −27.57 −27.695
FH_C_19_2 78.02 10.44 4.758 1.004 1.121 2.125 0.374 0.226 0.6 0.345 −37.34 −29.48 −27.53 −27.96 −27.52 −27.72789 −27.07 −27.47 −27.221
FH_C_19_3 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. −37.7 −29.59 −27.42 −28.19 −27.61 −27.88403 −27.1 −27.39 −27.209
FH_C_4_1 76.37 10.99 5.141 1.087 1.14 2.227 0.367 0.201 0.568 0.361 −37.62 −29.33 −27.55 n.d. n.d. −27.14 n.d. n.d. −4.96
FH_C_6_1 76.17 9.627 4.084 0.987 1.501 2.488 0.632 0.459 1.091 1.411 −38.99 −29.3 −27.42 −26.66 −27.63 −27.2452 −27.74 −27.73 −27.736
FH_C_6_10 40.47 17.1 14.8 4.461 6.662 11.12 3.038 2.218 5.256 4.693 −40.97 −31.47 −29.94 −29.61 −28.87 −29.16679 −28.59 −28.24 −28.442
FH_C_6_2 43.71 16.48 13.24 3.792 5.732 9.524 2.737 2.051 4.788 5.66 −38.81 −30.18 −27.63 −27.38 −27.06 −27.18741 −27.21 −27.33 −27.261
FH_C_6_3 71.99 11.33 6.383 1.432 1.761 3.193 0.569 0.364 0.933 0.553 −37.86 −29.33 −28.4 −27.52 −27.42 −27.46485 −26.41 −25.22 −25.946
FH_C_6_4 72.31 11 6.08 1.332 1.64 2.972 0.52 0.33 0.85 0.496 −38.12 −29.1 −28.1 −27.36 −27.63 −27.50899 −26.61 −25.13 −26.035
FH_C_6_5 80.25 8.16 3.511 0.704 0.782 1.486 0.235 0.148 0.383 0.186 −38.97 −29.21 −27.48 −27.02 −27.27 −27.15156 −25.18 −30.07 −27.07
FH_C_6_6 80.25 8.16 3.511 0.704 0.782 1.486 0.235 0.148 0.383 0.186 −39.16 −29.23 −27.53 −27.89 −27.83 −27.85843 −25.11 −29.33 −26.741
GARCIA ET AL.
FH_C_6_7 80.25 8.16 3.511 0.704 0.782 1.486 0.235 0.148 0.383 0.186 −39.07 −29.22 −27.51 −27.46 −27.55 −27.50736 −25.15 −29.7 −26.908
FH_C_6_8 71.51 10.45 5.746 1.25 1.55 2.8 0.493 0.316 0.809 0.316 −37.38 −29.33 −28.19 −27.86 −27.63 −27.73268 −26.79 −25.89 −26.438
FH_C_6_9 71.73 10.82 5.873 1.189 1.392 2.581 0.394 0.243 0.637 0.331 −38.88 −29.34 −28.45 −27.25 −27.09 −27.16371 −26.46 −25.29 −26.014
(continued )
1517
Table 2. Continued
1518
FH_C_7_1 74.24 10.88 5.48 1.28 1.49 2.77 0.56 0.35 0.92 0.68 −38.07 −29.16 −27.5 n.d. n.d. −27.37 n.d. n.d. n.d.
FH_C_7_2 74.27 11 5.56 1.28 1.49 2.77 0.55 0.34 0.89 0.47 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
FH_C_8_1 82.37 7.58 2.23 0.48 0.72 1.2 0.31 0.21 0.52 0.93 −37.93 −28.96 −27.65 −25.14 −27.7 −26.68 −25.84 −26.91 −26.275
FH_C_8_2 60.88 13.65 8.78 2.42 3.28 5.71 1.37 0.9 2.27 1.91 −39.16 −29.3 −27.83 −27.92 −27.16 −27.48 −27.58 −27.7 −27.628
FH_C_9_1 71.8 9.88 3.84 0.72 0.6 1.32 0.13 0.05 0.19 0.03 −37.6 −29.41 −27.75 −26.3 −27.53 −26.86 n.d. −27.62 n.d.
FH_N_1_3 80.89 7.32 3.73 1.01 1.21 2.22 0.5 0.32 0.82 0.5 −33.52 −27.94 −27.54 n.d. n.d. −27.12 n.d. n.d. n.d.
FH_N_1_1 80.5 7.3 3.76 1.05 1.28 2.33 0.55 0.36 0.92 0.63 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

