Organic Geochemistry 42 (2011) 727738

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

The organic geochemistry of oil seeps from the Sierra de Perij eastern foothills,
Lake Maracaibo Basin, Venezuela
M. Escobar a,c,, G. Mrquez b, S. Inciarte c, J. Rojas c, I. Esteves d, G. Malandrino c
a

CARBOZULIA, Av. 2 No. 55-185, Casa Mene Grande, Maracaibo 4002 A, Venezuela
Departamento de Ingeniera Minera, Mecnica y Energtica, Escuela Tcnica Superior de Ingeniera, Universidad de Huelva, 21819 Huelva, Spain
c
Postgrado de Geologa Petrolera, Facultad de Ingeniera, Universidad del Zulia, Maracaibo 4002, Venezuela
d
INZIT, Km. 15 va La Caada, sector Palmarejo Viejo, Maracaibo 1114, Venezuela
b

a r t i c l e

i n f o

Article history:
Received 25 February 2011
Received in revised form 19 May 2011
Accepted 7 June 2011
Available online 13 June 2011

a b s t r a c t
The organic geochemistry of samples from 11 oil seeps was studied. The samples were collected from the
Cachir area, Carboniferous Region of Tul (Lake Maracaibo Basin, Venezuela), associated with the Tigre
Fault. Biomarkers (hopanes, steranes, n-alkanes, acyclic isoprenoids, and aromatic steroids) were analyzed using gas chromatography-mass spectrometry (GC-MS). These hydrocarbon rich uids have undergone biodegradation (26 on the Peters and Moldowan scale), showing both the partial loss of n-alkanes
and the microbial degradation of isoprenoids and steranes. These oil seeps were generated from a mature
calcareous source rock that was deposited in a marine paleoenvironment under reducing conditions.
Moreover, these seeps are likely derived from the Cretaceous La Luna Formation that reached a level
of maturity near the peak of oil generation in the study area. The nature of the studied oil seeps, together
with the oil generation models reported for this rock unit in the study area, suggests that these oils are a
mixture of an initially heavy, altered oil and a second migrated light crude oil resulting from two generation pulses from the La Luna Formation. Evidence for the presence of light oil trapped in the study area
should prompt re-exploration in the northwestern coast of Lake Maracaibo in shallow reservoirs, previously discarded because they usually demonstrated a lack of light oils.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Although the relationship between petroleum migration and
seep occurrence is complex (Abrams, 2005), oil seeps can be used
to provide evidence of a viable petroleum system and critical information about the nature of the source rock, its maturity and the
migration of hydrocarbons in sedimentary basins (e.g., Rogers
et al., 1999; Abrams et al., 2001). Sutton (1946) reported numerous
oil seeps, gas emissions and asphalt deposits along the western
ank of Lake Maracaibo Basin (Zulia State). Some of these are very
close to the Tigre Fault and occur along a line paralleling the fault
in the foothills of the Sierra de Perij, western Venezuela (Link,
1952; Miller, 1962; Gallango et al., 2002; Fig. 1a). The author focused on the oil seeps from Inciarte, an area of 0.12 km2 covered
by asphalt lagoons in the southern part of Mara municipality and
on La Paz (current La Paz oileld, some 0.06 km2 in area). In fact,
these seeps were a guide to the discovery of the La Paz and La Concepcin oilelds by the Royal Dutch Shell Group in 1925 (Sutton,
1946).

Corresponding author at: CARBOZULIA, Av. 2 No. 55-185, Casa Mene Grande,
Maracaibo 4002 A, Venezuela. Tel./fax: +58 4143603496.
E-mail address: escomar24@gmail.com (M. Escobar).
0146-6380/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.orggeochem.2011.06.005

The Lake Maracaibo Basin (containing 700 oil producing elds

after drilling about 16,500 wells) covers an area of approximately
50,000 km2 (19,300 mi2). The main petroleum source rock is the
Cretaceous La Luna Formation, although other source rocks also
generated hydrocarbons (Talukdar et al., 1985, 1986; Tocco et al.,
1997).
Seeps discovered between the 1900s and the 1930s led to the
discovery well that generally produced asphaltic (<10 API gravity)
to heavy (1020 API) crude oils (Table 1; Stalder, 1981). Exceptions are parafnic crude oils from the Amana Field (Amana-1
and -7 wells, Fig. 1a). These light oils (around 40 API) display a
bimodal n-alkane distribution that are predominant over the
C12C20 and C25C33 intervals, as well as pristane (Pr) to phytane
(Ph) ratios of about 2.5 suggesting that they derived from an undetermined continental siliciclastic source rocks distinct from those
for the La Luna Formation in the northwestern coast of Lake Maracaibo (Escobar, 1987). This author applied McDowells model
(1975) to estimate that 91% of the total oil accumulated in this area
has been derived from the Cretaceous La Luna source rocks.
Escobar (1987) also reported that Miocene reservoir rocks produced high gravity (38 API) uids from the Peroc-1 and Pern-1
wells (Fig. 1a), which were briey reactivated in 1984. The phytane/n-C18 and pristane/n-C17 ratios of the oils are very low (0.3
and 0.2, respectively), suggesting that these crude oils originated

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M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

Fig. 1. (a) Location of the wells and oilelds known in the northwestern part of the State of Zulia until 1946, as well as the seeps from the Sierra de Perij foothills; (b) map of
the Tul Region; (c) Stratotype in the Cachir area.

