OTC 8642

Hydrate Hazards in the South Caspian Basin

E. Bagirov and I. Lerche, Dept. of Geological Sciences, University of South Carolina
Copyright 1998, Offshore Technology Conference
This paplII' was prepared tar prnentstion allha 1998 Otfshore Technology Conference held in
Houston, Texa. 4-7 May 1998,

away of surficial and near-surficial diapirs, volcanoes, and

mud islands; (xiii) massive overpressure caused by gas and
fluid in the mud material.
Under particular conditions anyone or all of these hazard
factors may be in effect at given times and for given locations.
Based on Azeri historical data from mud volcanoes onshore, statistical probabilities were evaluated for breccia, gas
eruptions, flaming, mud flows, earthquakes, and fissure
production (Lerche et aI., 1996), and were also used to provide
preliminary assessments for hazards to exploration rigs,
production platforms and pipelines in the offshore region of
the South Caspian Basin.
The remaining hazard factors in the above list do not have
good statistical data bases of historical events from which to
assess hazard probabilities in the offshore region, although
isolated events are recorded. For instance, Dadashev et al.
(1995) have compiled a temporal record of the appearances
and disappearances of the offshore Chigil-Deniz Bank over the
last 130 years, and of the numerous flame eruptions of Bakhar
Bank and Zenbil Island. But, by-and-large, data are
extremely sparse on mud diapirs and volcanoes in greater than
100 m of water. It then becomes difficult to provide hazard
probabilities for the majority of the remaining hazards in the
above list. An exception occurs for hydrates, because of direct
gravity-core sampling of hydrates at or near the crests of the
Buzdag, Elm and Abikh mud volcanoes (Ginsburg et aL, 1992;
Dadashev et al., 1995) in water depths of 480 m, 660 m and
600 m, respectively.
The probable hazard of dissociation of hydrates can thus be
estimated, albeit not too well, but a worst case hazard situation
can at least be provided. The purpose of this paper is to show
how the hazard estimate is made, and also to provide
recommendations on the data needed to obtain a more accurate
assessment. The hazard arises from the fact that hydrates are
only quasi-stable; if the temperature is increased at a fixed
pressure, or the pressure decreased at a fixed temperature, or
both, then it is easy to pass out of the stability field of
hydrates, with the occurrence of explosive dissociation.
Indeed, such an explosive dissociation of hydrates has been
inferred in the Barents Sea (after recent ice removal of about 3
km thickness) by the presence of numerous large craters on the
sea-floor (Solheim and Elverh0i, 1993). As weIl as natural
~hanges in the pressure and temperature regimes, an increase
I~ t~mperature. can also be produced by drilling into a mud
dIaplr, thereby Increasing the likelihood of triggering

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Abstract
The presence of c1athrates (gas hydrates) is well established
observationally in the offshore region of the South Caspian
Basin. This paper examines the potential hazards that can
occur from hydrates for exploration rigs, production platforms
and pipelines. Problems examined include hydrate formation
zones, and explosive dissociation as a result of mud flows
and/or uplift and rotation of submarine mud volcanoes. In
addition, flame initiation by dissociation is also examined as a
potential hazard, as are hazards due to drill penetration, warm
circulation mud, and drill-bit heating of hydrates.
Chemical composition of hydrates is shown to playa critical
role in hazard evaluation, and seismic identification
procedures for hydrate detection as bottom simulating
reflectors (BSRs) are encouraged. Seismically-identified
hydrates can be used to estimate thermal gradients in
sediments without invasive procedures being required, and so
to provide limits on the maximum thickness of hydrates in
sediments. In addition, seismic procedures also provide a way
of estimating hydrate composition. These non-invasive
methods allow identification of worst-case hazard possibilities
from hydrates.
Introduction
The offshore region of the South Caspian Basin is noted for a
variety of hazards associated with gas-charged mud volcanoes.
~ese hazards include: (i) breccia ejecta; (ii) gas eruptions;
(111) mud flows; (iv) flame ignition; (v) earthquakes
associated with eruptions; (vi) kilometer-long fissure
production to widths of a few meters and escarpments to a few
mete~s or tens of meters; (vii) slumping, pull-away and
rotatIon ~fvolcanic crests; (viii) gas-charging of overlying
waters; (IX) gas-charging of highly unconsolidated surficial
sedimentary layers, to the point that the seismic impedance of
the sediments is occasionally ~ than that of overlying
waters; (x) clathrate production and dissociation; (xi) vertical
and lateral motion of mud diapir crests; (xii) current washing

125

HYDRATFS HA7ARDS IN THE SOUTH CASPIAN BASIN

explosive behavior; while changes in pressure are brought

about by the mud weight in the borehole.

