Ill SIMPOSIO BOLIVARIANO

Exploracion Petrolera de las Cuencas Subandinas

Caracas, 13 al 16 de Marzo de 1988

THE FIVE OIL FAMILIES OF THE

LLANQS: BASIN

BY

SUSAN E. PALMER
JUDY A. RUSSELL

OCCIDENTAL INTERNATIONAL EXPLORATION AND PRODUCTION CO.

 CONTENTS

ABSTRACT

INTRODUCTION
REVIEW OF POSSIBLE SOURCE ROCKS

Tertiary
Late Cretaceous
Early Cretaceous
Pre-Cretaceous

OIL GEOCHEMISTRY

TIMING OF MATURATION / MIGRATION

OIL-SOURCE ROCK CORRELATION

LIST OF FIGURES

FIGURE 1 - Location Map with Oil Families and Structural Contours

on Top Cretaceous

FIGURE 2 - Generalized Stratigraphic Column with Source Rock

Information

FIGURE 3 - Summary of Migration / Maturation

FIGURE 4 - Cross Plot % Sulfur Vs. API Gravity

FIGURE 5 - Gross Ci5 + Hydrocarbon Composition

FIGURE 6 - Pristane / Phytane Vs. Pristane / N-C]7

FIGURE 7 - Stable Carbon Isotopic Composition

FIGURE 8 - Representative Gas Chromatogram of Ci5 + Saturate

Hydrocarbons, Tricyclic (a-h) and Pentacyclic (A-T)
Terpanes and Steranes (1-22) of the Five Oil Families
FIGURE 9 - C2g 20S/20R Sterane Ratio Vs. API Gravity

TABLES

TABLE 1 - Summary of Crude Oil Geochemistry for Five Oil Families

TABLE 2 - List of Identified Tricyclic Terpanes and Pentacyclic

Triterpanes

- 724 -
 THE FIVE OIL FAMILIES OF THE LLANOS BASIN

Abstract

Oils analyzed from the Llanos Basin were divided into five genetic families
based on their organic geochemistry. Possible source rocks were defined and
correlated with the oils. The thermal history of these source rocks was
determined using measured and calculated (Lopatin) maturity indicators. In
addition, the maturity and the geochemical features of the oils are used to
propose the oil generation and migration history of the oils.

Acknowledgement:
We thank the following technical staff members for the geochemical analyses:
Janie Heard, Shirley Sellers, Craig Schiefelbein, Janet Williamson and
Michael Bromiley. We recognized the previous work done by John Zumberge and
Denis Miiller while they were at the Cities Technology Center

- 725 -
INTRODUCTION

The presence of oil shows within the Carbonera to Cretaceous section for
most wells drilled in the Llanos Basin demonstrates that hydrocarbons
were generated and migrated through the basin. Figure 1 is a location
map showing regional structural contours on Top Cretaceous and location
of the oil families identified in this report and Figure 2 is a
generalized stratigraphic column of the Llanos Basin and foothills with
oil shows and source potential summarized.

Based on analyses of 53 oils obtained from the Llanos Basin, five oil
families were delineated (see Figure 1 ) . The five families show
important geochemical differences which can help in defining the
source-rock and the migration history of these oils. In addition to the
geochemical investigation of these oils, their thermal history was
modeled using the Lopatin calculations (Lopatin, 1971) and compared with
measured maturity values (vitrinite reflectance, sporomorph color and
Tmax) analyzed in our laboratory and published reports (Robertson
Research, 1983; Jordan, 1984; Asociacion Colombiana Geologio y Geofis del
Petroleo, 1982, 1985) for the source rocks (Figure 2 ) . Figure 3 is a
flow diagram for the timing of maturation and migration showing the
geologic constraints for both the paleodepocenter and the present-day
depocenter for the Llanos Basin. These constraints are: 1) the older
structures contain most of the reserves and is the "preferred" age (i.e.,
Cretaceous-Early Tertiary) of structuring; 2) the main entry of
freshwater is through unconformities (Late Cretaceous- Eocene) with many
of the reservoirs too deep (i.e., below 4,000 ft.) for biodegradation by
the Miocene time (Leon deposition); 3) precursors to the Andean Orogeny
began as early as the Late Cretaceous. These tectonic events cut off
portions of the paleodepocenter while total cut off was by the Andean
Orogeny (Miocene). These constraints limit the required time of source
rock maturation and migration from the paleodepocenter to the Late
Cretaceous until the Miocene. Remigration due to basin tilting and a
possible second pulse of source rock maturation and oil migration from
the present-day depocenter has occurred from the Miocene to Recent.

REVIEW OF POSSIBLE SOURCE ROCKS

Total organic carbon, Rock-Eval pyrolysis and visual kerogen analyses

performed in our laboratory and published information (Robertson
Research, 1983; Jordan, 1984; Asociacion Colombiana Geologos y Geofis.
del Petroleo, 1982, 1985) were used to evaluate the hydrocarbon source
potential and thermal maturity of Tertiary, Late Cretaceous, Early
Cretaceous and Pre-Cretaceous shaley intervals. The results are
summarized in the stratigraphic column shown in Figure 2 and are briefly
discussed below.

