Earth and Planetary Science Letters 184 (2000) 321^338

www.elsevier.com/locate/epsl

Methane-related authigenic carbonates of eastern

Mediterranean Sea mud volcanoes and their possible relation
to gas hydrate destabilisation
Giovanni Aloisi a; *, Catherine Pierre a , Jean-Marie Rouchy b ,
Jean-Paul Foucher c , John Woodside d and the MEDINAUT Scientic Party
a

Laboratoire d'Oceanographie Dynamique et de Climatologie, UMR 7617 CNRS-UMPC-IRD, Universite Pierre et Marie Curie,
4, Place Jussieu, 75252 Paris, France
b
Laboratoire de Geologie (CNRS-ESA 7073), Museum National d'Histoire Naturelle, 43, rue Buon, 75005 Paris, France
c
DRO/Environments Sedimentaires, IFREMER, P.O. Box 70, 29200 Brest, France
d
Free University, Faculty of Earth Sciences, De Boelelaan 1085, 1081 HV Amsterdam, The Netherlands
Received 4 April 2000; received in revised form 16 September 2000; accepted 20 October 2000

Abstract
Nautile submersible investigations of mud volcanoes and brine seep areas of the eastern Mediterranean Sea during
the MEDINAUT cruise in November 1998 discovered extensive areas of authigenic carbonate crusts associated with
methane emissions. Carbonate crusts form pavements, round slabs and circular mounds on the central, most active
parts of mud volcanoes and in a fault-related valley where brines have accumulated to form a submarine brine lake.
Authigenic carbonate nodules have been recovered from the same areas during the MEDINETH cruise in July 1999.
Large 13 C depletions of authigenic calcite, aragonite and dolomite indicate methane as a major carbon source for the
carbonate. Crust pavements are formed when methane from a freshly emplaced, methane-charged mud flow is oxidised
at the seafloor. In this environment, where bottom waters provide the sulphate and magnesium, aragonite is favoured
versus calcite and accounts for the majority of the methane-related authigenic carbonates. Calcite, when present,
contains significant amounts of Mg2 (high-Mg calcite), and possibly other divalent ions in its crystal lattice. In areas of
brine seep and accumulation, dolomitic nodules are present at shallow depth in the sediment. The 18 O enrichment of the
authigenic carbonates (up to 4x greater than calculated values for carbonates precipitating from modern eastern
Mediterranean bottom waters) is interpreted as due to precipitation from 18 O-rich fluids rather than as a temperature
effect. The source of the 18 O-rich fluids may be multiple and possibly includes the destabilisation of gas hydrates present
at shallow subbottom depth, and the seepage of relic Messinian brines. 2000 Elsevier Science B.V. All rights
reserved.
Keywords: mud volcanoes; authigenic minerals; carbonates; East Mediterranean; gas hydrates; stable isotopes

1. Introduction
* Corresponding author. Fax: +33-144277159;
E-mail: vanni@lodyc.jussieu.fr

Mud volcanoes are a surface expression of mud

intrusions through the sedimentary column and

0012-821X / 00 / $ ^ see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 1 2 - 8 2 1 X ( 0 0 ) 0 0 3 2 2 - 8

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Fig. 1. Location of the Olimpi area and the Anaximander Mountains area where a total of 20 Nautile dives explored mud volcanoes and brine seep areas during the MEDINAUT cruise in November 1998. Most areas were revisited and sampled by coring
during the MEDINETH cruise in July 1999. The Napoli, Milano and Amsterdam mud volcanoes and the Nadir Brine Lake occur in the Olimpi area. The Amsterdam, Kazan and Kula mud volcanoes occur in the Anaximander Mountains area.

form when rapidly advecting, overpressured,

mud- and methane-charged pore uids reach the
sea oor generating mud eruptions [1]. Methane,
which contributes to the overpressuring of mud
via its expansion, is also at the base of a variety
of physical, chemical and biological processes
which mud volcanoes share with other areas of
sea oor hydrocarbon gas seepage known as
cold seeps.
When rising methane is oxidised in the upper
part of the sedimentary succession it gives rise to
the widespread precipitation of carbonates [2].
Authigenic carbonates of this type have been recorded at many sites of active or recent hydrocarbon gas seepage in a variety of geological settings world-wide [2^8]. A number of these occur
on active mud volcanoes or surfaced mud diapirs
[9,10].
If pressure and temperature conditions are fa-

vourable, mud volcanoes, due to their high methane content, are a preferred location for the occurrence of gas hydrates [9,11]. There is growing
evidence that gas hydrate destabilisation plays an
important role in authigenic carbonate precipitation [4,6,7] and the study of present-day gas hydrate-related carbonates could provide a clue to
evaluate the role of gas hydrate in geological history.
In November^December 1998, during the
MEDINAUT cruise on the R/V Nadir, Nautile
submersible dives discovered authigenic carbonate
crusts formed on mud volcanoes and cold seep
areas in two parts of the eastern Mediterranean
(Fig. 1). Gravity cores taken in the summer of
1999 from the same sites during the MEDINETH
cruise on the R/V Professor Logachev recovered
authigenic carbonate nodules. This paper describes the mineralogical and geochemical charac-