Pressure-TemperatureStability Fields for Hydrates

The precise chemical composition of hydrates has a major role
to play in determining the stability domain of a hydrate.
Figure 1 shows how ethane addition to methane allows
hydrates to exist at lower pressures and higher temperatures
than for a pure methane hydrate. This stability sensitivity to
the hydrate composition is important because hydrates can
then exist at shallower overlying water depths and warmer seabottom temperatures than for pure methane hydrates. Note,
for instance, fiom Figure 1 that a hydrate composed of 10%
ethane - 90% methane at a temperature of 6OC is stable at
pressures m excess of about 20 atmospheres, but a 100%
methane hydrate is stable only at pressures exceeding about 40
atm (20 a m corresponds to about 200 m.w.e., and 40 a m to
400 m.w.e.; Baker, 1972). For Buzdag, seven gas hydrate
samples indicate a methane content from 59-87% and an
ethane content of 10-19%, with higher homologues making up
the balance (Ginsburg et al., 1992); while at Elm and Abikh
methane concentration in hydrates is between 81-96%, with
ethane and traces of higher homologues picking up the
remaining 4-19%. Also, direct sampling of gas hydrate waters
at the three sites indicates that it is water of mud volcano
origin and not sea water that is incorporated in the hydrates
(Ginsburg et al., 1992).
Hydrate concentration in the sediments cored from
the Vezirov diapir varies f h m 535% at water depths of about
500 m; while in the case of the Elm hydrates of the Azizbehov
sbucture, hydrate concentration in sediments reaches 1520%
(Ginsburg et al., 1992; Dadashev et al., 1995) in water depths
of 660 m.
The stability field of the known hydrates would
appear to indicate that around 200 m of water depth (at 6OC) is
sufficient to provide stability of an ethanelmethanehydrate,
that hydrates in gas-charged diapirs are likely to be a fairly
common occurrence, and to provide a fairly rich (5-35%)
content in surficial and near-surficial sediments.
Hazard Factors for Hydrates
Three factors are of importance in determining the dissociation
of hydrates. First is the temperature gradient in the sediments;
second is the composition of the hydrate, which determines the
critical pressure and temperature limits for hydrate existence;
third is the total sediment volume actually occupied by
hydrates.
In the case of the offshore South Caspian Basin,
regional temperature gradients would seem to be about 1.8ZC/lOO m, at least as deep as the Productive Series of the
Plio-Pleistocene (Tagiyev et al., 1996), while undisturbed
water bottom temperatures are around 4-6OC. However, the
presence of gas in mud diapirs is known to lower the
temperature in the crestal domain of a diapir and local
surrounds by up to 30-50C relative to regional measurements
at the same sediment depth (Bagirov and Lerche, 1996). For a
mud diapir of typical diameter 10 km,this lowered

OTC 8642

temperature corresponds to a lowering of the vertical

temperature gradient by about 0.3-0.5C/100 m, giving a total
temperature gradient in and near a diapir of around 1.31.7OCI100 m.
For a 10% ethane - 90% methane hydrate the critical
pressure for hydrate production is lowered fiom the 26 atm
needed for a pure methane hydrate at 0C to about 10 atm
(Baker, 1972) at 0C and the hydrate stability region is
increased (Figure 1). For a water depth, h,, a bottom water
temperature Tb, and a sediment density ps, the pressure P at a
distance z into the sediments is

where p, is the water density. The corresponding

temperature at a distance z into the sediments is

where G is the vertical thermal gradient. Because the stability

curves are almost parallel for methane hydrate and a hydrate
composed of 10Y0ethane - 90% methane (Baker, 1972), one
can write the pressure-temperature stability relation based on
the methane curve as

where Po is the critical pressure at OC and Tc is the

temperature in OC (Miller, 1972).
To estimate the total sediment thickness, z,, that
could maximally contain a 10% ethane 90% methane
hydrate, one then has the relation

where Tb is the bottom-water temperature in "C.