Table 1
General characteristics of the oil wells drilled in the Sierra de Perij foothills.
Well

Year

Depth (ft)

API gravity ()

Reservoir formation

Amana-1
Marem-1
Amboy-1
Vermor-1
Calentura-1
Len-1
Peroc-1
Pern-1
Zancada-1
Neopam-1
Neopod-1

1926
1930
1928
1928
1929
1929
1927
1929
1918
1930
1929

4184
6002
5316
5364
6743
1619
5600
3233
2235
6412
7504

32
19
510
1020
10
510
1020
17
510
15
720

Lower Misoa (C-5)

Misoa and Marcelina
Lower Misoa
Mito Jun
Cogollo
Granite Basement
Cogollo
La Quinta
Socuy
Guasare
Icotea

from a high maturity source rock. However, the low saturated

hydrocarbon proportions (29.4%) and relatively high concentrations in resins plus asphaltenes (45.5%) obtained for these crudes
are not consistent with high maturation (Tissot and Welte, 1984).
The origin of this light crude oil, in an area where the API gravity
of the petroleum generally ranges from 1825 (Hawkins and Chigne, 1982), has not been clearly established. A possible explanation
for these discrepancies may be that the heavy crude originally pro-

duced in these wells mixed with a lighter oil that migrated into the
reservoir after the wells were shut in and reached sufcient pressure in the reservoir rock to once more produce by natural ow.
Conduits for secondary migration can be set up when source rocks
are juxtaposed against horizons with higher permeabilities (e.g.,
sandstones) at faulting areas and other discontinuities (Miles
et al., 1993). However, the faults served in many cases as vertical
migration paths to allow hydrocarbon migration from the Cretaceous La Luna source rocks into the Eocene and Miocene sequences
(Talukdar et al., 1986; Escalona and Mann, 2006).
These circumstances have engendered this work, which reviews
the organic chemical signature of the 11 oil seeps in the Cachir
area (Fig. 1b) in order to correlate these seepage oils with the La
Luna Formation rocks in the northwestern coast of Lake Maracaibo
and to establish their relative degree of biodegradation and their
thermal maturity. Specically, the study examines the hypothesis
that the study area produced heavy crude oils in the early 20th
century and that these oils mixed with other lighter crude oils
years later, indicating that crudes that had reached advanced
stages of thermal maturity may have migrated to this part of the
Lake Maracaibo Basin in the past. This information is of great inter-

M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

est for oil companies, which can conduct exploratory surveys to

discover commercial oil accumulations at shallow stratigraphic
levels of the Tul Carboniferous Region.
2. Geological setting
The Lake Maracaibo Basin is located on the southwestern edge
of the Caribbean Sea in western Venezuela near its border with
Colombia. Parnaud et al. (1995) divided the stratigraphic column
of this basin into ve sequences based on tectonic events: (1) a
Jurassic rift sequence, (2) an EarlyLate Cretaceous passive margin
succession, (3) the transition to a compressive regime in the Late
CretaceousEarly Paleocene deposits when collision and obduction
of the Pacic volcanic arc overrode the South American plate and
emplaced the Lara Nappes, (4) Late PaleoceneMiddle Eocene foreland basin in front of the volcanic arc and emplacement of the Lara
Nappes, and (5) a Late EocenePleistocene sequence related to the
collision of the Panama arc with the South American plate.
The geology of the Sierra de Perij has been previously studied
(Sutton, 1946; Gonzlez de Juana et al., 1980; Kellogg, 1981;
Audemard, 1991; Lugo and Mann, 1995; Taboada et al., 2000;
Duerto et al., 2006; Guzman and Fisher, 2006; Mann et al., 2006;
James, 2009; Escalona and Mann, 2011; among others). Uplift of
the Perij Mountains occurred in the Oligocene; this orogenesis
culminates in the Plio-Pleistocene (Kellogg, 1984). According to
Miller (1962), the Sierra de Perij forms a part of the complex
branching northern Andes chain located at the west margin of Venezuela as a northward offshoot from the Eastern Cordillera of
Colombia. At approximately 9N latitude, there is a change in trend
from N20W, prevalent in the northern part of the Eastern Cordillera, to N25E for the Sierra de Perij. From this point, the Sierra
continues to a northern boundary at the edge of the Guajira Plains
at latitude 11100 N. Along its entire length, its crest forms the
international boundary between Venezuela and Colombia.
The main fractures associated with the Sierra de Perij fold belt
at the Lake Maracaibo Basin in the study area include the Tigre,
Perij, and Cuiba sinistral transcurrent faults (Gonzlez de Juana
et al., 1980). These faults are orientated approximately N60E
and may have originated along normal fault trends in the rifted
Jurassic South America-African margin (Lugo and Mann, 1995).
The Manuelote Syncline also is a well known fold in the area and
its axial plane shares traits with the trend of the Tigre Fault (Miller,
1962; Pindell et al., 1998).
This fault is a straight, high angle fault trending N35E along the
northwestern side of the Totumo-Inciarte anticline. It was classied as a left lateral transcurrent fault (Rod, 1956; Alberding,
1957). In the structural section of the Cachir River and the Aljibe
marsh creek, the Tigre Fault is evident at four points, dipping
85S. At some sites along the course of the Cachir River, the Tigre
Fault juxtaposes Tertiary rocks represented by the Paleocene
Marcelina Formation with Cretaceous rocks represented by Cogollo
Group limestones (Fig. 1c). At these locations, there is a huge number of hydrocarbon seeps along the plane of the fault, associated
with a zone of fractures and variations in the dip of the strata
planes (Duerto et al., 2006). This evidence accounts for the seeps
in the peneplain of the Cachir River, associated with the Tigre
Fault and its transverse fractures (Rojas, 2008). In addition, the
study area contains transverse faults that juxtapose rocks from
the Marcelina Formation with rocks from the Misoa Formation,
both impregnated with hydrocarbons (Sutton, 1946).
3. Materials and methods
Eleven seep samples (OS-1 to OS-11) were collected in the Cachir area (Fig. 2) and stored in glass jars prior to analysis. These