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teristics of these authigenic carbonates and discusses their relation to the seepage of methane
and the destabilisation of gas hydrates.
2. Methods
The carbonate content was determined on 80
samples of authigenic carbonate crusts, carbonate
nodules and unconsolidated pelagites and mud
breccia by reaction of 100 mg of powdered sediment with 5% HCl using a manocalcimeter (see
EPSL Online Background Dataset1 ). The estimated error is 1%. In the case of lithologies
composed of matrix and clasts (mud breccia
sediments and crusts derived from lithication of
mud breccia), the analysed samples are from
the matrix. The presence of ne-grained clasts
in the analysed subsamples cannot, however, be
excluded. X-ray diraction analyses were performed on the same set of samples using a Siemens D-500 instrument (Cu KK, Ni-ltered, radiation). The weight percentages of minerals were
estimated using the peak heights and manocalcimeter values. The estimated error is 5%. Smear
slides were made on unconsolidated sediments,
soft authigenic carbonate nodules and the soft,
inferior parts of crusts. The petrography of the
carbonate crusts was studied in thin section and
the morphology of the authigenic carbonate minerals was examined with a scanning electron
microscope (SEM).
The oxygen and carbon isotope compositions
were measured on the same set of samples using
a specic procedure when sediments contained
mixtures of calcite, aragonite and dolomite.
From these mixtures, the CO2 released after 20
min of reaction at 25C with 100% phosphoric
acid was considered to come solely from calcite
and/or aragonite [12]. However, it is impossible to
separate calcite and aragonite when they occur in
the same sample. Dolomite was isolated from the
carbonate mixture after 15 min of reaction in 1 N
acetic acid at room temperature which eliminates

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323

the calcite and aragonite components; the remaining dolomite was then reacted at 25C with 100%
phosphoric acid for 3 days. During this procedure, however, part of the dolomite reacts
with the acetic acid, and only the most resistant
dolomitic phases remain. The CO2 gas was analysed using a Finnigan Delta E triple collector
mass spectrometer. The isotopic compositions
are expressed in the conventional N notation relative to the Peedee belemnite (PDB) reference
[13]:
N 18 O x PDB
1000U18 O=16 O sample318 O=16 O PDB=18 O=16 O PDB
N 13 C x PDB
1000U13 C=12 C sample313 C=12 C PDB=13 C=12 C PDB

The analytical precision is 0.01% for both N18 O

and N13 C values. The N18 O values measured for
dolomite have been corrected by 30.8% for the
fractionation factor occurring at 25C during
phosphoric acid attack of the carbonate [14].
3. Authigenic carbonates of the eastern
Mediterranean mud volcanoes and brine
seep areas
3.1. In situ appearance
Seven mud volcanoes in the Olimpi area [15], at
a depth between 1700 and 2000 m, and in the
Anaximander Mountains area [16], at a depth between 1600 and 2000 m, were explored with the
Nautile submersible. In these areas, mud volcanoes form roughly circular edices up to 6 km
in diameter and 100 m in height. In addition,
the Nadir Brine Lake, located along a fracture
zone between the Maidstone and Moscow mud
volcanoes in the Olimpi area, was explored.
Here, brines originating from the underlying Messinian evaporites accumulated, forming a lake 250
m in diameter and more than 15 m in depth.
Carbonate crusts occur invariably in the central, most active parts of the mud volcanoes form-

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325

Plate 1. Nautile observations of in situ carbonate crusts on the mud volcanoes of the eastern Mediterranean (a^c) and their macroscopic structure (d^h). a: Crust pavements cover extensive areas on the central parts of mud volcanoes and are probably
formed by the degassing of methane-charged mud ows. Post-emplacement remobilisation of mud ows isolates polygonal portions of crusts (Amsterdam mud volcano, each crust polygon is approximately 2 m across). b: Circular crust slab probably associated with localised uid venting (Kazan mud volcano, slab is 1 m across). c: Circular crust mound probably associated with localised uid venting (Napoli mud volcano, mound is 2 m across). d: Type B crust from above (right) and in section (left)
(Kazan mud volcano, sample MN12BT3). e: Type A crusts are commonly traversed by sinuous tubular voids (left) which were
probably occupied by Pogonophora tube worms (right) (Napoli mud volcano, sample MN16BT5 [left]; Kazan mud volcano, sample MN12BT1 [right]). f: Type D crust, Moscow mud volcano, sample MN18BT2. g: Type C crust, Milano mud volcano, sample
MN17BT2. h: Nodule, Nadir Brine Lake, sample MNLGC05 s2 19^31.
6

ing either semi-continuous crust pavements from

a few millimetres to several decimetres in thickness (Plate 1a) or isolated circular slabs (Plate 1b)
and metric mounds (Plate 1c). On the Napoli mud
volcano and near the shores of the Nadir Brine
Lake, the crusts are associated with areas of brine
seepage and brine accumulation. Authigenic carbonate crusts also occur in association with uid
seepage on a 700 m high near-vertical rock face,
known as Faulted Ridge, in the Anaximander
Mountains area. In addition, gravity cores taken
during the MEDINETH cruise in the Nadir Brine
Lake and from the Milano and Napoli mud volcanoes show that authigenic carbonate nodules
are embedded in unlithied sediments from a
few centimetres to about 1 m subbottom depth.

