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Marine and Petroleum Geology, Vol. 14, No. 4, pp.

451468, 1997
0 1997 Published by Elsevier Science Ltd
All rights reserved. Printed in Great Britain
PII: s0294-9172(97)9991 l-l 0264-8172/97 $17.00+0.00
Geochemical evaluation of hydrocarbons and their
potential sources in the western. South Caspian
depression, Republic of Azerbaijan
Michael A. Abrams
Exxon Ventures (CIS), Inc., P.O. Box 4480, Houston, TX 77210-4480, USA
Akif A. Narimanov
SOCAR, Neftchilar Avenue 73, Baku 370004, Republic of Azerbaijan
Received 5 September 1996; revised 6 December 1996; accepted 23 December 1996
The western South Caspian depression, located in offshore Azerbaijan, contains significant
accumulations of oil and gas in Upper Tertiary fluvial-deltaic sediments. The active Tertiary
hydrocarbon system is a product of unique paleogeographic and tectonic events that led to
Paleogene deposition of organic-rich source rocks, rapid Pliocene subsidence concurrent with
voluminous supply of elastic sediments, and development of anticlinal traps with abundant shale
diapirs.
Molecular characterization of selected oil samples indicates most of the oils are sourced from
similar organic facies. The molecular characteristics are consistent with oils sourced from a
Tertiary, slightly calcareous, marine elastic facies. Examination of oil molecular characteristics,
oil-oil correlations, molecular characteristics of selected source rock samples, maturation models,
and potential migration pathways suggests the oil is not syngenetic, but most likely sourced from
deeper Miocene and older marine shales. Most of the oils have lowto moderate organic maturities
(VRE 0.75485) relative to conventional peak generation windows. Significant variations in oil
gravity and whole oil gas chromatogram character suggest post-emplacement bacterial and
fractionation alteration. Several oils display characteristics consistent with multiple phases of
trap charging. The bulk of reservoired gases examined in this study have been sourced from
mixed terrestrial-marine kerogen generated at organic maturities of VRE 0.80-1.00 with some
biogenic-low maturity mixing. None of the gases examined were sourced from the thermal
destruction of liquid hydrocarbons.
We postulate multi-stage hydrocarbon emplacement into evolving structural traps. The first
phase of emplacement occurred in the Middle Pliocene when tectonic movement and increased
subsidence initiated early trap/reservoir formation, hydrocarbon generation, and migration. Late
rapid subsidencefrom Quaternarytectonicactivityproduced additional hydrocarbonsto replenish
older, depleted traps and charge newly formed traps. This late tectonic activity also extensively
redistributed hydrocarbon accumulations, degassed some that were breached by faults, and
destroyed other oil pools. Thermal disequilibrium from the rapid subsidence delayed hydrocarbon
generation and increased the minimum depth required for the onset of liquid hydrocarbon
generation. 0 1997. Published by Elsevier Science Ltd.
Keywords: Azerbaijan; geochemistry; hydrocarbon systems; South Caspian
The South Caspian depression is a Tertiary back-arc
basin located in the offshore Republic of Azerbaijan.
Azerbaijan is located in the Caucasus region, bordering
Russia, Georgia, Armenia, Turkey, Iran, and the Caspian
Sea (Figure la) with approximately 86 600 km2 of land
area and a population of 7 million. It is one of the oldest
known oil producing regions in the world with a rich and
colorful petroleum exploration and production history
dating back to Alexander the Great. The soldiers of Alex-
ander the Great utilized these rich oil resources during
campaigns in the IV century BC from shallow hand dug
wells. The first oil well was drilled in Azerbaijan by a
Russian engineer, Semyenov, in the Bibi-Eibat area in
1848, 11 years prior to Colonel Drakes oil well in
Pennsylvania (Narimanov and Palaz, 1995). By 1913,
Azerbaijan produced 83% of the oil within the former
USSR (Narimanov and Palaz, 1995). Most recently there
has been increased interest in the area with the signing of
several multi-billion dollar production sharing agree-
ments including the Megastructure (Chirag, Azeri, and
deepwater Guneshli) (Figure Ib).
The South Caspian depression contains significant
accumulations of oil and gas with discovered reserves
estimated to be 20 plus GOEB (billion oil equivalent
barrels) and an additional 20 plus GOEB undiscovered
reserves making the South Caspian depression a world
class petroleum system. It is estimated there are up to
25 km of sediments in the basin center (Nadirov, 1990).
The relatively low geothermal gradients (around 1.5C
lOOm_) from rapid burial provide favorable thermal
451
452 Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
ERBAIJAN
TURKMENISTAN
IRA
km
O-
250
0 150
miles
+
-
cYsPLAN
.
SE4
A
8 +
SABAIL
+ i
Legend
BAKHAR FIELD NAME
GAS
Figure 1 (a) Index map of study area, Republic of Azerbaijan. (b) Map of fields with oil, gas and rock samples, Republic of Azerbaijan.
conditions for the preservation of hydrocarbons at rela- of reverse faulting and fracturing. Many structures are
tively great depths (up to lO+ km) (Nadirov, 1990). penetrated by mud diapirs and mud volcanoes. Most
Known hydrocarbon accumulations within the Azer- of the structures occur along clearly identifiable trends
baijan offshore areas are contained in Pliocene siliciclastic associated with underlying deep seated faults which were
reservoirs within structural traps. Structural styles range inherited from the Mesozoic and reactivated during the
from anticlinal folds to monoclines with various degrees Cenozoic. The majority of the accumulations are in
Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov 453
fluvialdeltaic Middle Pliocene sediments (Productive
series).
The present study focuses on the hydrocarbon accumu-
lations located in the onshore and near shore western
South Caspian depression (Figure Ib). Subsurface oil, gas
and rock samples were collected throughout the onshore
and offshore western South Caspian depression to ident-
ify oil and gas groups, and to correlate these hydro-
carbons to stratigraphic units which sourced them, based
upon molecular characteristics. The purpose is to gain a
better understanding of factors that influence hydro-
carbon generation, migration, and entrapment in the
western South Caspian depression.
Regional geology
The South Caspian depression is located on the Greater
Caucasus-Kopet Dag portion of the Alpine-Himalayan
fold belt. It is situated on thinned continental crust and
Lower Jurassic oceanic crust formed by back-arc spread-
ing after Triassic amalgamation of Iranian and Turan
blocks. From the mid-Jurassic into the Neogene, the
South Caspian was a depression on the shelf of Southern
Eurasia where episodic marine restriction led to the depo-
sition of organic-rich calcareous and diatomaceous black
shales (middle Eocene Kuma, upper Oligocene-lower
Miocene Maikop, and middle-upper Miocene Diato-
maceous). The collision of Arabia with Tuarides and
Pontide-Iranian blocks began to close the Caucasus
Ocean in the Miocene. A series of horsts and grabens
developed in response to extension forming many of the
early structural trends. By late Miocene-Pliocene, this
collision was accompanied by regional uplift of the col-
liding terranes and subsidence of the South Caspian oce-
anic crust loading up to 10 km of deltaic and lacustrine
elastics in the basin. This event lead to the development
of key reservoir facies, increased burial for maturation,
iiquification of basinal shales forming numerous shale
diapirs, and re-structuring of traps as well as the creation
of new structures (Figure 2).