FH_N_2_1 79.9 9.41 4.56 1.08 1.16 2.24 0.4 0.23 0.63 0.32 −35.2 −29.4 −26.4 n.d. n.d. −29.2 n.d. n.d. n.d.
FH_N_2_2 77.5 9.41 5.01 1.37 1.63 3 0.71 0.44 1.15 1 −35.5 −29.4 −27 n.d. n.d. −30 n.d. n.d. n.d.
FH_N_2_3 80.7 8.8 4.14 1 1.11 2.11 0.42 0.25 0.67 0.41 −35.1 −28.2 −27 n.d. n.d. −29.8 n.d. n.d. n.d.
FH_N_2_4 79.84 9.42 4.56 1.07 1.15 2.22 0.4 0.23 0.62 0.32 −35.24 −29.42 −29.21 n.d. n.d. −27.84 n.d. n.d. n.d.
FH_N_2_5 77.87 9.47 4.96 1.31 1.52 2.82 0.64 0.39 1.03 0.87 −35.47 −29.95 −29.39 n.d. n.d. −27.86 n.d. n.d. n.d.
FH_N_2_6 80.56 8.94 4.2 0.99 1.08 2.07 0.4 0.23 0.63 0.42 −35.07 −29.77 −28.17 n.d. n.d. −26.97 n.d. n.d. n.d.
FH_N_3_1 70.48 13.4 8.14 1.97 2.38 4.35 0.83 0.52 1.35 0.75 −37.1 −29.88 −28.89 −28.84 −27.87 −28.31 −27.84 −28.23 −27.99
FH_N_3_2 70.48 13.4 8.14 1.97 2.38 4.35 0.83 0.52 1.35 0.75 −36.61 −29.88 −29.01 n.d. n.d. n.d. n.d. n.d. n.d.
FH_N_3_3 70.48 13.4 8.14 1.97 2.38 4.35 0.83 0.52 1.35 0.75 −36.86 −29.88 −28.95 −28.84 −27.87 −28.31 −27.84 −28.23 −27.99
FH_N_3_4 75.7 10.42 6.54 2.06 2.16 4.22 n.d. n.d. n.d. n.d. −36.67 −30.04 −28.45 −29.04 −27.66 n.d. n.d. n.d. n.d.
FH_N_4_1 77.45 10.45 4.94 1.18 1.32 2.5 0.49 0.29 0.78 0.43 −36.03 −28.92 −28.11 −28.52 −27.4 −27.93 −27.47 −27.98 −27.661
FH_N_4_2 77.45 10.45 4.94 1.18 1.32 2.5 0.49 0.29 0.78 0.43 −36.2 −29.22 −28.4 −28.56 −27.73 −28.12 n.d. n.d. n.d.
FH_N_4_3 77.45 10.45 4.94 1.18 1.32 2.5 0.49 0.29 0.78 0.43 −36.12 −29.07 −28.26 −28.54 −27.57 −28.03 −27.47 −27.98 −27.661
FH_N_5_1 83.33 8.83 3.88 0.82 0.68 1.5 n.d. n.d. n.d. n.d. −38.73 −31.24 −30.09 n.d. n.d. n.d. n.d. n.d. n.d.
FH_N_5_2 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. −38.47 −28.58 −27.5 −27.26 −25.42 n.d. −27.08 −26.14 n.d.
FH_N_6_1 68.75 14.32 8.18 2.43 2.4 4.83 n.d. n.d. n.d. n.d. −38.74 −31.41 −29.99 −30.67 −29.09 n.d. n.d. n.d. n.d.
FH_N_6_2 66.76 14.59 6.9 1.79 2.03 3.82 0.91 0.54 1.45 1.56 −38.87 −29.55 −28.2 −27.57 −27.22 −27.38 −27.97 −27.11 −27.648
FH_N_6_5 82.65 7.52 2.66 0.61 0.59 1.2 0.22 0.11 0.33 0.23 −35.2 −26.7 −26.37 n.d. n.d. −25.55 n.d. n.d. n.d.
FH_N_7_1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. −38.82 −27.63 −26.53 −27.2 −25.9 n.d. −26.08 −25.24 n.d.
FH_N_8_1 82.94 4.93 1.44 0.33 0.34 0.66 0.14 0.08 0.22 0.2 −33.71 −25.6 −24.9 n.d. n.d. −24.6 n.d. n.d. n.d.
(continued )
Table 2. Continued
FH_N_9_1 79.21 7.35 2.52 0.6 0.67 1.28 0.31 0.19 0.51 0.49 −34.36 −26.43 −25.72 −26.92 −26.03 −26.45 −26.38 −25.85 −26.18
FH_N_9_4 79.31 9.43 3.88 0.91 0.93 1.84 0.35 0.19 0.53 0.4 −37.3 −28.64 −25.89 n.d. n.d. −27.43 n.d. n.d. n.d.
FH_S_1_1 76.17 10.65 4.57 0.84 1.07 1.9 0.33 0.25 0.58 0.5 −38.69 −28.82 −27.07 n.d. n.d. −27.44 n.d. n.d. −3.91
FH_S_1_2 76.25 10.62 4.52 0.83 1.05 1.88 0.32 0.24 0.56 0.41 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
FH_S_1_3 77.7 10.42 4.61 1.03 1.14 2.16 0.42 0.25 0.67 0.48 −38.31 −28.55 −26.95 n.d. n.d. −26.99 n.d. n.d. −2.38
FH_S_10_1 77.2 10.4 4.26 0.79 0.95 1.74 0.3 0.21 0.51 0.36 −38.71 −28.54 −27.41 n.d. n.d. −26.91 n.d. n.d. n.d.
FH_S_2_1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. −42.8 −27.7 −26.35 n.d. n.d. −26.5 n.d. n.d. n.d.
FH_S_2_3 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. −40.26 −27.61 −26.2 n.d. n.d. −26 n.d. n.d. n.d.
FH_S_5_1 74.25 10.45 4.95 1.05 1.46 2.51 0.44 0.33 0.77 0.13 −42.8 −27.69 −26.35 n.d. n.d. −26.5 n.d. n.d. n.d.
FH_S_5_2 76.71 10.38 4.45 0.8 1.01 1.81 0.22 0.16 0.38 0 −41.24 −27.91 −26.31 n.d. n.d. −26.24 n.d. n.d. n.d.
FH_S_5_3 75.15 9.77 4.26 0.8 1.02 1.82 0.24 0.16 0.4 0 −40.26 −27.61 −26.19 n.d. n.d. −25.99 n.d. n.d. n.d.
FH_S_8_1 68.55 13.06 8.52 1.74 2.04 3.78 0.48 0.31 0.79 0.32 −38.35 −30.04 −28.28 n.d. n.d. −27.92 n.d. n.d. n.d.
FH_S_8_3 73.82 11.34 5.61 1.05 1.34 2.39 0.39 0.29 0.68 0.41 −38.73 −29.23 −27.55 n.d. n.d. −27.34 n.d. n.d. −4.67
*n.d. = not detected.
GARCIA ET AL.
1519
to assess its nature and understand the observed vari- evaluate the origin and maturities of the gases in the
ability in the reservoirs. study area.
Except for four samples (two each in the eastern
and central foreland areas), gas samples plot in the
GEOCHEMISTRY OF GASES field of thermogenic origin (Figure 8) on diagrams
proposed by Schoell (1983) and Whiticar (1994).
Compositional and stable carbon and hydrogen iso- Those authors state that the key to distinguishing
topic values of gas samples (Table 2) were used to thermogenic from biogenic gas is the carbon isotopic
Figure 8. (A) δ13 C

versus dryness and
(B) δ13 C versus δD in the
C1 –C4 gas fraction. Most
of the gas samples
represent thermogenic
gases, as indicated by low
C1 ∕ðC1 + C2 Þ and higher
δ13 C and δD of methane.
In the foreland, four gas
samples of biogenic origin
were identified, based on
lower isotopic signature
and drier composition.
FH-N = northern foot-
hills; FH-C = central foot-
hills; FH-S = southern
foothills; FW-N = western
foreland north; FW-S =
western foreland south;
FC-N = central foreland
north; FC-S = central
foreland south; FE-N =
eastern foreland north;
FE-S = eastern foreland
south.