For instance, if z, = 0, then equation (4) requires
h, 2 po(pWg)-l exp ( ( 4 1 0 ) [0.04Tb + 3 x 10-~$]) .......(5)
which provides a minimum water depth to support hydrate
occurrence. For Po = 10 atm, Tb = 6OC, the minimum water
depth is hw,rnin 2 2 10 m; while for Tb = 4OC and Po = 10 atm,
the minimum water depth is reduced to hwPmin2 170 m. AS
the ethane concentration increases so the critical pressure Po at
0C is lowered below 10 atm, until, at 100% ethane, the
critical pressure is 5.2 a m (Miller, 1972) corresponding to a
minimum water depth of about 85 m at 4C. Once the water
depth is greater than the minimum needed for hydrate
production, it then becomes a simple matter to use inequality
(4) to estimate the maximum sediment thickness capable of
sustaining a hydrate.

Consider for illustration the Vezirov diapir in 500 m

of water, where the water-bottom temperature is 4OC. We
carry through the calculations for a 10% ethane 90%
methane hydrate (Po = 10 atm at OC), and with ps a 1.6
gcm-3, corresponding to near surficial unconsolidated
sediments. Then for hydrate existence one requires

where 2100 is the critical thickness z, in units of 100 m.

Inequality (6) is satisfied as long as 2100 is less than
about 5.2, corresponding to a hydrate potential thickness of z,
= 520m, at which depth into the sediments the temperature is
about (4 + 1.3x5.2)OC = 11C, and the dissociation pressure is
about 130 atm. From an explosive decompression viewpoint it
then would seem that a mud-diapir of radius R, filled to a
volume fiaction f with hydrates to a depth z,, has an explosive

volumetric potential, V, of

The free energy of hydrates upon dissociation is about A& = 48 kcaYmole of gas (Miller, 1972) and there is roughly a ratio
(glw) of one gas molecule for every 6 water molecules. Note
that an energy of 1 kcaYmole, if all converted to kinetic energy
of gas molecules, corresponds to about 500K; while if energy
equipartition occurs between gas and water molecules in the
hydrate at dissociation then the corresponding temperature
equivalent is about 70K per kcaYmole, i.e. between 280560K rise in temperature. Thus the explosive energy
available, E, at dissociation is
E = VA&.(gfw) kcal

.............................................................(8)

while an explosive pressure of about 130 atm is available.

For a 20% volume fiaction (f) of hydrate (10%
ethane-90% methane) in a 5 km radius (R) mud diapir, with
the hydrate extending to its maximum sediment depth (2,) of
about 500 m, the total hydrate volume is V = 8xlo9m3.
Because the volume V is roughly 117 hydrate gases, a total gas
volume of Vg, e 109m3 is available.
At equipartition of release energy, the corresponding
waterlgas temperature & is some 70 x (4-8)"K = 280-560K.
Thus the explosive mix would be at a temperature of between
about 290-570C. Given that the airlmethane self-ignition
temperature is about 537C (Guliev, 1996) it follows that: (a)
water would convert to steam; (b) the explosive pressure of
130 atm is compensated for by only 50 atm of overlying water
pressure, so that 80 atm of dynamic pressure is available to
blow a hole in the South Caspian ocean, releasing gas h m the
hydrates to combine with air and self-ignite; (c) a quantity of
super-heated steam will also be produced.
Discussion and Conclusion

