Regional Evaluation of Source

Rock Quality in Azerbaijan

from the Geochemistry of
Organic-rich Rocks in
Mud-volcano Ejecta
Gary H. Isaksen
ExxonMobil Exploration Co.,
Houston, Texas, U.S.A.
Adil Aliyev
Geological Institute of Azerbaijan,
Baku, Azerbaijan
Scott A. Barboza
ExxonMobil Upstream Research Company,
Houston, Texas, U.S.A.
David Puls
ExxonMobil Exploration Co.,
Houston, Texas, U.S.A.
Ibrahim Guliyev
Geological Institute of Azerbaijan,
Baku, Azerbaijan
ABSTRACT
R
ock ejecta brought to the surface by mud volcanoes offer a unique op-
portunity to characterize sedimentary units both within and beyond con-
ventional drilling depths. Present among ejecta from mud volcanoes in
the South Caspian Basin are the organic-rich rocks of the OligoceneMiocene
Maikop Formation, the primary source rocks for oil and gas in the region. These
rocks have total organic carbon contents as much as 7% wt. and hydrogen in-
dices as much as 500 mg hydrocarbons/g organic carbon. They are dominated by
marine, algal-amorphous organic matter accumulated under dysoxic to anoxic
conditions. When integrated, the rock analyses can aid in the reconstruction of
paleodepositional environments and paleogeography of source rock intervals
and, thus, help high-grade oil and gas exploration targets.
Chapter 10
Isaksen, G. H., A. Aliyev, S. A. Barboza, D. Puls, and I. Guliyev, 2007,
Regional evaluation of source rock quality in Azerbaijan from the
geochemistry of organic-rich rocks in mud-volcano ejecta, in P. O.
Yilmaz and G. H. Isaksen, editors, Oil and gas of the Greater Caspian area:
AAPG Studies in Geology 55, p. 5164.
51
Copyright n2007 by The American Association of Petroleum Geologists.
DOI:10.1306/1205839St551436
INTRODUCTION
The South Caspian Basin (SCB) is a prolific oil and
gas province. As a result of its very thick sedimen-
tary package (as much as 25 km [15 mi]), rapid sedi-
mentation rate (1012 km [67.5 mi] of sediment
fill deposited in the last 6 m.y.), and likely Jurassic
oceanic crust, the basin is relatively cool (Devlin et al.,
1999). Geothermal gradients range from 208C/km in
the Kura depression to 158C/km in the SCB proper.
Consequently, source rocks for oil remain imma-
ture for oil generation down to approximately 6 km
(3.6 mi). The rapid burial and compressional tectonic
regime has resulted in the formation of numerous
mud volcanoes, which are common in the Gobustan
area of eastern Azerbaijan and throughout vast re-
gions of the SCB.
Study Objectives
Lithoclasts brought to the surface by erupting mud
volcanoes offer a unique opportunity to characterize
the sedimentary section, which is generally too deep
to be sampled by conventional drilling. Although
lithoclasts from numerous sedimentary sections are
brought to the surface as ejecta, we have focused our
study on the organic-rich rocks. Many of the mud
volcanoes in the Gobustan area of Azerbaijan are
rooted within the OligoceneMiocene section of the
organic-rich Maikop Formation. When placed in the
context of petroleum explo-
ration, the rockejectashould
enable us to reconstruct the
paleodepositional environ-
ments fromwhichthe ejecta
originated, assess the source
rock potential of organic-rich
rocks, andassess the thermal-
maturity levels of sedimenta-
ry units located deeper than
conventional drill depths.
Geological Setting
The SCB, located within
the AlpineHimalayan oro-
genic belt, extends fromwest-
ern onshore Turkmenistan
throughout theSouthCaspian
Sea, including the Apsheron
Balkhan uplift, and north-
westward into the Kura de-
pression of Azerbaijan and
Georgia (Narimanov, 1993).
The Kura depression lies between the eastern parts of
the Greater and Lesser Caucasus fold belts (Figure 1).
The area that evolved into the SCB experienced
a major increase in accommodation and sediment
fill from the latest Miocene to the present day. The
cause of this is found in the regional tectonic his-
tory, as the collision of India and Arabia into the
Eurasian plate resulted in the formation of the Zagros
and Himalayan terrains, respectively. During the Ju-
rassic, the areas can be classified as a marginal basin
that underwent extension behind a volcanic arch
that extended eastwest along the northern margin
of the Tethys Ocean(ZonenshainandLePichon, 1986).
Geophysical studies of the deep crustal structure sug-
gest that the basin is underlain by oceanic or proto-
oceanic crust from the paleo-Tethyan Ocean (Reza-
nov and Chamo, 1969; Berberian, 1983; Priestley et al.,
1994). Subduction has occurred since the middle Mio-
cene (evidenced by folds along the Apsheron Arch),
with the Jurassic oceanic crust and sedimentary cover
moving beneath the TuranScythian margin of Eur-
asia. Following a period of tectonic quiescence, reacti-
vationoccurred during the late PlioceneQuarternary.
Accommodation space was rapidly filled in with 10
20 km (612 mi) of sediments caused by uplift and
erosion of hinterland areas (Caucasus and Himalaya
orogens and Russian platform) and drained by three
rivers: the Volga fromthe north, the Uzboy and Amu
Darya from the east, and the Kura from the west
FIGURE 1. Tectonic setting of the South Caspian Basin.
52 / Isaksen et al.
(Devlin et al., 1999). In general terms, the Mesozoic
and Cenozoic sections comprise 2025 km (12
15 mi) of sediment, with an 812-km (57.5-mi)-
thick Neogene section, a 58-km (3.15-mi)-thick
Pliocene section, and a 2-km (1.2-mi)-thick Quater-
nary section.
Geopressure
Large volumes of the Azeri subsurface are over-
pressured. Overviews of mechanisms for generating
overpressure in sedimentary basins include Osborne
and Swarbrick (1997) and Kopf (2002). Gretener and
Bloch (1992) define two broad geological conditions
for the formation of overpressuring: (1) compaction
disequilibrium, in which there is unrestricted lateral
flow and restricted vertical flow; and (2) sealed com-
partments, in which there are restrictions to both
lateral and vertical flow. In more detail, the various
causes of overpressuring are