The traps consist primarily of anticlines formed along
pre-existing fault trends along which reverse faulting or
inversion of earlier normal faults occurs (Figure 3). The
anticlinal trends are very large both in aerial extent and
vertical amplitude. Many of these anticlines are associ-
ated with mud diapirs which culminate in mud volcanoes
with active hydrocarbon seepage (Guliev and Feizul-
layev, 1996). The mud volcanoes can be extremely large
with relief up to 400m and diameters of several kilo-
meters.
The bulk of the oil reserves are found in the Middle
Pliocene Productive series (Figure 2). The Productive
series can be sub-divided into two distinct groups
(Ruehlman et al., 1995). The early Productive series is
dominated by quartz and minor sedimentary rock frag-
ments typical of the Paleo-Volga provenance to the north.
The late Productive series contains less quartz, more feld-
spar, and fragments of both sedimentary and volcanic
rock fragments more typical of sediments fed by the
Paleo-Kura in the west (Ruehlman et al., 1995). Oil is
also found in the Miocene Chokrak elastics and fractured
Oligocene-Miocene Maikopian shales (Klosterman et
al., 1997).
Oil group
Based on physical properties, gas chromatography, liquid
chromatography, and gas chromatography-mass spec-
trometry (GC-MS) all but one of the 73 onshore and
offshore western South Caspian depression oil samples
appear to belong to a single oil group (Abrams and
Narimanov, 1994) (Figure 4). Only the oil from
Sangachal-deniz # 551 well is sourced from a sig-
nificantly different organic facies (Figure 5). We define an
oil group as a series of oils generated from a similar
organic facies. This differs from an oil family which
defines a group of oils generated in and expelled from a
single, stratigraphically defined source rock (Allan and
Creaney, 199 1). Limited source rock data prevent the oils
from being separated into true oil families. The definition
of an oil group excludes variations due to maturity or
post expulsion alteration processes, such as biodegrada-
tion and phase segregation. Many of the oil samples appear
to have lost a significant amount of volatiles, based on ex-
amination of whole-oil gas chromatograms (Figure 6).
The single oil group is characterized by low sulfur,
medium to low API gravity, whole-oil gas chro-
matograms missing all or part of volatile fraction (C,-
C,,,), abundant methylcylcohexane (MCH) and toluene
associated with volatile loss, pristane to phytane ratios
1.4-1.6, pristane to n-C,, ratios l&4.35, and relatively
high saturate to aromatic ratios (ranging 1.5-2.5) (Figure
4). The saturate biomarkers are characterized by low
diasterane to regular sterane ratios, low hopane to sterane
ratios, CZ7 steranes more abundant than CZ9 steranes, low
20S/(20R + 20s) ratios, low tricyclic to pentacyclic ratios,
CZ9 hopane much less than CXO hopane, moretane peaks
present, C3.&, homohopane ratios less than 1.0, Cs4
tetracyclic much less than C,, tricyclic, oleanane present
(in relatively small concentrations), and Ts to Tm ratios
less than one (Figure 4). GC-MS-MS fragmentograms
from selected oil samples display C3,, regular steranes
which confirms input of marine algal matter (Figure 7).
The Co regular steranes are often confused with CjO 4-
methyl steranes which are abundant in algal-rich lacus-
trine-sourced oils.
Although this single oil group has very similar molec-
ular characteristics, there are differences in isotopic com-
position of the saturate and aromatic fraction. Oils
reservoired in Pliocene and younger rocks are isotopically
heavier by 14 per mil (less negative) than oils reservoired
in Miocene and older rocks (Figure 8). This observation
was first noted by Guliev and Feizullayev (1996). Guliev
and Feizullayev believe the isotopic shift reflects varying
contributions from different age source rocks of similar
organic facies; Middle-Lower Pliocene versus Miocene-
Oligocene sources (Guliev and Feizullayev, 1996).
Although, we agree the isotopic shift is due to varying
contributions from different age source rocks of similar
organic facies, our study indicates the key sources are
located in the Miocene-Oligocene and possibly as young
as Upper-Middle Miocene (see discussion in later section
for details). Secondary alterations, variations in organic
source facies, and differences in the level of organic
maturity could also cause an isotopic shift.
We interpret these oils to be sourced from a Tertiary,
slightly calcareous, marine anoxic elastic facies. Most of
these oils appear to have been generated prior to con-
ventional peak rate of generation (estimated to be VRE
0.95 for Type II marine source rocks, Tissot and Welte,
1984) based on API gravity, hydrocarbon composition,
pristane to n-C,, ratio relative to phytane to n-C,, ratio,
sterane isomerization %CZ9 20S/(20S+20R), Ts to Tm
ratio, relative amounts of moretane, and methyl-
454 Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
60
60
140
160
-
STRATIGRAPHY
SOUTHWEST CASPIAN BASIN
A(
TECTONIC
HISTORY
BACK-ARC
EXTENSION
LOWER KURA &
SW CASPIAN SHELF
AGE STAGE LITHOLOGY . RESERVOIRS
2
$ - - - - PRODUCING FIELDS
--T
2
; .:. . .- . ??KYURSANGYA
f ---
2 ---_
. KIROVDAG
KYURSANGYA
KALMAS
HISHOVDAG
KALMAS
, PIRSAGAT
i 0
DASHGIL
0
DUVANNY
1 1 DASHGIL
KYURSANGYA
1 GARASU
a
SULLA-DEN12
. PRODUCTIVE RESERVOIR
I=I
MARL, CALCAREOUS
A
SOURCE INTERVAL
MUDSTONE
SAND, SANDSTONE
IVVI
VOLCANIC ROCKS
I7
CLAY, CLAYSTONE, SHALE
m TUFF
ARGILLITE, FRACTURED ARG. CARBONATE
Figure 2 Stratigraphic column for western South Caspian depression
phenanthrene index. The sterane isomerization values
are exceptionally low for most of the samples analyzed
(Figure 9). This observation is not uncommon for Ter-
tiary oils from rapidly depositing basins where insufficient
time is present for complete sterane isomerization (Gran-
tham, 1986). This single oil group is found in reservoirs
as old as Miocene and as young as Upper Pliocene in the
western South Caspian depression.