Tertiary: Visual kerogen analysis shows that the Tertiary section

(Miocene-Paleocene) contains primarily terrestrially-derived humic (gas-
prone) kerogen, although there are some areas of marine amorphous
(oil-prone) kerogen. Most of the samples in the present- day depocenter

- 726 -
 NOTE: BARINAS BASIN OILS
ARE IN A DIFFERENT
• • FAiwiLi'FROM TiiE
,_ LLANOS OILS.

VENEZUELA

BARINAS-APURE BASIN

FAMILY 1

>>../""

FIGURE 1

OIL FAMILIES

LLANOS AND

BARINAS-APURE BASINS
OIL FAMILY *'
3,5/--
STRUCTURAL CONTOURS NEAR

TOP C R E T A C E O U S j

0 50
I I
MILES
S & C. I. = 2 5 0 0 '
**£& OIL FIELDS OR
PRODUCING WELLS

- 727 -
 FIGURE 2

GENERALIZED STRATIGRAPHIC COLUMN

LLANOS BASIN & FOOTHILLS

FORMATION FORMATION SOURCE ROCK (1) OIL PROD.*

AGE LLANOS ORGANIC
VR E (3)
FOOTHILLS LLANOS BASIN TOC (2) MATTER SHOWS ©

MIOCENE CAJA
GUAYABO
TO FM. GROUP
RECENT
MAR.
DIABLO FM. 0.94 HUMIC MATURE
_ 19-601 _

IMMATURE
LEON FM. 0.10- MARGINALLY!
1.40 HUMIC
MATURE
(0.40-0.60)

SAN
OLIGOCENE FERNANDO
FM.
UPPER/LOWER HUMIC IMMATURE-
0.37- MARGINALLY
CARBONERA (OCCASIONALLY
2.05 MATURE
FM.
MIXED) (0.38-0.70)

MARGINALLY
HUMIC MATURE
(0.60-0.90)

MARGINALLV
MATURE
IN WELLS TO
(0.40-0.90)
OVER
MATURE
1.70)
OUTCROPS
OVERMATURE?
(14rlQ+I _

NOTE: CHRONOSTRATIGRAPHIC UNITS MODIFIED AFTER J. BOGOTA-RUIZ (THIS SYMPOSIUM

AND J. ALUJA (OCCIDENTAL IN-HOUSE).
1 SOURCE ROCK ANALYSIS COMPILED FROM 37 OUTCROP SAMPLES COLLECTED BY OCCIDENTAL
PLUS PUBLISHED DATA AND WELL SAMPLES.
2 TOC = TOTAL ORGANIC CARBON
3 VRE = VITRINITE REFLECTANCE EQUIVALENT: DETERMINED BY MEASURED Ro, SPOROMORPH
COLOR (SCI), TMAX (ROCK-EVAL PYROLYSIS) AND CALCULATED BY LOPATIN (70 WELLS +
OUTCROP RESTORED SECTIONS).
- 728 - R2-SA-36(25)
 LLANOS BASIN-TIMING OF MATURATION/MIGRATION
LATE CRET. PALEOCENE ? EOCENE OLIGOCENE MIOCENE-PLIOCENE
[(ABSENT IN AREAS] RECENT

[-END BIODEGRADATION—|

I "PREFEREO" AGE OF STRUCTURES 1

< I-
o z
o < I ENTRY OF FRESH WATER ( UNCONF.) —j

I PRECURSORS TO ANDEAN OROGENY 1 I ANDEAN OROGENY j

UJ o

| PORTIONS OF PALEODEPOCENTER CUT OFF 1 | PALEODEPOCENTER 1

CUT OFF - TOTAL

I "REQUIRED" TIME OF MIGRATION 1- -7— [-REMIGRATION/SECOND P U L S E - " * - ?

— cc
MATURATION OF SOURCE ROCKS
NONMARINETO MAR GINAL MARINE
CD £
h - UJ
z o
UJ O POSSIBLE TJMSOF MIGRATION
co a.
UJ UJ
a: a
a.
CC
MATURATION OF SOURCE ROCKS
UJ
H MARINE/MARGINAL MARINE

UJ
CO
UJ O
O ■PULSE OF METAMORPHISM/DIAGENESIS- H
§£ |- ANDEAN OROGENY 1

<§
UJ
_J POSSIBLE TIME OF MIGRATION -"? I REMIGRATION I
<
a.
AT LEAST TWO PULSES OF MATURATION/ Ml GRATION (REMIGRATION)

.FIGURE.*
(Figure 1) and in outcrops are immature or marginally mature (vitrinite
reflectance equivalent or VRE = 0.4-0.6) and entered the oil window after
the Andean orogeny (Miocene-Recent). Organic richness varies from poor
(TOC = 0.10) to good (TOC = 1.40). Based on kerogen composition and
timing of maturity, the Tertiary section can be ruled out as a major
contributor to the oil found in the basin. It is possible that if any of
the Teritary is in the oil window, it is contributing to the present-day
pulse of hydrocarbon generation.
Late Cretaceous: The Late Cretaceous section found Mn wells of the
present-day depocenter contains primarily gas-prone kerogen. However,
the section in outcrop, both in the foothills and Eastern Cordillera,
contains more marine oil-prone kerogen with only occasional higher plant
influence. Maturity indicators show that in the present-day basin, the
Late Cretaceous is immature to mature (VRE = 0.4-0.9). In outcrop, there
are sections showing moderate maturity to overmaturity (VRE = 0.8-1.7+).
Organic richness varies from fair (TOC = 0.59) to excellent (TOC =
3.0+). Based on these results, the Late Cretaceous section could be a
major contributor to the oil found in the basin. This is especially true
for the more waxy oils found in the Central Llanos. The more marine
sections could have contributed to the marine oil found in the northern
and southern Llanos and could have experienced early maturation
(pre-Andean) (Figure 1). A portion of this marine section could have
entered the oil window (based on Lopatin calculations) during the Early
Tertiary (Eocene/01igocene) but definitely was in the generative stage by
the Andean Orogeny (Miocene).