rapid sedimentation rates where the escape of

pore waters cannot keep pace with burial

tectonic forces, especiallyincompressional regimes

thermal expansion of any type of pore fluid

volumetric expansion of formation waters relat-

ed to the transition of montmorillonite to illite

volumetric expansion of kerogen associated with

the generation of oil and gas

volumetric expansion caused by thermal break-

down (cracking) of heavier hydrocarbons to form
light hydrocarbons.
The high pressures in the
SCB area are considered to
be primarily caused by com-
paction disequilibrium be-
cause of relatively high sedi-
mentation rates during the
late Tertiary, gas generation
from both kerogen catagen-
esis and metagenesis, and
gas generation from thermal
cracking of generated oil.
Gaarenstroom et al. (1993)
noted that thermal cracking of as little as 1% of the
oil volume in closed systems can account for pres-
sures sufficient to increase the pore pressure from
hydrostatic to above lithostatic. Asignificant amount
of oil cracking has occurred within the Maikop and
deeper sections, where temperatures are high enough
for in-situ oil cracking given a thermal gradient of
208C/km.
GEOLOGY OF MUDVOLCANOES
Occurrence, Origin, and Characteristics
Mud volcanoes are ubiquitous both on- and off-
shore Azerbaijan, a region that is host to nearly 30%
of the worlds known mud volcanoes. These features
are typically associated with compressional tectonic
regimes and/or rapid sedimentation rates where
the mud extrusion (Figures 2, 3) is related to the pres-
sure release of overpressured, mobile shales. The main
mud volcanoes on- and offshore Azerbaijanare shown
by Figure 4. This data set is naturally biased toward
onshore occurrences, but recent sea-floor mapping has
revealednumerous, very large mud-volcanostructures
offshore with the appearance of seamounts.
Kuklakova andLebedev(1996) recognize twoclasses
of mud volcanoes in this basin. The most wide-
spread class is related to faults on brachy-anticlinal
and diapiric folds where the vent penetrates the
fold and at the crest to forma debris cone. These mud
volcanoes occur in the ApsheronBalkhan zone of
highs, the Baku archipelago, the Abikh and Shatskiy
FIGURE 2. Example of surface
expression of one of the
many mud volcanoes west of
Baku. The truck-wheel mark-
ings in the foreground serve
as a scale. Photo: G. H. Isaksen.
Evaluation of Source Rock Quality in Azerbaijan from Mud-volcano Ejecta / 53
zones of highs, andinthe basins onshore central zone.
Mud volcanoes of the second type are represented as
stocks or dikes. Their surface expression is typically as
small cones, and they occur in limited numbers on
highs as well as depressions. Atypical mud volcano of
the second type is Gryaznyy.
The two fundamental causes of diapir and diatreme
formationare (1) densityinversionand(2) hydrostatic
pressure. These can operate independently. The basic
premise for the density inversion process is a buoy-
ancy contrast within the sedimentary column. Such
buoyancy may be primary (e.g., sediment densities)
or secondary (e.g., fluid influx). The supply of fluids,
especially gases, and their volumetric expansion un-
der decreasing pressures, provides a strong buoyancy
force for vertical flow. Flows are typically triggered by
mechanical failure of the overburden rock because of
high pressures, as well as earthquakes. Bagirov et al.
(1996a, b), in a study with observational data from
533 earthquakes and 220 mud volcanoes throughout
the past 160 yr, noted a correlation between earth-
quake activity and mud-volcano activity, suggesting
that many mud volcanoes erupt between 0 and 5 yr
prior to earthquakes. The periodicity of flowand, thus,
eruptions is mainly related to three factors: compres-
sional tectonics, an increase in pressure caused by
the ongoing generation of gas, and the mechanical
compactionassociated with
each eruption. In their study
of mud volcanoes in accre-
tionary wedges in the Timor
area of Eastern Indonesia,
Barber et al. (1986) envisioned
the shales becoming over-
pressured as a result of over-
thrusting. Excess pressure is
releasedalongvertical wrench
faults, which cut through
the overthrust units; over-
pressured shales, containing
blocks of consolidated units,
rise along the fault zones as
shale diapirs (intrusive mech-
anism); and escaping water,
oil, and gas construct mud
volcanoes at the surface (ex-
trusive). McManus and Tate (1986) considered the
main driving mechanism to be connate waters flash-
ing into superheated steam, which is then forced
upward as hot mud.
Our seismic and structural analysis studies have
shown that most of the structures in the SCB are
large buckle folds overlying a regional ductile detach-
ment zone at depth (Devlin et al., 1999). In this in-
terpretation, upper Miocene to Holocene sediments
behaved in a relatively rigid fashion, deforming as
folds by bedding-parallel flexural slip. The detach-
ment surface is thought to be within the Maikop
shales presently at 1012-km (67.5-mi) depth. At
these depths, the Maikop shales are overpressured
because of a combination of factors described earlier,
including hydrocarbongenerationand thermal crack-
ing, and undercompaction as a result of the high
sedimentation rates. This is in agreement with the
findings of Hedberg (1974). Given a highly overpres-
sured gas at the upper Miocene and lower Pliocene
level, fracture-induced vertical-migration pathways
are developed that either feed into more porous sedi-
mentary units or develop further along preexisting
fault zones. It is not until the gas comes in contact
with significant volumes of formation waters and un-
consolidated sediments that it takes the form of a
mud-dominated system, which reaches the surface
FIGURE 3. The Toraguy mud
volcano in the Shamakha-
Gobustan district. Photo cour-
tesy of A. Aliyev, Geological
Institute of Azerbaijan.
54 / Isaksen et al.
as a mud flow or mud eruption with significant vol-
umes of gas released. Thus, it is more correct torefer to
