ISSN 0016-7029, Geochemistry International, 2010, Vol. 48, No. 5, pp. 517–522. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.A. Feizullaev, U.A. Movsumova, 2010, published in Geokhimiya, 2010, Vol. 48, No. 5, pp. 551–557.
SHORT COMMUNICATIONS
The Nature of the Isotopically Heavy Carbon Composition
of Carbon Dioxide and Bicarbonates in the Waters of Mud Volcanoes
in Azerbaijan
A. A. Feizullaev and U. A. Movsumova
Geological Institute, Academy of Sciences of Azerbaijan, pr. G. Dzhavida 29A, Baku, AZ 1143 Azerbaijan;
e-mail: akperf@yahoo.ru, u_movsumova@yahoo.com
Received June 17, 2008
DOI: 10.1134/S0016702910050083
INTRODUCTION
Mud volcanism is a global natural phenomenon, with
mud volcanoes occurring in 28 countries around the
world. Geologically, all mud volcanoes are restricted to
two tectonically active belts: Alpine–Himalayan and
Pacific. Many mud volcanoes are localized in Azerbaijan,
in which about 300 mud volcanoes of various morphology,
size, and activity were mapped on- and offshore (in the
Caspian Sea). All mud volcanoes bring clay breccia, water
(sometimes with oil films), and gas to the surface, and
some of these volcanoes periodically erupt with the com-
bustion of their gas and the ejection of rock fragments.
Although the comprehensive study of mud volcanoes
in Azerbaijan, including the examination of their solid,
liquid, and gaseous products, was launched long ago,
some problems related to these structures remain unset-
tled as of yet. One of these problems is the genesis of СО2
of superheavy carbon isotopic composition that is typical
of many mud volcanoes in the Shamakha–Gubustan dis-
trict of Azerbaijan. Isotopically superheavy СО2 is that
with δ13C of > 5‰, because only СО2 genetically related
to marine carbonates is usually thought [1, 2] to have pos-
itive δ13C values, which are, however, commonly no
higher than 5‰.
The first fundamental isotopic–geochemical studies
of gases at mud volcanoes in Azerbaijan were conducted
almost simultaneously by Valyaev et al. [3] and Dadashev
[4]. Later Guliev et al. [5] examined gases from some mud
volcanos in Azerbaijan. These researchers have deter-
mined that gases at mud volcanoes contain СО2 with iso-
topically unusually heavy carbon, with δ13C of up to
+25.6‰. Bicarbonates in waters at mud volcanoes in
Azerbaijan also show positive δ13C values (up to
+19.8‰). The genesis of isotopically superheavy carbon
in СО2 is of undeniable scientific interest.
517
NATURE OF ISOTOPICALLY HEAVY CARBON IN
CARBON DIOXIDE
Carbon dioxide always accompanies methane in natu-
ral gases, including those from mud volcanoes. The gases
of mud volcanoes are usually dominated by methane and
contain subordinate amounts of carbon dioxide, except
some mud volcanoes in Sakhalin, Kerch Peninsula, Tai-
wan, and Sicily, in which carbon dioxide is the predomi-
nant gas component.
The СО2 concentrations in gases from Azerbaijani
mud volcanoes ranges from 0.05 to 18.2‰. The δ13C of
СО2 from more than 80 examined volcanoes broadly var-
ies: from –49.6 to +25.6‰, with almost 60% of the anal-
yses having positive δ13С values and approximately 45%
having δ13С of СО2 > 5‰. The spatial distribution of δ13С
of СО2 is zonal (Fig. 1). The values of δ13С of СО2 is cor-
related with the СО2 concentrations: the isotopic compo-
sition of СО2 becomes heavier with increasing
СО2content in the gas.
In order to understand the genesis of isotopically heavy
CO2 from mud volcanoes, we collected, generalized, and
analyzed extensive literature data, and this allowed us to
identify a number of possible sources of isotopically heavy
CO2.
According to Galimov [6], isotopically heavy CO2 can
be generated by the destruction of organic matter and by
the hydrolysis of carbonates and/or be of fermentation
genesis.
One of the possible mechanisms generating isotopi-
cally heavy CO2 is microbial reduction, which involves the
initial generation of CO2 of isotopic composition similar
to that of carbon in the source. This CO2 is eventually
partly reduced to CH4 enriched in the light isotope 12C,
whereas the residual CO2 is thereby enriched in the heavy
isotope 14C; i.e., these parameters should be negatively
correlated. However, as follows from Fig. 2, no such
dependence is detected in the distribution of carbon iso-
topes in the gases of mud volcanoes in Azerbaijan. Con-
versely, the carbon isotopic compositions of CO2 and CH4
generally become heavier simultaneously. The values of
518 FEIZULLAEV, MOVSUMOVA

