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ARTICLE IN PRESS
0264-8172/$ - se
doi:10.1016/j.m
�CorrespondE-mail addr
Marine and Petroleum Geology 25 (2008) 457–472
www.elsevier.com/locate/marpetgeo
Complex plumbing systems in the near subsurface: Geometries ofauthigenic carbonates from Dolgovskoy Mound (Black Sea)
constrained by analogue experiments
Adriano Mazzinia,�, Michael K. Ivanovb, Anders Nermoena, Andre Bahrc,Gerhard Bohrmannc, Henrik Svensena, Sverre Plankea,d
aPhysics of Geological Processes, University of Oslo, P.O. Box 1048, 0364 Oslo, NorwaybMoscow State University, Vorobjevy Gory, Moscow 119992, Russia
cResearch Centre Ocean Margins, University of Bremen, Post Box 330 440, D-28334 Bremen, GermanydVolcanic Basin Petroleum Research, Oslo Research Park, 0349 Oslo, Norway
Received 28 April 2007; received in revised form 20 September 2007; accepted 3 October 2007
Abstract
Targeted sampling on the Dolgovskoy Mound (northern Shatsky Ridge) revealed the presence of spectacular laterally extensive and
differently shaped authigenic carbonates. The sampling stations were selected based on sidescan sonar and profiler images that show
patchy backscatter and irregular and discontinuous reflections in the near subsurface. The interpretation of acoustic data from the top
part of the mound supports the seafloor observations and the sampling that revealed the presence of a complex subsurface plumbing
system characterized by carbonates and gas. The crusts sampled consist of carbonate cemented layered hemipelagic sedimentary Unit 1
associated with several centimetres thick microbial mats. Three different carbonate morphologies were observed: (a) tabular slabs,
(b) subsurface cavernous carbonates consisting of void chambers up to 20 cm3 in size and (c) chimney and tubular conduits vertically
oriented or forming a subhorizontal network in the subsurface. The methanogenic origin of the carbonates is established based on visual
observations of fluids seepage structures, 13C depletion of the carbonates (d13C varying between �36.7% and �27.4%), and by thin
carbonate layers present within the thick microbial mats. Laboratory experiments with a Hele–Shaw cell were conducted in order to
simulate the gas seepage through contrasting grain size media present on the seafloor. Combined petrography, visual observations and
sandbox simulations allowed a characterization of the dynamics and the structures of the plumbing system in the near subsurface. Based
on sample observations and the experiments, three observed morphologies of authigenic carbonates are interpreted, respectively, as (a)
Darcian porous flow through the finely laminated clayey/coccolith-rich layers, (b) gas accumulation chambers at sites where significant
fluid escape was impeded by thicker clayey layers forming the laminated Unit1 and (c) focussed vertical fluid venting and subhorizontal
migration of overpressured fluids released from (b). The Hele–Shaw cell experiments represent a promising tool for investigating shallow
fluid flow pathways in marine systems.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Black Sea; Shatsky Ridge; Dolgovskoy Mound; Anaerobic methane oxidation; Authigenic carbonate; Hele–Shaw cell modelling
1. Introduction
The Black Sea mud volcanoes, diapirs and cold seepshave been a target of investigation of numerous marineexpeditions with the aim of investigating the mechanismsof hydrocarbon-rich fluids seepage (Ivanov et al., 1989;
e front matter r 2007 Elsevier Ltd. All rights reserved.
arpetgeo.2007.10.002
ing author.
ess: [email protected] (A. Mazzini).
Ginsburg et al., 1990; Ivanov et al., 1992; Limonov et al.,1994; Woodside et al., 1997; Ivanov et al., 1998; Bohrmannand Schenck, 2002; Ergun et al., 2002; Kenyon et al., 2002).Differently shaped authigenic carbonates (slabs, chimneys,irregular, blocky) have been observed and sampled fromvarious sites of the Black Sea Basin often associated withmicrobial colonies (Woodside et al., 1997; Peckmann et al.,2001; Thiel et al., 2001; Michaelis et al., 2002; Mazziniet al., 2004). The precipitation of these carbonates is
ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472458
considered to be the result of coupled sulphate reductionand anaerobic methane oxidation (AOM) operated byconsortia of archaea and bacteria (Ritger et al., 1987;Valentine and Reeburgh, 2000; Michaelis et al., 2002;Boetius and Suess, 2004).
The authigenic carbonates collected worldwide have abroad variety in shape and mineralogy. This variety isinterpreted to be related with a combination of numerousfactors; the four main ones include the varying rate andcomposition of the seeping fluids, the type of sedimentwhere fluid seepage occurs and the type of biota thriving atthe seepage sites (Mazzini, 2004). Several authors tried tomodel the various carbonate shapes based mainly onmorphological and petrotraphy studies (e.g. Kulm andSuess, 1990; Michaelis et al., 2002; Diaz-del-Rio et al.,2003; Mazzini et al., 2004, 2006). However a modell-ing approach trying to combine these disciplines withanalogue laboratory modelling has not been investigated indetail yet.