the subsurface expression of mud volcanoes as gas-
dominated diatremes. We have adopted the distinc-
tions made by Brown (1990); i.e., mud diapirs are de-
fined by a single-phase viscous flow, whereas mud
diatremes have polyphase flow of water and/or gas
causing fluidization. Geoscientists at the Geological
Institute of Azerbaijan (GIA) have estimated that ap-
proximately 500 m
3
(17,600 ft
3
) of gas is released dur-
ing the eruption of onshore mud volcanoes in Go-
bustan. Eruptions from some of the offshore mud
volcanoes are known to release orders of magnitude
larger volumes of gas. Naturally, such violent erup-
tions in the offshore areas are severe hazards for ship-
ping and drilling operations. Dadashev et al. (1992)
described onshore mud volcanoes that sent 50-m
(164-ft)-wide columns of flames more than 200 m
(660 ft) into the air. A physical model for the mech-
anism of eruption and gas ignition was proposed by
Ivanov and Guliev (1988). In their model, ascending
gas, traveling at twice the speed of sound, will com-
press when it encounters physical restrictions along
the vertical-migration pathway. Such rapid compres-
sioncancause gas toheat adiabaticallyandself-ignite.
Indeed, more than 1000 yr ago, the Caspian region
was known as the land of eternal fires because of
burning oil and gas seeps and mud-volcano eruptions,
and these pillars of fire were worshipped by the Zoro-
astrians (Yergin, 1991). During World War II, German
pilots relied on these burning sites as navigational
aids. Today, several places exist where gas is burn-
ing as it flows from outcropping sedimentary units
(Figure 5). Ejecta found within the surface mud flows
are known to have originated from all sedimentary
units along the stem of the gas diatreme, both from
its deeper, predominantly gaseous state and its shall-
ower mud and gas state.
FIGURE 4. The main onshore and nearshore mud volcanoes in Azerbaijan. The different circles denote no oil, an oil film,
or larger amounts of oil found near the volcano.
Evaluation of Source Rock Quality in Azerbaijan from Mud-volcano Ejecta / 55
Rates of mud flow at the surface of mud volca-
noes varies greatly, from a continuing flux of mud
and water at rates of 25 cm/yr (0.82 in./yr) for mud
volcanoes onthe Barbados Ridge (Langsethet al., 1988)
to infrequent, but violent, eruptions of 38,000 km/yr
(23,600 mi/yr) (Kopf, 2002). Measurements and es-
timates made by Bagirov et al. (1996a) on onshore
Azerbaijan mud volcanoes showed that the released
gas volumes could be described by an exponential
distribution with an average value of 590 10
6
m
3
/yr
(20.8 10
9
ft
3
/yr). Guliev et al. (1992) reported an an-
nual flux of 20 Azeri mud volcanoes of 1.3731 m
3
/yr
(4625,800 ft
3
/yr) with an average of 89.5 m
3
/yr
(3160.6 ft
3
/yr). In their study of the Mediterranean
Ridge, Kopf and Behrmann (2000) estimated flow
rates of 60300 km/yr (37186 mi/yr) (approxi-
mately 1 km/day [0.6 mi/day]) for conduit widths of
23 m (6.69.8 ft).
High pressures and violent eruptions of gas, fluid,
or mud are known to rip lithified clasts from the in-
truded strata. Geological and geochemical analyses
of such lithified ejecta provide important informa-
tion about subsurface conditions. Schulz et al. (1997)
acquiredthermal-maturitydata onejecta samples from
the Napoli mud volcano to infer the likely mobiliza-
tion depth, whereas Robertson et al. (1996) studied
the likely origin of the ejecta. Chemical character-
ization of the oil- and gas-generative capability of
organic-rich ejecta was done by Akhmanov (1996) in
his study of the Mediterranean Ridge.
Cronin et al. (1997) recovered OligoceneMiocene-
age clasts as much as 1 m (3.3 ft) in size from sea-floor
mudvolcanoes ontheeastern
Mediterranean Ridge, where
deep-towedvideofootage over
one of the volcanoes showed
clasts up to several meters
across within the crater area.
In some cases, temporary
blockage of gas-dominated
diatremes can cause the host rock near the vertical
stock to mechanically fail and form clasts once the
obstruction is removed.
RESULTS AND DISCUSSION
Source Rocks: Insights from Outcrops
The Maikop Series constitutes a diverse assemblage
of lithofacies. During the early to middle Oligocene,
the SCB experienced a major restriction in marine cir-
culation, the consequence of which was the develop-
ment of anoxic bottom waters and enhanced preser-
vationof marine, planktonic organic matter. Acessation
of input of coarser clastics tothe basinis evidencedby
the predominance of clay-silt-size clastics, fine-scale
(millimeter to centimeter) lamination of the shales,
development of calcareous lithologies, and, based on
the preservation of organic matter, an inferred oxic-
anoxic boundary in the water column. In her study
of outcrop samples along the Belya River in the west-
ern Pre-Caucasus, Saint-Germes (1998) reported car-
bonate contents as much as 25% in the Oligocene
Miocene (lower Maikop) section and a rapid decrease,
to less than 5%, into the middle Miocene (younger
Maikop) shales. Interbedded marls are, however, found
sporadically through most of the early to middle Mai-
kop section. In contrast, the upper Maikop is char-
acteristically devoid of calcareous units.
Thermally immature outcrops of the lower Maikop
along the Kura depression have total organic carbon
(TOC) contents upward to 4 wt.%and hydrogen index
(HI) values as much as 350 mg hydrocarbons (HC)/g
FIGURE 5. More than 1000 yr
ago, the Caspian region was
known as the land of eternal
fires because of burning oil
and gas seeps and mud-volcano
eruptions. Today, several
places exist where natural gas
is burning as it flows from out-
cropping sedimentary units.
Photo: G. H. Isaksen.
56 / Isaksen et al.
organic carbon (C). Outcrops near Angicharan repre-
sent more proximal facies deposited near the north-
western margin of the Kura depression. The richest
samples are dominated by algal and algal-amorphous
organic matter. These typically occur as 1030-cm
(412-in.)-thick light-gray to dark-gray claystones al-