3.2. Macroscopic texture of the carbonate crusts

and nodules
The crusts have been divided into four types of
lithofacies on the basis of macroscopic textural
characters (Table 1):
b

Type A ^ Massive crusts, lithied mud breccia:

this is by far the most common crust type
which occurs as pavements (Plate 1a) and
builds mounds (Plate 1c). These consist of a
conglomerate in which millimetre- to centrimetre-sized rock fragments are immersed in a
ner matrix/cement and strongly resemble debris ow deposits, indicating that they derive
from the lithication of mud breccia. They

Table 1
Description of the dierent types of authigenic carbonates studied
Type of authigenic
carbonate

Location

In situ morphology

Texture

Associated fauna

Type A crust

Amsterdam, Kazan, Milano

and Napoli mud volcanoes

pavements up to several dm
thick and metric mounds

tube worms and

bivalves

Type B crust

Amsterdam, Napoli and

Kazan mud volcanoes;
Nadir Brine Lake
Napoli, Moscow and
Milano mud volcanoes
Moscow and Amsterdam
mud volcanoes;
Nadir Brine Lake
Milano and Napoli mud
volcanoes;
Nadir Brine Lake

pavements up to 15 cm
thick and circular metric
slabs
thin pavements up to a
few mm thick
pavements up to 10 cm
thick

conglomerate with mm to
cm clasts immersed in a
ne-grained matrix/cement;
abundant sinuous tubular
voids
ne-grained carbonate
cement; sinuous tubular
voids can be present
cementation of abundant
mm-sized clasts
from hard limestone (top)
to friable chalk (bottom)

Type C crust
Type D crust
Nodules

roughly spherical bodies

up to 7 cm in diameter

pteropods
bivalves
^

conglomerate with mm to
^
cm clasts from mud volcanoes
and ne-grained cement from
the Nadir Brine Lake

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G. Aloisi et al. / Earth and Planetary Science Letters 184 (2000) 321^338

Plate 2. Thin-section photomicrographs of carbonate crusts. a: Mud breccia texture is recognisable in type A crusts by the presence of sedimentary rock fragments immersed in a ne-grained matrix/cement (polarised light, Kazan mud volcano, sample
MN12BT9/10). b: Bioclasts lled with aragonite needles (100U5 Wm) in a type A crust (polarised light, Napoli mud volcano,
sample MN16BT5). c: Stubby aragonite needles (150U20 Wm) lling a vein in a type A crust (polarised light, Napoli mud volcano, sample MN16BT4). d: Fossiliferous micrite with well-preserved bioclasts (mainly pelagic foraminifers) immersed in a negrained matrix/cement makes up most of the type B crusts (polarised light, Nadir Brine Lake, sample MN19BT2(2)) e: Contact
between a type B crust (acicular aragonite, bottom) and a type D crust (microcrystalline calcite, top) (polarised light, Amsterdam
mud volcano, sample MN13BT6).

are centimetres to decimetres in thickness (fragments up to 15 cm thick have been sampled)

and are traversed by a great number of sinuous
tubular voids generally under 1 cm in diameter

(Plate 1e). Commonly, lithication decreases

with depth in the sediment. These crusts are
internally grey and are covered with a thin
dark red or dark brown coating, probably com-

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posed of iron oxides, on the upper surface.

Colonisation of the crusts by xed benthic fauna is common. Bivalves and tube worms account for the majority of the benthic organisms
observed. Both living and dead individuals have
been found attached to the upper and lower
parts of crusts. Living Pogonophora tube
worms sometimes occupy the sinuous voids
(Plate 1e). Carbonate crust formation around
the tube worms which had originally colonised
unconsolidated sediment and subsequent removal of their chitinous tube probably results
in the formation of the tubular voids.
Type B ^ Massive crusts, lithied pelagites :
these are well-lithied crusts which are up to
15 cm thick and show no internal texture other
than a ne-grained carbonate cement (Plate
1d). They probably result from the lithication
of pelagites, as suggested by the abundance of
well-preserved pteropods in most crusts. When
they occur on mud volcanoes, they imply a
certain time lag between mud ow emplacement and methane seepage, necessary for the
pelagites to accumulate. They can occur as circular slabs (Plate 1b) bearing radially oriented
holes which could have been pathways for the
migration of uids or free gas. In the Nadir
Brine Lake area, type B crusts are somewhat
dispersed on the seaoor near areas of brine
seep and have smooth, polished surfaces indicating that they have been dissolved to a certain extent. Tubular voids similar to those of
type A crusts are common.
Type C ^ Thin crusts, lithied mud breccia:
these crusts are a few millimeters thick, cover
decimetre portions of mud volcanoes, are fragile and contain a great number of mm-sized
clasts and bivalve shells (Plate 1g), indicating
that they result from the lithication of the
top few millimetres of mud breccia ows.
Type D ^ Chalky aspect, lithied pelagites :
these are centimetre-thick, ne-grained, whitish
to light grey crusts which show variable degrees
of lithication, from hard limestone (top) to
friable chalk (bottom) (Plate 1f). They show
no evidence of mud breccia structure and probably derive from the lithication of pelagites.
The upper surface is covered with a brown

327

coating of iron oxides. They have been distinguished from type B crusts in that they show no
evidence of being associated with the seepage of
uids or with uid-related benthic fauna (uid/
gas conduits or tubular voids).
Nodules: these are roughly spherical bodies of
indurated sediment up to 7 cm in diameter
(Plate 1h). They were recovered at a depth between 70 and 90 cm from the Nadir Brine Lake
where they are dark grey and composed of cemented ne-grained, reduced sediments of the
brine lake; in the Milano and Napoli mud volcanoes nodules are present at depths from 5 to
18 cm where they consist of an indurated conglomerate with millimetre to centimetre mud
breccia clasts.