Early Cretaceous: Little is known about the Early Cretaceous since no

wells penetrated this section. In the foothills and Cordillera, the
kerogen type varies from gas-prone to oil-prone and is overmature in all
the sampled locations. Organic richness varies from low to high; there
are occasional samples with TOC's as high as 3.5%. It is possible that
the Early Cretaceous could have contributed to the older pulse of oil
found in the basin, because this section entered the oil window (Lopatin)
during the Late Cretaceous or Early Tertiary (Paleocene/01igocene) and
could have migrated into structures of this age. The section probably
became overmature due to the metamorphism and volcanism associated with
the Miocene Andean Orogeny.

Pre-Cretaceous: The Pre-Cretaceous section in wells contains mainly

humic (gas-prone) kerogen; although, again, there are a few samples with
moderate amounts of marine amorphous kerogen indicating a possible
oil-prone source. The Pre-Cretaceous samples thus far studied are
organic-lean. In general, much of the section found in the northern part
of the basin is thought to be overmature due to slight metamorphism. The
southern portion may not have undergone deep burial or metamorphism and
thus may not be overmature. Source type varies from gas-prone to
oil-prone and organic carbon ranges from 0.19-1.37+%. Whether the
Pre-Cretaceous section was an important contributor to the oil found in
the basin is open to question. If it was, then the timing of oil

- 730 -
generation and migration was very critical since there are major
unconformities between known traps and source. Maturity indicators of
the oil found in the basin show that it came from a source(s) that was
moderately mature (VRE = 0.8-0.9). Lopatin calculations indicate that
the Pre-Cretaceous section was in this maturity range in Jurassic/Early
Cretaceous. However, at this point, the Pre-Cretaceous section is not
considered a major source for the oil analyzed in the Llanos.

OIL GEOCHEMISTRY
Listed in Table 1:
The Llanos Basin oils are divided into genetic groups based on their
organic geochemical characteristics (Table 1) and these individual groups
are discussed below. Geochemical data derived from individual oil
samples are shown in Figures 4 to 9. A location map showing the
distribution of the genetic groups is given in Figure 1.
Family 1 oils are from northern Llanos Basin. As shown in Table 1, these
oils have features indicating that their source is marine with some
terrestrial input. For example, the organic sulfur content is moderate
(0.4-0.6%) and the C]5 + gross hydrocarbon composition is
naphthenic-paraffinic (Figures 4 and 5 ) . Also, the pristane/phytane
ratios are moderate (1.2 to 1.6%) which is characteristic of marine oils
(Connan and Cassaou, 1980) and the stable carbon isotopic composition of
the C15+ saturate and aromatic hydrocarbons plot below the best
separation line for marine and nonmarine oils (Sofer, 1984). These data
are displayed in Figures 6 to 7. Gas chromatographic and gas
chromatographic/mass spectrometric (GC/MS) data also indicate a marine
source environment with some terrestrial influence; representative
patterns for Family 1 oils are given in Figure 8. First, the gas
chromatographic distribution of the n-paraffins is dominated by the
shorter-chain components (n-C]5 to n-C2o)> generally attributed to
marine organic matter. A small wax component (n-C25+) is also present
indicating input from land plants; thus, the resulting pattern is
semi-waxy. The tricyclic terpane distributions of Family 1 oils have low
amounts of the C]g and C20 (peaks a and b) components relative to
C23 which is characteristic of marine oils and source rocks (Zumberge,
1987). Pentacyclic terpane distributions feature the C27 to C35
hopanes, with abundant C28~C31» C33-C36 extended tricyclic
terpanes and oleanane. The presence of oleanane is of major interest
because it signifies the source rock received input of land-derived
higher plant (i.e., Angiosperms) matter and also that the source rock is
Cretaceous or younger in age (Ekweozor and Okeye, 1979). The C27 to
C29 sterane distributions contain a mixture of rearranged and "normal",
biologically-derived steranes. The relatively abundant rearranged
steranes indicate that the organic matter was deposited in a clastic
(clay-rich) rather than a carbonate environment (Ensminger, et a!.,
1978). The sterane distribution also shows that marine organic matter