ternating with fine-grained sandstones. The paleo-
depositional environment is interpreted as a marine
shelf, where the accumulation of clays and plank-
tonic algae was periodically interrupted by transport
of sand into the basin. Proximity to shoreline is indi-
cated by the presence of herbaceous and woody or-
ganic matter. More distal facies outcrop near the vil-
lage of Perekyushkyul approximately 20 km (12 mi)
west of Baku (Figure 6). Here, the lower Maikop is pres-
ent as a more uniform succession of clays with only
minor influx of coarser grain sizes. Total organic car-
bon contents and HIs range from 1 to 3% and 150
to 400 mg HC/g organic C, respectively.
The middle Maikop outcrops near Perekyushkyul
contain organic-rich claystones with TOC contents of
11%andHIs as muchas 600 mg HC/g organic C. These
are present as discrete, very dark claystones with a bed-
set thickness of 1m(3.3ft) andcontainapredominance
of algal organic matter. As expected, the most algal-rich
kerogens are observed within units associated with in-
ferred maximum flooding surfaces in the transgressive
systems tract of a sequence-stratigraphic classification.
Oil and Gas Generation and Migration
The rapid sediment fill and relatively cool ther-
mal structure of the basin has also influenced the
timing of oil andgas generationfromthe Maikop and
diatomaceous source rocks. Because the predominant
oil-prone constituent in the Maikop kerogen is ma-
rine algal organic matter, the kinetics of oil and gas
generationfollow, as expected, those of classical type II
kerogens from other basins (e.g., Paris basin, North
Sea). This is true for a heating rate of 18C/m.y. How-
ever, the heating rate in the SCB has been much higher,
near 168C/m.y. during the PliocenePleistocene and
as much as 188C/m.y. during the last 20,000 yr. Tem-
perature measurements from wells in the Kura basin
and SCB show gradients of 20 and 14168C/km, re-
spectively. Peak oil generationoccurs near 1508C, and
onset and termination of oil generation would occur
near 110 and 1758C, respectively.
In our study area, the basal Maikop is interpreted
to be near depths of 1314 km (8.078.69 mi) and
temperatures of 1952108C. Under such high tem-
peratures, there is both late-stage conversion of ker-
ogen to gas, as well as thermal cracking of free oil to
gas. If pressure-relief sites are poorly developed, large
overpressured compartments will develop, especially
as thermal cracking of only 1% of oil volume in a
closed systems can account for pressures sufficient to
increase the pore pressure from hydrostatic to above
FIGURE 6. A total of 52 separate, lithified rock fragments were collected from most of the mud-volcano and outcrop
locations shown here.
Evaluation of Source Rock Quality in Azerbaijan from Mud-volcano Ejecta / 57
lithostatic (Gaarenstroomet al., 1993). Inareas where
crude oil was able toaccumulate, including migration
pathways in the mudrocks and siltstones, the in-situ
thermal cracking of oil will leave pores lined with pyro-
bitumen, which could block pore throats and im-
pede migration. Secondarily, highpressures are caused
by undercompaction because of the inefficient re-
lease of pore waters during burial. This is associated
with thermal expansion of water, which further aids
in fluid migration in the subsurface. Barker (1972)
and Magara (1974) presented the relations between
specific water volume (i.e., water expansion) and in-
creasing burial depth for different geothermal gra-
dients. For example, with a geothermal gradient of
158C/km, the specific volume of water would increase
from 1.0 cm
3
/g (0.061 in.
3
/g) at surface conditions to
1.05 cm
3
/g (0.064 in.
3
/g) at 10 km (6 mi).
Taken together, these processes cause a significant
degree of overpressure in the Maikop, and the basal
Maikop in particular. Undercompacted mudrocks
will be fluidized and try to reequilibrate. The process
of reequilibration causes vertical pressure relief and
development of gas diatremes. Suchconduits canserve
as important migration pathways for oil and gas.
MUD-VOLCANO EJECTA
Because the main focus of this study was the
source rock potential of the ejecta, sampling was nat-
urallybiasedtowardthe fine-grainedrocks (mudstones,
shales, and siltstones) thought, from initial visual
descriptions, to be organically enriched. A total of
52 separate, lithified rock fragments were collected
from 14 mud volcanoes and 3 outcrop locations
(Figure 6). The samples are listed in Table 1, along
with a visual description, age estimate, and the spe-
cific mud volcanoes from which the samples were
derived. We chose our sampling sites to obtain the
best possible regional understanding of subsurface
rock properties.
Evaluation of Data Integrity
Tabulateddata fromRock-Eval pyrolysis (Bordenave
et al., 1993) should always be interpreted together
with the corresponding pyrograms. This enables
1) the evaluation of the validity of T
max
, produc-
tion index (S
1
/[S
1
+ S
2
]), and hydrogen index
(HI; mg HC/g organic C) data
2) a check on the presence of bitumen (free hydro-
carbons typically having stained the rock being
analyzed)
Within our sample set of 52 rock samples, 11 sam-
ples have only a minor or no development of an
S
2
peak (representing pyrolyzable kerogen). For these
samples (S
2
less than 0.15 mg/g), the reported T
max
value is erroneous, and the production index (PI) and
HI values are questionable (Table 2). Other samples
contain free bitumen, observed as a shoulder, or sec-
ondpeak, inthe S
2
peak. Whenpresent, suchbitumen
elutes early in the S
2
peak as less energy is required
to thermally degrade bitumen relative to kerogen.
Samples with bitumen are marked by an asterisk in
Table 2. The remaining data in Table 2 are considered
reliable.
Prior to any evaluation of organic richness, organic
matter quality, and molecular characterization, one
must ascertain if the rock sample has been stained
by in-migrating hydrocarbons (i.e., hydrocarbons
generated from a different source unit). The degree
of staining can be determined from the PI of the