The purpose of performing these calculations has been to

provide estimates and ranges for potential hazards h m
hydrates in the South Caspian Basin. The problem of
addressing every nuance of every possible situation is avoided
by using empirical measurements to provide ranges of
parameters that can influence hydrate dissociation. In that
way one can estimate a likely worst case scenario.
It would appear that hydrates can occur in as shallow
as 50 m of water, if the hydrate composition is dominated by
ethane, while 150-250 m of water is needed at a 90% methane
composition.
It would appear that stability of hydrates can occupy
as much as about 500 m of sediments when overlain by about
400-500 m of water. The cooling of the crestal regions of a
mud diapir by the low thermal conductivity of gas-charged
sediments is partly responsible for this large thickness of
potential hydrates. The corresponding dissociation pressure is
about 130 atm, quite capable of blasting a hole through the
overlying 500 m of water, which only provides a retaining
pressure of 50 atm, leaving a residual 80 atm of dynamic drive
pressure. Note that if the 80 atmospheres of pressure is
converted to a dynamic drive on the mud, then a column of
mud to a height of about 800 m can be produced. Thus, on the
order of 1 km (or a little less) can be extruded from the mud
diapir at a maximum speed of around 0.0 1-0.1 kmlsec, so that
a hazard event would take on the order of 10-lo2 sec to
become established. This speed of hazard development is so
fast as to require constant monitoring for its actualization
probability. Dissociation energy is sufficiently large to
produce temperatures of 290-570C, enough to convert
seawater to super-heated steam, and enough for self-ignition of
released methane in contact with air.
The identification by seismic methods of the top of a
hydrate layer in sediments can be used directly to estimate the
temperature gradient in the sediments as follows. The seismic
information is depth-converted from two-way travel-time to
physical depth using a velocity analysis code, so that both the
depth of overlying water, h,, and the depth, D, into the
sediments to the top of the detected hydrate reflector are
known. Then the total pressure to the top of the hydrate
reflector can be estimated. Hence one can use equation (4) in
reverse to determine the temperature gradient given some
assessment of likely composition of the hydrate (so that the
critical pressure Po at 0C can be estimated), and an estimate
of water-bottom temperature. Thus, directly from seismic one
can estimate the temperature gradient in a hydrate-bearing
mud diapir, and so one can then estimate the maximum depth
into the diapir at which hydrates could exist. In this way
seismic information alone can provide an estimate of a worstcase hazard from hydrate dissociation.
As noted by Claypool and Kaplan (1972), sediments
have seismic velocities of 2.2-2.5 kmlsec under conditions that
support hydrate formation, compared to normal velocities of
1.7-1.9 kmtsec for similar sediments without hydrates. This
increase in seismic velocity can be used as a diagnostic of the
thickness of hydrates, an increase in seismic velocity at
shallow sediment depth with a deeper decrease to a more
normal seismic velocity trend is indicative of a hydrate zone.

The seismic reflection amplitude off the top of a hydrate

should be about 6-12%. Thus, as well as being used to
estimate temperature gradients in the presence of hydrates,
seismic reflection information can also provide an indication
of hydrate thickness.
Combining the two procedures, each of which
provides a depth limit to hydrate occurrence, permits an
estimate to be made of hydrate composition because, while the
increased seismic velocity is relatively insensitive to hydrate
composition, the temperature stability & sensitive (Figure 1).
Thus if one can estimate the base of the hydrate zone fiom
seismic velocity information, and because one can also
estimate the temperature at the hydrate base position, as well
as the total sediment plus overlying water pressure to the
hydrate base, then one can use the pressure-temperature
stability diagrams of Figure 1 to estimate the hydrate
composition. A quantitative method is given in the Appendix.
Dynamic motion of a mud diapir can also lead to
explosive dissociation of a hydrate-bearing mud diapir.
Shown on figure 2 is a schematic of a diapir both before and
afler slippage and rotation along a decollement surface,
showing how a hydrate can rise above the stability line,
leading to explosive behavior. Of even greater concern is the
fact that submarine mud diapirs are known to exhibit flows
down their flanks, thereby changing their topography. Internal
sediment failure of the unconsolidated mud can then lead to
pressure and temperature changes within the sediments, which
may inhibit or enhance hydrate dissolution. Catastrophic
hydrate hazard associated with the reshaping of a mud diapir
would seem to be a problem of pressing concern, but one
which is difficult to evaluate fiom the viewpoints of either
time-of-occurrence, or interval-between-occurrences.
Buoyancy effects of hydrates on unconsolidated
sediments are also relevant. Hitchon (1972) provides
estimates of hydrate densities of p~ = 0.8-0.9 gcm-3. For a
sediment, of density p,, containing a disseminated fraction, f,
of hydrates, the bulk density is p~ = ps - f(ps-p~);if this
density is less than that of the overlying seawater, of density
p,, then the mix of hydrates and sediments is buoyant. The
critical fraction of hydrate admixture necessary to achieve
buoyancy is then f 2 @s-pw)/(ps-p~).
For ps 1.6 gcm-3, pw 1.03 gcm-3, and p~ % 0.8
gcm3, then f 2 70%. The South Caspian measurements ( to
about 1- 1.2 m depth into the sediments) (Ginsburg et al., 1992)
indicate a fraction of only up to 35% hydrate, so that the
observed sediment-hydrate mixes are not buoyant.
(Alternatively: for a hydrate fhction of 35% the sediment
density, p,, should be less than 1.15 gcm-3 if buoyancy is to
be achieved).
However, Ginsburg et al. (1992) also report finding
crystals of hydrate (5 cm x 2 cm area, 2-4 mm thick) sitting on
the ocean floor in 500 m of water. And these crystals are
clearly buoyant relative to overlying sea-water. At a waterdepth of hw the buoyancy pressure is