729

samples were collected from the bottom of the respective surface

accumulations, where uids seep out of the rocks, and therefore
were taken from what appeared to be the most recently released
material. The oil seep samples were dehydrated with warm toluene (ASTM D1796 standard method; American Society for Testing
and Materials, 2004).
An aliquot of approximately 0.05 g of each oil seep was separated into its constituent fractions (SARA method) using conventional procedures. Briey, asphaltenes were precipitated with nheptane in a 1:40 v:v ratio in accordance with the ASTM D3279
standard method (American Society for Testing and Materials,
2007); each sample was passed through a batch reactor in constant
agitation for 1 h at 60 C, followed by a 12 h inactive period
(Speight, 2007). Later, soluble remnants (maltenes) were separated
on activated alumina (Activity I, 80200 mesh) into saturated, aromatic and resin fractions by liquid adsorption chromatography (De
la Cruz et al., 1997).
The saturated and aromatic hydrocarbons were subsequently
analyzed using gas chromatography-mass spectrometry (Agilent
Technologies 6890 GC coupled to an Agilent 5973 Mass Detector).
An HP-5MS capillary column (30 m  0.25 mm, lm thickness
0.25 lm) was used. Oven temperature was programmed to run
from the initial temperature of 80 C (hold for 4 min) to 290 C at
4 C/min, then to 290 C for 20 min. Helium was used as carrier
gas with a ow rate of 2.4 ml/min. The gas chromatograph was
equipped with a splitless injector at 270 C. Ions at m/z 99, 177,
178, 184, 191, 192, 198, 217, 231 and 253 were scanned with a
dwell time of 0.1 s. The overall precision of the integrated peak
areas from reconstructed ion chromatograms is 13%.
Inductively coupled plasmaatomic emission spectroscopy
(ICPAES) was used for the quantitative analyses of vanadium
and nickel concentrations (using the ASTM D-5708 standard;
American Society for Testing and Materials, 2005) through a Perkin-Elmer Optima 3000 spectrometer. Sulfur contents were measured using a LECO S-144DR analyzer.

4. Results and discussion

4.1. Bulk geochemical data
The bulk, sulfur and trace metal (V, Ni) composition of the eleven oil seep samples is given in Table 2. Group type analyses (SARA
fractions expressed as weight percentage) indicate that the oil
seeps have a composition high in resins and asphaltenes (47
80%, average 63%), whereas the aromatic hydrocarbon fraction ranged from 627% (average 21%) and the saturates ranged between
4% and 29% (average 16%). These values are generally characteristic
of heavy crude oils subjected to microbial degradation (Tissot and
Welte, 1984).
Table 2 also shows sulfur, vanadium and nickel concentrations
for the samples analyzed. These values are typical of biodegraded
oils (Hunt, 1996). Despite the fact that these concentrations can
be inuenced by biodegradation or thermal maturity, the V/Ni ratios are similar due to the structural similarities among organometallic compounds that contain vanadium and nickel (Lewan, 1984).
Similar API gravities (1115), V (9001100 ppm) and Ni (95
105 ppm) concentrations, V/Ni ratios (10.611.2) as well as sulfur
contents (5.56.5%) for the seep samples are observed in crude oils
from nearby reservoirs, such as Eocene Boscn (Escobar and Pasquali, 1989), Eocene La Paz (Escobar et al., 1989b), Eocene Mara
and Cretaceous Mara Oeste (Lpez et al., 1995; Lpez and Lo Mnaco, 2004). These similarities could indicate that the petroleum
accumulated in these reservoirs and the petroleum seeping out
in the study area are very likely affected by similar alteration processes (Escobar, 1987). Moreover, high sulfur contents, V/Ni ratios

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M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

Fig. 2. Location of the study seeps in the Cachir area.

Table 2
Bulk geochemical, sulfur and trace metal data of the Cachir oil seep samples.
Sample

Latitude

Length

Saturates

Aromatics

Polars

V (ppm)

Ni (ppm)

V/Ni

S (wt%)

OS-01
OS-02
OS-03
OS-04
OS-05
OS-06
OS-07
OS-08
OS-09
OS-10
OS-11
Uncertainty

N1201989
N1201989
N1201698
N1201177
N1201023
N1200202
N1200032
N1199866
N1199691
N1199140
N1199328

E802000
E802000
E801835
E801518
E801568
E800805
E800650
E800490
E800466
E799594
E799930

4
22
29
27
8
21
15
17
14
9
7
3

27
6
25
22
25
26
22
25
25
22
13
3

69
72
47
51
67
53
64
59
61
69
80
3

953
931
925
945
980
954
853
990
984
1102
1058
1

86
85
85
89
92
89
79
90
88
104
100
1

11.1
10.9
10.9
10.6
10.6
10.7
10.8
11.0
11.2
10.6
10.6
0.1

5.41
5.47
5.41
5.52
5.72
5.33
5.64
5.61
5.60
6.36
5.90
0.01

Note: All crude oil fraction data are expressed in weight percentages.