Rock-Eval pyrolysis technique (Bordenave et al., 1993).
Samples with a PI greater than 0.2 are likely stained by
in-migrated hydrocarbons. Within our sample set,
consisting of 52 samples, 30 samples have a PI greater
than0.2, and10 have a so-calledbitumen shoulder
developed onthe S
2
peak of the Rock-Eval pyrograms.
Of these 30 samples, 20 samples (67%) have TOC
values less than 1%; implying that any staining is of
such a small magnitude that it has not affected the
overall assessment of the rocks organic richness
(TOC) or organic matter quality (HI).
Organic Richness and Quality
All samples were analyzed for their TOC content
and by Rock-Eval pyrolysis (Table 2) to establish or-
ganic matter quality (HI) and thermal maturity (T
max
).
Total organic carbon contents range upward to 12.4%
wt., and HI values range to 588 mg HC/g organic C.
Maikop and upper Miocene mud-ejecta samples are
oil prone and can be classified as type II kerogens.
Most upper Maikop and some Maikop mud-ejecta
samples have HI values less than 200 mg HC/g organic
C and are, accordingly, classified as type III kerogens.
Sarmatianmud-ejecta samples are also oil prone, with
HI values from400 to 600 mg HC/g organic C, where-
as Chokra-age mud ejecta have more of a type III
kerogen.
Organic-matter Quality and Maturity
All samples collected as ejecta from the mud vol-
canoes and screened according to the S
2
peak devel-
opment criteria discussed earlier, have T
max
values
less than 4408C (Table 2). T
max
values about 4358C
58 / Isaksen et al.
Table 1. Lithofacies and estimated ages for rock clasts derived from mud volcanoes.
Number Volcanos Name Sample
Number
Type Age Microfauna Complex
1 Bozdag-Gyuzdeg 0 Shale Upper Miocene
(Sarmatian)
Not found
2 3 Sandstone Upper Miocene
(Sarmatian)
Elphidium regina, Elphidium macellum
3 5 Shale Upper Miocene
(Sarmatian)
Porosononion subgranosus
4 8 Shale Maikop Globigerina officinalis, Globigerina bulloides
5 Akhtarma-Karadag 9 Shale Upper Maikop Not found
6 10 Shale Upper Maikop Not found
7 11 Shale Upper Maikop Not found
8 13 Shale Upper Maikop Caucasina sp.
9 Touragai 16 Shale Maikop Subbotina officinalis, Nonion sp.
10 18 Shale Eocene Discorbis rotundus, kidneylike radiolaria
11 19 Shale Maikop Subbotina officinalis, Nonion sp.
12 20 Shale Upper Miocene Elphidium macellum, Nonion sp.
13 25 Shale Paleogene Kidneylike radiolaria
14 26 Shale Miocene Not found
15 27 Shale Maikop Not found
16 28 Shale Upper Maikop Not found
17 29 Shale Eocene Cibicides lectus vassl, Planulina costata
(Hantk.,) Cibicides praeuhgerianus chal.
18 Lokbatan 32a Shale Upper Miocene Not found
19 32c Shale Chokrakian Not found
20 32d Shale Maikop Not found
21 Bakhar 33 Shale Sarmatian Nonion boganowici, Elphidium macellum,
Elphidium regina
22 34 Shale Maikop Globigerina officinalis, Florelus boucanus
23 36 Shale Maikop Pieces of Globigerina officinalis, fish remains
24 37 Shale Upper Miocene Elphidium macellum, Nonion sp.
25 Bozdag-Kobi 39 Shale Sarmatian Porosononion subgranosus, Elphidium regina
26 Dashgil 42 Shale Miocene Porosononion martkobi, Elphidium aculeatum,
Elphidium marcellum
27 Sarynja 47 Dolomite Maikop
28 Ayaz-Akhtarma 53 Shale Paleogene Abundant kidneylike radiolaria
29 54 Shale Maikop Not found
30 Korturdag 56 Shale Maikop Globigerina officinalis, Globigerina
bulloides, Cibedes sp.
31 59 Shale Chokrakian Spiratella andrussovi, Floribus boucanus
32 60 Shale Lower Paleogene Suttalites trumpyi, Subbotina variata,
Globoratalia psuedobulloides
33 63 Shale Chokrakian Spiratella andrussovi
34 Bulla Island 68 Shale Not found
35 70 Shale Not found
36 71 Siderite
37 Big Kyanizdag 74 Dolomite Chokrakian
38 76 Shale Maikop Nonion nizamiformis, Globigerina sp.
39 77 Shale Sarmatian Porosononion subgranosus, Nionion martkovi,
Elphidium regina
40 78 Shale Upper Miocene Not found
41 Nardaran Akhtarma 85a Shale Upper Miocene Not found
42 85c Shale Upper Miocene Not found
Evaluation of Source Rock Quality in Azerbaijan from Mud-volcano Ejecta / 59
Table 2. Analytical results from Rock-Eval pyrolysis and total organic carbon analyses.
Sample
Number
Quantity T
max
* S
1
** S
2
*** S
3 3
y
PI
yy
PC*
yyy
TOC
b
Hydrogen
Index
bb
Oxygen
Index
bbb
GIA-0 100.7 425 3.07 50.04 2.32 0.06 4.42 10.52 476 22
GIA-3 99.4 425 11.83 59.39 2.71 0.17 5.91 10.67 557 25
GIA-5 99.3 430 0.66 13.17 1.55 0.05 1.15 3.12 422 50
GIA-8 96.2 433 0.21 1.19 1.71 0.15 0.11 1.20 99 143
GIA-9 92.2 420 0.21 0.44 0.62 0.33 0.05 0.77 57 81
GIA-10 101.8 435 0.13 0.51* 3.92 0.20 0.05 0.78 65 503
GIA-11 97.9 423 0.18 0.48 0.91 0.27 0.05 0.98 49 93
GIA-13 99.9 440 0.15 0.40 3.68 0.28 0.04 0.67 60 549
GIA-16 99.9 365 0.19 0.08 0.96 0.73 0.02 0.12 67 800
GIA-18 95.6 439 0.29 1.23 1.30 0.19 0.12 1.23 100 106
GIA-19 95.1 432 6.98 11.29 0.83 0.38 1.52 1.92 588 43
GIA-20 95.0 431 1.46 29.13 0.91 0.05 2.54 5.84 499 16
GIA-25 101.8 431 0.23 0.22 0.62 0.52 0.03 0.42 52 148
GIA-26 104.9 432 0.44 1.22* 0.63 0.27 0.13 0.51 239 124
GIA-27 101.8 468 0.16 0.23 3.24 0.42 0.03 3.11 7 104
GIA-28 98.4 439* 1.81 3.29* 0.76 0.35 0.42 1.69 195 45
GIA-29 97.5 444 0.25 0.19 0.68 0.57 0.03 0.44 43 155
GIA-32a 100.6 421 6.33 62.66 2.66 0.09 5.74 11.39 550 23
GIA-32c 95.9 356 0.19 0.04 1.44 0.86 0.01 6.04 1 24
GIA-32d 95.7 412 0.95 5.49 1.34 0.15 0.53 4.11 134 33
GIA-33 92.1 409 0.05 0.14 0.74 0.28 0.01 0.36 39 206
GIA-34 99.7 320 0.16 0.08 0.80 0.67 0.02 0.22 36 364
GIA-36 92.7 301 0.04 0.02 0.48 0.67 0.00 0.08 25 600
GIA-37 95.1 330 0.07 0.04 0.39 0.70 0.00 0.14 29 279
GIA-39 92.3 429 0.28 5.94 0.67 0.05 0.51 2.38 250 28
GIA-42 98.4 386 0.10 0.06 1.03 0.62 0.01 12.39 0 8
GIA-47 100.0 421 0.05 0.12 0.32 0.31 0.01 0.30 40 107
GIA-53 103.6 426 0.30 0.95* 0.50 0.24 0.10 1.14 83 44
GIA-54 100.0 385 0.05 0.24 0.26 0.18 0.02 0.34 71 76
GIA-56 95.2 345 0.06 0.18 0.14 0.25 0.02 0.41 44 34
GIA-59 84.0 411 0.90 5.17 0.60 0.15 0.50 3.60 144 17
GIA-60 93.0 426 0.15 0.87 0.74 0.15 0.08 0.74 118 100
GIA-63 96.4 416 0.44 1.57 0.64 0.22 0.16 2.57 61 25
GIA-68 95.5 388 0.10 0.15 0.69 0.42 0.02 0.31 48 223