which, with hw z 500 m, has the numerical value Pbuoy 10

atm. Because the hydrate crystals are buoyant there must then
be a binding affinity of hydrates to the sediments which
exceeds 10 atm. When sediments are disturbed by mud flows,
volcanism, etc., it is interesting to speculate that if the binding
affinity is removed, then hydrate buoyancy can lead to a rapid
rise of hydrate crystals through the overlying water until the
critical pressure depth is reached (about 100-200 m depth of
water depending on hydrate composition), when hydrate
crystals will dissociate releasing methane and ethane gas
bubbles which continue their rise to the ocean surface. Thus,
during times of diapiric slumping, volcanic activity or
submarine mud flows, one anticipates an increase in bubbling
of methane and ethane gases at the ocean surface fiom hydrate
dissociation, a strong surficial indicator of enhanced
submarine activity associated with mud diapir evolution.
The natural hazard of submarine methane hydrates is
already substantial in the South Caspian Basin, as attested to in
records of offshore flaming eruptions (Dadashev et al., 1995).
But man-made triggering of the hydrate hazard must also be
considered. For instance, drilling into a mud diapir will raise
the mudhydrate temperature either by direct drill-bit heating
or by warm circulating mud heating. In either event, heating
hydrate-bearing mud above about 11C will dissociate the
hydrates, leading to explosive release of pressure, and to
possible rig annihilation.
Accordingly, this hazard is, perhaps, one that should
be of serious concern to oil companies drilling in offshore
regions of the South Caspian Basin.
Acknowledgments
The work reported here was supported by the Industrial
Associates of the Basin Modeling Group at USC.

References
Bagirov, E.B., and Lerche, I., 1996, Quantitative Dynamic
1.
Modeling of Mud Diapirism: Evolution of the Vezirov
Diapir, Evolution of the South C w i n : Geologk
Risks(eds. I. Lerche, E. Bagirov, R.
Nadirov, M. Tagiyev and I. Guliev), Azerbaijan Academy
of Sciences, Baku, pps. 574-625.
Baker, P.E., 1972, Experiments on Hydrocarbon Gas
2.
Hydrates in Unconsolidated Sand, in
MarineSediments.
(ed. I.R. Kaplan), Plenum Press, New
York, pps. 227-234.
Claypool, G.E., and Kaplan, I.R., 1972, The Origin and
3.
Distribution of Methane in Marine Sediments, in Natural
in m n e Sedi(ed. I.R. Kaplan), Plenum
Press, New York, pps. 99-139.
Dadashev, F.G., Guseynov, R.A., and Aliyev, AS., 1995,
4.
Map of Mud Volcanoes of the Caspian Sea (Explanatory
Notes), Geological Institute of the Azerbaijan Academy of
Sciences, Baku. 20 pps.
Ginsburg, G.D., Guseynov, R.A. Dadashev, A.A., Ivanovq
5.
G.A., Kazantsev, S.A., Solov'yev, V.A., Telepnev, E.V.,
Askeri-Nasirov, R Ye., Yesikov, A.D., Mal'tseva, V.I.,
Mashirov, Yu.G., and Shabayeva, I. Yu., 1992, Gas
Hydrates of the South Caspian, International Geology
Review 765-782.
Guliev, I.S., 1996, Model of Mud Volcanism, in &f&@!
6.