and Ni concentrations in all the samples may indicate that the corresponding source rocks were deposited in a marine carbonate
environment under euxinic or very reducing conditions (Galarraga
et al., 2008). During deposition of carbonate facies, bacterial sulde
is not completely sequestered by iron and nickel ions will precipitate in metal suldes rather than form organometallic compounds
in contrast to stable vanadyl ions leading to high V/Ni ratios (Lewan, 1984; Lo Mnaco et al., 2007).
4.2. Organic matter source and depositional environment
Molecular parameters (pristane/phytane, dibenzothiophene/
phenanthrene, homohopane index, among others) for saturated
and aromatic fractions separated from the oil seep samples are
listed in Table 3. GCMS analyses (m/z 191) for terpane and sterane
(m/z 217) biomarkers are shown in Fig. 3 for three representative
samples, two signicantly biodegraded (OS-01 and OS-11) and a
third slightly degraded sample (OS-08).

The nearly identical terpenoid distribution of the samples from

the Tul region (Fig. 3a, b and g) indicates a common origin. The
similarity among the m/z 191 fragmentograms is corroborated by
the homohopane index values (Table 3), with an average of 0.16
and a relative standard deviation of 0.02, together with the predominance of C35 regular hopane over the C34 homolog in all oil
seeps (Fig. 3a, b and g). These results suggest marine input to the
organic matter deposited under highly reducing conditions (Peters
and Moldowan, 1991). There is a high abundance of the C23 tricyclic terpane with respect to the other tricyclic homologs (Fig. 3a, b
and g); consequently, the C24/C23 and C21/C23 tricyclic terpane ratios not exceeding 0.34 (Table 3) also are indicative of oil seeps
deriving from organic matter deposited in a carbonate marine
environment under reducing conditions (Waples and Machihara,
1991). Finally, the near absence of tetracyclic terpanes and the
similar values in the proportion of C30 hopane with respect to C23
tricyclic terpane (C30H/C23TT, Table 3) in the majority of the samples (average 1.65 and standard deviation of 0.64) also indicate a

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M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

Table 3
Geochemical indicators of source depositional environment for saturate and aromatic fractions in oil seep samples from the Tul Region.
Sample

C27/C29ST

C35/C31C35

C24/C23TT

C21/C23TT

Pr/Ph

C30H/C23TT

DBT/P

OS-01
OS-02
OS-03
OS-04
OS-05
OS-06
OS-07
OS-08
OS-09
OS-10
OS-11

0.31

1.01

0.71
1.30
1.19
1.18

0.15
0.14
0.17
0.15
0.15
0.18
0.12
0.16
0.17
0.19
0.13

0.30
0.29
0.25
0.27
0.26
0.22
0.24
0.24
0.26
0.26
0.24

0.21
0.18
0.20
0.23
0.22
0.22
0.22
0.19
0.21
0.20
0.22

0.47

0.81
0.72
0.60

0.72
0.47

0.94

2.33
1.50
2.17
1.17
1.22
1.38
2.84
1.56
1.27
1.38
1.32

1.32
1.36
1.35
1.37
1.31
1.40
1.35
1.44
1.42
1.38
1.30

Notes: C27/C29ST = C27-regular sterane/C29-regular sterane; C23/C24TT = C23-tricyclic terpane/C24-tricyclic terpane; C23/C21TT = C23-tricyclic terpane/C21-tricyclic terpane; DBT/
P = dibenzothiophene/phenanthene; and homopane index or C35/C31C35; C30H/C23TT = C30-hopane/C23-tricyclic terpane. Uncertainties of 0.02.

Fig. 3. (a), (c) and (h), respectively, m/z 191, m/z 217 and m/z 177 ion fragmentograms for the OS-08 sample; (g), (e) and (f), the same ion fragmentograms for the altered
OS-11 oil seep; (b) and (d), respectively, m/z 191 and m/z 217 ion fragmentograms showing hopanoid and sterane distributions for the OS-01oil seep.

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M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