composition and relative amounts of methane. Carbon isotopic compositions for the C2 –C4
Biogenic gas is isotopically lighter and is composed compounds in each sample are similar, with most
almost exclusively of methane, whereas thermogenic differences being lower than 3‰. The exception is
gases are isotopically heavier and contain more C2+ one sample from the foreland with an anomalously
unless they are thermally overmature. low δ13 C3 value. The trend displayed by C2 –C4 iso-
Only four samples showed light δ13 C methane topic profiles for the studied gases is subparallel, typ-
(<−50‰) and light deuterium (δ2 H methane ical of a common source (Figure 10). The isotopic
<−200‰) coupled with lower C2+ (values above 10 shift toward heavier values indicates an increase in
for the C1 ∕ðC2 + C3 Þ molar ratio). These samples thermal maturity. The negative shift in δ13 C3 of the
from the central and eastern foreland could be low- sample from the central foreland sector (Figures 9,
maturity gas or mixed biogenic and thermogenic gas 10) is likely to be an analytical artifact. No conspicu-
(Schoell, 1983). In the case of mixed gases, the bio- ous evidence of biodegradation (e.g., positive spikes
genic component could be produced directly from in δ13 C values of propane and n-butane) was found
the microbial activity on the organic matter, or it in the studied gases.
could be the product of in-reservoir petroleum The C1 is strongly depleted in δ13 C in the sample
biodegradation. from the eastern foreland sector (Figure 10), a feature
Gas from oil fields in the foreland is isotopically that is commonly attributed to the presence of bio-
lighter in δ13 C of ethane and propane, confirming genic gas. Relatively minor δ13 C depletion may be
the lower maturity of these gases as compared to gas related to less mature gas and, according to
from the foothills, which has C2 and C3 relatively Prinzhofer et al. (1995), it may also indicate isotopic
enriched in 13 C (Figure 9). Most of the gases from fractionation related to long-distance migration
the foothills and western foreland represent fluids (Prinzhofer and Pernaton, 1997).
expelled at maturity higher than the peak-oil window The isotopic and compositional information for
(more than 0.8% Ro equivalent), reaching the gas the C2+ hydrocarbon gases suggest they could have
window in the northern foothills. been generated from a single source rock or from
Figure 9. The δ13 C–C2

versus δ13 C–C3 and the
estimated vitrinite reflec-
tance (Ro ) (Schoell,
1983). Gases from the
foreland show a lower
thermal maturity than the
gas samples from the
foothills. FH-N = northern
foothills; FH-C = central
foothills; FH-S = southern
foothills; FW-N = western
foreland north; FW-S =
western foreland south;
FC-N = central foreland
north; FC-S = central
foreland south; FE-N =
eastern foreland north;
FE-S = eastern foreland
south.
GARCIA ET AL. 1521

Figure 10. The δ13 C
isotopic signatures of the
gas hydrocarbons. The
observed subparallel
trend in the C2−C4
signatures suggests a
common source of the
analyzed gas samples.
Depletion in δ13 C of
methane may indicate
biogenic gas contribution
to the foreland samples.
FH-N = northern foothills;
FH-C = central foothills;
FH-S = southern foothills;
FW-N = western foreland
north; FW-S = western
foreland south; FC-N =
central foreland north;
FC-S = central foreland
south; FE-N = eastern
foreland north; FE-S =
eastern foreland south.
different sources with analogous carbon isotopic Differences were interpreted in terms of changes in
compositions, at different levels of thermal maturity organic matter, lithology, and oxygenation levels, as
and, in certain cases, with a later contribution of bio- well as varying degrees of biodegradation.
genic gas. The late-expelled mature and overmature Several geochemical parameters confirm the con-
gases are concentrated in the foothills and western tribution from two different source rocks. A terrig-
foreland oil fields. These are drier gases with a enous origin for oil produced in the foothills is
heavier carbon isotopic signature. Based on the inte- suggested by the abundance of high-molecular
grated interpretation of gas and oil data, it is plausible weight n-alkanes, the bimodal n-alkanes distribution
that hydrocarbons were generated from more than (Figure 11), the odd-over-even predominance
one source in the basin. Nevertheless, such sources ðnC23 − nC25 Þ, and the high pristane/phytane ratios
would necessarily have a high degree of carbon iso- (Peters et al., 2005).
topic homogeneity to explain the relatively narrow Saturated biomarkers also show strong evidence
range of δ13 Cwholeoil measured in the studied samples for two different oil types. In Figure 11, a comparison
(average of −26.46‰ ± 1.40‰). This interpretation is made between the GC-MS (m∕z 191) signature of a
reconciles the apparent paradox of similar δ13 C in marine oil from the eastern foreland with that of a ter-
gases with more than one source. rigenous oil from the northern foothills. Significant
differences are observed in the relative concentration
of the tricyclic terpanes. We highlight the relative
GEOCHEMISTRY OF OILS abundance of the extended ðC27+ Þ tricyclic terpanes
as well as the predominance of C23 among the low
The geochemical characteristics of oils from the molecular-weight tricyclics in marine oils.
Llanos basin are complex and reflect the effects of Compared to oils generated predominantly from
source-rock type, maturity, and alteration processes. marine organic matter, oils that show significant ter-
After a detailed visual assessment of the mass chro- rigenous contribution have higher relative propor-
matograms, selected compounds were plotted to iden- tions of C19 and C20 tricyclic terpanes and oleanane
tify the main differences among samples (Table 3). (Figure 12). These compounds are indicators of