E . m O V AND I. LERCHF

OTC 8647

Hazards. (eds. I. Lerche, E. Bagirov, R. Nadiuov, M.

7.

8.

9.
10.

11.

Tagiyev and I. Guliev), Azerbaijan Academy of Sciences,

Baky pps. 549-573.
Hitchon, B., 1972, Occurrence of Natural Gas Hydrates in
in-M
Sedimentary Basins, in-Gases
(ed. I.R. Kaplan), Plenum Press, New York, pps. 195-225.
Lerche, I., Bagirov, E., Nadirov, R., Tagiyev, M., and
Guliev, I., (eds.), 1996, -ouht
. . and ProbabHazaTcls. Azerbaijan
GeAcademy of Sciences, Baku, 625 pps.
Miller, S.L., 1972, The Nature and Occurrence of Clathrate
(ed I. R.
Hydrates, &&gal Gases in
Kaplan), Plenum Press, New York, pps. 151-177.
Solheim, A., and Elverheri, A., 1993, Gas-related seafloor
craters in the Barents Sea Geo-Marine Letters 2L 12-19.
Tagiyev, M.F., Nadirov, RS., Bagirov, E.B., and Lerche, I.,
19%, Geohistory, Thermal History and Hydrocarbon
Generation History of the north-west South Caspian
. Basin,
.
in Evolutionof the South C a s o i a n : G e o b s S u k s
md Por(eds. I. Lerche, E. Bagirov, R
Nadirov, M. Tagiyev and I. Guliev), Azerbaijan Academy
of Sciences, Baku, pps. 50-106.

Appendix-A Quantitative Procedure for Hydrate

Composition Determination From Seismic Data
Suppose the water depth, h,, the physical depth to the top of
the hydrate reflector, zl, and the depth, q(>zl), to the base of
the hydrate reflector are all inferred from seismic velocity
information. Then the pressures P, = gh,p,,
PI = P, +
(zl - hw)gps, and P2 = PI + gpS(z2 zI) are estimated as is the
bottom-water temperature Tb. The hydrate stability equation
(4) can be written in the generic form

where b and c are fixed constants, and Po is hydrate

composition specific (Figure 1).
Then let the temperature at the hydrate top be TI and
at its base be T2 with geothermal gradient G, so that TI = Tb +
G(zl-h,), T2 = TI + G(z2-zI)= TI + GH, where H is the
measured hydrate thickness.
Then

Equation (A2) can be solved for the geothermal gradient G,

which is the only unknown.
Then

so that the critical pressure Po at OC is also determined.

Hence from figure I one can find out which hydrate
composition curve corresponds to the value Po, and so the
hydrate composition is found.

Figure Captions

Figure 1. Pressure-temperature stability fields for hydrates of

different compositions (after Baker, 1972).
Figure 2. Sketch of the influence of rotation of a mud diapir
on hydrate positioning relative to the hydrate stability
line: (a) before rotation; (b) after rotation.

METHANE
90% METHANE
10% ETHANE

HYDRATE
REGION

TWO-PHASE
REGION

I
5

I
10

I
15

I
20

I
25

TEMPERATURE ("C)

Fig. 1

(a)

Before Rotation

a level
Hydrate Stability Line

----

Y Hydrate Top Surface

///////////////sediment

/// \
\

-Decollement

Surface

(b) After Rotation

S

a level
Hydrate Stability Line
Hydrate Top Surface

/ / / / / / / / / / / / / / I
Sediment

/// \
\
\
\

+Decollernent

'.

Surface

Fig. 2