The anomalous oil is from a Miocene elastic reservoir
tested in the Sangachal-deniz # 551 well. This Sangachal-
deniz # 55 1 oil is characterized by pristane to phytane
ratios less than one, higher sulfur, increased C,,, normal
alkanes (waxy), lower saturate hydrocarbon fraction, and
severe volatile loss (missing C,-C,3) (Figure 5). This oil
was sourced from a more restricted marine source facies
containing some terrigenous input. The Sangachal-deniz
# 55 1 oil was also generated prior to peak rate of gen-
eration (estimated to be VRE 0.95 for Type II marine
source rocks) based on hydrocarbon composition, pri-
stane to n-Cl7 ratio relative to phytane to n-Cl8 ratio,
sterane isomerization %CZ9 20S/(20S+20R), Ts to Tm
ratio, relative amounts of moretane, and methyl-
phenanthrene index (Figure 5). We believe this oil sample
most likely represents a relatively unique localized source
facies-reservoir relationship based on the evaluation of
oils from many different fields and age reservoirs.
All the oils sampled have relatively low sulfur contents,
generally less than 0.50%. Marine source rocks are typi-
cally enriched in organic sulfur generating oils with sulfur
contents in excess of 0.75%. An excess amount of iron
during deposition of the South Caspian depression source
rock facies, which precluded sulfur incorporation into
the organic matter, could account for the very low sulfur
content in all the South Caspian basin oils. Or, possibly
a more restricted landlocked setting where less SOd2- was
present, as was salinity.
Secondary alteration
Biodegradation
Biodegradation is the alteration of petroleum by micro-
organisms (primarily bacteria) usually in association with
Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov 455
AZERBAIJAN
I
TURKMENISTAN
KURA BASI N -----+- semi !CASPI AN BASI N L
CASPIAN SEA
I
INDEX MAP
VE: 10X
Figure 3 Cross-section across Southwest Caspian depression.
meteoric, sodium-sulfate-rich waters at temperatures
below 80-90C. Biodegradation is evidenced by a number
of progressive effects including loss of normal paraffins
and the development of a large unresolved hump on the
whole oil gas chromatogram (Tissot and Welte, 1984).
The near total loss of n-alkanes represents a relatively
minor degree of biodegradation at a geochemical scale
but has a huge impact on oil quality. Biodegradation is
commonly associated with water washing which removes
the more soluble hydrocarbons (chiefly the aromatics,
benzene, and toluene and possibly the light paraffinic
hydrocarbons) while fresh water flows through the res-
ervoir .
Several fields display biodegradation effects (up to and
including near total loss of normal paraffins) including:
Kalmas, Dashgil, Duvanny, Umbaki, and Adzhiveli
Vost. Oil samples with partial loss of light-end n-paraffins
and therefore more obvious concentrations of methyl-
cyclohexane (MCH) and toluene, are also the result of
early biodegradation (Figure IO). The microorganisms
have begun to destroy the light-end n-paraffins, but not
the more resistant aromatic compounds such as toluene,
and MCH. Fields which show this partial biodegradation
include Pirsagat, Kalmas, Garabag, Kyursangya, Bulla-
deniz, and Duvanny-deniz. Reservoir temperatures for
offshore fields Bakhar (37-55C), Bulla-deniz (S@-SYC),
Duvanny-deniz (27-55C), and Garasu (5 1 C) indicate
reservoir temperatures for these fields are generally less
than the 70-75C bacterial cut-off and thus bacterial
I O
LEGEND
Scum Facie8
II - Marine, on Prone
III - Terresttial. Gas Prone
??OU(6 Condensate, or Gas) Field
activity could be ongoing today. No water analyses were
available to determine present day in situ water com-
positions.
Fractionation
Fractionation is the separation of distinct hydrocarbon
phases in the reservoir due to pressure reduction from
erosion or fault movement, or the introduction of a gas
charge (Thompson, 1987). Residual oils exhibit signifi-
cant loss of the volatile fraction (C,-C,), with the remain-
ing light hydrocarbons enriched in the higher boiling
point light aromatic and naphthenic compounds. Several
whole-oils display gas chromatogram traces with charac-
teristics consistent with the residual fraction: Pirsagat,
Bulla-deniz, and Garasu (Figure 6). The higher amounts
of cyclohexane and other aromatic compounds in many
of the western Southwest Caspian depression crude oil
samples are believed to be due to evaporative loss or
phase transformation, not a source facies with increased
plant material.
Multiple charge
Several oil samples display characteristics consistent with
more than a single charge event. The resulting reservoired
oil displays a whole oil gas chromatogram indicating
two or more separate and distinct times of hydrocarbon
emplacement.
456 Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
DUVANNY #516
RESERVOIR: MIDDLE PLIOCENE VIII SAND
24.36
16.41
12.46
.56 !
I I I I I I I 1
0.00 10.00 20.00 30.00 40.00
100000
80000
60000
PENTACYCLIC
TERPANES
I
40000 -
TRICYCLICS E
II-
20000 -
20 30 40 60 60 70 SO 20 30 40 50 60
TIME (min.) TIME (min.)
100000
STERANES IL
ti 80000
f
s 60000
:
4 40000
20000
Figure 4 Whole-oil gas chromatogram and 191 and 217 m/z ion fragmentograms for major oil group, western South Caspian depression.
A Umbaki Field oil collected from the Miocene res-
ervoir appears to result from an early charge of normal oil
which was subsequently biodegraded (napthenic hump),
followed by a second hydrocarbon charge of non-
degraded crude (Figure Ila). The relatively large
napthenic/unresolved hump, loss of high molecular weight
alkanes, and degraded isoprenoids suggest a relatively
high level of biodegradation (level 4, Alexander et al.,
1983) yet the lower boiling point normal alkanes, which
are normally the first compounds to be degraded, are
present. The lower boiling point normal alkanes should
not be present at this stage of biodegradation suggesting
these hydrocarbons came after the initial biodegradation.
The identification of more than one charge is usually very
difficult. The most recent charge must be in small enough
volumes as to not overwhelm the previous charges. The
Umbaki oil is located onshore within a Miocene reservoir
where later charges from younger sources would be
limited.
A Kyursanga Field sample oil collected from the
Middle Pliocene reservoir suggests a low maturity oil
mixed with a higher gravity oil (Figure I lb). The high
molecular weight compounds; high pristane to n-C,,, high
phytane to n-C,,, and hopanes/sterane signature on
whole-oil gas chromatogram, indicate a low maturity oil
whereas the low molecular weight compounds indicate a
higher temperature or different source facies contri-
bution. The two different signatures would suggest a two
phase charge. A similar signature could also be the result
of fractional condensation, phase separation during
migration to the trap then recombination.