Table 3. Geochemical Parameters of Oil*
Sample ID Hopanes Esteranes Tricyclic TR19 TR20 TR21 TR22 TR23 TR24 TS TM H29 M29 OL H30 M30
F_C_1_1 482.73 191.6 288.11 n.d. 21.08 24.8 6.94 42.72 26.15 25.82 27.53 69.63 10.21 12.91 113.66 20.52
F_C_1_2 1217.59 203.31 393.83 n.d. 40.94 31.45 7.28 54.92 38.39 41.34 73.33 182.44 27 29.61 290.9 56.49
F_C_10_1 1253.21 854.99 572.39 n.d. 45.99 59.11 17.23 89.27 60.23 87.52 87.99 149.66 33.09 40.87 232.68 54.24
F_C_5_1 1398.32 559.75 471.83 n.d. 37.16 42.69 12.68 68.87 43.99 79.48 73.7 159.45 28.2 24.17 260.69 40.96
F_C_6_1 1136.85 347.84 500.69 n.d. 37.98 41.07 10.1 68.69 50.94 55.91 72.48 155.51 19.04 38.7 264.83 44.67
F_C_7_1 721.54 253.46 312.25 12.6 13.61 14.31 n.d. 46.27 37.59 33.13 65.42 108.68 20.33 46.99 165.86 31.84
F_C_7_2 647.01 246.12 298.67 17.45 14.97 16.33 6.96 43.76 34.07 32.57 59.1 93.87 19.17 39.36 148.51 28.63
F_C_8_2 1316.77 1112.85 672.48 n.d. 51.19 68.85 18.84 103.75 70.18 104.76 96.1 148.16 35.2 55.62 232.86 52.46
F_C_9_1 601.73 328.07 253.49 n.d. 27.51 25.67 8.47 40.1 24.95 44.59 41.1 77.97 10.85 12.65 132.37 22.04
F_E_1_1 593.09 376.01 701.04 n.d. 39.47 55.12 10.91 100.9 71.36 27.75 26.71 75.6 11.42 15.65 145.32 20.96
F_E_2_1 604.14 178.21 350.96 n.d. 29.01 27.77 5.32 50.01 37.2 23.77 32.8 89.09 12.24 19.06 143.95 25.33
F_E_3_1 481.26 270.65 504 n.d. 31.47 39.92 7.87 76.24 49.16 26.44 23.3 64.26 8.14 16 121.97 17.41
F_E_5_1 841.73 427.18 390.19 n.d. 28.91 36.49 10.25 54.31 38.84 60.54 49.8 96.8 20.87 15.77 173.14 28.72
F_W_1_1 826.47 436.66 1423.94 40.01 78.38 100.82 28.15 213.18 181.72 35.14 77.24 141.81 18.94 62.53 185.28 37.76
F_W_13_1 1685.53 1153.77 774.3 n.d. 60.32 80.47 22.45 119.25 86.15 135.51 134.66 184.45 51.2 51.21 272.93 73.31
F_W_2_1 676.06 325.54 649.5 n.d. 42.8 49.48 15.02 102.69 78.05 36.59 55.74 96.9 12.81 33.76 145.39 28.22
F_W_6_1 1724.23 1509.86 804.78 n.d. 57.28 78.87 24.64 114.64 91.09 137.85 114.71 182.92 47.58 55.73 303.21 76.94
FH_C_20_3 183.82 90.17 243.09 21.69 21.98 14.22 3.92 28.24 25.91 13.74 16.57 28.52 4.11 27.14 42.77 5.04
FH_N_1_1 365.61 120.1 351.19 69.16 52.53 18.72 5.67 32.2 34.56 36.94 22.04 49.97 4.16 64.29 65.05 n.d.
FH_N_1_2 298.76 134.8 396.91 65.85 54.17 24.49 6.47 39.65 34.76 39.11 22.24 52.06 5.44 75.75 65.6 8.72
FH_N_10_2 497.42 147 298.62 51.17 48.9 16.75 6.23 29.28 24.16 45.97 29.93 73.8 6.12 78.08 93.27 13.32
FH_N_3_1 435.36 56.94 134.83 45.07 21.27 9.3 3.06 11.93 5.84 22.49 27.97 63.97 4.19 28.75 95.78 10.77
FH_N_5_1 143.58 20.75 97.52 40.84 20.78 6.05 1.54 6.65 4.36 8.55 12.85 25.89 2.73 7.4 33.2 3.48
FH_N_6_1 1102.53 214.46 408.34 86.22 66.03 26.7 8.32 38.9 29.97 70.98 76.64 152.51 16.63 77.18 217.58 33.53
FH_N_6_1 192.71 42.15 116.24 32.17 15.96 8.02 1.27 12.62 6.36 12.16 8.93 23.67 5.21 19.3 40.23 5
FH_N_6_2 935.61 168.27 548.2 66.65 78.4 46.19 10.64 71.66 57.03 42.29 65.41 133.79 13.73 43.23 218.59 28.06
FH_N_8_1 537.56 109.67 218.36 28.42 44.14 14.63 6.81 22.92 18.1 20.61 34.6 71.73 7.76 13.92 124.59 16.24
FH_N_9_1 454.2 148.79 456.3 48.78 59.17 35.35 7.53 58.76 47.98 25.1 32 66.23 6.81 28.33 108.99 13.23
FH_N_9_2 305.94 65.91 206.5 44.21 35.51 14.02 4.01 20.44 17.69 17.18 21.21 46.7 4.79 24.41 70.1 11.09
FH_S_1_0 162.03 157.06 626.65 21.04 70.71 67.45 21.68 107.85 73.93 10.98 17.26 27.05 2.61 15.79 40.17 5.45
FH_S_11_1 205.87 102.91 292.67 31.17 24.99 16.52 5.19 34.12 31.05 15.12 17.74 32.44 1.57 30.81 46.26 5.62
FH_S_11_2 589.74 201.81 526.01 56.95 55.64 30.68 8.2 63.39 55.24 37.9 37.44 98.63 10.73 62.39 129.07 16.93
FH_S_2_1 234.96 129.71 566.07 31.01 68.36 58.54 19.01 95.74 67.47 12.56 22.7 37.43 3.2 28.1 61.23 9.12
FH_S_6_1 213.17 189.18 616.64 20.27 64.13 61.24 20.16 100.82 68.12 14.36 20.16 31.96 2.92 19.85 50.95 6.61
FH_S_8_1 283.52 190.56 658.38 27.77 68.5 61.29 19.35 105.83 69.55 18.3 27.08 43.16 3.2 32.93 73.3 10.02
GARCIA ET AL.
(continued )
1523
Table 3. Continued
1524
Sample ID H31S H31R H32S H32R H33S H33R H34S H34R H35S H35R D27baS D27baR D27abS D27abR D27baS D27baF PP/Dias
F_C_1_1 44.9 30.64 29.53 22.09 17.81 12.93 10.76 7.38 6.19 7.42 21.48 10.94 3.29 5.69 11.39 6.97 1.02
F_C_1_2 140.77 92.28 86.29 65.18 46.42 31.37 28.35 17.97 12.66 12.26 18.14 9.45 3.27 5.35 9.2 5.8 1.25
F_C_10_1 100.3 71.64 76.91 56.61 53.62 36.98 42.2 25.65 32.59 19.67 124.35 73.6 37.91 41.99 70.38 48.5 0.59
F_C_5_1 125.33 89.83 86.41 65.71 67.13 46.06 57.84 36.65 53.84 37.58 74.27 43.35 23.2 23.06 41.15 27.67 0.63
F_C_6_1 110.57 75.39 77.37 54.29 43.94 29.62 27.09 17.31 14.65 15.15 37.29 21.7 10.8 11.7 19.85 12.93 0.93
F_C_7_1 74.41 47.41 44.41 34 24.94 16.03 13.75 8.97 8.28 6.88 28.6 19.58 8.68 9.85 15.42 11.15 n.d
F_C_7_2 62.23 40 40.85 29.78 21.98 15.12 13.94 8.26 8.29 6.35 30.51 20.78 9.26 11.05 16.57 11.86 n.d
F_C_8_2 94.33 67.89 74.94 58.41 58.39 39.5 45.92 26.37 35.72 23.26 160.98 94.61 48.45 54.3 93.42 59.24 0.6
F_C_9_1 45.64 31.64 34.61 24.02 21.77 14.43 15.27 9.87 9.74 6.75 53 29.14 14.57 15.43 28.41 17.93 0.64
F_E_1_1 58.27 38.05 35.77 27.37 25.17 18.28 15.06 10.42 11.47 16.58 29.48 16.19 6.28 8.95 15.91 9.76 1.34
F_E_2_1 67.96 45.32 41.58 31.1 23.16 16.51 13.91 9.28 7.16 8.25 16.08 8.36 3.6 4.95 8.85 5.02 1.21
F_E_3_1 48.07 29.84 28.84 21.72 19.21 13.8 10.99 7.46 7.47 10.45 24.85 13.56 5.37 8.12 13.56 8.39 1.19
F_E_5_1 67.8 49.08 49.02 35.55 33.58 23.07 25.46 14.83 16.73 14.13 58.58 35.73 18.46 19.78 33.08 21.19 0.68