single geochemical type were of oils. It is noteworthy that three oil

seeps (OS-01, 03 and 07) have C30H/C23TT values >2 (Table 3). We
could not nd any supporting evidence of different organic facies
in relation to the origin of these oil seeps (Hoffmann et al., 1984)
or different maturity levels (Sajg, 2000) among them. A slight
depletion of diterpanes with respect to triterpanes in experimentally water washed oils had been noted (Kuo, 1994). This could
be an alternative explanation to account for these anomalous results. Though the relative abundance of C27, C28 and C29 steranes
(ST) and the TT/ST ratio are used to determine the type of organic
matter (Huang and Meinschein, 1979), these molecular parameters
are dependent on the effects of biodegradation (Seifert and Moldowan, 1979). Only a few samples had been subjected to such severe
alteration that they contained no recognizable free steranes (OS02, OS-04, OS-5, and OS-11; see Fig. 3e). The steranes also are depleted in the OS-01 sample (see Fig. 3d). By contrast, the remaining
samples (Table 3) could indicate a marine input to the organic matter of the source rock (Volkman et al., 1998). Finally, the absence of
18a(H)-oleanane has been commonly reported in the marine
crudes of the Lake Maracaibo Basin (Talukdar et al., 1986; Alberdi
and Lpez, 2000).
Both the cross plot of dibenzothiophene/phenanthrene (DBT/P)
vs. the sulfur content and the relationship between C24/C23 and
C22/C21 tricyclic terpane ratios are used as a paleodepositionalenvironmental indicator of sedimentary rocks (Hughes et al.,
1995). The majority of the samples (OS-01, OS-04, OS-05, OS-06,
OS-08, OS-09, and OS-11) display DBT/P ratios greater than one,
sulfur contents of about six, Pr/Ph ratios <1 and C22/C21TT ratios
>1 (Fig. 4a, b and c), indicating that the source unit for these seeps
is lithologically a marine carbonate mixed with sulfur rich black
shales (Peters et al., 2005).
As shown in a representative m/z 184 + 198 fragmentogram
(see Fig. 5b), the methyldibenzothiophene distribution in the aromatic fraction shows a V pattern, with the rst-eluting isomer
(4-methyl) being largest and the last-eluting isomer (1-methyl)
next largest. The middle peak of the V pattern (2 + 3 methyl) is
the lowest peak. These features are typical of crudes deriving from
a carbonate marine source rock (Wang and Fingas, 1995). As stated
above, all data indicate that the oil seep samples are residual
hydrocarbons from oils that were generated from marine carbonate rocks deposited under reducing conditions that subsequently
migrated to the surface. All of the above corroborates the reports
of various authors (Hedberg, 1931; Sutton, 1946; Gonzlez de Juana et al., 1980; Escobar, 1987; Prez, 1991) that considered the
Cretaceous La Luna Formation from western Venezuela as the most
probable source rock of these oil seeps.
4.3. Thermal maturity
The review of m/z 99 representative mass fragmentograms
(samples OS-08 and OS-01) indicated that all the seep samples
have low n-alkane contents (see Fig. 6a and b). These hydrocarbon
rich uids have a Pr/Ph ratio consistently <1 (Table 3) despite the
fact that this value may have been affected (to a greater or lesser
degree) by biodegradation at several of the seeps (Peters et al.,
2005). Alkanes are the rst to be removed during early stages of
microbial degradation (Peters et al., 2005), and therefore the values
of maturity parameters based on these hydrocarbons could be the
result of biodegradation and not of generation from mature source
rocks.
Phenanthrene and methylphenanthrene homologs are present
in appreciable proportions in all the oil seep samples (m/z
178 + 192; Fig. 5a); their relative intensities provide three thermally sensitive parameters, methylphenanthrene indices and
methylphenanthrene ratio (see Table 4). The methylphenanthrene
indices, MPI-1 and MPI-2, are widely used as aromatic hydrocar-

Fig. 4. (a), (b) and (c), respectively, plots of DBT/P vs. S (%), C24/C23TT against C22/
C21TT and DBT/P vs. Pr/Ph for some of the studied seep oils.

bon based maturity parameters. MPI-1 and the methylphenanthrene ratio are often used in estimating the equivalent vitrinite
reectance value %Rc1 and %Rc2, respectively (Radke and Welte,
1983; Radke et al., 1984). However, MPI-1 and MPI-2 ratios may

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M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

Fig. 5. (a), (b) and (d), m/z 178 + 192, m/z 184 + 198, and m/z 231 ion fragmentograms for a representative sample (OS-01); (c), (e) and (f), m/z 253 ion fragmentogram for the
samples OS-01, OS-11 and OS-08. Notes: Alpha and beta represent 5a(H) and 5b(H) series; dia, R and S refer to monoaromatic diasteroid hydrocarbons, 20R and 20S isomers,
respectively.

Table 4
Molecular maturity parameters for the saturates and aromatics in natural hydrocarbon seep samples from the Tul Region.

Fig. 6. (a) and (b) m/z 99 ion fragmentograms showing n-alkane distribution for the
OS-08 and OS-01 samples.

be no longer valid above biodegradation degree 5 due to signicant

changes in relative abundance of the methylphenanthrene isomers
at advanced stages of biodegradation (Huang et al., 2004). Variations in the type of organic matter or lithology in the source rock
can affect methylphenanthrene ratios. Indeed, Cassani et al.
(1988b) noted that high MPI-1 and PP-1 corresponded with the
high carbonate content in La Luna source rocks.
Despite this drawback, both ratios have been used as indicators
for the maturity, although they must be interpreted with caution.
The MPI-1 and %Rc1 values calculated for the samples range from
0.860.95 and 0.920.94, respectively. Table 4 also gives the %Rc2
(range 0.961.03) values. In accordance with results in the litera-

Sample

Ts/(Ts + Tm)

% 22S

MA ratio

MPI-1

MPI-2

% R1

% R2

OS-01
OS-02
OS-03
OS-04
OS-05
OS-06
OS-07
OS-08
OS-09
OS-10
OS-11

0.71
0.78
0.69
0.75
0.78
0.68
0.68
0.65
0.70
0.74
0.75

61
57
61
64
60
60
58
63
57
60
60

0.62
0.64
0.51
0.53
0.48
0.42
0.53
0.50
0.58
0.56
0.44

0.87
0.94
0.89
0.95
0.96
0.91
0.90
0.89
0.92
0.93
0.86

0.94
1.00
0.95
0.98
1.01
0.96
0.95
0.99
0.94
0.98
0.97

0.92
0.96
0.93
0.96
0.96
0.94
0.94
0.93
0.96
0.96
0.92

0.98
1.00
0.96
1.00
0.99
0.96
0.96
1.03
0.96
0.97
1.02

Notes: % 22S or C31ab 22S/(22S + 22R) = 17a,21b(H)-29-homohopane ratio (%);