GIA-70 102.7 431 0.21 0.55 1.66 0.28 0.06 0.69 80 241
GIA-71 95.2 428 2.25 22.10 0.82 0.09 2.02 7.18 308 11
GIA-74 117.2 434 0.31 2.01 0.62 0.13 0.19 0.90 223 69
GIA-76 95.8 438 0.27 2.32 2.67 0.10 0.21 1.66 140 161
GIA-77 93.1 430 0.26 0.54 0.42 0.32 0.06 1.48 36 28
GIA-78 97.8 424 2.33 8.87* 0.60 0.21 0.93 4.82 184 12
GIA-85a 118.1 426 0.25 0.81* 0.75 0.24 0.08 0.45 180 167
GIA-85c 143.0 432 0.07 0.22 0.34 0.25 0.02 0.29 76 117
AZ98-01 87.5 412 0.41 25.46 1.72 0.02 2.15 7.91 322 22
AZ98-02 96.3 440 1.17 1.13* 1.03 0.51 0.19 0.65 174 158
AZ98-03 101.2 439 0.10 0.14 6.75 0.42 0.02 0.38 37 1776
AZ98-04 98.4 421 0.31 0.93 1.90 0.25 0.10 1.31 71 145
AZ98-05 98.1 418 0.25 0.58 0.87 0.30 0.06 0.95 61 92
AZ98-06 96.9 404 0.46 2.42 1.64 0.16 0.24 2.32 104 71
60 / Isaksen et al.
are considered representative of the onset of oil-
window maturation, i.e., where subsurface tempera-
tures have reached levels of 80908C. Thus, most
ejecta samples are immature for hydrocarbon gener-
ation. Twoof the four ejecta samples withT
max
values
of 4354408Chave bitumenstaining as evidenced by
the bitumen shoulder on the S
2
peak. This bitumen
may indeed represent the earliest yield product from
a maturing source rock as opposed to in-migrated hy-
drocarbons from a nonassociated source rock.
With a geothermal gradient of 208C/km in the
Kura Valley (data from the Azerbaijan Institute of
Deep Oil and Gas), we can infer that the early-mature
ejecta samples are derived from about 4 km (2.5 mi)
depth. This applies for samples GIA-18 (Koun/
middle Paleogene) and GIA-76 (Maikop), from the
Osmanbozdag and Boyuk Kamizadag mud volcanoes,
respectively.
Further insight to the organic-matter type and
thermal-maturity level of the samples is obtained from
visual kerogen analyses. Here, the rocks mineral ma-
trix is dissolved by HCl and HF acids, and the result-
ing kerogen concentrate is viewed under the micro-
scope. The results are tabulated in Table 3. The Maikop
samples GIA-8, GIA-19, GIA-32d, and upper Miocene
and Sarmatian (GIA-0) have a predominance of ma-
rine, algal-amorphous organic matter. With the ex-
ception of the GIA-19 sample, these are all thermally
immature based on the thermal alteration index
(TAI), which measures the temperature-induced color
change among spores, pollen, etc. (Staplin, 1969). The
GIA-19 sample is a Maikop sample from the Osman-
bozdag mud volcano and is thermally more mature
(TAI 2.0), in agreement with the GIA-18 sample from
the same mud volcano mentioned above.
The upper Maikop (GIA-28 and GIA-51) and up-
per Miocene samples (GIA-32a, GIA-39, and outcrop
AZ98-09) have a predominance of herbaceous (spores
and pollen) organic matter and secondary amounts
of amorphous and woody material. It thus appears,
from this limited sample set, that this area experi-
enced a greater input of terrigenous higher plant
material during the late Miocene. The Paleogene sam-
ple (GIA AZ98-09) is also dominated by herbaceous
material, withsecondary amounts of algal-amorphous
and woody-inertinitic material.
Based on the geochemistry results discussed thus
far, it appears that the Maikop section evolved from
an overall transgressive system during early to middle
Maikop (shorelines moved farther away fromour sam-
pling points), followed by a highstand system during
late Maikop and upper Miocene (shorelines and asso-
ciated terrigenous input, closer to our sampling sites).
Sulfur analyses (Table 4) confirmed the assump-
tion that sulfur bound within the organic matter of
SCB source rocks is very low. Organic sulfur contents
are in the range of 0.010.03%. Most free sulfur has
bound with iron and formed pyrite. This implies that
the depositional environment during early diagenesis
contained an abundance of active iron sites on clay
mineral that acted to scavenge any free sulfur. Pyritic
sulfur contents range from 0.32 to 2.39%.
Timing of Hydrocarbon Generation
Kinetics analyses were carried out on three sam-
ples (GIA-5, GIA-19, GIA-39, and AZ98-08). These
show a consistency of maximum yields around 49
53 kcal/mol. Furthermore, the unimodal distribu-
tion suggests uniformcomposition of reactive organic
Table 2. (cont.).
Sample
Number
Quantity T
max
* S
1
** S
2
*** S
3 3
y
PI
yy
PC*
yyy
TOC
b
Hydrogen
Index
bb
Oxygen
Index
bbb
AZ98-07 101.7 432 0.22 1.97 0.53 0.10 0.18 1.04 189 51
AZ98-08 91.5 423 0.42 16.78 0.67 0.02 1.43 4.46 376 15
AZ98-09 100.7 421 0.38 17.43 0.56 0.02 1.48 2.28 764 25
AZ98-10 92.8 423 0.43 5.74 0.87 0.07 0.51 6.98 82 12
*T
max
= temperature index ( 8C).
**S
1
= free hydrocarbons (mg HC/g of rock).
***S
2
= residual hydrocarbon potential (mg HC/g of rock).
y
S
3
= CO
2
produced from kerogen pyrolysis (mg CO
2
/g of rock).
yy
PI = S
1
/(S
1
+ S
2
).
yyy
PC* = 0.083 (S
1
+ S
2
).
b
TOC = total organic carbon (wt.%).
bb
Hydrogen index = mg HC/g organic carbon.
bbb
Oxygen index = mg CO
2
/g organic carbon.
Evaluation of Source Rock Quality in Azerbaijan from Mud-volcano Ejecta / 61
matter, i.e., similar type of algal-amorphous and her-
baceous organic matter as indicated by visual kerogen
analyses.
Implications for Oil and Gas Exploration
Rock ejecta correlated to the Oligocene to lower
Miocene Maikop Series are organically rich and con-
tain a predominance of algal-amorphous organic
matter. These rocks constitute the principal oil-prone
source rocks in the sedimentary sections affected by
mud volcanoes. Potential for oil generationis also pres-
ent in the middleupper Miocene diatomaceous suite,
albeit as a lesser quality source rock than the Maikop.
The loworganic-sulfur content (less than 0.03%) is in
agreement with the generation of sweet crudes and
an absence of H
2
S gas throughout the area.
In our study area, the basal Maikop is interpreted
to be near depths of 1314 km (8.078.69 mi) and
temperatures of 1952108C. Under such high tem-
peratures, both late-stage conversion of kerogen to
gas and thermal cracking of free oil to gas are present.
Consequently, late charges of gas may displace oil in
certain trap configurations.
CONCLUSIONS