Gas evaluation
Mud volcano and hydrate gases
Dadashev and Guliev (1989) examined gas composition
and isotopic ratios of methane (C,) and carbon dioxide
(CO,) from several onshore mud volcanoes. Their results
indicate the hydrocarbon gases are sometimes thermal in
origin and sometimes biogenic. They can be divided into
three distinct groups on the basis of methane and carbon
dioxide stable carbon isotope ratios. The first group
(Group I) includes Abikha, Uchtepe, Akhtarma, and
Karadag volcanoes (Xl3 - 35.9 to -41.5%0); the second
group (Group II) includes Shorbulak, Gekmaly, Bozdag,
Kobiisk, and other volcanoes (6C -44.6 to -46.6%0);
and the third group (Group III) includes the Bog-boga
and Kirmaku volcanoes (6C - 55 to - 60%0). The first
two groups of mud volcano gases have been interpreted
by Guliev and Feizullayev (1996) to be thermal in origin
based on the isotopic ratios of methane and carbon diox-
ide, and the amounts of ethane (C,) to butane (C,) relative
to methane (C,). The Group I gases appear to have a
higher temperature origin than Group II gases based on
the isotopic ratios of methane. The heavier isotopic ratios
of the Group I gases could also be due to differences in the
isotopic ratios of original source organic matter and/or
secondary alterations (bacterial alteration). The Group
Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
457
SANGACHAL DEN12 #!%I
RESERVOIR: MIOCENE
12.09
9.42
1.42 ;
I I I I I I I I
0.00 10.00 20.00 30.00 40.00
140000
s
z 100000
PENTACYCLIC
2 TERPANES
f
s
60000
20000
0
20 30 40 50 60 70 80
TI ME (min.)
120000
80000
i
STERANES &
60000 DIASTERANES
20 30 40 50 60
TI ME (min.)
Figure 5 Whole-oil gas chromatogram and 191 and 217 m/z ion fragmentograms for Sangachal-deniz #551 oil sample.
III data show that the gases formed biogenically or at the
very earliest stages of burial.
Ginsberg et al. (1992) collected submarine hydrates in
the South Caspian Sea. They concluded waters associated
with mud volcanoes played a key role in hydrate forma-
tion. The hydrates are postulated by them to be due to
the discharge of gas-saturated formation waters and gases
at sites exposed by erosion. The hydrate gases are
enriched in ethane (C,) to butane (C,) homologs relative
to onshore mud volcanoes gases. The high abundance of
these heavier homologs (12.2% and greater), isotopic
ratios of methane 6C13 as heavy as -44.8%0, and associ-
ation with oil seepage suggest the gas is of thermal origin.
SAMPLING LOSS EVAPORATIVE FRACTIONATION
10.23 VOLATILE
-
BULLA DFSHDRE 14
ADB MID. PLIDCENE V
Some isotopic ratios of methane as light as W3 - 57.3%0
could be the result of thermogenic gases mixing with
shallow bacterial gas from the biodegradation of oil
seepage.
Reservoired gases
Natural gases occur in a variety of environments. Bac-
terial processes form gases in continental swamps and
marine sediments. Such gases are almost exclusively
methane, which is isotopically light, and not associated
with oils. In deeper strata, natural gases are formed by
AOE: ID. PLIDCENE VII
8.28
7.77
6.25
4.74
3.23
1.72
i
i , , , ,
0.W
I I I I I I I I I,
5.M) 10.00 15.0 20.M) 25.02 2mO 35.00 40.00
Rgure 6 Differentiation between volatile loss caused by sampling/storage (a) and evaporative fractionation (b).
458 Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
Geochemical evaluation of h ydrocarbons: Michael A. Abrams and Akif A. Narimanov 459
EXAMINATION OF ISOTOPIC COMPOSITION
OF RESERVOIRED CRUDE OILS
Isotopic Composition of Aromatic Fraction
- 28. 5 - 28 - 27. 5 - 27 - 28. 5 - 26 - 25. 5 - 25 - 24. 5
I Dlinrmnl~ r or c mmi r ad nils
- ..- -_.._ .___. _.._- _.._
A Miocene & older reservoired oils
0 Lower Maikop
m
- 23. 5 0"
P.
z
- 24. 5 s
D
E:
I .
=t
- 25. 5 0
J
0
G
- 26. 5 z
2
i p"
n
- 27. 5 2
Z
- 28. 5
Figure 8 Cross plot isotopic composition of saturate and aromatic fraction for oils with rock extract isotopic composition of saturate
and aromatic fraction data.
processes of thermal alteration of organic matter in
source rocks and/or the thermal destruction of
petroleum. Gases formed by thermal processes have a
greater amount of wet components (C,,) and are iso-
topically heavier. Secondary processes can radically alter
the original molecular composition as well as the isotopic
composition (James, 1990).
The gas samples analyzed in this study are pre-
dominantly hydrocarbon gas with less than 1.0% non-
hydrocarbon gas (CO, and N2). No H&S was detected.
The hydrocarbon portion (air free basis) ranges 91.C~
98.0% for methane, 0.4&4.20% for ethane, 0.20-1.60%
for propane, 0.02-0.40% for normal-butane, O.OO-0.30%
for normal-pentane, and 0.0@0.34% for hexane plus
hydrocarbons. The wetness index [(C,-C&-C,) x 1001
ranges from less than 1.0% to 7.20%. The isotopic com-
position of methane ranges from 6C - 55.0 to 36.3%0.
Using the various published gas interpretation schemes
by James (1983, 1990), Schoell (1983) and Stahl (1977)
we believe the bulk of reservoired gases examined in this
study have been sourced from mixed terrestrial-marine
kerogen (Type III-II) generated at VRE 0.80-1.00 with
some notable exceptions (Figure Z2). Several samples may
have been generated at slightly higher temperatures and
BIOMARKER MATURATION CROSS PLOT
:-^-I
0. 3 -
F
0. 2 -
0. 1 -
.
.
.
.
.
.
. .
. . ??? ?? ?
? ? ? ?
0 i
I I I I I I I
0 0. 1 0. 2 0. 3 0. 4 0. 5 0. 6 0. 7
STERANE 20s/20r
Figure 9 Biomarker maturation cross plot (TAS, tri-aromatic steranes, versus sterane 2OS/2OR).
460 Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
MAIKOP
I.661
0.00 10. 00 20. 00 30. 00 4( IO
9. 06
DASHOIL 15
MID. PLIOCENE VII
7.59
5. 13
,
I
0.00 10. 00 20. 00 30. 00 40. 00
4. 56
3. 20
1. 73 ;
I I I I I I I
Fi gur e 10 Biodegraded oils, western South Caspian depression.
a single gas sample from a Sabail exploration test possibly
reflects a low maturity and bacterial gas mix (Abrams
and Narimanov, 1994). The isotopic and compositional
data provided in this study do not support thermal crack-
ing of marine sourced oils into gas. In addition, the data
do not support a significant biogenic-low temperature or
high temperature contribution, although there is evidence
of some limited bacterial and low temperature contri-
bution.