4. Results
4.1. Petrography
Thin sections of type A crusts (Plate 2a) show
sub-millimetre fragments of sedimentary rocks
immersed in a ne-grained matrix/cement. Commonly, the rock fragments are not in contact with
each other suggesting that the original unlithied
sediment was matrix-supported. Aragonite occurs
either as microcrystalline cement where individual
grains rarely exceed 20 Wm in length, or as larger,
elongated crystals when crystal growth occurs in
an unconned space such as an empty bioclast or
a vein. When lling bioclasts, aragonite forms radially disposed acicular crystals (100U5 Wm)
(Plate 2b); when lling veins aragonite crystals
are bigger and stubby (150U20 Wm) and increase
in size towards the centre of the vein (Plate 2c).
SEM observations show that aragonite needles
often seed on aragonitic bioclasts such as pteropods (Plate 3a). Pyrite is often associated with
aragonite (Plate 3d).
Type B crusts in thin section often appear as a
fossiliferous micrite where well-preserved bioclasts
(mainly pelagic forams) are immersed in a negrained matrix/cement (Plate 2d). Radially disposed acicular crystals of aragonite ll some foraminifers. SEM observations of the microcrystalline calcitic cement show that crystals are about

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329

1^5 Wm in size and have irregular surfaces (Plate

3b). When growing in a cavity, calcite crystals
have a more regular rhombohedral shape (Plate
3c). Acicular aragonite can be locally predominant when lling bioclasts and cavities (Plate
3e). In one case from the Amsterdam mud volcano (sample MN13BT6) the contact between a
type B crust (acicular aragonite, Plate 2e, bottom)
and a type D crust (microcrystalline calcite, Plate
2e, top) is visible in thin section.
Well-crystallised dolomite rhombs about 1 Wm
in size are an important constituent of authigenic
carbonate nodules in the sediments of the Nadir
Brine Lake (Plate 3f). Framboidal pyrite was
commonly observed with the SEM in the same
nodule samples.
4.2. Mineralogy
4.2.1. Unlithied pelagites and mud breccia
sediments
In order to obtain the reference mineralogy of
unlithied sediments, X-ray diraction analysis
was carried out on four samples of pelagites and
seven samples of mud breccia. Pelagites are composed of carbonates (23^69%), clay minerals (16^
22%), quartz (5^11%) and minor quantities of
feldspars (1^3%) and halite ( 6 2%); mud breccia
is composed of clay minerals (18^47%), carbonates (6^37%), quartz (8^27%), halite (1^15%)
and minor quantities of feldspars (2^5%) and gypsum (1^5%). Halite may be formed due to postsampling recrystallisation following the evapora-

6
Plate 3. SEM photographs of authigenic cements. a: Aragonite needles seeding on a pteropod shell in a type A crust
(Napoli mud volcano, sample MN16BT5). b: Roughly equigranular, anhedral calcite crystals about 1^5 Wm in size in a
type B crust (Kazan mud volcano, sample MN10BT6).
c: robable calcite rhombs with well-dened shape growing in
a cavity of a type A crust (Kazan mud volcano, sample
MN10BT?). d: Authigenic pyrite associated with stubby aragonite crystals (Napoli mud volcano, sample MN16BT2).
e: Acicular aragonite crystals lling a cavity in a type B
crust (Amsterdam mud volcano, sample MN13BT6). f: Wellcrystallised dolomite rhombs about 1 Wm in size in carbonate
nodules from the sediments of the Nadir Brine Lake (Nadir
Brine Lake, sample MNLGC05 sec2 19^31 cm).

Fig. 2. Carbonate fraction composition of authigenic carbonate crusts and nodules.

tion of pore waters. However, halite crystals and

crust fragments of authigenic origin have been
found in the sediments of the Napoli mud volcano
[17] and it is possible that part of the halite found
in the present study is also of authigenic origin.
The carbonate fraction of pelagites and mud breccia sediments is dominated by calcite (Fig. 2)
while aragonite and dolomite are present in small
amounts (11% or less of the carbonate fraction in
weight). The major diraction peak of calcite has
, apd(104) values between 3.026 and 3.033 A
proaching that of stoichiometric calcite (3.035
). A small calcite peak with d(104) values cenA
is also present in mud brectred around 2.993 A
cias. The examination of smear slides shows that
nannoplankton (coccoliths), foraminifers and calcitic bioclasts account for the calcite content of