F_W_1_1 81.84 49.99 49.73 33.01 26.99 16 17.23 10.13 11.72 11.75 37.12 21.48 9.76 9.09 20.39 12.59 1.36
F_W_13_1 118.12 82.15 93.47 72.63 79.04 48.52 58.85 34.75 48.56 31.21 177.27 110.08 60.76 67.1 106.45 69.58 0.64
F_W_2_1 61.99 40.69 39.26 28.54 24.08 16.4 16.53 10.27 11.51 10.48 37.4 19.49 9.27 9.56 19.67 11.97 1.1
F_W_6_1 129.91 100.94 98.59 73.1 78.2 53.2 64.09 38.3 47.79 29.38 208.8 133.95 68.54 71.06 126.52 82.73 0.51
FH_C_20_3 14.49 10.12 9.65 6.74 4.3 2.29 2.28 1.31 1.07 0.88 6.57 3.56 1.91 1.43 3.33 1.98 1.55
FH_N_1_1 22.77 17.22 19.46 11.09 11.93 5.03 5.08 3.09 1.67 2.32 10.58 6.75 2.81 4.12 5.98 3.1 n.d
FH_N_1_2 21.27 13.62 20.33 10.52 14.63 5.47 4.81 3.02 n.d. n.d. 11.47 7.52 3.26 3.7 6.46 3.83 n.d
FH_N_10_2 32.59 20.29 28.84 15.81 16.53 7.24 7.2 4.18 2.7 2.76 13.9 9.91 4.46 5.08 8.27 5.27 n.d
FH_N_3_1 40.1 27.43 29.61 21.32 14.41 9.71 9.26 5.55 3.55 2.49 4.98 2.2 0.65 1.71 2.64 1.35 1.37
FH_N_5_1 12.23 8.32 8.8 5.86 3.35 2.31 1.98 1.29 0.68 0.39 2.06 0.96 0.68 0.46 1.13 0.57 0.86
FH_N_6_1 92.05 67.77 79.61 50.41 43.8 23.38 21.61 13.3 7.95 7.07 19.17 13.46 6.4 6.86 11.28 7.62 n.d
FH_N_6_1 18.94 11.94 13.47 9.39 6.5 4.51 4.06 2.39 1.46 1.32 3.75 1.5 0.62 0.99 1.96 1.06 1.63
FH_N_6_2 94.69 69.7 69.3 46.4 37.53 20.98 16.98 10.17 5.64 5.07 17.22 10.41 4.48 4.87 9.35 5.96 n.d
FH_N_8_1 56.9 38.3 41.49 28.91 23.77 13.98 11.87 7.57 4.72 3.81 16.21 9.91 5.14 3.63 9.99 6.41 n.d
FH_N_9_1 42.7 30.85 32.23 18.51 19.15 8.68 7.75 4.29 2.24 n.d. 19.02 11.6 5.45 4.95 10.79 6.89 n.d
FH_N_9_2 29.07 20.82 20.51 12.53 10.22 5.49 4.37 2.64 1.73 1.17 7.12 4.36 2.3 1.89 4.13 2.25 n.d
FH_S_1_0 14.39 9.14 8.23 5.37 3.76 1.98 2.33 1.23 1.15 0.74 16.67 10.06 4.94 4.13 8.46 6.22 1.5
FH_S_11_1 16.67 11.49 10.75 7.44 4.64 2.59 2.42 1.4 0.94 0.97 8.57 4.24 2.29 2.04 4.04 2.41 1.38
FH_S_11_2 51.64 33.14 37.78 23.05 26.54 11.31 10.02 6.54 4.92 5.78 16.41 10.84 4.47 6.59 10.36 6.62 n.d
FH_S_2_1 21.15 13.76 13.33 9.44 5.19 3.02 2.68 1.68 1.31 1.1 11.83 9.27 4.17 4.08 6.99 4.54 1.69
FH_S_6_1 18.96 13.17 10.49 7.44 5.39 2.58 2.82 1.65 1.72 0.79 16.11 10.56 6.22 4.71 8.02 6.93 2.07
FH_S_8_1 24.17 17.07 16.63 10.14 6.82 3.64 3.07 2.13 2.19 2.26 18 10.88 5.67 5.07 9.4 5.75 1.96
*TR19 = tricyclic terpanes C19; TR20 = tricyclic terpanes C20; TR21 = tricyclic terpanes C21; TR22 = tricyclic terpanes C22; TR23 = tricyclic terpanes C23; TR24 = tricyclic terpanes C24; TS = 22, 29, 30-trisnorneohopane; TM = 22, 29, 30-
trisnorhopane; H29 = hopane C29; M29 = moretane C29; OL = oleanane; H30 = hopane C30; M30 = moretane C30; H31S = C3117α,21β(H)-22Shomohopanes; H31R = C31 17α,21β(H)-22Rhomohopanes; H32S = C32 17α,21β(H)-
22Shomohopanes; H32R = C32 17α,21β(H)-22Rhomohopanes; H33S = C3317α,21β(H)-22Shomohopanes; H33R = C3317α,21β(H)-22Rhomohopanes; H34S = C3417α,21β(H)-22Shomohopanes; H34R = C34 17α,21β(H)-
22Rhomohopanes; H35S = C3517α,21β(H)-22Shomohopanes; H35R = C3517α,21β(H)-22Rhomohopanes; D27baS = 13β(H)17α(H)20S-cholestane (diasterane); D27baR = 13β(H)17α(H)20R-cholestane (diasterane); D27abS = 13α(H)
17β(H)20S-cholestane (diasterane); D27abR = 13α(H)17β(H)20R-cholestane (diasterane); D27baS9 = 13β(H)17α (H)20S-cholestane (diasterane) from m/z 259 mass fragmentogram; D27baR9 = 13 β (H)17 α (H)20R-cholestane (diaster-
ane) from m/z 259 mass fragmentogram; TPP/Dias = Terpanes poliprenoids/Diasteranes; n.d. = not detected.
vascular plants and angiosperm precursors, respec- Biodegradation of the marine oils, especially
tively (Peters et al., 2005). In the marine oils, C23 is from the south portion of the foreland, is suggested
the dominant compound among the low molecular- by several biomarkers. An increase in oil biode-
weight tricyclic terpanes, whereas the oleanane index gradation intensity is accompanied by an increase
below 0.2 indicates more of marine algal than terrig- in 22, 29, 30 trisnorneohopane (Ts)/22, 29, 30-
enous input. The tricyclics/steranes ratio also reflects trisnorhopane (Tm), diasteranes/steranes, and homo-
a dominance of terrigenous input in the oil samples hopane indices, as well as in the moretanes/hopanes
from the foothills. This ratio compares tricyclics, and C28 ∕C29 hopanes ratios. In contrast, the TPP/
which are related to algal or bacterial lipids, with ster- diasteranes and the C27 ∕C29 steranes ratios decrease
anes which typify marine organic matter with a major with biodegradation (Table 3). Most of these geo-
contribution of planktonic and/or benthonic algae chemical parameters are normally used as indicators
(Moldowan et al., 1985). of the source or maturity of the oil. However, in this
The tetracyclic polyprenoids (TPP)/diasteranes dataset, the variations of these biomarkers ratios
ratio and the homohopane index also corroborate the are strongly related to biodegradation intensity. This
more terrigenous nature of the oil samples from the is also evidenced by physical properties, such as
foothills (Figure 12). Higher relative concentrations low API gravity and high proportions of NSO-
of C30 TPP in foothills oils indicate lacustrine or shal- compounds, as well as by specific biodegradation
low marine conditions (Holba et al., 2003), because indicators such as the significant concentrations of
they seem to originate from precursors of freshwater C29 25-norhopanes (Peters et al., 2005).
algae (Peters et al., 2005). In contrast, the foreland oils As an additional tool for oil correlation, the iso-
show higher homohopane ratios, which indicate highly topic signatures of the n-paraffins were measured in
reducing marine conditions (Peters et al., 2005). samples of the two proposed oil families and in one
Relative proportions of C27 , C28 , and C29 ster- additional sample representing biodegraded marine
anes are frequently used to indicate the type of oils (Figure 15). Terrigenous and marine oils are iso-
organic matter input (Peters et al., 2005). The relative topically different only in the range of the low
dominance of the C27 homologs in oils from the molecular-weight n-paraffins (C17 –C23 ). The terrig-
foreland (Figure 11) suggests that they originate enous oils usually show heavier carbon isotope ratios
from marine source rocks. This parameter must be (slightly more than 2‰ in the C20 n-alkane).
used with caution as it is typically affected by In the biodegraded sample, the remaining n-
biodegradation. alkanes are isotopically heavier (up to 2‰) than the
Biodegradation seems to increase the original nonbiodegraded marine oils (Figure 15). This could
isotopic signature (δ13 C) of the oils, because the low be because of the effect of biodegradation on the iso-
API gravities correlate with the selective preservation topic signature of the oils, as already observed in the
of the 13 C-enriched fraction in oils (Figure 13). whole-oil isotopic values (Figure 13). Alternatively,
However, it was not possible to assess the effect of the heavier isotopic signature of this sample could
biodegradation alone, because the overall carbon iso- be explained by mixing with oils generated by
topic range of the oils is around 2.5‰ and includes another source rock (not identified in this study).
the combined effects of source, maturity, and biodeg- Even if the conclusion regarding the isotopic sig-
radation (Figure 13). nature of the n-alkanes is speculative and difficult to
Biodegradation is also evidenced by a depletion support without further analyses, we present it as an
of n-paraffins in the gas-chromatograms of additional tool to identify the origin and the effect of
the marine oils, as well as by the presence of C29 alteration process on the oil samples.
25-norhopane (Peters et al., 2005) in oils from the Biodegradation has complicated the source iden-
southern part of the foreland and the southern tification and the maturity assessment of the oils in
foothills. The more biodegraded oils show a larger the study area because of its effects on biomarker
unresolved complex mixture or “hump” on the gas- ratios (Dzou et al., 1999) and because biodegradation
chromatogram (Figure 14). induces a relative increase in the diamondoid
GARCIA ET AL. 1525