In 2005 a joint venture of Training Through Researchand METRO Research Programmes (TTR15 cruise),visited the Shatsky Ridge focussing on the study ofDolgovskoy Mound (DM) situated along the north-western Shatsky Ridge (Fig. 1(A)).
This paper reports the data and the observationscollected from the DM during the TTR15 cruise(Akhmetzhanov et al., 2007). Petrography and geochemicalstudies on a unique authigenic carbonate collection werecomplemented by laboratory modelling studies represent-ing a novel approach for seepage studies. The describedmultidisciplinary approach, including sandbox laboratorysimulations, aims to give new insights into the marinesubsurface plumbing system.
2. Geological setting
Despite the numerous cruises exploring the Black Sea,little documentation is available from the Shatsky Ridgeregion that was broadly explored mainly by Russianscientists during the last decade (e.g. Grinko et al., 2004;Afanasenkov et al., 2005a).
The Shatsky Ridge is located between the TuapseTrough and the Eastern Black Sea Basin. The ridge hasno bathymetric expression observable on the seafloordue to a thick cover of Cenozoic sediments. The ridgeoverlies continental crust (Starostenko et al., 2004) andappeared as a positive structure on the seafloor duringthe Cretaceous separating the deep water basins of theGreat Caucasus from the new ‘‘young’’ Eastern BlackSea Basin (Nikishin et al., 2003). Since no deep drillinghas ever been conducted in the Eastern Black Sea region,most interpretations are based on the geology of thesurrounding coast areas and seismic investigations. Recentseismic investigations (2001–2004) revealed structures,suggesting that a significant portion of the ridge consistsof Late Jurassic carbonate build-ups (Afanasenkov et al.,2005a, b).
More detailed bathymetric studies were conducted in1996 by the RV Gelendzik completing a Simrad EM-12Smultibeam mosaic along the Shatsky Ridge and the TuapseTrough (Andreev, 2005). This mosaic combined with thepreviously acquired seismic data allowed the identificationof several new structures (possible mud volcanoes) in thesetwo areas.
3. Sedimentary units and authigenic carbonates from the
Black Sea
A common pattern of three distinct modern sedimentaryunits characterize most of the deep water areas of the BlackSea (Andrusov, 1890; Degens and Ross, 1972; Ross andDegens, 1974; Shimkus et al., 1975). Below the seafloor, thetypical geological sequence includes three main units:(a) Unit 1 consists of thin alternating coccolith ooze(mostly Emiliania huxleyi) and clayey sediment laminae.The thickness of the clayey laminae can occasionally reachseveral centimetres. At seepage locations, Unit 1 (andsometimes Unit 2) can be interbedded by exotic centimetrethick structureless and light coloured clayey layers. Theorigin of these so called ‘‘Degens layers’’ has been discussedfor long since their first discovery and several hypotheseshave been suggested (Degens et al., 1978). Degens et al.(1978) initially proposed a turbidite origin of these layers,Calvert et al. (1987) linked them to mudflow events,however the most likely hypothesis is the one described byKempe et al. (2001) that suggested the localized expulsionof fluidized and overpressured clayey sediments on theseafloor. (b) Unit 2 consists of thin laminations of sapropel;(c) Unit 3, interpreted to be lacustrine facies, consists oflaminations of terrigenous (silty–clayey) sediment, com-monly containing hydrotroilite layers. These units reachtheir maximum thickness in the central part of theBlack Sea; Units 1 and 2 are on average 30 cm thick, whileUnit 3 can reach several metres in thickness (Ross andDegens, 1974).Likewise for the sedimentary units, a broad pattern of
authigenic carbonates has been described by Mazzini et al.(2004). The typification includes: Type U1 (consisting oflayered slabs of carbonate cemented clayey and coccolithooze laminae from Unit 1); Type U2 (consisting oflayered slabs of carbonate cemented sapropelic Unit 2),Type U3 (layered carbonate cemented Unit 3), Type MSa
(structureless micrite-cemented clay) usually forminglaterally extensive pavements at the seafloor or withinUnit 1. This type of slabs possibly represents the carbonatecementation of the described ‘‘Degens layers.’’ Carbonatetypes U1 and MSa were sampled from the study areadescribed in this paper.