- 731 -
 FIGURE 4
API GRAVITY VS PERCENT SULFUR
LLANOS BASIN OILS

.5 1.0 1.5 1.8

PERCENT SULFUR

- 732 -
 FIGURE 5
GROSS C15+ HYDROCARBON COMPOSITION
LLANOS BASIN OILS

1 0 0 % PARAFFINS

A FAMILY 1

+ FAMILY 2

■++- FAMILY 3

<} FAMILY 4
X FAMILY 5

#A
TERRIGENOUS A ♦
OILS

A &~ A

MARINE
OILS

100% i100%
"7V ~7T -7T NAPHTHENES
AROMATICS
 FIGURE 6

PPJSTANE/PHYTANE VS PRISTANE/N-C17 - LLANOS BASIN OILS

5.3-1

♦ Fam. 4

5jr1

PHISTANE / N-C17

- 734 -
 FIGURE 7
STABLE CARBON ISOTORC COMPOSITION - LLANOS BASIN OILS
C15+ SATURATE AND AROMATIC HYDROCARBON FRACTIONS

ISOTOPIC COMP - SATURATE HYDROCARBONS

- 735 -
 FIGURE 8: REPRESENTATIVE GAS CHROMATOGRAM OF C , 5 + SATURATE HYDROCARBONS,
TRICYCLIC (a-h) AND PENTACYCLIC ( A - T ) TERPANES, AND STERANES ( 1 - 2 2 ) OF THE FIVE
FAMILIES OF THE LLANOS BASIN OILS.
(SEE TABLE 2 FOR IDENTIFICATION OF TERPANES AND STERANES)

FAMILY 1

TRICYCLIC TERPANES («-h) PENTACYCLIC TERPANES

FAMILY 1 F/ MILY 1 STERANES (1-22)

E3 REARRANGED

<"» EXTENDED ■ I 5«(H)

TRICYCLIC TERPANES

M. .pJ^iliUi AMV-AW
 FAMILY 2

TnlCYCLIC TERPANES (a-h) P E N T A C Y C L I C TEP.PANES

FAMILY 2

■NONMARIHE"
PATTERN

OITERPANES
/
^EXTENDED
TRICVCLIC TERPANES

%lMm^t
.OLP
1.1imi mum •ma
r 1 r——i 1 1 1 1 1 r-—i— -i 1 1 r~
M 40 4S BO 03 80 80 US 66 BS 00 BS Bi

FIGURE 8 CONT.
CO Z
o
o
> .3 03XVlAHi3H3Q
oo
LJJ
CC
<
O
LL u.

- 738 - q^/^.nq .-o H

 FAMILY 4

TRICVCLIC TERPANES (l-h) PEHTACVCLIC TERPANES

FAMILY 4 OEMETHVLATEO C ,
STERANES (1-2J)

to
I

" EXTENDED
TRICVCLIC TERPANES

ijjMUlJJJi^ **M4JJ.
W 35 40 43 BO 6Q

FIGURE 8 CONT.
 FAMILY 5

T R I C Y C U C TERPANES (»-h) PENTAOYCLIC TERPANES

FAMILY 5 =AMILY 5 STERANES ( 1 - 2 2 )

z
t
OfTERPANES

DIMETHVLATEOC.

: ^EXTENDED
THICYCLIC TERPANES

LJMH
1 r~—i 1 1 r-
33 40 « X 63 7D 72 74 76 78

FIGURE 8 CONT.
 API GRAVITY CBQ°R

MIGRATION TREND
TRANSFORMATION

CD \f

fa—1:
was prominent in the Family 1 oils. In this regard, the C27 steranes
are approximately twice as abundant as C29 (based on heights of the
5 H-C27 and C29 components) which is characteristic of marine algal
kerogen (Moldowan, et al., 1985).
Oil Families 2, 3 and 5 from the central and southern Llanos Basin
(Figure 1) share some similar geochemical features which are indicative
of a more terrestrial setting for the source rock in comparison to the
marine character of Family 1 oils. For example, the chromatographic
patterns of the C]5+ saturate fractions show abundant C25+
n-paraffins relative to the n-Cl5 to n-C20 fraction characteristic of
marine oils (Figure 8 ) . Abundant C25+ n-paraffins are generally
attributed to source rocks rich in land-derived organic matter. The
GC/MS data, especially the tricyclic terpane distributions, also indicate
terrestrial source organic matter for Family 2, 3 and 5 oils. The lower
molecular weight tricyclic terpanes, C19 and C20» are abundant
relative to C23, a feature characteristic of land plants (Reed, 1977
and Zumberge, 1987). The C27 to C29 sterane distributions show
abundant C29 relative to C27 steranes which also implies a higher
plant, rather than algal, input. Rearranged steranes are abundant in the
sterane distributions of all three oil families which, as was the case
for Family 1 oils, indicates a clastic rather than a carbonate source
rock. Pentacyclic terpane distributions contain oleanane, an indicator
for land-plant input and Cretaceous or younger source rocks. Lastly,
these three families contain diterpanes (tentatively identified) which
are indicative of higher plant input (Philp, et al., 1981). To
summarize, oil Families 2, 3 and 5 have waxy to semi-waxy n-paraffin
distributions and terpane-sterane distributions indicative of significant
input by land-plant organic matter.

However, although these three families have the above features in common,
other geochemical data show different histories of migration,
biodegradation, remigration and mixing of oils. The geochemical
parameters of the Family 2 oils of the central Llanos Basin all indicate
a terrestrial source (Table 1). In addition to the chromatographic data
discussed above, the low organic sulfur content (0.03 to 0.3), paraffinic
gross C15+ hydrocarbon composition, high pristine/phytane ratios (2.3
to 3.6) and "nonmarine" stable carbon isotopic compositions of the C15+
saturate and aromatic hydrocarbons all show that Family 2 is derived from
a terrestrial source.