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G. Aloisi et al. / Earth and Planetary Science Letters 184 (2000) 321^338

the unconsolidated sediments. Authigenic calcite,

aragonite and dolomite are minor components.
Other minerals which were not detected with Xray diraction due to their low concentrations
include pyrite, glauconite and biotite.
4.2.2. Authigenic carbonate crusts and nodules
Lithication of unconsolidated sediments is
brought about by the precipitation of calcite, aragonite and dolomite cements which are present in
variable proportions in the analysed crusts (Fig.
2). Dolomite and aragonite are considered of authigenic origin (some aragonite may, however, derive from pteropods) whilst calcite is both of authigenic, biogenic and detrital origin. Some
compositional trends can be followed in the dierent types of crusts and nodules. In type A crusts
aragonite is the most abundant authigenic carbonate (often s 70% of the carbonate fraction), calcite and dolomite being important in only a few
crusts. Type B and C crusts contain mixtures of
calcite and aragonite in variable proportions
(aragonite is predominant in type C crusts) whilst
in type D crusts calcite predominates (generally
s 90% of the carbonate fraction). Nodules have
the highest dolomite concentration (up to 90% of
the carbonate fraction) although they can also be
composed nearly entirely of calcite. Dolomite
concentrations in the crusts are otherwise low
(often 6 20% of the carbonate fraction). Whilst
dolomite^calcite and aragonite^calcite mixtures
are common, dolomite and aragonite have not
been found together in the same sample. Dierences of crust and nodule mineralogy by area are
not obvious. It is clear, however, that dolomiterich nodules occur in areas of brine seep and accumulation (Nadir Brine Lake area and Napoli
mud volcano).
The position of the major diraction peak of
. Shifts of
calcite varies between 3.035 and 2.965 A
d(104) values away from that of stoichiometric
) can be due to Ca2 substitution
calcite (3.035 A
2
by Mg as well as by other divalent ions. The
distribution of d(104) values of calcites is bimodal
(Fig. 3). One group of calcites centred around
corresponds to low-Mg calcites, whilst
3.028 A
another group of calcites has d(104) values ap , indicating an MgCO3 content
proaching 2.998 A

Fig. 3. Distribution of d(104) values for calcites and dolomites.

of approximately 12 mol%. Often, both major

diraction peaks coexist in one sample. Values
of d(104) for dolomites vary in the range 2.886^
(most frequent values are around 2.900
2.934 A

A), that is, from stoichiometric dolomite (2.886

) to values greater than those typical of ankerite
A
). These d(104) variations reect variable
(2.904 A
amounts of substitution of Mg2 by Ca2 and,
possibly, Fe2 or Mn2 [18]. The (113/104) peak
height ratio for Fe-free dolomite is 0.3; for ankerite (Ca(Mg,Fe)(CO3 )2 ), this ratio is 0.06. Where
enough dolomite was present in the samples enabling the measurement of the (113/104) peak
height ratio, values were found ranging from 0.3
to 0.19, suggesting a minor amount of Fe2 incorporation in the dolomite crystal lattice.
4.3. Stable isotope composition
The carbon and oxygen isotope compositions
of unlithied pelagites vary between 0.31 and
2.24x and between 0.37 and 2.8x, respectively
(Fig. 4a) and mostly reect precipitation from
eastern Mediterranean surface waters at variable
temperatures and variable N18 O values [19]. In
mud breccia samples, however, the N13 C values
are a few per mil lower than those of pelagites

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331

Fig. 4. Carbon and oxygen isotope compositions of carbonates from mud volcanoes and methane/brine seep areas of the eastern
Mediterranean. a: Unlithied pelagites, mud breccia sediments and authigenic carbonate crusts and nodules by type. b: Authigenic carbonate crusts and nodules by area.

(34.86 to 30.31x) indicating the probable admixture of carbonate issued either from sedimentary organic matter or from methane oxidation.
The N18 O values of mud breccia (between 30.73
and 0.97x) indicates precipitation of carbonates
either at warmer temperatures or from waters less
saline than those of modern pelagic environments.
The carbon and oxygen isotope compositions
of authigenic carbonate crusts and nodules show
a much greater variability (Fig. 4b). The N13 C
values of calcite and aragonite range from
346.7 to 3x. Type A and B crusts and nodules
show the greatest 13 C depletion (from 345 to
310x), indicating a methane-derived carbon
source for most of these crusts. Type C and D
crusts have higher and less variable N13 C values
(from 33.2 to 3x) indicating seawater as the
major carbon source of the carbonate. The N13 C
values of dolomite were measured on three samples (see EPSL Online Background Dataset1 ) and
vary from 332.98 to 36.59x, the lowest values
being associated with the nodules from the Nadir

Brine Lake. The N18 O values of calcite and aragonite vary between 1.07 and 7.08x, with nodules and type B crusts having the highest values
( s 5x). The N18 O values of dolomite vary from
3 to 7.24x. The great variability of the oxygen
isotope composition suggests that controls other
than temperature are important in dening this
parameter. The highest N18 O values are associated
with authigenic carbonates from brine seep areas
(Napoli mud volcano and Nadir Brine Lake).
5. Discussion
5.1. Methane oxidation and pore water N13 C4 CO2
anomalies in zones of uid venting and mud
volcanism
Pore water N13 C4CO2 in surface sediments affected by methane migration and seepage is controlled by the biologically mediated oxidation of
methane carried out by micro-organisms. At the

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base of the sulphate reduction zone, the anaerobic

oxidation of methane is coupled with sulphate
reduction :
3
3
CH4 SO23
4 ! HCO3 HS 2H2 O