4. Methods and experimental setup
The marine expedition was conducted with the RVProfessor Logachev equipped with the long range sidescansonar OKEAN, single channel seismic system, MAK-1 M
ARTIC
LEIN
PRES
S
2070 m
1970 m
SENW
2020 m
Shatsky Ridge
35°0'E 36°0'E
45°0'N
44°0'N
37°0'E 38°0'E 36° 40.5'E 36° 41'E 36° 41.5'E 36° 42'E39°0'E30'
30'
30'
30'
45°0'N
44° 1'N
44° 1.5'N
44°0'N
30'
30'
30'
30' 30' 30'
35°0'E 36°0'E 37°0'E 38°0'E 39°0'E30' 30' 30' 30'
1600
10001400
1200800
1800
2000
600400
200
20
10
50
100
Dolgovskoy
Tuapse Trough
Tuapse Trough
Shatsky Ridge
BS347G
MAK58BSMAK58BS
500
500
BS347G
BS349GrBS349Gr
BS346GrBS346Gr
BS348GBS348G
17:0018:0019:0020:30 20:00
acoustic shadows
A B
C
Fig. 1. (A) Bathymetric map around the study area with Shatsky Ridge and Dolgovskoy Mound (red dot), inset of Black Sea map; (B) detail from MAK58BS sidescan sonar line (perimeter framed in
image C) through Dolgovskoy Mound with sampling stations and (C) sub bottom profiler and image of deep towed MAK58BS sidescan sonar line through Dolgovskoy Mound.
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ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472460
deep towed high resolution 100 kHz sidescan sonar systemand 5 kHz subbottom profiler, with a TV remote controlledgrab, and a 1.5 tonnes gravity coring device that sampledthe targeted locations. The samples collected were de-scribed and selected for further analyses.
Thin sections of carbonate samples were studied usingboth optical and electronic microscopes. X-ray diffraction(XRD) analyses were performed on bulk carbonatesamples to determine the dominant carbonate phase.
Carbon and oxygen isotopic analyses were completed onbulk carbonate samples at the Institute for EnergyTechnology at Kjeller, Norway. Carbonate cements wereground and digested with a 0.1ml 100% H3PO4 solutionfor 2 h at 30.0 1C in a vacuumed environment. The releasedCO2 was transferred to a Finnigan MAT DeltaXP isotoperatio mass spectrometer (IRMS), for determination of d13Cand d18O. Results are reported in % relative to the VPDBstandard (Table 1). The precision for d13C is 70.1% and70.2% for d18O.
Sandbox experiments on granular media (Gidaspow,1994; Jaeger et al., 1996) were conducted at the Physics ofGeological Processes Laboratory (University of Oslo) on aquasi two dimensional Hele–Shaw cell (e.g. Woolsey et al.,1975; Tanaka and Toyokumi, 1991; Nichols et al., 1994)consisting of two 600� 600� 12mm3 glass plates 8mmdistant from each other. Several set-ups and tests have beencollected before selecting the ideal parameters where thesubsurface deformation in fluid flushed discontinuousmedia are best observable. The cell was filled with an18 cm thick interval of spherical Beijer glass beads(ø ¼ 420–840 mm) interbedded by a 0.3mm thick layer ofdevolite (china clay) in the upper part. Air was used as theanalogue fluid to induce overpressure in the media. Air wasflushed in the system through an inlet with inner diameter
Table 1
Summary of sampling points described and main petrographic, morphologica
Sample number Structure d13C%(VPDB)
BS346–2.1 Vertical chimney –
BS346–2.2 Vertical chimney –
BS346–2.3 Cavernous �27.4
BS346–2.4 Slab �36.7
BS346–2.5 Cavernous �36.4
BS346–2.6 Horizontal tube �33.5
BS346–2.7 Slab �33.5
Pv ¼ pyrite, MgCC ¼Mg calcite, CC ¼ calcite, Qz ¼ quartz.aAverage estimates.
of 3.8mm, placed 6.3 cm into the cell in order to preventpreferential flow along the bottom and edges of the cell. Airflux and pressure data (i.e. monotonic increase of air flowand pressure drops across the sedimentary media) werecollected in real time by an Omega pressure sensor andOmega FV-135 flow meter. The pressure sensors wereplaced by the air inlet and at the top of the bed. Pictureswere taken during the experiment using a high resolutiondigital camera at a rate of 10 images per second.Experiments were performed in a two dimensional set-upand the quantitative measurements of the pressure andflow velocity are thus not directly applicable to a threedimensional setting. The walls of the Hele–Shaw cell setdefinite limits on the deformation of the top layer.Furthermore there exists friction between the walls andthe flowing grains that does not occur in natural systems(Mourgues and Cobbold, 2003). Nevertheless, adding athird dimension does not introduce any new physicaleffects in the processes of interest. The main processes ofinterests (i.e. Darcy flow in porous media and deformation)and their scaling are independent of the number of spatialdimensions (Gidaspow, 1994). Therefore two dimensionalexperiments capture the same physical processes as in athree dimensional setting. Further experiments were donein order to constrain the parameters controlling thedeformation of the media. This was achieved using Beijerglass beads as single media and varying its thickness h
(Fig. 8(A)) from the major permeability contrast (i.e. hererepresented by the interface between the inlet and the glassbeads) to the surface. In this way the deformation observedon the contact between the inlet and the Beijer glass beadsfollows the same principles of the deformation occurringbetween the glass beads and the impermeable clayey layeras the abrupt permeability contrast (from higher to lower
l and geochemical characteristicsa
d18O%(VPDB)
XRD analyses
%a
Comments
– Py ¼ 100 Black iron rich mineral (pyrite)
from central part of seepage pipes
– Py ¼ 100 Black iron rich mineral (pyrite)
from central part of seepage pipes
�0.8 CC ¼ 100 White calcite minerals associated
with bacterial mats
0.2 CC ¼ 100 Carbonate cement from
laminated slab Type U1
�0.4 CC ¼ 100 White calcite minerals close to
pyrite deposits
0.1 Py ¼ 100 Carbonate crystals (isotopes
analyses) close to black iron-rich
mineral (XRD analyses) from
tubular shaped precipitate
0.0 MgCC ¼ 37,
CC ¼ 37,
Qz ¼ 26
White slab Type MSa capping
Type U1 crust
ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 461
permeability) generates a zone of overpressured fluids. Thisset-up allowed us to acquire a significant amount of datasimply by changing the thickness h of the single granularmedia.