MPR = 2-MP/1-MP; MPI-1 = 1.5(2-MP + 3-MP)/(P + 1-MP + 9-MP); MPI-2 = 3(2MP)/(P + 1-MP + 9-MP);%Rc1 = 0.4 + 0.6MPI-1;%Rc2 = 0.94 + 0.99log MPR; Ts/Tm =
18a(H)-22,29,30 trisnorneohopane/17a(H)-22,29,30 trisnorhopane; MA ratio or
MA(I)/MA(I + II) = C21+22-monoaromatic
steroids/C21+22+27+28+29-monoaromatic
steroids. Uncertainties of 0.02, except % 22S (2%), % R1 and % R2 (0.1%).

ture (e.g., Akinlua et al., 2007), when comparing MPI-1 and MPI2 values, the latter are relatively higher. %Rc2 values also are
slightly high compared to %Rc1 values. These results all show a
similar maturation level of organic matter for all the samples:
around the peak oil generation of the oil window for type II kerogens (Tissot and Welte, 1984).
Several molecular parameters were obtained from the hopanoid
distributions (m/z 191) and from the monoaromatic steroid (m/z
253) characteristic signals (Figs. 3a, b, g, 5c, e and f). These data
permit the determination of the level of thermal maturation of
the source rocks that generated these oil seeps, which are related

734

M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

to thermally mature light crudes. Additionally, the cracking ratio

MA(I)/MA(I + II) can be used to determine the level of maturity
reached by organic matter (Seifert and Moldowan, 1978; El-Gayar,
2005); MA(I) and MA(II) are dened as the whole content of C21
plus C22 monoaromatic steroids and the sum of all C27C29 compounds, respectively (Peters et al., 2005). The values on the order
of 5060% (Table 4) are indicative of materials generated from kerogens covering a maturity range around the maximum peak oil
generation of the oil window (Tissot and Welte, 1984). Unfortunately, the presence of numerous unresolved humps (Fig. 5d) made
it impossible to use C27C29 triaromatic steroids (m/z 231) to corroborate the maturity level of the organic matter for the samples.
This might be due to contamination with unknown products.
The predominance of 18a(H)-22,29,30 trisnorneohopane over
17a(H)-22,29,30 trisnorhopane (Table 3) [Ts/(Ts + Tm)] exceeding
0.65 and a low standard deviation of 0.2 conrms that the source
rocks which generated the oil seeps were thermally mature (Seifert
and Moldowan, 1981). The 22S hopane percentages (see Table 4)
for the samples (averaging 60%, standard deviation of 2.7%) indicate maturity of the precursor organic matter (Seifert and Moldowan, 1978). The diagram for MA(I)/MA(I + II) vs. Ts/(Ts + Tm)
shows that all oil seeps plot in the mature eld (Fig. 7).
4.4. Biodegradation of oil seeps
Thermal maturity and source determination of organic matter
in oil seeps can be problematic since n-alkanes, isoprenoids, steranes and the remaining biomarkers can be affected by geochemical
processes such as biodegradation (Bennett and Larter, 2008). Indeed, several common molecular parameters are not suitable for
establishing the thermal maturation of organic matter in the oil
seeps studied since these ratios may be altered by microbial degradation. Table 5 provides information on its current state of preservation for each biomarker family and establishes its level of
alteration according to the biomarker biodegradation scale proposed by Peters et al. (2005). Representative ion chromatograms
are shown in Fig. 3 (peak identications of terpanes and steranes
are in the Appendix). The partial absence of n-alkanes in several
seep samples (OS-01, OS-05, OS-06, OS-08, OS-09, and OS-11) indicates a level 2 for biodegradation (Peters et al., 2005). The remaining samples are ranked at biodegradation degree 3, which means
that they have a near total absence of n-alkanes (Peters et al.,
2005). By contrast, no sample is ranked at biodegradation degree
5, dened by the total absence of acyclic isoprenoids (Peters
et al., 2005). In some of the samples (OS-01, OS-02, OS-04, OS-05,

Fig. 7. Correlation of thermal maturation parameters based on MA(I)/MA(I + II) and

Ts/(Ts + Tm) ratios.