Geochemical evaluation of potential source rocks
Rock samples were collected from onshore and offshore
conventional core subsamples and outcrops to identify
key source facies present in the western South Caspian
depression. The rock samples range in age from Upper
Cretaceous to Middle Pliocene. These rock samples do
not properly represent all probable organic facies due to
poor core recovery and limited penetrations below the
Pliocene preventing extensive sampling of most older
facies.
3. 00
3
l J HBAKl ~21
YAI KOP
0. 65
t
6. 71
6. 67
4. 42
2. 26 ;
I I I I I I I
0.00 10.00 20. 00 30. 00 40. 0
10. 97
SANGACHAL DEN12 381
MID. PLIOCENE Y
9. 10
7. 23
5. 36
3. 49
1. 63 {
I I I I I I I
0.00 10. 00 20. 00 30. 00
40. 00
6. 67
6. 63
4. 69
3. 76
2. 61
1. 67 ;
I I I I I I I
0.00 10. 00 20. 00 30. 00 40. 00
Eocene and Upper Cretaceous
The Upper Cretaceous is believed to be a deep marine
facies composed of mottled elastic and detrital-carbonate
flysch deposits (Clarke, 1993). None of the Upper
Cretaceous rock samples contained total organic carbon
greater than 1 .O%. Bailey et al. (1996) identified potential
source rocks in the Late Cretaceous which may be related
to several surface oil seeps.
Several Eocene core samples from onshore Lower
Kura area did contain sufficient total organic carbon and
elevated hydrogen indices to be classified as a potential
source rock (Figure 13). The molecular characteristics of
Eocene rock extracts are consistent with a low-maturity
siliclastic algal-bacterial mix deposited in an anaerobic
marine environment: high saturate to aromatic ratio, low
sulfur content, pristane greater than phytane, high pri-
stane to n-C,, and phytane to n-C,, ratios, low tricylic
terpanes, C,, tetracyclic terpane greater than C,, tricyclic,
high C,, to C,, homohopane ratio, diasterane to regular
sterane ratio greater than one, C,, hopane much less than
the CzO hopane, hopane to sterane ratio between 2 and 3,
moretane present, oleanane present, Cl7 slightly less than
Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov 461
26. 16
LOW MATURITY OIL
16. 02
. 76
I
0.00 10. 00 20. 00 30. 00 40. 00
Figure 11 Examples of multiple charge oils: (a) Umbaki Field and
(b) Kyursangya Field.
Cz9 sterane, isotopic ratio of saturate fraction 6C - 28.0
to -29.0, and isotopic ratio of aromatic fraction 6C13
-27.0 to -28.0%0 (Figure 24).
Oligocene-Early Miocene (Maikopian)
During the Oligocene to Early Miocene further collisions
of micro continents with Eurasia resulted in the for-
mation of a restricted back-arc basin with stagnant con-
ditions conducive for the accumulation of an organic-
rich algal source rock (Clarke, 1993). Published source
rock data, as well as the rock samples collected in this
study, all demonstrate the Oligocene to Early Miocene
(Maikopian) fine grain rocks from the onshore Lower
Kura contain sufficient total organic carbon content and
elevated hydrogen indices to be classified as good oil-
prone source rocks (Figure 13) (Piggott et al., 1996;
Javadova et al., 1996; Bailey et al., 1996).
Geochemical characteristics of selected organic rich
immature Oligocene-Early Miocene core samples indi-
cate a low-maturity siliclastic algal-bacterial mixture
deposited in a reducing marine environment. Extracts
display the following molecular characteristics: sulfur
content greater than l.O%, low normal paraffins, high
isoprenoid compounds, pristane greater than phytane,
pristane and phytane much greater than n-C,, and n-
C8, low tricylic terpanes, high C,,/C,, homohopane, low
diasteranes to regular steranes, Cz9 hopane much less
than the Co hopane, high concentrations of moretane,
low hopane to sterane ratios, oleanane present, isotopic
composition of saturate fraction 6C13 - 28.0 to - 29.0%,
and isotopic composition of aromatic fraction 6C3
-27.0 to -28.0%0 (Figure 14). In addition, pyrolysates
for selected Oligocene-Early Miocene rock samples have
relatively high concentrations of paraffinic compounds
which decrease rapidly with increasing carbon number,
alkene/alkane doublets up to Co, lower concentrations
of aromatic compounds such as toluene, xylenes, and
naphthalenes, and lower concentrations of polar com-
pounds (phenols, creasols . etc.) indicating these source
rock samples will yield large volumes of liquid hydro-
carbons and little gas.
Activation energies for selected organic-rich immature
Oligocene-Early Miocene rock samples range between
47 and 64 kCa1 mol- with sample medians between 53
and 57 kCa1 mol-. A single Muradkhanaly well sample
did contain slightly different energy activation dis-
tribution (5664 kCa1 mol-). This higher value is most
likely due to the elevated organic maturity (VRE 0.68-
0.78; estimated from T,,,). Hydrocarbon generation cal-
CROSS-PLOT OF DELTA
ETHANElPROPANE 81 WETNESS
VRE: 0. 65* VFtE=1. 25* Vi ETNESSCP' %
LOW
MATURI TY
t
J .
- - - - .
MOREALGAL
t
+
?
LESS ALGAL
(MORE HUM/C)
1. I
.
- .
.
. I. +.
. .
.
?? .s 9
. .
.
-6 -4 -3
Delta Elhane and Ropsne Ikotopic CampMon
Figure 12 Organic maturity and source facies evaluation for selected gas samples.
462 Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
FOR ROCKS WITH TOC> 0.75%
1000 ,
s 800 -
L
2 600 -
s 500 -
3 POOR
P
400 -
SOURCE
zi
8 300 -
A
g
$ 200 -
&
NON
SOURCE
0
EXCELLENT
SOURCE
GOOD
f
??
soURoCE
0
00
Q @
Q
4
0
??Diatom Suite-Upper Miocene
@ Upper Maikoplan
@I Mlddle Malkopian
0 Early Maikoplan
POOR
SOURCE
; h&c.pian Und,,,e,entiated
(Oligocene-Miocene)
A Eocene
_
MEASURE&OTAL ORGANIC CARBON (WT%)
NOTE: Pm PIIoEme *.ctbm not
penetr.tell I Df*hOm lwJ ama. 0 Rock orgmlc Maturity Less Than YRE 0.55
Figure 13 Cross plot total organic carbon and hydrogen index for samples with total organic carbon greater than 0.75%.
culated from kinetic measurements on these Oligocene-
Early Miocene rock samples is similar to typical Type II
marine source rocks (Tissot and Welte, 1984). This would
indicate the Maikopian source rocks do not generate
hydrocarbons at lower levels of thermal maturity.