5. Results
5.1. Acoustic survey: the structure of the mound
A sidescan sonar survey was conducted in order to selectthe primary targets for further sampling. Sidescan sonarline MAK58BS was acquired in a NW–SE direction alongthe Shatsky ridge (Fig. 1(C)).
The acoustic image shows that the mound has asubcircular shape with a diameter of approximately900m and a height of more than 70m (Fig. 1(B) and(C)). The mound is highly asymmetric and shows at leastthree sharp positive features on its top part. The north-western (and probably southern) slope is steep and slumpdeposits (possibly representing mud breccia) are observed
500 m
Fig. 2. Slab shaped carbonates. (A) Seafloor image showing laterally extensiv
finely laminated and carbonate cemented sedimentary Unit 1; note some sm
(arrowed); (C) thin section image perpendicular to lamination showing layering
in image (C) showing alternations of darker pyrite-organic-calcite-rich layers
at its foot. The south-eastern slope is gentler and isinterrupted by a sharp step in its middle part. A moatframes the foot of this slope. Backscatter record appearspatchy throughout the structure, revealing areas withstronger reflection where carbonate crusts and/or coarsersediment deposits (e.g. mud breccia) are inferred. Strongbackscatter is not observed in the central part of thestructure. The record of weak and medium backscatteringsignal between time marks 18:31–18:37 is associated withpartial recording error when the fish was rapidly pulled upalong the steep slope close to the top of the structure.Both sidescan sonar and subbottom profiler records are
inconsistent with other profiles from the deep parts of theBlack Sea. Usually sonar images are characterized by weakgrey monotonous backscatter, and profiler displays flatrelief and relatively deep penetration of the acoustic signalthrough the stratified Quaternary deposits. The imagesrecorded around the DM show the opposite. The sonarimage shows a complex backscatter consisting of patches ofdifferent size and shape while the profiler reveals irregular
200
d
l
d
d
l
l
5 cm
e carbonate slabs; image view approximately 1.2m; (B) hand specimen of
all degassing vesicles on the upper surface filled by microbial colonies
of alternated coccolith-rich and clay-rich layers; (D) detail of area framed
(d) and lighter coloured clay-rich layers (l).
ARTICLE IN PRESS
8 cm
5 cm
2 cm 500 μm
Fig. 3. Cavernous shaped carbonate. (A) Seafloor image showing irregular morphology; image view approximately 1.2m; (B) large block of carbonate
cemented sedimentary Unit 1, the internal part of the block is void and coated by thick mats of microbial colonies; the upper part if the block is
characterized by up to 1 cm sized degassing vesicles and several centimetres sized ‘‘chimney like’’ features that pierce the hollow block; the deformed
carbonate cemented laminae are visible throughout the block; on the central part of the carbonate sample are visible pipes horizontally oriented and tubes
that form an intricate network in the subsurface; (C) details from area framed in image (B) showing some of the pipes horizontally oriented; (D) example
of cavernous hand specimen entirely coated with thick pinkish microbial mat in the internal part; (E) details of microbial mat with authigenic carbonate
layers precipitating inside (arrowed); (F) thin section image of sparitic authigenic carbonate precipitating within the microbial mat.
A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472462
ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 463
morphology with numerous positive shapes a few meters inheight and with no layering of sedimentary units.Numerous subcircular depressions up to tens of meters insize were also observed through the sonar record. Some ofthese features resemble the pockmarks observed in othersettings. Areas with very strong backscatter are presentbetween time mark 16:20–16:40 and 17:10–17:20 starboardside. This type of backscatter is not associated with sharprelief and is interpreted as (a) lithological heterogeneity dueto deposits from the distal part of the Kerchensky Fan or(b) associated with localized hydrocarbon-rich fluidsseepage (e.g. authigenic carbonate). However, in case ofthe section from 19:20 to 20:20 we can observe cleartopographic image with strong backscatter towards thesidescan and accompanied by acoustic shadow. Theapparent subcircular form of this feature might beinterpreted as the existence of a mud volcano with craterwalls (?). A similar kind of buried mud volcanoes or largecollapse structures have been observed previously in the
Fig. 4. ‘‘Chimney-like’’ carbonates. (A) Image showing chimney-like carb
approximately 1.2m; (B) hand specimen showing sections of chimneys entirely
(framed in image B) entirely consisting of black framboidal pyrite, the reddish c
(D) thin section image of pyrite framboid aggregates.