OS-10, and OS-11), regular steranes are partially or totally depleted

(biodegradation degree 6 or higher, see Fig. 3e), whereas the low
presence of the 25-norhopanes (10-demethylhopanes) in these
six samples is consistent with a severe process of microbial degradation (Bennett et al., 2006). The 25-norhopane biomarkers appear
to result from the alteration of the C10 methyl group in the regular
hopanes and are easily detected in a representative m/z 177 fragmentogram (OS-11 sample; see Fig. 3f). Nevertheless, these biomarkers are absent in four samples (OS-03, OS-07, OS-08 and OS09, see Fig. 3h). In addition, none of these oil seeps range between
biodegradation degrees 8 and 9, showing evidence of a very slight
alteration of hopanes. Finally, monoaromatic steroids appear intact
in all the samples, which suggests that none of them reaches degree 10.
It should be noted in Table 5 that eight of the 11 samples (all
except for OS-06, OS-08, and OS-09) show various non-correlative
and very distinctive degrees of biodegradation. Various scales of
biodegradation ranked according to a common alteration sequence
for each of a series of biomarker families with different resistances
to microbial degradation (e.g., Wenger et al., 2002; Peters et al.,
2005). Nevertheless, exceptionally there are modications in the
usual order of the sequence (Larter et al., 2003). Additionally, there
are scarcely any cases in which bacteria have been able to degrade
only n-alkanes and steranes, as is observed in these oil seeps.
While there have been a few studies dealing with oil seeps from
nearby areas and affected by very heterogeneous degrees of biodegradation (Bojesen-Koefoed et al., 2005; Snchez and Permanyer, 2006), we are aware of few previous studies that have
reported the occurrence of any oil seep affected simultaneously
by very distinctive and uncorrelated degrees of biodegradation
(e.g., Cassani et al., 1988a).
Although we cannot preclude other possibilities to account for
this anomalous pattern, the most probable explanation consists
of the dilution of an initial heavy crude that was severely degraded
near the surface with a second, thermally mature light oil affected
by slight biodegradation and then the subsequent migration of this
mixture to the surface. This would account for the heterogeneous
degrees of biodegradation observed in most of the samples. The
aforementioned light crude was not detected in the exploratory
drilling programs in the early part of the 20th century in this part
of the Maracaibo Basin (Table 1 and Fig. 1), suggesting it might
have migrated more recently. This migration may have occurred
as a result of the movement of petroleum trapped in deeper stratigraphic levels through migration paths (e.g., faults) that were reactivated by very recent tectonics. Alternatively, this petroleum may
have been generated and expelled extremely recently from La Luna
Formation source rocks. The thermal evolution models of this unit
that have been reported (Blaser and White, 1984; Talukdar and
Marcano, 1994), together with evidence of the primary petroleum
migration established based on calcareous La Luna rock cores collected from some wells (Escobar et al., 1989a), suggest that the La
Luna Formation might currently be generating petroleum in the
north-central region of the western shoreline of Maracaibo Lake
(Escobar, 1987). A third permutation of this hypothesis also presumes the existence of two oil pulses: a rst oil charge would have
been severely biodegraded when the reservoirs were shallow, in
contrast with a second La Luna oil charge that would have undergone slight biodegradation as the reservoirs subsided and became
hotter. Reservoirs that did not subside sufciently to curtail microbial growth would contain only heavily degraded oil, such as
encountered by the early exploration wells in the study area.
Lastly, the observations can be explained by a possible scenario
that requires a long period of continuous oil charging. Here, unaltered La Luna oil was generated and migrated into stacked reservoirs at varying depths in the past. Crude oils in the shallower
reservoirs were heavily biodegraded, while oils in the hotter

735

M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

Table 5
Brief description of the preservation levels for the analyzed biomarker families and biodegradation degrees, in accordance with the Peters et al. (2005).
Sample

n-Alkanes

Isoprenoids

Steranes

25-Norhopanes

Hopanes

PM degrees

OS-01
OS-02
OS-03
OS-04
OS-05
OS-06
OS-07
OS-08
OS-09
OS-10
OS-11

Scarce
Very scarce
Very scarce
Very scarce
Scarce
Scarce
Very scarce
Scarce
Scarce
Very scarce
Very scarce

Nearly intact
Depleted
Depleted
Nearly intact
Nearly intact
Nearly intact
Very depleted
Nearly intact
Nearly intact
Depleted
Nearly intact

Depleted
Removed
Intact
Removed
Removed
Intact
Intact
Intact
Intact
Affected
Removed

Very scarce
Scarce
Absent
Very scarce
Very scarce
Scarce
Absent
Absent
Absent
Very scarce
Scarce

Intact
Nearly
Intact
Nearly
Nearly
Intact
Intact
Intact
Intact
Nearly
Nearly

2/6
3/4/7
3/4
3/7
2/7
2
3/4
2
2
3/4/6
2/7

intact
intact
intact

intact
intact

Fig. 8. (a) and (b) m/z 217 and m/z 191 ion fragmentograms for the La Luna rock extracts of the Tul region.

736

M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

reservoirs would have remained non-biodegraded. Later in time, a

migration conduit would have allowed the unaltered crude oil to
ow into the shallower reservoir and mix with the oil that would
have previously undergone heavy biodegradation. However, the
fact that the seep oils still retain a portion of the unaltered oil
might suggest that the seepage to the surface is fairly recent and
that their occurrence is likely due to recent tectonic activation of
the local faulting systems.
Such a mixing of crude oils with distinct degrees of biodegradation (characterized by the presence of 25-norhopanes in nearly
non-degraded light crudes) also has been reported from the Bolivar
Coast region of Lake Maracaibo, northwestern Venezuela (Gallango
et al., 1985; Alberdi et al., 2001). The high gravity oil accumulates
in shallow stratigraphic traps that are sealed by plugs of severely
biodegraded asphaltic crude.
4.5. Geochemical correlations
All the studied oil seepages are esentially of the same genetic
type and were derived from the same marine source rocks (probably La Luna Formation). The origin of these mature oil seeps from
the marine organic source has been indicated by conventional
analyses and molecular parameters from special analyses by GC
MS (Table 3 and Fig. 4).
An attempt has been made to identify the La Luna rock extracts
as the source for the oil seeps in the Cachir area based on the comparison of geochemical data and chromatographic characteristics of
the oil seep samples with those previously reported for some La
Luna rock extracts (P-114, 14RN-1X and 33F-1X; Fig. 1) from the
northwestern coast of Lake Maracaibo by Escobar (1987). A positive
correlation exists between the nickel, vanadium and sulfur contents
of the studied oil seeps and rocks of the La Luna Formation in this
region. The La Luna rock extracts showed average concentrations
of sulfur, vanadium and nickel of about 8%, 1900 and 180 ppm,
respectively, and V/Ni ratios of approximately 10.4 (Escobar,
1987). This latter value is similar to those reported in Table 2. With
respect to the distribution of steranes and terpanes, the oil seeps
(Fig. 3a, b, c, d and g) show very similar patterns to those of the
La Luna rock extracts (Escobar, 1987) from the Tul region
(Fig. 8a and b). The tricyclic terpane distributions of the oil seep
samples can be used as evidence for their generation from the organic rich facies of the aforementioned La Luna extracts. Both contain abundant C23 tricyclic terpane that predominates over other
homologs. The La Luna source rocks also are characterized by the
absence of 18a(H)-oleanane, 22S hopane percentages >50% and
the predominance of the stereoisomers of C27 sterane over those
of C29 sterane, suggesting a marine origin and a mature stage. On
the basis of the relative abundance of C27, C28 and C29 steranes,
the La Luna rocks appear to be well correlated to the majority of
the oil seep samples. Variation in Ts/(Ts + Tm) between the La Luna
rock extracts and the studied seeps may be related to factors such as
mineral catalyzed rearrangement from Tm to Ts (Bakr and Wilkes,
2002).
In summary, the geochemical source rock evaluation (Escobar,
1987), identication of oil seepage type and source correlations
have indicated that the studied oil seep samples in the Cachir area
are derived from the marine organic matter of the La Luna
Formation.
5. Conclusions
After analyzing 11 oil seep samples along the Carboniferous
region of Tul (Lake Maracaibo Basin), the values of several molecular geochemical parameters (known to be usually unaffected by
biodegradation) have led to the conclusion that these oil seeps