Claypool and Kaplan [7] believe that the δ13С values of

isotopically heavy CO2 generated by the microbial reduc-
–5 tion of CO2 (δ13С = –20‰) before CH4 can (theoreti-
I cally) be higher than +75‰ (in a closed system). Thereby
0 the isotopically heavy CO2, which is a residual product,

Sea
should have δ13С values increasing with decreasing CO2
concentrations [8].
10
However, the systems discussed herein are rather open
III
than closed. Moreover, samples from Azerbaijani mud
1015 II volcano show the opposite relations (Fig. 3). Because of
this, the process of microbial reduction can hardly be
–15 20 Baku invoked to explain the genesis of isotopically heavy СО2 in
15
Azerbaijani mud volcanoes.
IV 10 Considering the decomposition process of carbonate
0 rocks with an initially isotopically heavy carbon isotopic
5 composition, it is pertinent to mention available literature
n

data on siderite with an isotopically heavy carbon isotopic

Caspia

–20
5 +21‰ [8].
Fig. 1. Schematic map showing variations in the δ13С PBD of
carbon dioxide at mud volcanoes in Azerbaijan.
Oil- and gas-bearing areas: (II) Caspian–Gubinskaya; (II)
Apsheron; (III) Shamakha–Gobustan; (IV) Kura.
δ13С of methane in equilibrium with isotopically heavy
CO2 (>5‰) varies within a narrower range (from –49.6 to
–37.3‰) compared with the analogous values of CH4
(from –61.2 to –36.6‰) in association with СО2 having
an lighter (<5‰) carbon isotopic composition.
composition [9, 10] and dolomite related to organically
enriched rocks and with δ13С values of approximately
According to experimental results of Kissin and
Pakhomov [11], the decomposition of carbonates in the
presence of water begins at a temperature of 75°С and
reaches a maximum at 150°С. The synthesis of isotopi-
cally heavy СО2 in the gases of Azerbaijani mud volcanoes
can hardly be caused by this mechanism due to a number
of reasons. First of all, it should be mentioned that the sed-
imentary succession of the Southern Caspian Basin
(SCB) consists mostly of terrigenous rocks. Carbonate
rocks of marine genesis are widespread, first of all, in the
Cretaceous complex and cannot generate СО2 with an
isotopically heavy carbon isotopic composition because,
as was mentioned above, their δ13С values are no higher
than 5‰. At mud volcanoes (Airantekan, Demirchi, and

CO2, ‰
0 5 10 15 20 25 30
30

20 20
10
δ13CO2, ‰

0 0
δ13СO2, ‰

–10
–20
–20
–30
–40
–40
–60 –50
–70 –60 –50 –40 –30 –20
δ13CH4, ‰ –60
1 2 1 2

Fig. 2. Correlation between the carbon isotopic composition of Fig. 3. Correlation between the δ13С values and СО2 con-
methane and carbon dioxide in gases from (1) mud volcanoes centrations in natural gases from (1) mud volcanoes and
and (2) deposits in Azerbaijan. (2) deposits in Azerbaijan.