Sorokin Through (Ivanov et al., 1998) and MediterraneanRidge (Ivanov et al., 1996). An alternative interpretationsuggests that these features could represent the remains ofthe channel-levee system recorded in SE part of this line.The acoustic reflectivity of the bottom deposits arechanging significantly along the subbottom profiler record,suggesting strong lithological heterogeneity.
5.2. Seafloor and carbonate observations
TV line profiles around the top part of DM were selectedbased on the acquired sidescan sonar images. A prelimin-ary report of the seafloor sampling and observations with adiscussion of the results was initially given by Mazzini et al.(2007). The TV record revealed the presence of numerousescarpments (up to 1–2m high), differently shapedcarbonate deposits and localized microbial mats. The threegravity core sampling stations retrieved ordinary hemi-pelagic sequences, showing distinct carbonate cemented
onates rising from the seafloor (framed on dashed line); image view
cemented by framboidal pyrite; (C) details of internal part of the chimney
olour represents the oxidation that appeared the day after the sampling and
ARTICLE IN PRESS
-10-2 -1 1 20
-15
-20
-25
-30
-35
-40
-45
-50
δ13C
(%
o V
-PD
B)
δ18O (%o V-PDB)
NIOZ MV
Odessa MV
Dolgovskoy M
Fig. 5. Stable carbon and oxygen isotope values of authigenic carbonates
from Dolgovskoy Mound compared with values obtained from Odessa
and NIOZ Mud Volcanoes (Mazzini et al., 2004).
A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472464
layers (Type U1 and Type MS) and sandy-silty intervals.Spectacular samples were recovered from the topmost partof DM (station BS346Gr, �1965m water depth) were thesidescan sonar record had high backscatter and where theTV images showed an irregular seafloor. Using a TVremote controlled grab, a large collection of authigeniccarbonates (up to 60 cm wide) was retrieved onboard. Therecovery revealed that these carbonates have a complexgeometry in the subsurface. Analyses and observations(Table 1) distinguished three main shapes of carbonatefeatures: (a) slab, (b) cavernous and (c) chimney-like andtubular.
The slab type carbonates appear laterally extensive onthe seafloor (Fig. 2(A)) and mainly consists of carbonatecemented Unit 1 sometimes capped or interbedded by alayer of carbonate Type MSa (cf. Section 3). The thicknessof these slabs can vary from a few centimetres up to10–15 cm (Fig. 2). Microbial colonies were observedthriving as a thin dark biofilm on the interface betweenthe carbonate cemented sedimentary layers. Thin sectionobservations are identical to the one described by Mazziniet al. (2004) showing the fine laminations of alternatedclay- and coccolith-rich layers. Microscopy also showsthat carbonate precipitation occurs prevalently along thecoccolith-rich layers where pyrite framboids and microbialremains are also highly concentrated (Figs. 2(C) and (D)).
The irregular features observed on the seafloor(Fig. 3(A)) appear in the subsurface as deformed andstacked carbonate cemented sedimentary intervals (Unit 1)that encase carbonate-coated cavernous structures (up to25–30 cm2 in size, Figs. 3(B) and (D)). These cavities arecemented by carbonate Type U1 occasionally interbeddedby Type MS (high magnesium calcite). Approaching thethick microbial mats in the internal part, the lowmagnesium carbonate Type U1 is much better crystallized.The internal part of these large voids is commonly coatedby light coloured sparitic calcite and by several centimetresthick microbial colonies of differing colours (i.e. mainlypinkish, but also whitish and yellowish, Figs. 3(D) and(E)). Within these thick mats, millimetre scaled layers ofcalcite were observed forming distinct horizons. XRDanalyses and thin section images of the carbonate coatingthe subsurface chambers and growing within the microbialmats show sparitic low magnesium calcite devoid of anysiliciclastic admixture (Fig. 3(F)).
Several types of ‘‘chimney-like’’ and tubular carbonatesamples are associated with these cavernous structures.
Fig. 6. Hele–Shaw sandbox analogue simulation of fluid induced deformat
conditions: the porous granular media (dark grey) is interlaid in the top part of
by an arrow; (B) At P ¼ 2276Pa diffusive air seepage through the porous gran
seepage is impeded and when the required overpressure is reached, a displace
occurs when the overpressured fluids are gathered underneath the impermeable
3530 to 3632Pa); (E) the deformation persists and fluids continue to seep latera
the fluid to breach the impermeable clayey media in the extensional zones (P ¼
the amount of fluids seeping from depth and is coupled with lateral seepage defo
reading and flow velocity of the fluid during the experiment. Corresponding fi
Chimneys erect vertically in the water column (Fig. 4(A)).At these sites the carbonate thickness and verticaldeformation is prominent and a positive relief withhigh concentrations of microbial mats are observed.The internal part of these chimneys is often completelyfilled by framboidal pyrite, but it is not uncommon toobserve a central void conduit that pierces the wholechimney (Figs. 4(B) and (C)). XRD analyses and thinsection images confirm the sole presence of pyriteaggregates together with microbial remains. Tubular
features (up to 5 cm in diameter) can also branch offfrom the lower part of the cavernous structures, forminga network that extends horizontally in the subsurface(e.g. Fig. 3(C)).