When all the pore water-dissolved sulphate is consumed, rising methane can reach the lower limit
of the oxic zone of sediments or, in zones of active
venting, it will come into direct contact with seawater. In both cases, it will be oxidised in an
aerobic environment. Both anaerobic and aerobic
oxidation of methane are associated with a kinetic
isotope eect for carbon which tends to concentrate the lighter 12 C isotope in the produced CO2
[20^22]. As a result, following methane oxidation,
pore water N13 C4CO2 decreases. The N13 C4CO2 of
pore waters will then depend on the relative abundance of carbon derived from the normal seawater source (w1.0x), from the marine organic
matter source (w323x) and from oxidised
methane (3110x to 330x).
Methane oxidation in correspondence to uid
venting produces the same pore water N13 C4CO2
anomaly on mud volcanoes and in normal sediments (e.g. in pockmarks). The circular slabs and
metric mounds observed on the mud volcanoes of
the eastern Mediterranean are most probably related to methane venting from discrete portions of
the seaoor to bottom waters.
A slightly dierent scenario is to be envisioned
when dealing with pore waters of mud volcanic
sediments not aected by active uid venting.
Eruptions produce mud which ows down the
anks of the mud volcano as debris ows [17]
experiencing limited or no mixing with bottom
waters during ow movement [23]. Thus, freshly
emplaced mud ows probably bear oxygen-free,
methane-charged pore uids inherited from deeper levels in the sedimentary succession. Dissolved
sulphate may be present if sulphate-bearing evaporites are part of the underlying sedimentary succession. After the emplacement of a mud ow,
methane oxidation will occur at the sediment^
water interface. In evaporite-free areas, the depth
of methane oxidation will then depend on the
balance between upwards loss of methane-charged
water due to mud compaction (consolidation),

and
and downwards diusion of dissolved SO23
4
O2 due to chemical gradients or to bioturbation
through benthic activity from bottom waters into
pore waters. Conditions such as these are probably responsible for the formation of the crust
pavements that cover large portions of the explored mud volcanoes.
5.2. Pore water chemistry controls on the
mineralogy of methane-derived authigenic
carbonates
Methane-derived authigenic carbonates precipitate from diagenetic uids which are most probably supersaturated with respect to all of the carbonates found (calcite, aragonite and dolomite).
Mineralogy should therefore be determined by
dierences in mineral growth rate [24].
Aragonite precipitation is favoured over calcite
at high SO23
concentrations and Mg2 /Ca2 ra4

Fig. 5. N18 O values as a function of the relative abundance

of the two calcite families in samples containing calcite as a
unique carbonate phase.

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G. Aloisi et al. / Earth and Planetary Science Letters 184 (2000) 321^338

tios (e.g. at seawater values) [25], and where phosphate concentration are kept low by the limited
amount of organic matter oxidation [26]. Conditions similar to these should be met at the seaoor
when the rising methane-charged pore waters
meet bottom waters and where sulphate reduction
by anaerobic methane oxidation keeps rates of
organic matter oxidation and phosphate production low explaining the predominance of aragonite in type A and B crusts.
The bimodal distribution of calcite d(104) values suggests the existence of two sources: a lowMg biogenic source with d(104) values centred
, and a high-Mg authigenic source
around 3.028 A
. Fig. 5
with d(104) values centred around 2.998 A
is a plot of the relative abundance of the two
calcite families where calcite is the unique carbonate phase (soft sediments and all authigenic carbonates are included) against N18 O values of the
calcite mixture. The samples are distributed along
a mixing line joining two end-members : unlithied mud breccia composed only of low-Mg calcite
and with N18 O values close to zero and calcite
crusts composed entirely of high-Mg calcite with
N18 O values of nearly 6x. Thus, methane-derived
calcites (with only a few exceptions, see below) are
high-Mg calcites which were precipitated under
similar conditions as aragonites (sulphate and
Mg environment). The source of Mg2 could lie
both in the methane-charged, rising uids or in
the bottom waters. The estimated average Mg
(12 mol%) is comparable with that of methanederived calcites from the Oregon/Washington subduction zone (average 12 mol% [2]), from Ban
Bay (14^18 mol% [4]) and with that of high-Mg
calcite cements unrelated to methane seepage
from the deep eastern Mediterranean Sea (8^12
mol% [27]). However, a certain dispersion of
d(104) values exists around the high-Mg calcite
end-member (Fig. 3) and this may reect changing saturation states and, possibly, varying temperatures of precipitation [28].
Three methane-derived crust samples from the
Nadir Brine Lake area and one methane-derived
crust collected from a brine seep on the Napoli
mud volcano represent exceptions in that they are
composed entirely of low-Mg calcite and have