GEOCHEMISTRY INTERNATIONAL Vol. 48 No. 5 2010

 THE NATURE OF THE ISOTOPICALLY HEAVY CARBON COMPOSITION
others) whose ejected rock fragments contain Late Creta-
ceous limestone, the δ13С values of СО2 are negative
(from –26.3 to –0.1‰). Even if isotopically heavy СО2 is
generated by these carbonates, the carbon isotopic com-
position of СО2 should have become heavier with depth.
However, inasmuch as the depth of the СО2 source of the
mud volcanoes is unknown, it is now impossible to test
this hypothesis.
There are literature data suggesting that CO2 enriched
in the 13C isotope can be synthesized by the biodegrada-
tion of oil [12–14]. This process is caused by the shallow
depths at which the hydrocarbons occur and by their oxi-
dation in contact with mineralized waters. Isotopically
heavy carbon dioxide can be generated in this situation by
the microbial fermentation of saturated hydrocarbons,
and the δ13С values can thereby reach +25.9‰ [12].
The model for the genesis of this СО2 involves two
stages. During the first of them, oxygen provided by infil-
trating atmospheric precipitates is consumed by hydro-
carbon-oxidizing bacteria. This process synthesizes alco-
hols and fatty acids.
The second stage involves the fermentation of the oxi-
dation products with the partial reduction of CO2 to CH4.
Later CO2 with a heavy carbon isotopic composition can
be accumulated as either a gas or precipitated secondary
carbonates.
Valyaev and Grinchenko [15] also believe that the pre-
dominant source of isotopically heavier CO2 in natural
gases, including CO2 at mud volcanoes, can be the oxida-
tive destruction of hydrocarbons. According to these
researchers, this process takes place in a zone transitional
from strongly reducing to oxidizing environments. The
coupled redox processes facilitate the chemical transfor-
mation of hydrocarbon (carbonaceous) compounds in the
open systems.
The presence of isotopically superheavy CO2 and the
possibility of its generation by the oxidative destruction of
hydrocarbons was mentioned by Zarttman et al. [16],
Wasserburg et al. [17], Wilhelm et al. [18], and
Galimov [6].
The synthesis of isotopically heavy CO2 during the fer-
mentation of organic matter (OM) is thought to occur at
relatively shallow depths and at relatively low tempera-
tures typical of diagenesis [19]. The process of fermenta-
tion terminates at high temperatures and, correspond-
ingly, the rate of CO2 synthesis gradually decreases with
depth. Thereby the carbon isotopic composition of the
fermentation-generated CO2 is controlled only by the
fractionation coefficient in the СО2–СН4 system, and the
δ13С value of СО2 in the system increases with increasing
CO2 amount.
The mechanism of oil biodegradation/fermentation is
able to most realistically explain the nature of isotopically
heavy CO2 at Azerbaijani mud volcanoes, as follows from
the following facts.
First of all, all oils brought to the surface at mud vol-
cano are biogenically degraded, except the oil at the
northwesternmost volcano of Demerichi at the offsets of
GEOCHEMISTRY INTERNATIONAL Vol. 48 No. 5
519
(a)
15 Pr Ph 20 25 30
(b)
15 Pr Ph 20 25 30
Fig. 4. Examples of gas–liquid chromatograms of the satu-
rated fraction of oils from mud volcanoes in Azerbaijan.
(a) Biodegraded oil (Kyrlykh mud volcano) and (b) non-bio-
degraded oil (Demirchi mud volcano).
the Greater Caucasus (Fig. 4). It is interesting that Demir-
ichi volcano rests on relatively older rocks and has the iso-
topically heaviest carbon isotopic composition of its
methane (from –36.6 to –37.0‰), and the δ13С of the
carbon dioxide varies from –26.3 to –1.8‰.
Second, according to our histograms of the distribu-
tion of δ13С for CO2 and CH4 separately for mud volca-
noes with and without oil shows, the heaviest δ13С values
of CO2 and the lowest δ13С values of CH4 are typical of
mud volcanoes with oil shows (Fig. 5).
The considerations and reasoning presented above in
relation to the nature of isotopically heavy CO2 pertain to
the period of time when no data were available on the car-
bon isotopic composition of CO2 at deposits: these data
were obtained almost 15 years later. This information sig-
nificantly bridges the gap in knowledge about this problem
and make the conclusion in [22] more realistic.
The overall number of gas samples from the deposits
was close to 50, with these samples spanning a strati-
graphic range of rocks from the Paleogene to Middle
Miocene, at depths from a few hundred to almost 6600 m.
The δ13С values of the examined CO2 samples varied from
–18.7 to +21.5‰ (averaging at 2.8‰). Approximately
43% of the gas samples had δ13С of CO2 heavier than 5‰.
The most important issue is that the processing of the
data allowed us to determine that all positive values of δ13С
of CO2 are restricted to depths of no more than 2 km,
regardless of the stratigraphic affiliation of the rocks from
which the gas samples were taken (Fig. 6).
2010
520 FEIZULLAEV, MOVSUMOVA

60 δCO2, ‰ δ13CO2,‰
50
Frequency, %
–35 –25 –15 –5 5 15 25
40 0
30
1000
20
10
2000
0
–40 –30 –20 –10 0 10 20 30
3000

Depth, m
60 δCH4, ‰
50
Frequency, %

4000
40
30
5000
20
10 6000
0
–60 –55 –50 –45 –40 –35 7000
1 2

Fig. 5. Histograms of the distribution of δ13С СО2 values (in

‰) of CO2 and CH4: (1) mud volcanoes with oil shows and Fig. 6. Variations in the carbon isotopic composition of carbon
(2) mud volcanoes without oil shows. dioxide in gases at some deposits in Azerbaijan with depth.