5.3. Geochemical analyses
Carbon stable isotope measurements on the authigeniccarbonates (Table 1) reveal d13C varying from �27.4%to �36.7% and d18O values from �0.8% to 0.2% (Fig. 5).No significant variations of d13C and d18O were observedin carbonate measured from the different samples.The lightest carbon values are observed in carbonates
ion of an heterogeneous sedimentary package. (A) Initial experimental
the box by a impermeable thin layer of clay (black); the air inlet is indicated
ular media; once the air reaches the impermeable clayey layer the diffused
ment occurs on the interface between the two media; (C, D) deformation
clayey layer; the deformation increases with pressure (pressure varies from
lly. Microfractures and sediment unconformities develop, allowing part of
3415Pa); (F) vertical seepage towards the open surface cannot cope with
rmation; pressure drops to P ¼ 2960Pa and (G) diagram showing pressure
gures are indicated by arrows.
ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472466
precipitating close to the microbial mats. To our know-ledge no other stable isotope data from authigeniccarbonates from the Shatsky Ridge has been documented.
5.4. Hele–Shaw sandbox simulation
As previously described (cf. Section 3) localized varia-tions and discontinuities exist in the thickness of the clayeylayers present in Unit 1. The working hypothesis is thatsince some of the described impermeable clayey laminaehave thickness greater than centimetre scale, theycan impede more efficiently the seepage of fluids, hencecreating overpressure in the subsurface and furtherdeformation. This hypothesis was tested with the Hele–Shaw sandbox experiment aiming to observe the fluidbehaviours through overpressured lithologically discontin-uous units (Fig. 6(A)). Hence particularly significant werethe deformations occurring on the interface between thegranular and clayey media.
Constant monitoring of the pressure drop and the flowvelocity during the experiment (Fig. 6(G)) allowed tocouple visual observations with these physical parameters.The sequence of images shows that at low air fluxes and atpressure drop of 2276 Pa, the fluid seeps with a Darcianflow distributing evenly through the permeable granularmedia lying underneath the low permeability clayey layer(Fig. 6(B)). The laterally continuous impermeable clayeylayer cannot accommodate the flow and impedes theseepage of fluids towards the surface. As the fluid fluxincreases, overpressure on the interface between thegranular and the clayey media is sufficient (i.e. pressure ¼3530 Pa) to gradually lift vertically and deform the toplayers (Fig. 6(C)). As the overpressure build-up increases,the bulging becomes more prominent as well as the lateralseepage of fluids below the impermeable layer (Fig. 6(D)).During this phase the pressure rises from 3530 to 3632 Pa.During the vertical deformation, compression occurson the top part of the bulge and extension along the lowerflanks where weakness spots become more distinct
Fig. 7. Conceptual evolutionary cartoon of fluids seepage and carbonate prec
near subsurface moving by Darcian flow through parallel layered sediment dep
seepage occurs and when the seeping fluids reach thicker clayey layers, their ris
accumulated and (C) microbial colonies grow in the internal part of these cham
The overpressured fluids continue to move laterally, forming a network of pipe
Note: the fish has a purely cosmetic purpose for the cartoon, as we are consid
(Fig. 6(E)). To this abrupt fracturing corresponds a suddenirreversible pressure drop (3415 Pa). This extension allowsthe fracturing and thus the seepage of fluids through theclayey layer, forming a subvertical conduit (Fig. 6(F)). Atthis point the pressure drops further to 2960 Pa.
6. Discussion
6.1. Microbial reactions and differentiated authigenic
minerals precipitation
Ground truthing confirmed the interpretation of theacoustic data. Sampling showed that a complex plumbingsystem exists in the subsurface of the study area.The carbonate 13C depletion revealed by stable isotopeanalyses supports the idea that the extended microbialcolonies mediate the oxidation of hydrocarbon-rich fluid,resulting in carbonate precipitation. This is also supportedby stable carbon isotopic analyses (d13CCH4
as low as�75.1%) of free gas collected from the sediments in the TVgrab (V. Blinova, pers. comm.). The three describedcarbonate types are interpreted as the result of threedifferent mechanisms of fluid seepage and carbonateprecipitation.Striking mineralogical differences have been described
between the chimney features (entirely coated by framboi-dal pyrite) and the internal part of the cavernous features(sparitic calcite). As already documented by other authorsthese two minerals are, respectively, the by-product ofsulphate reducing bacteria (SRB) and methane oxidizing(MO) archaea (e.g. Hovland et al., 1985; Ritger et al.,1987; Boetius et al., 2000). Bahr et al. (2007) completeddetailed lipid biomarker analyses on the thick microbialcolonies in the cavernous features, detecting the presence ofSRB and MOAs. Our visual and petrography observationscould suggest that SRB thrive more abundantly in thechimney and tubular features where focussed fluid seepageoccurs, while preferentially MO flourish where no sus-tained seepage occurs, forming thick mats and inducing
ipitation in the subsurface. (A) Fluids rising from greater depth reach the
osits; (B) details from area framed in image A. When more sustained fluid
e is impeded and deform the soft sediment creating chambers where gas is
bers (pink framing line) and precipitation of authigenic carbonate occurs.