Likewise, Family 3 oils of central and southern Llanos have nonmarine

indicators similar to Family 2, but these oils are distinct because of
their isotopically positive C15+ saturate and aromatic hydrocarbons
(with respect to Family 2) and because of differences in their sterane
and terpane distributions (Table 1). Family 3 oils have two features
which show that they are a mixture of biodegraded and nondegraded oils.
The gross C15+ hydrocarbon composition is naphthenic-aromatic rather
than paraffinic; this is unusual for waxy to semi-waxy oils. In
addition, demethylated hopanes are present in all Family 3 samples,
- 742 -
indicative of severe biodegradation. Thus, the presence of demethylated
hopanes in Family 3 oils indicates that they are a mixture of a waxy and
biodegraded oil. The genetic affinity of the biodegraded oil is not
known. It could be either an early pulse of the waxy oil that was
biodegraded, or an oil from a different source rock.
Some oils in Family 3 lack n-parafins and show the effects of
biodegradation. These oils occur at depths greater than 10,000 ft.
suggesting that the reservoirs were at one time much shallower
(3000-4000 ft) and penetrated by oxygenated meteoric water permitting
biodegradation. It is not possible to delineate the timing of
biodegradation of these deeply-reservoired oils, but it is assumed that
by Leon deposition these reservoirs were deeper than 4000 ft (the end of
bacterial action). The oils may have been a semi-waxy oil that was
biodegraded and then the reservoir subsided halting the biodegradative
process. Alternatively, a cycle of biodegradation of an undefined oil,
mixing with a semi-waxy oil, further biodegradation and, finally,
subsidence could have occurred.

Family 5 oils of southern Llanos Basin present a similar history of

biodegradation and mixing with a waxy, terrestrially-derived oil as
described for Family 3 oils. However, some major important geochemical
differences should be noted. The Family 5 oils are a mixture of a high
sulfur oil of possible marine (carbonate?) origin and a waxy oil.
Biodegradation causes an increase in the sulfur content of an oil, but
the biodegraded oil is diluted by a low-sulfur waxy oil. In comparison,
Family 3 oils have low sulfur contents and are also mixtures of
biodegraded and waxy oils. The resulting sulfur content of the Family b
oils is 1.1 to 1.3%. A genetic relationship with Family 2 is suggested
because the terpane-sterane distributions of Family 2 and 5 oils are
similar. The isotopic compositions of Family 5 oils plot near the
biodegraded, low sulfur Family 3 oils described above and fall on the
marine side of the best separation line in Figure 7. The high sulfur
content and isotopic data suggest that the biodegraded oil component in
Family 5 oil was derived from a marine source rock and evokes a marine
source area to the south or southwest.

Family 4 is a collection of central and southern Llanos Basin semi-waxy

to waxy oils with moderate (0.3 to 0.5%) to high (1.2 to 1.7%) sulfur
content and "marine" isotopic compositions. Tricyclic and pentacyclic
terpane distributions indicate both marine and higher plant input (see
Table 1). The presence of demethylated hopanes shows that these oils are
a mixture of semi-waxy or waxy oil and a biodegraded precursor. The
"marine" isotopic composition (Figure 7) and the moderate to high sulfur
content suggest that this precursor oil (oils?) was of marine origin.
The intermediate isotopic composition of these oils, with respect to the
low sulfur Family 2 and high sulfur Family 5 oils, suggests that the
semi-waxy oil could be related to Family 2 and that the biodegraded oil
could be the same as that present in the Family 5 oils. However, while
both Family 2 and Family 5 oils contain tricyclic terpane distributions

- 743 -
indicative of land-derived kerogen (i.e., C^g and C20 greater than
C23). the Family 4 oils have a marine pattern (C19 and C20 less
than C23). These differences in indicators of marine-nonmarine input
could be due to varying proportions of the biodegraded precursor oil and
the later influx of semi-waxy and/or waxy oil. The "marine" tricyclic
terpane pattern could be enhanced in the biodegraded marine precursor
oil, as these compounds withstand biodegradation (Seifert and Moldowan,
1979). In contrast, the pentacyclic terpanes of the biodegraded oil
would be diminished due to formation of the demethylated hopanes. Thus,
the pentacyclic terpane pattern of the biodegraded oil could be
overwhelmed and obscured by the addition of a semi-waxy or waxy oil. The
steranes in Family 4 oils may be a mixture of the proposed marine
precursor and the semi-waxy/waxy oil and do not have distinctive
indicators of either marine or nonmarine sources.

TIMING OF MATURATION/MIGRATION

Some of the Early to Late Cretaceous source rocks in the paleodepocenter

(based on Lopatin calculations) entered the start of generation (VRE =
0.6) by Late Cretaceous to Early Tertiary. The peak of generation (VRE =
0.8-1.0) was by Early-Middle Tertiary (Eocene/01igocene). Much of the
section in the paleodepocenter became overmature due to the metamorphism
and volcanism associated with the Andean Orogeny and was totally cut off
from further generation and migration. The Cretaceous section in the
deepest part of the present-day depocenter is currently in the peak of
oil generation. This implies possible multipulses of oil generation and
migration. The relationship between API gravity and the sterane 20S/20R
ratio can be used to describe relative oil maturity and effects of
biodegration, and migration (e.g., Zumberge, personal communication).
Based on the 20S/20R sterane ratio of the oils in Families 1 to 5, the
maturity of the source rocks that generated them is indicated as VRE =
0.7 to 0.9, i.e., main phase of oil generation (Figure 9 ) . This fits
well with the Cretaceous as a possible source for the Llanos oils.