Middle and Late Miocene
By Late Miocene, the South Caspian was an enclosed
seaway semi-isolated from marine influences. The sedi-
mentation consisted of alternating marine and non-mar-
ine deltaic, turbidites and flysch/molasse (Clarke, 1993).
Several Middle and Late Miocene core samples analyzed
in this study contain total organic carbon and hydrogen
indices indicating good source potential as well as poor
source potential (Figure 13). Recent studies by Piggott et
al. (1996), Rinaldi (1996) Bailey et al. (1996) and
Javadova et al. (1996) have reported similar results.
The molecular characteristics of the higher quality
Middle and Late Miocene rock extracts are similar to the
Late OligoceneeEarly Miocene rock extracts except in
the isotopic composition of saturate aromatic fractions.
The Middle and Late Miocene rock extract saturate and
aromatic carbon isotopes are less enriched in carbon 13
relative to carbon 12 by approximately 24 per mil (Fig-
ure 9).
Pyrolysates from a single Diatomaceous Suite rock
sample have relatively high concentrations of paraffinic
compounds, lower concentrations of aromatic com-
pounds, and lower concentrations of polar compounds
indicating good potential to yield liquid hydrocarbons.
The relative amount of paraffinic compounds to aromatic
and polar compounds shifts slightly indicating a less
reducing environment and therefore slightly more gas
prone character.
Pliocene to Pleistocene
The Pliocene to Pleistocene sediments are represented
by flysch/molasse and marginal marine to non-marine
deltaic sediments (Clarke, 1993). All of the Pliocene
(Middle) core samples collected for this joint study con-
tained total organic carbon (TOC) less than 1 .O%. These
low TOC values are consistent with the interpreted pale-
ofacies (marginal to non-marine). Pyrochromatographic
studies by Narimanov (1986, 1993) also indicated that the
Pliocene contains limited source potential. Narimanov
(1986, 1993) did note a slight increase in organic content
in Lower Pliocene samples, but not a sufficient increase
for the rocks to be classified as a good liquid prone source
(1 .O% of total organic carbon).
Maturation evaluation
Maturation measurements
Estimates of organic maturity for core samples are based
on T,,, and mean random vitrinite reflectance (R,). T,,,,
is the temperature corresponding to maximum hydro-
carbon generation during pyrolysis (S2 peak, Tissot and
Welte, 1984). T,,,,, provides crude estimates of maturity
for immature to mature samples, but not for overmature
samples. T,,,,, for low TOC samples nearly always pro-
vides unreliable maturation estimates. Mean random
reflectance values in oil (R,) measures the amount of
incident light which is reflected from the surface of the
coal maceral vitrinite. Histograms for multiple vitrinite
reflectance measurements on individual macerals are
examined to estimate the true in situ reflectance versus
reworked populations.
T,,,,, and R, data from three onshore wells indicate that
the Miocene and younger section (less than 5000m)
is immature at these on-structure onshore locations
(Figure 15). Peak hydrocarbon generation (R,, = 0.95, for
a typical Type II marine source rock) probably occurs
between 5000 and 5500m in the onshore areas.
Insufficient maturation measurements are available to
determine depths for peak oil generation in the offshore
areas. Maturation data published by Korchagina et ul.
(1988) for selected wellbores, outcrops, and mud vol-
canoes indicate that sufficient maturation for significant
hydrocarbon generation will occur deeper than 700&
8000 m.
Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
463
Field / Well: Muradkhanly 35 (4,495-4,500 m)
Age: U. Eocene
TOC: 1.29%
% S: 0.26%
HI: 276 m g/gm
EOM: 715 ppm
EOCENE CORE
OLIGO-MIOCENE CORE
Field I Well: Muradkhanly 3 (2,760 m)
r
Ion 191.30
Time (min.)
Ion 217.30
20 30 40 50 60
Time (min.)
TOC: 2.11%
% s: 1.12%
HI: 344 m g/gm
EOM: 1705 ppm
Ion 191.30 30H
Pentacyclic Terpaner
Time (min.)
I
Ion 217.30
Time (min.)
Figure 14 Whole-bitumen gas chromatograms and 191 and 217 m/ z ion fragmentograms for core extracts: Eocene and Oligocene-
Miocene core.
Maturation models
The great depths to peak hydrocarbon generation and
delayed timing of hydrocarbon generation in the offshore
areas estimated by thermal models are due to non steady-
state thermal conditions which result from rapid sedi-
histories based on stratigraphic input from wells and
seismic profiles for several sites demonstrate the rapid
subsidence as well as complex histories (Figure 16). Sedi-
mentation rates have been estimated to be as high as
2.9m per 1000 years in the South Caspian depression
Upper Tertiary section (Groves et al., 1996). The Eocene
mentation (Abrams, 1996; Crews et ul., 1996). Burial to Middle Pliocene period displayed relatively constant
464 Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
DEPTH (m)
Iax 431 442 449 4%
1 0.5 1.0 1.5
I I I
. .
.
TOTAL VITRINITE
REFLECTANCE HISTOGRAMS
VITRINITE REFLECTANCE
VITRINITE REFLECTANCE
WELL: KERZEG KVLLVTEPE NO. 293
DEPTH: 2420-2425 METERS
AGE: MIOCENE
WELL: KARADAG No. 352
DEPTH: 3198-3195 METERS
AGE: MIOCENE
WELL: KARADAG No. 391
DEPTH: 3200-3210 METERS
AGE: PLIOCENE
VlTRlNlTE REFLECTANCE
Figure 15 Maturation profile, vitrinite reflectance (I?,,) and T,,,,.
sedimentationsubsidence, while subsidence increased in
the Late Miocene to early Pliocene, followed by localized
brief periods of uplift and erosion. Subsidence re-initiated
in Middle Pliocene, with a dramatic increase in sedi-
mentation rate, again followed by a brief period of uplift
and erosion. Minimal subsidence and sedimentation in
the Upper Pliocene and Early Quaternary was followed
by a dramatic increase in subsidence and very late local-
ized uplift and erosion.
We used the Platte River Associates basin modeling
program BasinMod to estimate current subsurface matu-
ration and temperatures in areas where well penetrations
are not sufficient to characterize the deeper Upper Oli-
gocene (lower Maikopian) source rocks. The estimated
timing of hydrocarbon generation for an Upper Oli-
gocene (lower Maikopian), Type II marine source was
based on a 1-D basin model. We utilized a variable heat
flow model with a slightly higher background heat flow
prior to 8 my. The present day heat flow was calibrated
to measured sub-surface temperatures, or estimated when
no temperature information was available. Present day
basal heat flow ranged 33.537.7mW m-* (0.8s
0.90HFU). In this paper we show results at two on-
structure locations, Pirsagat located just onshore, and
Bakhar located offshore.