s and tubular features that extends horizontally through the soft sediment.
ering anoxic conditions (i.e. water depth �2000m).
ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 467
precipitation of calcite (i.e. in the large voids in thesubsurface). However this is a speculative suggestion sincecomparative analyses from the microbial colonies thrivingin the pyrite-rich chimneys are currently not available.
0 10 20 300
500
1000
1500
2000
2500
π 1 =
vc μ
h /
(C
k),
[1
]
π2 =
Deforma
L=0.8 cm
P2
h
L
In
Fig. 8. (A) Schematic drawing of the experimental set-up. The air is injected
pressure P ¼ P1–P2 is measured with sensors. The height h is measured fro
deformation occurs. In the development of the phase diagram h is measured fro
pictures in Fig. 6, the main permeability contrast is between the surface and the
phase diagram marking the onset of the fluid-induced deformation. The diamo
solid line shows the best fit to the measured values; g(p2) can be extrapolated a
Mound.
6.2. Gas hydrates fuelling from the subsurface?
DM lies in the gas hydrate stability field. The hypothesisthat significant deposits of gas hydrates were present at this
40 50 60 70 80
h / L, [1]
tion
Static bed
Flow meter
P1
Glass beads
Flow control
let
through the vertical pipe into the bed. The critical Darcy velocity vc and
m the surface down to the permeability contrast at which the sediment
m the top of the inlet to the surface. In the experiment represented by the
bottom of the clay layer where the deformation occurs. (B) Dimensionless
nds show the measurements of the normalized critical Darcy velocities, the
nd applied to similar cohesion controlled settings, such as the Dolgovskoy
ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472468
location is certainly fascinating and could perfectly fit withthe morphology of the described features. The subsurfacecavities could represent the volume occupied by former gashydrate deposits that were subjected to dissociation.Nevertheless this possibility might be ruled out since theobserved oxygen isotopic values are not consistent withcements that precipitated from fluids enriched in 18O(as it should be in case of gas hydrate dissolution).The recorded isotopic range (�0.8%od18Oo0.2%)instead reveal that the cements precipitated from afluid in isotopic equilibrium with the seafloor temperaturethat averages around 9 1C (Friedman and O’Neil,1977; Swart, 1991). This is consistent with the absence oftypical features of gas hydrate dissociation in the grabretrieved onboard.
6.3. The subsurface plumbing system: mechanisms of fluids
seepage and carbonate precipitation
Based on the observations and experimental results, andtaking into account the previously published data, thefollowing section suggests conceptual models of authigeniccarbonate formation and fluid seepage for the studyarea. The Hele–Shaw sandbox simulation may deciphersome of the mechanisms of fluid seepage-induced matrixdeformation.
Where local fluid seepage is not sustained, Darcian flowprocesses prevail and the formation of slab features occurs(Fig. 7(A)). During this type of microseepage no significantdeformation occurs as observed on the carbonate cementedslabs and during the sandbox experiments (Figs. 2 and6(B)). The cementation process of almost identical slabshas been studied in detail by Mazzini et al. (2004, Fig. 12)after comparing a large collection of carbonate cementedsedimentary units from different regions of the Black Sea.The petrography observations presented in this paperalso confirm that the vertical seepage of hydrocarbon-richfluids is impeded by clayey layers. At this interfacemicrobial colonies thrive and induce precipitation ofmicritic carbonate cement that extends within the moreporous coccolith-rich layers. This model is also stronglysupported by microbial mats observed thriving preferen-tially underneath thicker clayey intervals. The seepage offluids continues vertically through microfractures andmicrovesicles (see Fig. 5(D) in Mazzini et al., 2004) untilanother clayey layer will halt the fluid rise, initiating newAOM and carbonate precipitation. The thickness of the
Table 2
Physical parameters used in the Hele–Shaw sandbox and existing in natural s
Setting C (Pa) K (m2) L (
Hele–Shaw 102 1.33� 10�9 3.8
Offshore seepsa 106 10�13 L
aAverage estimates.