This definitely established fact clearly testifies to a We also identified a correlation between δ13С of CO2 and
near-surface nature of the isotopically heavy CO2, rules that parameter of CH4 (Fig. 2), similarly to the analogous
out the participation of temperature, and hence, invali- correlation for mud volcanoes.
dates the hypothesis that this CO2 was synthesized via the These compositional and isotopic variations obviously
hydrolysis of carbonates and the thermodestruction of suggest hydrocarbon transformations in oils at shallow
organic matter. depths in the stratigraphic sequences.
At the same time, this fact provided further support for The enrichment of CO2 in the light 12C isotope with
the conclusion about the fermentation-related genesis of increasing depths detected at the deposits (Fig. 6) provides
evidence in support of CO2 synthesis via thermocatalytic
isotopically heavy CO2. Similar to the situation at mud
processes during the metamorphism of organic matter.
volcanoes, the values of δ13С of CO2 at the deposits
become heavier simultaneously with a significant increase
(up to 25%) in the CO2 concentration in the gases (Fig. 3). NATURE OF BICARBONATES
WITH ISOTOPICALLY HEAVY CARBON
IN THE WATERS OF MUD VOLCANOES
Carbon isotopic composition of bicarbonates in the waters of
mud volcanoes The study of the isotopic composition of bicarbonate
–
waters (НС O 3 ) at some mud volcanos in Azerbaijan
Mud volcano δ13 C HCO3 , ‰
resulted in the discovery of an unusually isotopically heavy
composition of their carbon: δ13С from –0.8 to +19.8‰
Chaikurbanchi +9.1 (average +10.7‰) (Table 1).
Demirchi +3.1 According to Kharaka and Carothers [23], bicarbon-
Airantekan +10.0 ates with isotopically heavy carbon are generated by the
oxidational destruction of OM. Our data corroborate this
Sheitanud +17.7 conclusion.
Solakhi +16.0 –
First, the δ13С of НС O 3 and СО2 are fairly strongly
Bakhar +11.9 correlated in gases from mud volcanoes (Fig. 7a).
–
Perekishkyul’ +19.8 Second, the δ13С of НС O 3 is positively correlated
Dzhagirli (southern) +7.0 with the СО2 concentration in the gases of the mud volca-
Goturdag –0.8
noes (Fig. 7b).
Bicarbonates with isotopically heavy carbon (δ13С up
Cheildag (western) +13.0 to +28‰) were found in the waters of oil fields [23].

GEOCHEMISTRY INTERNATIONAL Vol. 48 No. 5 2010

 THE NATURE OF THE ISOTOPICALLY HEAVY CARBON COMPOSITION 521

25 formed in contact with atmospheric СО2 (with δ13С of

(a) approximately –7.0‰). Considering the fact that marine
bicarbonates contain carbon roughly 6–8‰ isotopically
20 heavier than the carbon of atmospheric CO2, one can cal-
culate the possible δ13С of bicarbonates in waters at mud
δ13HCO3, ‰

15 volcanoes; this value was estimated at 1.3‰ + (6–9)‰ =

.3–10.3‰. These average calculated values are in good
10 agreement with the arithmetic averages of the measured
δ13С values (+10.7‰) of bicarbonates contained in
waters at mud volcanoes.
5

0
CONCLUSIONS
Our analysis of isotopic–geochemical data on gases
and bicarbonates in waters at mud volcanoes in Azerbaijan
–5
–10 0 10 620 30 led us to conclude that the isotopically heavy carbon of the
δ13CO2, ‰ СО2 and bicarbonates is most probably synthesized by the
25 fermentative destruction of hydrocarbons in an open sys-
(b) tem. This process takes place at shallow depths (no deeper
20
than 2 km) and, correspondingly, at low temperatures (no
higher than 40°С for the Southern Caspian Basin) and is
associated with an increase in the СО2 concentration in
δ13HCO3, ‰

15 the gas. Isotopically heavy СО2 of the gas phase in contact

with the waters of mud volcanoes synthesizes bicarbonates
10 with isotopically heavy carbon in these waters.
This process is also typical for shallow-depth oil–gas
fields.
5

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Fig. 7. Correlation between the carbon isotopic composition of
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