Many of the Family 3 oils and some of the Family 4 oils are more mature
(VRE = 0.9) than Family 1, 2 and 5 (VRE = 0.7 to 0.8) oil. However,
caution must be used when interpreting these data for Families 3, 4, and
5 because these oils are a mixture of biodegraded and nondegraded oils
and the sterane composition is therefore influenced by the relative
proportion of the two oil components. Of interest with respect to
migration is the range in API gravities shown for oils of similar
maturities (Figure 9 ) . Oils with higher API gravities (e.g., 40°) have
migrated further than oils with lower gravities (30°). Both Family 1 and
2, which are not mixtures, have 10-degree ranges in API gravity for oils
with similar 20S/20R and VR/E values. One example in Family 2 is Oil A
and Oil B. In this example, Oil A is more basinward and in a deeper
reservoir, but is of a lower gravity (32°) than Oil B (40°) which is
shallower, more eastward and in a stratigraphically higher reservoir.

- 744 -
The range in API gravity is also distorted by the effect of water washing
and biodegration, even within Family 1 and 2. Thus some of the lower API
gravity oils in Figure 9 were altered after migration and may plot with
oils which did not experience a relatively long distance migration.

Migration of the oils probably took place simultaneously with source rock
maturation and oil explusion. This means that if the Cretaceous was the
source, then the oil was moving through the deltaic packages of the
Cretaceous during the Early-Middle Tertiary. Any trap with this age
structural component could contain oil. Unfortunately, later Andean
(Miocene) tectonics caused basinal tilting and younger faults and
possible remigration of petroleum. The oil could then be lost if no
structures remained. The younger (or rejuvenated older), normal
up-to-the-basin faults (which may have had a strike-slip component) found
in the central Llanos could be possible conduits through which the
redistribution (remigration) of the oils moved into younger and younger
strata (Carbonera Sands) eastward. In addition, if there is a younger
pulse of oil generation and migration occurring after the Miocene Andean
orogeny, then the younger faults played an important role for migration.

OIL-SOURCE ROCK CORRELATION

Our analyses of 37 outcrop samples from the Miocene to the Paleozoic of

the Eastern Cordillera support the previous review of the possible source
rocks for the oils in the Llanos Basin (Figure 2 ) . Rock-Eval and TOC
data show moderate amounts of organic matter for the total section and
that the Early Cretaceous to Paleozoic section, having no pyrolysis
yield, is overmature. Kerogen analysis was performed on 12 samples. The
results indicate that eight samples (from the San Fernando, Chipaque,
Une, Guadalupe, Early Cretaceous and Lower Paleozoic) are oil-prone. The
remaining four (from San Fernando, Chipaque and Guadalupe) are
gas-prone. Vitrinite reflectance and spore coloration studies show that
the Oligocene-Miocene and Upper Cretaceous are immature with respect to
oil generation. However, the Tmax readings indicate that all of these
samples were in the main phase of oil generation. This conflict among
maturity parameters may be due to weathering of the outcrops; the problem
with the data has not been resolved. The Early Cretaceous and Lower
Paleozoic both are overmature. Based on TOC and kerogen composition five
outcrop samples were chosen for extract analysis.

The results of the extract analysis for oil-source rock correlation

indicate that the Cretaceous Une has a positive correlation to the Family
3 waxy oils based on gross C15+ hydrocarbon composition, stable carbon
isotopic composition and terpane-sterane distributions. The rock extract
data indicate that this could generate a terrigenous (waxy) oil. It is
rated as a good to \/ery good source rock for oil. Also, the low maturity
Chipaque samples contain a mixture of marine and nonmarine kerogen with
fair oil source possibility ratings and correlate best with oil Family 1
because of their isotopic composition and sterane distributions. The

- 745 -
remaining Guadalupe sample is also of low maturity and has a fair rating
for oil; it may generate a waxy oil similar to Family 2 oils but this is
supported only by the gas chromatograms of the C15+ saturates and
isoprenoid ratios. The correlations are all speculative because of the
few samples analysed. Also» the low maturity of the samples makes
characterization of the oil they would generate difficult. Thus, no
strong positive source rock-oil correlation exists for any of the rock
samples studied to date.

- 746 -
 TABLE 1
SUMMARY OF CRUDE OIL
GEOCHEMISTRY OF LLANOS BASIN

INTERPRETATION OF
FAMILY 1 - NORTHERN LLANOS DEPOSITIONAL ENVIRONMENT
% s Moderate (0.4-0.6) Marine-Terr.

API 25° to 30°

Gross HC Comp. Naphthenic-paraffinic Marine-Terr.

Sat. GC's Small C25+ (wax) component

present, CPI = 1.00 to Marine
1.03 (odd predom.)

Pr/ph Moderate (1.2 to 1.6) Marine

Pr/n-Cl7 Low (0.5 to 0.7)

Isotopes Relatively negative compared Marine

to Family 2, plot below best
separation line

Tricyclic C19 and C20 ("a" and "b") low Marine

terpanes relative to C23 ("e")

Pentacyclic Extended tricyclic terpanes Terr.

terpanes abundant, Oleanane present,
DM (demethylated hopane) absent
Ts > T m

Steranes C27 > C29 RA 'k. Norm Marine, Clastic

- 747 -
FAMILY 2 - CENTRAL LLANOS
%s Low (0.03 to 0.3) Terr.