333

high N18 O values. Brines from the Nadir Brine

Lake have Mg2 concentrations up to 10 times
smaller and Ca2 concentrations slightly higher
than normal Mediterranean seawater (Haese, personal communication). Furthermore, the brines
seeping from the top of the Napoli mud volcano
are depleted in sulphate by a factor of three with
respect to normal Mediterranean bottom water
[29]. In low-Mg and low-sulphate environments
such as these, low-Mg calcite precipitation is not
inhibited and will prevail over aragonite and highMg calcite [24] forming the observed methane-related brine seep carbonates.
The highest dolomite concentrations occur in
nodules from areas of brine seep and accumulation (Nadir Brine Lake and Napoli mud volcano).
Dolomite precipitation is favoured when dissolved
sulphate, an important inhibitor of dolomite
growth, is absent or present at very low concentrations [30,31] and where high supersaturation
helps overcome the low-temperature kinetic barriers associated with dolomite precipitation [32].
The common presence of pyrite in the nodules
indicates that sulphate reduction is active, possibly favouring dolomite precipitation.
Of the studied crusts, only the methane-related
crusts from the Nadir Brine Lake show evidence
of surface dissolution. The bottom waters of the
eastern Mediterranean are presently supersaturated with respect to calcium carbonate and probably were so during all of the Pleistocene [33].
Furthermore, no evidence of dissolution can be
seen on other crusts unrelated to methane seepage, either in the Nadir Brine Lake area or in
other areas. Dissolution of the carbonate crusts
thus requires a mechanism provoking local undersaturation of bottom waters. Similar dissolution
features have already been observed in methanerelated authigenic carbonate crusts [4] and are
tentatively explained by high methane uxes
which favour aerobic rather than anaerobic oxidation. During aerobic oxidation of methane,
pCO2 increases and pH decreases [34], possibly
leading to the dissolution of carbonates. Variations in the upward methane ux may therefore
result in subsequent periods of carbonate crust
build-up and dissolution.

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G. Aloisi et al. / Earth and Planetary Science Letters 184 (2000) 321^338

5.3. Origin of the 18 O enrichment in the

methane-derived authigenic carbonates
The oxygen isotope composition of authigenic
carbonates is a function of temperature and mineralogy, which aect oxygen isotope fractionation, and of uid N18 O. Theoretical N18 O values
for carbonates precipitating in the present eastern
Mediterranean
bottom
waters
(T = 13C;
N18 O = 1.5x SMOW) have been calculated according to the experimental equations for calcite
(assuming a 12% MgCO3 content) [35], for aragonite [36] and for dolomite [37]:
calcite : 1000 ln K 2:78U106 T 32 32:89
0:06 Mg mol%
aragonite : T  C 20:634:34N18 Oarag 3N 18 Owater
dolomite : 1000 ln K 2:62U106 T 32 2:17
The theoretical equilibrium N18 O values are equal
to 2.9x for calcite, 3.3x for aragonite and
5.3x for dolomite.
The majority of measured N18 O values are higher than the theoretical values (up to 4x in calcite
and aragonite and 2x in dolomite, Fig. 4a,b).
Furthermore, the N18 O of the authigenic carbonate phases is underestimated in samples containing calcite of pelagic origin (0.37 6 N18 Ox 6 2.8).
Higher than expected N18 O values could be explained if the precipitation occurred during the
Last Glacial Maximum (LGM). During this period, surface waters in the Aegean Sea (the source
for deep water formation in the eastern Mediterranean) reached a minimum of 8C in winter [38].
Supposing that authigenic carbonate precipitation
occurred during the LGM, which is also characterised by a global increase of about 1.5x in the
N18 O values of the water masses, calcite, aragonite
and dolomite would have N18 O values of 5.7, 5.9
and 7.9x, respectively, possibly explaining the
elevated N18 O values of authigenic carbonates.
However, a synchronous triggering mechanism
common to all the studied mud volcanoes is
needed for the crusts to have the same age. The

possibility that pressure/temperature conditions

during the LGM induced the synchronous destabilisation of gas hydrates on mud volcanoes does
not seem probable because the combined eect of
bottom water temperature decrease (about 5C)
and sea level drop (about 100 m) during the
LGM had a stabilising eect on gas hydrates
(see phase diagram in De Lange and Brumsak
[29]).
Alternatively, if the crusts were precipitated in
modern bottom water conditions, their high N18 O
values were produced by precipitation from 18 Orich uids. In the EPSL Online Background Dataset1 the calculated N18 Owater values at a temperature of 13C are shown for calcite/aragonite mixtures using a weighted average accounting for
variable concentrations of the two phases [35,36]
and for dolomite [37]. Most calculated values are
greater than 1.5x, the present-day N18 O value of
Mediterranean bottom water. A number of possible sources for the 18 O-rich water exist.
Martin et al. [39] have interpreted a positive
1.4x N18 O anomaly of pore uids in the Manon
mud volcano (Barbados Accretionary Prism) as
due to gas hydrate destabilisation. The same interpretation was proposed by Hesse et al. [40] for
pore uids from the Middle America trench that
have N18 O values up to 3.31x. 18 O-rich carbonates related to gas hydrate dissociation have
been reported for a number of cold seep environments worldwide [4,6,7]. During the formation of
gas hydrates from interstitial water, there is a
preferential incorporation of water containing
the heavier isotopes into the gas hydrate structure
[41], so that the remaining pore water becomes
18
O-depleted. The 18 O fractionation factor between tetrahydrofuran hydrate and liquid water
has been estimated experimentally by Davidson
et al. [42] to be 1.0026. Matsumoto et al. [43]
estimated the value of K to be in the range of
1.0034^1.0040 on the basis of oxygen isotopic
measurements on gas hydrate and interstitial
water from Ocean Drilling Program Leg 164. In
closed systems the fractionation eects may be
considerably increased, and the pore solutions
after gas hydrate crystallisation may be depleted
by a few per mil in 18 O relative to the original
water [44]. Conversely, gas hydrate decomposition