The maximum present level of organic maturation for
BURIAL HISTORY - PIRSAGAT
0
1wO
f
2000
300
8 4Do9
F
P
5000
P
:I
60 50 40 30 20 10 0
TIME (Ma)
Figure 16 Example of burial history, Pirsagat site.
Fm
Qaps
N2
Nl
DIATOM
MAIKOP
EOCENE
Geochemical evaluation of h ydrocarbons: Michael A. Abrams and Akif A. Narimanov
465
RATE OF HYDROCARBON GENERATION
PIRSAGAT BAKHAR 54
100
90
3
80 5
0.5 70 g
6
iz
308
e
c
,
50 z
%
40
I
z
2 30 d
8
20 v
i?
5 . :
10
5
llllllllllllllll I I
40 35 30 25 20 15 10 5 0
TIME (Ma)
I---
Figure 17 Rate of hydrocarbon generation: (a) Pirsgat and (b) Bakhar.
the proposed Upper Oligocene source rock at the Pirsagat
location is 0.75 VRE (Figure 17~). This corresponds to
early, pre-peak oil generation for a Type II marine source
rock. The Pirsagat modeling site shows two major pulses
of hydrocarbon generation, one at 6 my, and the other at
2my. These two pulses result from burial, uplift, and
subsequent reburial. The oil sample from the Pirsagat
field also appears to display characteristics of a multiple
charge although the mixture of hydrocarbons may be due
to generation from two separate age source rocks and
not a single source rock which is heated in two separate
pulses of burial. Note that the discrete pulses of hydro-
carbon generation found in our models may be an artifact
of the inability of most thermal modeling programs to
handle extreme burial rates-thermal transient effects and
not actual separate phases of generation.
The maximum present level of organic maturation for
the proposed Upper Oligocene source rock at the Bakhar
location is also 0.75 VRE (Figure 17b). This again cor-
responds to early, pre-peak oil generation for a Type II
marine source rock. The Bakhar modeling site shows
only a single pulse of hydrocarbon generation, as do the
oil samples from this field.
Off-structure maturation modeling sites, in the basinal
deeps away from the uplifts, display suppressed (lower)
temperatures when compared to similar depths on the
corresponding on-structure site. We believe this is a
consequence of non-steady state conditions. The sedi-
mentation rates are extremely high in the off-structure
areas relative to the on-structure sites. The rapidly
deposited sediments do not have sufficient time to ther-
mally equilibrate. Measured temperatures are much
lower than those expected if equilibrium conditions were
present (Figure 18). This difference between steady state
and transient conditions requires greater depths off-struc-
ture before sufficient temperatures for hydrocarbon gen-
eration and delays the peak rate of generation, as
compared to on-structure sites. This also allows liquid
hydrocarbons to be generated and thermally preserved
at much greater depths than would normally be expected.
COMPARISON OF STEADY STATE AND
TRANSIENT TEMPERATURES
BAKHAR 54 ON-STRUCTURE
TEMPERATURE (DEG C)
20 40 80 80 ml 120 140 160 180 200
BAKHAR 54 OFF-STRUCTURE
TEMPERATURE (DEG C)
0 50 100 150
2000
200
4000
250
Figure 18 Differences between steady state and transient sub-
surface temperatures.
Hydrocarbon source evaluation
There is much uncertainty about the key source or
sources which generated the large volumes of oil and
466 Geochemicai evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
gas currently reservoired in the western South Caspian
depression. The limited number of organic-rich rock sam-
ples, similarity of organic facies from different age rocks,
and lack of penetration beyond the Pliocene from off-
shore wells, preclude a conclusive hydrocarbon to source
correlation. Early studies assumed the majority of hydro-
carbons were sourced from the surrounding Middle
Pliocene marginal marine and non-marine shales even
though the concentration of organic matter is low due to
the high sedimentation rates (Narimanov, 1986). It is our
belief the western South Caspian depression oils have
been sourced from a series of Oligocene to Miocene
organic-rich marine shales. The onshore Miocene and
older reservoired oils are most likely sourced from the
early Maikopian organic-rich sections whereas the youn-
ger Middle Pliocene reservoirs are most likely sourced
from the Middle-Upper Maikopian and possibly youn-
ger Diatomaceous organic-rich sections. The reservoired
gases most likely have been sourced from a slightly more
oxygenated organic-rich Middle to Late Miocene to pos-
sibly Early Pliocene marginal marine organic-rich shales.
These conclusions are based on the following obser-
vations:
1.
2.
3.
4.
5.
6.
Oil source facies versus paleogeography: Oils are sour-
ted from basinal restricted marine source facies (sap-
ropelic). This restricted marine source facies existed
throughout the Eocene to Middle Miocene and pos-
sibly as late as the early part of the Late Miocene, but
not in the very Late Miocene to Early Pliocene and
younger section.
Multiple source rocks within Lower Tertiary: Isotopic
differences between Pliocene and Miocene and older
reservoired oils reflect stratigraphically different
source rocks with similar source facies characteristics.
Oil to oil correlations: Oils within the onshore Umbaki
field, reservoired in Middle Miocene Chokrak rocks,
have similar molecular characteristics and isotopic sig-
natures as oils reservoired in the older Oligocene to
Early Miocene Maikopian rocks. A Middle Pliocene
sourced oil could not have migrated into both the
Chokrak and Maikopian reservoirs, given our current
understanding of the structural history.
Gas source facies versus paleogeography: The bulk of
the gas has been derived from mixed marine organic-
rich source facies (more humic and less anoxic). Such a
source facies with sufficient and correct type of organic
matter only exists in the Middle to Late Miocene and
Early Pliocene.
Middle Pliocene organic maturity: The level of organic
maturity for the western South Caspian depression
Middle Pliocene and younger section is insufficient
to generate large volumes of hydrocarbons based on
organic maturation measurements and thermal
models.
Late OligoceneeMiocene organic maturity: The level
of organic maturity for the western South Caspian
depression Miocene and older section is sufficient to
generate large volumes of hydrocarbons within the
current hydrocarbon field drainage areas based on
thermal models.