API 30° to 40° —

Gross HC Comp Naphthenic to paraffinic Terr.

Sat. GC's Light ends are low in some oils, Terr.

Waxy to semi-waxy
CPI = 1.02 to. 1.04 (odd predom.)

Pr/ph High (2.3 to 3.6) Terr.

Pr/n-Cl7 Low (0.5) to high (1.98)

Isotopes Intermediate to Family 1 and 3, Terr.

plot above best separation line

Tricyclic Cig and C20 ("a" and "b") high Terr.

terpanes relative to C23 ("e"), diterpanes,
present similar to Family 3

Pentacyclic Extended tricyclic terpanes Terr..

terpanes abundant, Oleanane present
DM (demethylated hopane) absent
T s < Tm

Steranes C27 ^ C29 RA ~ Norm. Clastic

- 748 -
FAMILY 3 - CENTRAL AND SOUTHERN LLANOS

% s Low (0.06 to 0.5) (Terr.)

API 21.2° to 40.2° (biodeqraded to —

mature)

Gross HC's Naphthenic-Aromatic, mix of biode­ Mix

Comp. graded + paraffinic oil?

Sat. GC's Waxy to semi-waxy; semi-waxy with Terr.

abundant l i g h t ends, CPI = 1.01 to
1.04 (odd predom.)

Pr/ph High (2.8 to 4.6) ex. for one Terr.

biodegraded o i l
Pr/n-Ci7 Low (0.45 to 0.50)

Isotopes Positive (-25.5 to -26.5 S 13c Terr.

sat.) relative to Family 2 and
plot above best separation
line

Tricyclic Cig and C20 ("a" and "b") high Terr.

terpanes relative to C23 ("e"), diterpanes
present

Pentacyclic Low extended tricyclic terpane Terr.

terpanes relative to T s , Oleanane present,
DM (demethylated hopane) present,
T
s > T m except for one oil

Steranes C29 > C27» RA > Norm Terr., Clastic

Comment: Mix of waxy or semi-waxy oil with biodegraded oil (nonmarine)

- 749 -
 VIA DE MIGRACION
DEL PETROLEO

ACUMULACION DE
PETROLEO

Fig.10- Secci6n esquematica de la3 poslbles vias de

migracidn y acumulaclon de hidrocarburos.

776 -
 GUA-502

L E Y E N D A
FALLAS EXTENSIONALES CONTORNO ESTRUCTURAL k. MIGRACION DE HIDROCARBUROS PRINCIPALMENTE ACUMULACION

o
EN SEO. DE PETROLEO Y GAS
;.':_. LIMITE DEL FRENTE OE PRINCIPALMENTE ACUMULACION
NAPAS LIMITE DE LAS AREAS DE GAS
DE DRENAJE POZOS PERFORADOS
L I M I T E OE EROSION DEL PRINCIPALMENTE ACUMULACION
CRETACICO OE PETROLEO

Fig.11- a) Mapa estructural del tope del Cretacico de la

Subcuenca de Guarumen.
b) Areas de drenaje y direcci6n de migraci6n y
acumulacidn de petr61eo y gas en la Subcuenca
de Guarumen.
FAMILY 4 - CENTRAL LLANOS

%s Moderate (0.3-0.5) to high Marine

(1.2 to 1.7)

API 14.5° to 31.6° —

Gross HC Naphthenic-Aromatic, mix of biode­ Mix

Comp. graded + paraffinic oil

Sat. GC's Waxy Terr.

Pr/ph High to very high (3.0 to 5.2) Terr.

Pr/n-Ci7 Low (0.5 to 0.75)

Isotopes Plot near Family 5, below best Marine

separation line

Tricyclic Cig and C 2 o ("a" and "b") less Marine

terpanes than C23 ("e"), small amount
of diterpanes

Pentacyclic Extended tricyclic terpanes Terr.

terpanes abundant, Oleanane present
DM (demethylated hopane) present
Ts > T m

Steranes C27 > C29. RA > Norm. Clastic

Comment: Mix of waxy oil with biodegraded (marine?) oil.

- 750 -
FAMILY 5 - SOUTHERN LLANOS

%s High (1.1-1.3) Marine ?

API 22° to 25° —

Gross HC Naphthenic-Aromatic mix with biode­ Mix

Comp. graded oil

Sat. GC*s Waxy Terr.

Pr/ph High (4.53) Terr.

Pr/n-Cn Low (0.45)

Isotopes Plots near biodegraded Family 3, Marine

below best separation line

Tricyclic C19 and C20 ("a" and "b") Terr ?

terpanes greater than C23 ("e"), similar
to Family 2, diterpanes
present

Pentacyclic Extended tricyclic terpanes Terr.

terpanes abundant, Oleanane present,
DM (demethylated hopanes) large
Ts < T m

Steranes C27 ^ C29, similar to Family Clastic

2. RA slightly greater than normal

Comment: Family 5 oils could be a mix of a nonmarine (Family 2/3) with a

high sulfur (carbonate?) biodegraded oil. Biodegraded oil is
different than Family 3 biodegraded oil.