The mud-ejecta samples are immature to early

mature with respect to hydrocarbon generation.

With a geothermal gradient of 208C/km, the early-

mature ejecta samples are likely derived from
about 4 km (2.5 mi) depth. (This applies for
samples GIA-18 [Koun/middle Paleogene] and
GIA-76 [Maikop], from the Osmanbozdag and
Boyuk Kamizadag mud volcanoes, respectively.)

Organic sulfur contents of the organic matter are

low. Free sulfur present in the depositional envi-
ronment from early sulfate reduction has mostly
Table 3. Summary of organic carbon and visual kerogen data.
Sample
Number
Age Total
Organic
Carbon
Organic
Matter
Type
Visual Abundance Normalized (%) Alteration
Stage*
Thermal
Alteration
Index**
AL
y
AM
yy
H
b
W
bb
I
{
GIA-0 Upper Miocene 10.52 Am(Al); H; 11 44 44 0 0 1 to 1+ 1.2
GIA-8 Maikop 1.2 Am(Al); ; 33 67 0 0 0 1+ to 2 1.5
GIA-19 Maikop 1.92 Am(Al); H
{{
; 22 44 33 0 0 2 to 2 2
GIA-28 Upper Maikop 1.69 H; W; Am-1 0 13 50 25 13 3 to 3+ 3.2
GIA-32a Upper Miocene 11.39 Am(Al); H
{{
; 22 44 33 0 0 1+ to 2 1.6
GIA-32d Maikop 4.11 Am(Al); H; 27 36 36 0 0 1 to 1+ 1.2
GIA-39 Upper Miocene 2.38 H
{{
; Am(Al); W-I 9 27 45 9 9 2 to 2 2
GIA-59 Chokrakian 3.6 H; Am(Al); W(I) 8 23 46 15 8 2 2.2
AZ98-01 Paleogene 7.91 H; Am(Al); W 9 18 64 9 0 1+ 1.4
AZ98-09 Upper Maikop 2.28 H; Am(Al); W(I) 15 15 46 15 8 1+ to 2 1.6
*Alteration stage = degree to which kerogen macerals have been thermally altered on a scale from 1 to 3+.
**The thermal alteration stage is an equivalent scale from 1 to 3.5 (Staplin, 1969).
y
AL = algal.
yy
AM = amorphous.
b
H = herbaceous.
bb
W = woody.
{
I = intertinite.
{{
Organic matter types column notation: predominant = 60100%; secondary = 2040%; trace = 020%.
Table 4. Sulfur analytical data from ejecta and
outcrop samples.*
Sample Total S Sulfate S Pyritic S Organic S
GIA-0 2.63 0.21 2.39 0.03
GIA-5 1.09 0.22 0.86 0.01
GIA-19 0.60 0.13 0.45 0.02
GIA-32a 2.37 1.11 1.24 0.02
GIA-32d 1.89 1.62 0.26 0.01
GIA-39 2.00 0.88 1.11 0.01
GIA-59 3.38 1.36 2.00 0.02
GIA-76 0.56 0.23 2/60 0.02
GIA-78 4.85 2.23 2.60 0.02
AZ98-08 1.09 0.15 0.91 0.03
*Data are reported in percent inorganic matter.
62 / Isaksen et al.
bound with iron to form pyrite. The results are
the generation of sweet crudes and gases.

The Maikop samples are, for the most part, domi-

nated by algal organic matter. As with the Maikop
outcrops, the lithology andorganic matter content
of the Maikop can vary significantly from lami-
nated shales to sandstones and marine algal to
herbaceous and terrigenous organic matter.