Conclusions
The South Caspian Basin with its world class hydro-
carbon accumulations and great potential for the future
discovery of significant hydrocarbon accumulations, is
the product of unique paleogeographic and tectonic
events. Paleogene deposition of organic-rich source
rocks, rapid Pliocene subsidence, voluminous supply of
elastic sediments for high quality reservoirs, and devel-
opment of anticlinal traps form an active Tertiary hydro-
carbon system. The multi-stage hydrocarbon
emplacement from several different age organic-rich
source rocks can be seen in the geochemical charac-
teristics and hydrocarbon distribution and phase. Most
of the oils examined in this study display similar organic
source facies based on molecular characteristics. but also
display a distinctive isotopic separation of the saturate
and aromatic hydrocarbon fractions by reservoir age. A
similar isotopic separation of the saturate and aromatic
hydrocarbon fractions can be seen within the organic-
rich potential source rocks from the Lower, Middle, and
Upper Maikopian and Diatomaceous suite rocks. This
isotopic separation is most likely due to the varying con-
tributions of oils from different age sources of similar
organic facies. In addition. the bulk of the reservoired
gases have been sourced from an organic facies different
from the liquid hydrocarbons. These gases are not from
the thermal destruction of the oils, but generated from a
younger more gas prone source facies at conventional
generating temperatures. Several of the oil samples dis-
play characteristics consistent with multiple phases of
hydrocarbon charges. These different phases of hydro-
carbon charge could have been the result of complex
subsidence and uplifts noted in the burial histories, or
charging from different source rocks as they undergo
deeper burial and generation. The biodegradation of an
initial oil charge and fractionation from later reservoir
pressure depletion or the introduction of a gas phase
provides additional evidence of the complex burial histor-
ies.
The source rocks for the oils are postulated to be Oli-
gocene to Miocene marine elastic shales based on oil-
source correlations as well as our understanding of the
paleogeography and geologic setting. The oil maturity
appears to be lower than the conventional oil window.
This lower than normal maturity could be the result of
rapid expulsion from strong hydrodynamic forces and
not lower than normal source rock activation energies,
but also could be due to anomalously high heating rates.
The bulk of the reservoired gas is believed to be sourced
from Middle to Late Miocene mixed marine shales. There
is some evidence of limited mixing with early formed gas
(biogenic-low maturity). But we did not see any evidence
of thermal cracking of liquids into high temperature gas.
The three key events critical in the formation of hydro-
carbon accumulations in the western South Caspian
depression are as follows; first the deposition of excellent
source rocks in the Late Oligocene to Late Miocene,
second the Middle Pliocene increased subsidence which
drives the early maturation-hydrocarbon charge, struc-
turing, and deposition of the major reservoir system, and
lastly, the Late Quaternary increased subsidence which
drives the late hydrocarbon charge and re-distribution of
hydrocarbons.
Acknowledgements
The authors thank Exxon Exploration Company, Exxon
Ventures (CIS) Inc., and SOCAR for permission to pub-
Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
467
lish this study. The authors also thank Bernie Vining,
James Siegmann, Mary Jo Klosterman, Fikret Dadashev,
Nadir Giyasov, Kyamran Agaev, and John Ruehlman
who assisted with sample collection and geological dis-
cussions. Quentin Ballard, Nadia Patent, Greg Berg,
Glenda Farris, and especially Ted McReynolds provided
technical support. Conventional oil and rock analyses
were preformed at Core Laboratories. Special analyses
and gas compositional/isotopic composition were per-
formed at Exxon Production Research Company. Glenn
Hieshema (EPR) did the GC-MS-MS and Dave Curry
(EPR) the kinetics/P-GC analysis. Allen (W.A.) Young,
K. 0. Stanley, and Jim Allan provided technical con-
sultations. We would like to thank BP for providing
several rock samples. The manuscript was reviewed by
W. A. Young, G. M. Gaskins, George Ramsayer, and
Steve Creaney. We would also like to thank the Marine
and Petroleum Geology reviewers, Neil Piggott and Barry
Katz, and editor, D. G. Roberts for providing excellent
editorial assistance.
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Analytical program
Oil analysis
The State Oil Company of Azerbaijan Republic
(SOCAR) provided crude oil samples collected from
exploration wells and stored in bottles until sub-sampled.
Many of the oil samples display deterioration which may
have occurred during sampling, handling, or storage.
Insufficient data are available to determine the extent or
exact cause of volatile loss.
Whole oil gas chromatograms were run on a Varian
3400 using a temperature program of 12C min from 0
468 Geochemical evaluation of hydrocarbons: Michael A. Abrams and Akif A. Narimanov
to 350C. Another aliquot of each crude oil was evap-
orated at 40C under nitrogen. The asphaltenes were
precipitated with pentane then refrigerated and centri-
fuged. The de-asphalted portion was dried at 40C. The
column was prepared using a 10&200 mesh silica gel
grade 923 under ambient pressure and temperature uti-
lizing a gravimetric procedure.
The isolated saturate and aromatic hydrocarbon frac-
tions were analyzed by gas chromatography-mass spec-
trometry on a HP 5971 MSD/5890 II GC using a
temperature program of 100C held for 20s 20C/min
to 170C 1.5C min- to 290C 2C min to 340C
and 5min hold. For the aliphatic steranes, ions were
monitored at m/z 217, 218, and 259 while m/z 177, 191,
and 205 ions were monitored for tricyclic and pentacyclic
triterpanes. Known standards were used to identify and
quantify key compounds.
Gas analysis
Gas samples were collected from the production well-
head using 300-cm3 seamless stainless cylinders at or near
well-head pressures. Individual gas components were sep-
arated and analyzed at Exxon Production Research
Company using conventional gas chromatography
methods. The stable isotopic composition of indivi-
dual components were analyzed using a VG903 mass-
spectrometer.
Rock analysis
SOCAR provided subsamples of conventional core
samples. Each rock sample was analyzed for total organic
carbon (TOC) with a LECO analyzer. Rock-Eva1 pyrol-
ysis was then run on samples with TOC greater than
1 .O%. Rock samples with sufficient quantity and quality
of organic material were extracted for the study of soluble
organic matter (SOM). Approximately 5&100 g of pow-
dered rock material was placed in a pre-extracted thimble
and extracted using methylene chloride for a period of
24 h. The extracts were then analyzed by the same pro-
cedures enumerated above for the oils using gas chro-
matography (GC), high pressure liquid chromatography
(HPLC), 6C3 saturate and aromatic fractions (isotopic
composition), and gas chromatography-mass spectro-
metry (GC-MS and GC-MS-MS).
Selected samples were chosen for hydrocarbon gen-
eration kinetics evaluation. Kinetic analysis was per-
formed on a temperature calibrated Pyromat II. Splits of
each sample were pyrolyzed at five linear heating rates
between 1 and 50C min-. Resulting pyrolysis data were
then analyzed using the Lawrence Livermore National
Laboratory computer program, KINETICS to deter-
mine the kinetic parameters most consistent with the
data. Calculated kinetic parameters include the dis-
tribution of activation energies and a single frequency
factor (A factor). Pyrolysis-gas chromatography (P-
GC), the analysis of volatile products from thermally
decomposed organic-rich rock samples was also per-
formed on a portion of the sample suite. The pyrolytic
products are trapped and their compositions analyzed
using conventional gas chromatography to separate and
identify compounds.