- 751 -
 TABLE II

Peak Molecula
[LIST OF IDCNTIFItD TRICVCLIC TLRPANLS (DI1ERPANLS) 1 Designation Formula
A C27H46 1 8 a ( H ) - 2 2 , 29, 3 0 - t r i s n o r h o p a n e " T l "
Peak Molecular Molecular B C27«46 17c(H)-22', 29, 3 0 - t r i s n o r h o p a n e " T m "
1 Designation Formula Weiqht R-f.roup 1 BP C
28H48 17..(H), 1K»(H), ?1S(H)-?H, 30-bi s n o ' h o p j n o
Ci9H34 ?M -CH3 DME C
29H50 . I p i i i e t h y l a l M hopani' at A/11 r i w |

b
' C C
29H50 17a(H), 21B(H)-30-no-hopane
C?nH 3 6 276 -C2"S
D C29H50 176(H), 21a(H)-30-normoretane
c
l C21H3R 290 -C3H7 OL C
30H52 Oleanane
C? C?lH 3 « 29C1 -C3II7 E C
30H52 17a(H), 21B(H)-hopane
F C
30H52 17B(H), 21<i(H)-moretane
c
3 C
21H38 29(1 -C3H7
G C3lH 5 4 17a(H), 2lB(H)-3U-homohopane (22S)
d
l C22H40 304 -C4H9 H C31H54 17a(H), 21s(H)-30-homohopane (22R)
d2 C2?H40 3(14 -C4H, I C30HS2 gammacerane
J C31H54 176(H), 21o(H)-3t)-homomoretane
6 C23H42 318 -c 5 "n
K - C32H56 17a(H), 21B(H)-30, 31-bishomohopanp (22S)
f C?4"44 332 H
-C6 13 L C3?H 5 6 17o(H), 2 1 6 ( H ) - 3 0 , 31-bishomohopane (22R)
q C25 H 46 346 -C7H1S M C32H56 176(H), 2 1 a ( H ) - 3 0 , 31-bishomomoretane
N C33H58 17a(H), 2 l B ( H ) - 3 0 , 3 1 , 32-trishomohopane (22S)
hl C26"48 360 -CRH17
0 C33H58 17a(H), 21B(H)-30, 3 1 , 32-trishomohopane (22R)
h2 C
26H48 360 "CRH17 C
Q 34H60 17o(H), 21B(H)-30, 3 1 , 3 2 , 33-
i-i C
2R- C 31 | tetrakishomohopane (22S)
xtended diterpanps R 17a(H). 216(H)-3I), 3 1 , 3 2 , 33-
m-p c
33" c 36 1 C34H6O
tptraHshnmohop^np (22R)
S C35H62 17a(H) , 21B(M)-3r), 31 , 3 ? , 33, 14-
pentakIshoroohopane (22S)
T C35"62 17a(H), 2 1 B ( H ) - 3 0 , 3 1 , 32, 33, 34-
1 Telracyclic Terpane 1
pentakishomohopane (22R)

I T 330 (TC) C24«42 330

LIST OF IDENTIFIED STERANES 1

Molecular Molecular
1 Peak Formula Weight Sterane Identification |
C
27 H 48 3>2 13;(H), 17 .(H) diacholestane (20S) 1
1 2' C27H4R 372 13i(H), 17.(H) diacholestane (20R) 1
1
1 3 C
27 H 48
C27H4R
372
372
13.(H), 17c(H) diacholestane (20S)
13,(H), 17 : {H) diacholestane (20R) t
1
1
1" C
28 H 50 386 13f(H) 17 .(H)diaergostane (20S) 1
1 5 C
2R H 50 386 Rearranqed C 2 R sterane 1
1 6 C
28 H S0 386 Rearranqed C 2 S sterane
1 7 C
28 H 50 ■386 13i(H), 17,(H) diaergostane (20R) 1
1 8 C27"48 372 5,(H) cholestane (20S) + 56(H) cholestane (20R) 1
1 9 C
27 H 48 372 5,(H), 1 4 f ( H ) , 17f(H) cholestane (20R) + 1
C29H52 400 13r(H), 17,(H) diastfgmastane (20S) 1
1 10 C27H48 372 5,(H), 14f(H), 176(H) cholestane (20S)
1 11 C27H4R 372 5.(H) cholestane (20R)
1 12 C
29 H 52 400 Rearranqed C 2 9 sterane 1
1 13 C 2 gH 5 2 400 Rearranged C 2 9 sterane 1
1 14 C29H„ 400 Rearranged C 2 g sterane 1
15 C
2R H 50 386 5,(H) ergostane (20S)
16 C
28 H 50 386 5„(H), 1 4 f ( H ) , 17f(H) ergostane (20R) +
5 R ( H ) ergostane (20R)
7 C
28 50H 386 5,(H), 14.3(H), 17;'(H) erqostane (20S)
1' 18 C
28 H 50 386 5,(H) ergostane (20R)
1 19 C
29 H 52 400 5«(H) stigmastane (20S)
1 20 C
29 H 52 400 5..(H), 14c(H), 17n(H) stiqmastane (20R) +
5 r (H) stigmastane (20R)
1 21 C29H52 400 5,(H), 14|.(H), 17»(H) stiqmastane (20S)
1 22 C
29 H 52 400 5,(H) sttgmastane (20R)

Assumes 8i-(H), 9.(H), H , ( H ) , 17,(H) unless otherwise stated.

dia 1 rearranqed

- 752 -
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