Figure 11. (A) Gas chromatogram fingerprints of oil samples from foothill and foreland oil fields. More marine oils (right) show a
unimodal distribution of the n-alkanes, whereas terrigenous oils (left) show a bimodal distribution. Loss of light compounds may
reinforce the unimodal distribution of normal alkanes in the marine oils. (B) Terrigenous oils can be distinguished from the marine-
derived oils by ratios such as C23 ∕C19 tricyclic terpanes, total tricyclics/total steranes, and tetracyclic polyprenoids (TPP)/diasteranes,
as well as by the homohopane and oleanane indices in the gas chromatograph–mass spectrometer (GC-MS) m∕z 191. These two oils
show differences in the steranes trend, as well as in the TPP and diasteranes concentrations (GC-MS m∕z 217 and 259, respectively,
shown in C and D). TPP compounds are considered specific biomarkers for lacustrine organic matter. Diasteranes are rearranged ster-
anes, which are useful to distinguish clay-rich source rocks (Peters et al., 2005).
concentrations, as demonstrated by Springer et al. co-occur in samples from the southern foothills.
(2010), thus preventing estimates of the extent of sec- This geochemical signature suggests mixing of
ondary cracking (Dahl et al., 1999). previously biodegraded oils with light oils arriving
Mixing of oils seems to be a pervasive process in in a second charge (Volkman et al., 1983).
the study area, which is demonstrated by geochemical 2. High concentrations of both C29 stigmastane and
3- and 4-methyldiamantanes occur in samples
characteristics such as the following.
from the western foreland. Similar trends were
1. Significant concentrations of C29 25-norhopanes interpreted by Springer et al. (2010) as the result
(which indicate intense biodegradation) and abun- of mixing of low-maturity oils with very mature
dant low-molecular-weight n-alkane compounds light oils (condensates) that migrated from a deep
highly susceptible to biodegradation (Figure 16) source.