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G. Aloisi et al. / Earth and Planetary Science Letters 184 (2000) 321^338

liberates 18 O-rich water molecules which can contribute signicantly to the 18 O enrichment of the
interstitial waters [45]. Gas hydrates have been
sampled with Kasten and gravity coring from
the Kula and Amsterdam mud volcanoes during
the MEDINETH cruise. Furthermore, decreased
salinity upon core recovery from the Milano and
Moscow mud volcanoes is interpreted as due to
gas hydrate dissociation during core recovery (De
Lange, personal communication). Similar decreased salinities measured during ODP Leg 160
in sediments of the Milano mud volcano are interpreted as deriving from the decomposition of
massive gas hydrates accumulations more than 40
m thick [29]. However, a gas hydrate source for
the diagenetic uids implies that gas hydrates are
being destabilised and further investigations are
needed to propose possible mechanisms of destabilisation on eastern Mediterranean mud volcanoes.
Methane-related crusts and nodules in the Na-

335

dir Brine Lake area and on the Napoli mud volcano, however, are 2x enriched in 18 O with respect to methane-derived crusts in other areas
(Fig. 4b) and this may be due to the seepage of
brines that inherit a 18 O enrichment during evaporation [46]. On the Napoli mud volcano, pore
water N18 O values up to 8x at 10 m depth in
the sediment [29] are otherwise dicult to interpret.
Other diagenetic processes can lead to an increase in pore water N18 O and it is not possible
to evaluate their importance on the basis of isotopic data of carbonates alone. For example, Dia
et al. [47] reported N18 O values up to 7.48x in
mud volcano uids on the island of Trinidad
which are interpreted as formed during high-temperature interaction of uids with wall rocks. Furthermore, clay dehydration [48] and low-temperature alteration reactions with interbedded
volcanics [49] can also produce increases in pore
water N18 O; to evaluate their importance needs
further investigations.
5.4. Carbonate crusts unrelated to methane
oxidation

Fig. 6. Carbon and oxygen isotope composition of authigenic

carbonate crusts unrelated to the seepage of methane (type C
and D). Previously studied crusts of the eastern Mediterranean [33] are reported for comparison.

The occurrence of authigenic carbonate crusts

of Quaternary age unrelated to methane seepage
has been widely reported from the Mediterranean
Sea [33]. Cementation of pelagites is thought to
occur during cold periods of non-deposition or
low sedimentation rates possibly related to deepsea currents [50] and results in the precipitation
of high-Mg calcite in the uppermost part of
the sediments [33]. Type D crusts, which derive
from the lithication of pelagites, are composed
mainly of high-Mg calcite and, with one exception (see below), have isotopic compositions similar to those recorded by Allouc [33] (Fig. 6).
Type C crusts have similar isotopic compositions
but are composed of calcite^aragonite mixtures.
Two type C crusts (MNLBCO6 bottom and
MNLBC07, both from the Napoli mud volcano)
and one type D crust from the Amsterdam
mud volcano (MN13BT6-2) are enriched in aragonite, possibly of methanogenic origin and are
therefore slightly depleted in 13 C (33.2 6 N13 C
x 6 0.31).

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G. Aloisi et al. / Earth and Planetary Science Letters 184 (2000) 321^338

6. Conclusion

References

Methane emission from the mud volcanoes and

brine seep areas of the eastern Mediterranean induces the precipitation of authigenic carbonates in
the form of crust pavements, mounds, slabs and
nodules. Crust pavements, which account for the
majority of the methane-related authigenic carbonates, are produced by the post-emplacement degassing of methane-charged mud breccia. In this
particular setting methane oxidation happens near
the seaoor, probably in a sulphate, high-Mg2 /
Ca2 environment which favours the precipitation
of aragonite versus calcite. When present, authigenic calcite contains signicant quantities of
Mg2 (high-Mg calcite) and possibly other divalent ions in its crystal lattice. Calcites precipitating
under the inuence of Mg2 -poor brines, however, are signicantly depleted in Mg (low-Mg
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possible to discriminate between dierent sources
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destabilisation of gas hydrates at shallow subbottom depths is a good candidate process. In the
areas of brine seep (Nadir Brine Lake and Napoli
mud volcano), the diagenetic uids may be enriched in 18 O due to the seepage of 18 O-enriched
relic Messinian brines.

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Acknowledgements
The captains and crew members of the research
vessels Nadir and Professor Logachev and of the
submersible Nautile provided helpful assistance at
sea, their work is greatly appreciated. This work
has been supported by grants from TOTAL/
FINA/ELF and Enterprise Oil Italia s.p.a. for
the PhD of Giovanni Aloisi. This project has received the nancial support of IFREMER (Nadir
and Nautile), the Institut National des Sciences de
l'Univers of CNRS (INSU Grant 99/13) and of
NWO (Project 750.199.01). Reviews by Ryo Matsumoto, Gerhard Bohrmann and Joris Gieskes
greatly improved the manuscript.[FA]

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