are residual hydrocarbons from a thermally mature crude oil, very

likely generated from the Cretaceous source rocks of the La Luna
Formation. This crude oil may have been originally light and it
shows evidence of being affected by microbial degradation, thus
API gravity has certainly been reduced, which is conrmed by
molecular data and the average percentage of polar compounds
(60%).
The main outcome of this research is that most of the oil seep
samples analyzed show various degrees of biodegradation that
are not correlative and are very distinctive, revealing that the study
samples may be mixed uids that displayed different levels of biodegradation. In addition, there is a small presence of norhopane
biomarkers (degree 6) derived from the alteration of the C10
methyl group in the regular hopanes. It appears that a previously
altered heavy crude was diluted by a second migrated light crude
oil, with the resulting mixture reaching the surface through natural
hydrocarbon seeps. The two aforementioned oils may be the result
of two generation pulses from the La Luna source rock or from a
single oil charging event involving reservoirs are varying depth
that later mixed.
The potential for lighter hydrocarbons being present in the region suggests that the oil industry should take on new drilling programs to explore for oilelds in the north-central region of Lake
Maracaibos western shoreline. In the past, this zones Tertiary
shallow petroleum reservoirs have been systematically rejected
as the crudes found were generally heavy and of low commercial
value.
Acknowledgments
The authors are grateful to the two reviewers (Dr. Manuel
Martnez and a second anonymous referee) for their comments
which helped to improve the original version of this work. We also
thank Dr. Clifford C. Walters (ExxonMobil Research & Engineering
Co., NJ) and Dr. Suhas C. Talukdar (Weatherford Laboratories,
Texas) for critical reading of the manuscript.
Appendix A
Main terpanes, hopanes, steranes and diasteranes identied in
the mass chromatograms.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22

C1-Tricyclic terpane
C22-Tricyclic terpane
C23-Tricyclic terpane
C24-Tricyclic terpane
C25-Tricyclic terpane
C24-Tetracyclic terpane
C26-Tricyclic terpane
18a(H)-22,29,30 Trisnorneohopane
17a(H)-22,29,30 Trisnorhopane
17a,21b(H)-30-Norhopane
17a,21b(H)-Hopane
17a,21b(H)-29-Homohopane 22S
17a,21b(H)-29-Homohopane 22R
17a,21b(H)-29-Bishomohopane 22S
17a,21b(H)-29-Bishomohopane 22R
17a,21b(H)-29-Trishomohopane 22S
17a,21b(H)-29-Trishomohopane 22R
17a,21b(H)-29-Tetrahomohopane 22S
17a,21b(H)-29-Tetrahomohopane 22R
17a,21b(H)-29-Pentahomohopane 22S
17a,21b(H)-29-Pentahomohopane 22R
5a-Pregnane

M. Escobar et al. / Organic Geochemistry 42 (2011) 727738

23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43

20-Methyl-5a-pregnane
13b(H),17a(H)-Diacholestane 20S
13b(H),17a(H)-Diacholestane 20R
5a(H),14a(H),17a(H)-Cholestane 20S
5a(H),14b(H),17 b(H)-Cholestane 20R
5a(H),14a(H),17b(H)-Cholestane 20S
5a(H),14a(H),17a(H)-Cholestane 20R
5a(H),14a(H),17a(H)-Ergostane 20S
5a(H),14b(H),17b(H)-Ergostane 20R
5a(H),14b(H),17b(H)-Ergostane 20S
5a(H),14a(H),17a(H)-Ergostane 20R
5a(H),14a(H),17a(H)-Stigmastane 20S
5a(H),14b(H),17b(H)-Stigmastane 20R
5a(H),14b(H),17b(H)-Stigmastane 20S
5a(H),14a(H),17a(H)-Stigmastane 20R
C20-Tricyclic terpane
C27-Pentacyclic terpane
13a(H),17b(H)-Diacholestane 20R
13b(H),17a(H)-Diaergostane 20S
13b(H),17a(H)-Diaergostane 20R
13a(H),17b(H)-Diaergostane 20R

Associate EditorCliff Walters

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