Figure 11. Continued.
Even though alteration processes prevent detailed properties follow a geographical trend that is related
assessment of thermal maturity in the study area, we to the structural domain of the traps, the current depth
can infer that the terrigenous oils come from a very of the reservoirs, and the geochemical signature of the
mature source responsible for most of the gas and oils. This relationship allows us to propose a regional
light oils accumulated mainly in oil fields of the foot- petroleum charge model, based on geochemical inter-
hills. Marine oils have lower maturity as indicated by pretation and the basin history. This model could
the low concentration of diamondoids when not improve prediction of petroleum behavior in unex-
extensively biodegraded (Springer et al., 2010). plored areas of the basin by comparing the target sec-
tor with analogs in the studied area.
The petroleum accumulations in the study area
DISCUSSION originated from multiple pods of two different source
rocks. One mostly marine (type II organic matter)
Observed differences in petroleum behavior in the source rock provided the petroleum trapped mainly
study area of the Llanos basin are mainly because of in the foreland and the southern foothill regions.
the varying proportion of gas in the fluids (affecting Reservoirs in the central and northern foothills were
GOR, Psat, and Bo values) and the composition of filled with petroleum from a more terrigenous source
the liquid phase (API gravity). These physical rock (Figure 12).
GARCIA ET AL. 1527

Figure 12. Plot of selected biomarker ratios (tricyclics, oleanane, tetracyclic polyprenoids (TPP), diasteranes and homohopanes),
showing differences between marine- and terrigenous-sourced oils. Oleanane and TPP are thought to be higher plant- and freshwater
algae-markers, respectively, whereas C23 tricyclic and homohopanes are related to algae or bacteria deposited in reducing marine envi-
ronments. FE-N = eastern foreland north; FC-N = central foreland north; FW-N = western foreland north; FE-S = eastern foreland
south; FC-S = central foreland south; FW-S = western foreland south; FH-N = northern foothills; FH-C = central foothills; FH-S =
southern foothills.
Because no marine source rocks have been were later eroded during the Andean orogeny
clearly identified east of the Guaicaramo fault (Garcia, 2008). Thus, the charge of marine oils must
immediately underneath the oil field (Figures 1, 2), have occurred before the onset of the Eastern
the most likely source for the oils produced in the Cordillera uplift, during the late Oligocene and early
foreland consists of Upper Cretaceous (Turonian) Miocene (Mora et al., 2010). Migration of the petro-
marine shales (La Luna and Chipaque Formations). leum took place along laterally continuous
For a discussion of the attributes of this source rock, Cretaceous and Paleogene sandstones, covering long
the reader is referred to Rangel et al. (2000) and distances from the paleo-pods to shallow reservoirs
Ramon et al. (2001). These marine shales crop out located to the east. The charge from paleopods was
in the Cordillera Oriental, where they are thermally interrupted because of deactivation of the petroleum
overmature due to burial induced by the accumula- kitchens as a result of uplift and concomitant erosion,
tion of thick sequences of Paleogene rocks, which which removed the source rocks and younger

Figure 13. Isotopic signature of the
oils (δ13 C). Biodegradation increases
the original values in the marine fore-
land samples. In the foothills, mature
oils have a lighter isotopic signature.
FE-N = eastern foreland north; FC-N =
central foreland north; FW-N =
western foreland north; FE-S = eastern
foreland south; FC-S = central foreland
south; FW-S = western foreland south;
FH-N = northern foothills; FH-C =
central foothills; FH-S = southern
foothills.
sequences during basin inversion related to the area, where no evidence of biodegradation was
Andean Orogeny. observed.
Petroleum from the initial Oligocene charge has Assuming that all reservoirs in the foreland were
undergone varying degrees of biodegradation, which filled by the same Oligocene petroleum charge,
ultimately control API gravities. The highest levels observed differences in biodegradation are related to
of biodegradation were observed in samples from the temperature evolution and filling histories of the
the southwestern sector of the foreland (<25° reservoirs. The study area was presumably tilted to
API and greater relative concentration of C29 the northwest during petroleum charge (Hermeston
25-norhopane). The intensity of biodegradation and Nemcok, 2013), and the reservoirs in the
decreases toward the northeastern part of the study southern area were in shallower and cooler conditions
Figure 14. Gas chromatography of marine-sourced oils. A larger unresolved complex mixture and depletion of n-paraffins and isopre-
noids are geochemical indicators of intense biodegradation in the study area.
GARCIA ET AL. 1529

Figure 15. Carbon
isotopic signature of
n-alkanes in three
selected samples.
This trend can be used
as an indicator of an oil’s
origin and extent of
biodegradation.
than those in the northern area. Longer residence thermally overmature fluids such as the gases and
times of the oils in reservoirs with temperatures lower condensates in the northern foothills. On the other
than 80°C (176°F) progressively increased the extent hand, Hermeston and Nemcok (2013) showed the
of biodegradation toward the southern part of the shifting of the foreland depocenter to the north, from
basin. the early Miocene to the present, as response to the
Biodegradation stopped when reservoirs in the oblique convergence between the Eastern Cordillera
western foreland and foothills reached temperatures and the Llanos foreland basin. In these areas, terrig-
above 80°C (176°F) as they became buried under enous source rocks underwent maximum sedimentary
the Miocene and Pliocene molasse or the fold belt, loading, reaching thermal maturity and eventually
respectively (Figure 17). Thicker stratigraphic units contributing to the last pulse of petroleum charge.
were accumulated in the western portion of the fore- These light fluids were likely expelled during the
land as the result of increased flexural subsidence in last 5 m.y., and the main mechanism of migration was
the foredeep of the basin. These geologic and charge vertical flow along faults and fractures. Although
histories explain why reservoirs containing heavier most of the gas was trapped in oil fields close to the
oils are currently found at greater depths. petroleum generation pods (foothills), some of this
The second oil type was primarily trapped in oil gas seems to be present throughout the basin, in
fields in the central and northern foothills. decreasing proportions toward the east.
Biomarkers and isotopic signatures of these fluids, Light oils, or the liquid phase of the latter charge,
as well as their high GORs, suggest that they were reached reservoirs in the western part of the foreland
generated by highly mature source rocks containing and possibly mixed with the previously trapped fluids
more proximal organic facies (mostly terrigenous in some areas. Light oils and gases improved the
type III kerogen). physical properties of oils related to the previous
Upper Cretaceous Gachetá Formation and pos- petroleum charge, especially to the south, where bio-
sible Paleogene source rocks (Dzou et al., 1999) that degradation played a more important role on these
underwent maximum structural loading and were earlier trapped fluids.
buried beneath the foothills deformation zone could One of the main exploratory implications of the
have reached temperatures high enough to yield proposed model is that traps containing marine oils

Figure 16. Sample showing simultaneous occurrence of C29 25-norhopane in the GC-MS (gas chromatography-mass spectrometer)
m∕z 191 and low-molecular-weight n-paraffins in the GC fingerprint. This characteristic indicates that the original oil was biodegraded
and refreshed later on. GC-WO = gas chromatography-whole oil.
were charged in the pre-Andean deformation stage. history were done on the basis of a detailed burial his-
This implies that the migration pattern and the fetch tory of the reservoirs. The longer the reservoirs
areas for those fluids should be assessed by means remained at low temperatures after charge, the higher
of structural reconstructions of the reservoirs during the extent of biodegradation.
the charge time. The original (prebiodegradation) Most of the traps containing marine oils in the
density of the marine oils (API gravities) could also Llanos foreland are associated with normal faults.
be estimated if a reconstruction of the temperature Delgado et al. (2012) argued that this faulting was
GARCIA ET AL. 1531