Based on the geochemistry results, it appears that

the Maikop section evolved from an overall trans-
gressive system during early to middle Maikop
(shorelines moved farther away from our sam-
pling points), followed by a highstand system
during late Maikop and upper Miocene (shore-
lines and associated terrigenous input closer to
our sampling sites).
ACKNOWLEDGMENTS
We thank the Geological Institute of Azerbaijan
and ExxonMobil Exploration Company for permis-
sion to release these data.
We also extend our thanks to William J. Devlin
with ExxonMobil and Ken O. Stanley (deceased) for
helpful insights into the basin history and regional
tectonics and early reviews of the manuscript.
REFERENCES CITED
Akhmanov, G. G., 1996, Lithology of mud breccia classes
from the Mediterranean Ridge: Marine Geology,
v. 132, no. 14, p. 151164.
Bagirov, E., R. Nadirov, and I. Lerche, 1996a, Statistical risk
assessment from the historical records: Energy Explo-
ration and Exploitation, v. 14, no. 6, p. 535583.
Bagirov, E., R. Nadirov, and I. Lerche, 1996b, Earthquakes,
mud-volcano eruptions and fracture formation haz-
ards in the South Caspian Basin: Statistical inferences
from the historical record: Energy Exploration and
Exploitation, v. 14, no. 6, p. 585606.
Barber, A. J., T. R. Charlton, and S. Tjokrosapoetro, 1986,
Mud volcanoes, shale diapirs, wrench faults, and
melanges in accretionary complexes, Eastern Indo-
nesia: AAPG Bulletin, v. 70, no. 11, p. 17291741.
Barker, C., 1972, Aquathermal pressuring Role of tem-
perature in development of abnormal-pressure zones:
AAPG Bulletin, v. 56, no. 10, p. 20682071.
Berberian, M., 1983, The southernCaspian; a compressional
depression floored by a trapped, modified oceanic
crust: Canadian Journal of Earth Sciences, v. 20, no. 2,
p. 163183.
Bordenave, M. L., J. Espitalie, P. Leplat, J. L. Oudin, and
M. Vandenbroucke, 1993, Screening techniques for
source rock-evaluation, in M. L. Bordenave, ed., Ap-
plied petroleum geochemistry: Paris, France, Editions
Technip, p. 217278.
Brown, K. M., 1990, Nature and hydrogeologic significance
of mud diapirs and diatremes for accretionary systems:
Journal of Geophysical Research, v. 95, p. 8969 8982.
Cronin, B. T., M. K. Ivanov, A. F. Limonov, A. Egorov,
G. G. Akhmanov, A. M. Akhmetjanov, and E. Kozlova,
1997, New discoveries of mud volcanoes on the east-
ern Mediterranean Ridge: Journal of the Geological
Society (London), v. 154, part 2, p. 173182.
Dadashev, F. G., A. M. Dadashev, A. Ya. Kabulova, B. Yu.
Galant, and V. I. Yagubov, 1992, Vodorastvorennyye
gazy porod Yuzhno-Kaspiyskoy vpadiny (Gases dis-
solved in water in rocks of the South Caspian Basin):
Geologiya Nefti I Gaza, v. 2, p. 3033.
Devlin, W. J., J. M. Cogswell, G. M. Gaskins, G. H. Isaksen,
D. M. Pitcher, D. P. Puls, K. O. Stanley, and G. R. T.
Wall, 1999, The South Caspian Basin: Young, cool,
and full of promise: Geological Society of America
Today, v. 9, no. 7, p. 19.
Gaarenstroom, L., R. A. J. Tromp, M. C. de Jong and A. M.
Brandenburg, 1993, Overpressures in the central North
Sea: Implications for trap integrity and drilling safety,
in J. R. Parker, ed., Petroleum geology of northwest
Europe: Proceedings from the 4th Conference: The
Geological Society (London), p. 13051313.
Gretener, P. E., and G. Bloch, 1992, Geopressures: Two dis-
tinctively different kinds of conditions (abs.): AAPG
Annual Meeting Program, v. 1, p. 4849.
Guliev, I. S., N. V. Klyatsko, S. A. Mamedova, and S. F. Suley-
manova, 1992, Oil andgas productionandreservoir prop-
erties of sediments of the southern Caspian Basin: Li-
thology and Mineral Resources, v. 27, no. 2, p. 169176.
Hedberg, H., 1974, Relation of methane generation to
undercompacted shales, shale diapirs and mud volca-
noes: AAPG Bulletin, v. 58, p. 661673.
Ivanov, V. V., and I. S. Guliev, 1988, A physico-chemical
model of mud volcanism, in Problems in the oil and
gas content of the Caucasus: Moscow, Nauka, 9 p.
Kopf, A., and J. H. Behrmann, 2000, Extrusion dynamics
of mud volcanoes on the Mediterranean Ridge accre-
tionary complex, in B. C. Vendeville, M. Yossi, and
J. L. Vigneresse, eds., Salt, shale and igneous diapirs
in and around Europe: Geological Society (London)
Special Publication 174, p. 169204.
Kopf, A. J., 2002, Significance of mud volcanism: Reviews
of Geophysics, v. 40, no. 2, p. 52.
Kuklakova, L. S., and L. I. Lebedev, 1996, Some features of
mud volcanism of the South Caspian: Translated from
Kaspiyskoye More, p. 96103, 1990, Nauka, Moscow:
Petroleum Geology, v. 30, no. 4, p. 346349.
Langseth, M. G., M. A. Hobart, and G. K. Westbrook, 1988,
Geophysical survey of a mud volcano seaward of the
Barbados Ridge accretionary complex: Journal of Geo-
physical Research, v. 93, no. B2, p. 10491061.
Magara, K., 1974, Aquathermal fluid migration: AAPG
Bulletin, v. 58, no. 12, p. 25132526.
Evaluation of Source Rock Quality in Azerbaijan from Mud-volcano Ejecta / 63
McManus, J., and R. B. Tate, 1986, Mud volcanoes and the
origin of certain chaotic deposits in Sabah, East Ma-
laysia: 5th Geological Society of Malaysia; Geology,
Mineral and Energy Resources of Southeast Asia. Re-
gional Congress (Geosea V), Kuala Lumpur, Malaysia,
April 913, 1984: Bulletin of the Geological Society of
Malaysia, v. 19, p. 193205.
Narimanov, A. A., 1993, The petroleum systems of the
South Caspian Basin, in A. G. Dore, J. H. Augustson,
C. Hermanrud, D. J. Stewart, and O. Sylta, eds., Basin
modeling: Advances and applications: Norwegian Pe-
troleum Society Special Publication 3, p. 599608.
Osborne, M. J., and R. E. Swarbrick, 1997, Mechanisms
which generate overpressure in sedimentary basins: A
reevaluation: AAPG Bulletin, v. 81, p. 10231041.
Priestley, K., C. Baker, and J. Jackson, 1994, Implications of
earthquake focal mechanismdata for the active tectonics
of the SouthCaspianBasinand surrounding regions: Geo-
physical Journal International, v. 118, no. 1, p. 111141.
Rezanov, I. A., and S. S. Chamo, 1969, Reasons for absence
of a granitic layer in basins of the South Caspian
and Black Sea type: CanadianJournal of EarthSciences,
v. 6, no. 4, p. 671678.
Robertson, A. H. F., K. C. Emeis, C. Richter, M. M. Blanc-
Valleron, I. Bouloubassi, H. J. Brumsack, A. Cramp,
G. J. DeLange, and E. DiStefano, 1996, Mud volca-
nism on the Mediterranean Ridge (ODP Leg 160):
Proceedings of the Ocean Drilling Program: Initial
Reports, v. 160, p. 521526.
Saint-Germes, M., 1998, Etude sedimentologique et geo-
chimique de la matiere organique duBassinMaykopien
(OligoceneMiocene inferieur) de la Crimee a LAzer-
baidjan: Ph.D. thesis, Universite Pierre et Marie Curie,
Paris, France.
Schulz, H. M., K. C. Emeis, and N. Volkmann, 1997, Or-
ganic carbon provenance and maturity in the mud
breccia from the Napoli mud volcano: Indicators of
origin and burial depth: Earth and Planetary Science
Letters, v. 147, no. 14, p. 141151.
Staplin, F. L., 1969, Sedimentary organic matter, organic
metamorphism, and oil and gas occurrence: Bulletin
of Canadian Petroleum Geology, v. 17, p. 4766.
Yergin, D., 1991, The prize: The epic quest for oil, money
and power: New York, Simon and Schuster, 881 p.
Zonenshain, L. P., and X. LePichon, 1986, Deep basins on
the Black Sea and Caspian Sea as remnants of Meso-
zoic back-arc basins: Tectonophysics, v. 123, no. 14,
p. 181211.
64 / Isaksen et al.