Figure 17. The extent of biodegradation depends on the time elapsed between trap filling and when the reservoirs were buried
deeply enough to reach temperatures over 80°C (176°F). Labeled lines in the figure represent the simulated reservoir temperature
for three modeled wells. Oils in the southern part of the study area (sector 2) were exposed longer to biodegradation conditions, as indi-
cated by the arrows‘ extension. Oils in sector 3 also were strongly biodegraded, but they receive a late charge of light oils (from terrig-
enous sources), increasing the API gravities and the GOR of these fluids. Map shows the location of the modeled wells in the foreland.
FW-N = western foreland north; FC-N = central foreland north; FE-N = eastern foreland north; FE-S = eastern foreland south; FC-S =
central foreland south; FW-S = western foreland south.
caused by the late Oligocene–early Miocene onset of kitchens of marine source rocks, thereby ending
thrust-induced denudation of the eastern flank of the the first expulsion phase. Biodegradation of marine
Eastern cordillera. During the mid-Miocene and oils in Eocene to early Miocene reservoirs, which at
Pliocene, the advance of the deformation front into current depth and temperature are out of biodegra-
the foothills and the orogenic loading on the basin dation zone, also suggests that such reservoirs were
enhanced the flexure and caused further normal charged before most of the Miocene sedimentation.
faulting. Subsequently, the complex deformation history
The current trap distribution and geometric of the basin (Delgado et al., 2012; Hermeston and
configuration was likely reached during the Nemcok, 2013; Silva et al., 2013) may explain the
Pliocene toward the end of the complex deforma- active process of petroleum mixing and trap
tion history of the basin. Charge of these traps with reconfiguration.
marine oils must have happened before the onset of High GOR, Psat, and Bo values can be expected
the Eastern Cordillera uplift, which fossilized the in traps formed during basin inversion (after the late

Oligocene), which should be mainly filled by petro- The amount of late gas-rich terrigenous petroleum
leum from the late charge. Earlier marine-derived oils contribution is also a factor, which in turn is con-
could have their physical properties enhanced when trolled by the distance from the local kitchens of ter-
mixed with terrigenous oil from the second charge. rigenous source rock. As a general rule, GOR values
The probability of oil mixing increases in the traps should decrease toward the eastern foreland and
located in the foothills and western foreland (i.e., near increase in the foothills.
the generation pods). The low content of hydrocarbon gases (undersa-
turated fluids with GOR values ranging from 1 to
CONCLUSIONS 10 m3 ∕m3 ½32 ft3 ∕ft3 ) in oil fields of the central and
eastern foreland areas could be associated with an ini-
Evaluation of physical properties of petroleum sam- tially low-gas expelled petroleum or, more likely, be
ples from oil fields in the Llanos basin, Colombia, the result of reduced pressure, separation of a gas
allowed us to propose criteria to distinguish oils from cap, and gas leakage from very shallow reservoirs
different origins and to identify alteration processes. (which were later buried to their current depth).
It should be possible to forecast the bulk properties Minor quantities of biogenic gas reached these reser-
of petroleum, such as gravity (API) and gas content voirs, accounting for the lightest carbon isotopic sig-
(GOR), in unexplored areas of the basin using the nature of methane.
proposed petroleum charge model, based on geo- Later deformation stages (in the last 5 m.y.),
chemical parameters and the geological evolution of related to the Andean uplift, modified the shape and
the basin. size of early traps and also created new traps, such
One of the main controls on the physical proper- as those formed in several structural wedges of the
ties of oils was the evolution of the oil kitchens, which thrust belt (northern foothill) and those formed in
is in turn closely linked to the complex deformation the foreland, associated with east-verging faults.
history of the Eastern Cordillera and Llanos basin. Additionally, the formation of the fold-and-thrust
By late Oligocene time, the eastern flank of the belt (foothills) allowed the establishment of oil kitch-
Eastern Cordillera was being exhumed (Mora et al., ens that were restricted to local areas of maximum
2010). This deformation event caused the uplift of structural loading where the more proximal (terrig-
Cretaceous marine source rocks, thus ending the first enous) facies of the Upper Cretaceous Gachetá
charge event. Subsequently, the more widespread Formation generated gas and light oils.
mountain building and orogenic advance caused sig- In most of the early traps, the thermally mature
nificant movement of foreland depocenters to the east hydrocarbons refreshed the previously biodegraded
(Silva et al., 2013). The shifting of the foreland depo- oils, enhancing the physical properties of the fluid
center to the north (Hermeston and Nemcok, 2013), (API and GOR). In the younger traps, located in the
controlled the spatial distribution and timing of the deformed belt (northern foothills), the second pulse
oil kitchens for the later petroleum charge pulse. remained unmixed and preserved from biodegrada-
Early deformation phases (Oligocene–early tion, resulting in the highest API and GOR values of
Miocene) resulted in the formation of large, low- the study area.
relief traps, along the basin. These traps were charged
by oil generated from Cretaceous marine shales of the
Chipaque Formation. Most of the reservoirs were
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Controls on petroleum AUTHORS

composition in the Llanos Diego Fernando Garcia Bautista ∼

basin, Colombia: Implications 37, #8-43, 7th Floor, Bogotá, Colombia;

for exploration Diego Fernando Garcia Bautista holds a B.Sc.

AAPG Bulletin, v. 99, no. 8 (August 2015), pp. 1503–1535 1503

• composition of the organic matter in the source rock and its

Petroleum expelled from source rocks containing types I or II

1504 Controls on Petroleum Composition

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1506 Controls on Petroleum Composition

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1510 Controls on Petroleum Composition

Sample Depth Reservoir Saturation Oil Gravity

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Sample Depth Reservoir Saturation Oil Gravity

1512 Controls on Petroleum Composition

Sample Depth Reservoir Saturation Oil Gravity

Figure 6. Plot of satu-

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Figure 7. (A) Gas–oil

1514 Controls on Petroleum Composition

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Controls on Petroleum Composition

Gas Composition (mol%) Gas Isotopic Ratio (δ13 C, in ‰)

Controls on Petroleum Composition

Gas Composition (mol%) Gas Isotopic Ratio (δ13 C, in ‰)

Figure 8. (A) δ13 C

1520 Controls on Petroleum Composition

Figure 9. The δ13 C–C2

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1522 Controls on Petroleum Composition

Controls on Petroleum Composition

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1526 Controls on Petroleum Composition

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1528 Controls on Petroleum Composition

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1530 Controls on Petroleum Composition

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1532 Controls on Petroleum Composition

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1534 Controls on Petroleum Composition

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