carbonate cemented slabs depends on the duration of thefluid flow seepage and on local variations in the clayeylayer thickness.A different mechanism involving a significant amount of
free gas seepage is necessary to explain the carbonate-cemented decimetre scaled cavities and tubular features. Atthese locations the thicker and more impermeable clayeylayers within Unit 1 (including also the Degens layers)impede the immediate release of a more sustained seepageof hydrocarbon-rich fluids (Fig. 7(B)). The gas saturatedfluids entrapped in the subsurface deform the softsedimentary layers, forming large, laterally elongated voidareas (Fig. 3). A similar behaviour is observed in theHele–Shaw experiment when sufficient overpressure isaccumulated to initiate the deformation (Fig. 6(C)). Belowthe seafloor, microbial colonies grow inside these cavities,inducing the precipitation of carbonate minerals via AOM.Once the system reaches these conditions if more fluids areprovided (e.g. cf. Fig. 6(F) in the Hele–Shaw simulation)focussed vertical seepage occurs through the chimneys,releasing part of the overpressure created within thecavernous features (Fig. 4). As carbonate and pyriteprecipitation continues, a solid cage inside and aroundthe cavernous structure forms, preventing further deforma-tion of the sedimentary layers and, of course, furtherreducing permeability of the seeping fluids. Additionally, aprogressive decrease of the chimney’s diameter (due tocontinuous precipitation of authigenic minerals) inducesnew internal overpressure. Since seepage of fluids at theseafloor cannot cope with the amount of gas rising fromdepth, the subsurface plumbing system has to furtheradjust, forming complex networks of tubes, pipes andcavernous structures that extend laterally (Figs. 7(C) and3(C)). The described model is reproducible at variousdepths (e.g. where the thicker clayey layers occur) and canexplain the presence of the superposed cavernous structurescollected from Unit 1.
6.4. Dimensional analysis from the Hele–Shaw sandbox
experiments
Numerous landers have been distributed at severaloffshore seepage and venting sites with the aim to completelong-term measurements of the seeping fluids (e.g. Leiferet al., 2004; Marinaro et al., 2006; Person et al., 2006).A problem with this type of monitoring is that it cannottake into account the subsurface deformations or consider
eepage environments
m) m (Pa s) h (m) vc (m/s)
� 10�3 17.6� 10�6 h vc
10�4 10�1 10�3
ARTICLE IN PRESS
C*
C*
h/L=10
log10
(k/μ ), [m2/Pas]
log 10
(C),
[Pa
]
0
2
4
6
8
10
12
Deformation
Static bed
Ultimate strength of materials
h/L=10 000
log10
(k/μ), [m2/Pas]
log 10
(C),
[Pa
]
−18 −16 −14 −12 −10 −8 −6 −4
−18 −16 −14 −12 −10 −8 −6 −4
0
2
4
6
8
10
12
−10
−9
−8
−7
−6
−5
−4
−3
−2
−1
0
−10
−9
−8
−7
−6
−5
−4
−3
−2
−1
0
Deformation
Static bed
Ultimate strength of materials
1mm/yr
1mm/yr
1m/s
1m/s
log1
0 of
cri
tical
Dar
cy v
eloc
ity [
m/s
]lo
g10
of c
ritic
al D
arcy
vel
ocity
[m
/s]
deformation on offshore seeps
Fig. 9. Plots showing how the sediment cohesion C, which is the least constrained parameter, depends on sediment permeability over fluid viscosity k/mwhen varying the critical Darcy velocity vc in two different extreme values where h/L ¼ 10,000 (image A) and h/L ¼ 10 (image B); plots based on phase
diagram in Fig. 8(B). The plots highlights that: (1) vc increases for increasing cohesion C and permeability k of the sediment, and decreasing fluid viscosity
m; (2) when increasing the size of the feeder channel L compared to the sediment height above the permeability contrast h, the bed deforms at lower vc at
given C and k/m. The dashed line represents the ultimate strength of any material, which acts as an absolute upper limit of the cohesion. The value C*
(i.e. 1010 Pa) corresponds to 1/10 of the shear modulus (Braeck and Podladchikov, 2007). Therefore, our estimates of cohesion are limited by this value.
A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 469
the rheology of the sediments during the fluid seepage.Sandbox experiments could provide further information inorder to quantify the mechanism of fluid seepage. In orderto estimate if the Hele–Shaw technique has relevance alsofor natural seepage systems, we have used a quantitativeapproach to the data collected.
In cohesion controlled systems the weight of the over-burden can be neglected, when looking at the topsurface sediments (e.g. the topmost layers in marineseepages). For this reason our analysis focused on fivedimensional parameters: the critical fluid Darcy velocityvc (m/s) at which the deformation of the sediment occurs;
ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472470
the cohesion C (Pa); the permeability of the bed over theviscosity of the fluid k/m (m2/Pa s); the inlet diameter L (m)and the depth of the permeability contrast at whichdeformation occurs h (m). When using dimensionalanalysis, the problem is reduced to two dimensionlessparameters p1 ¼ Ck/mhvc and p2 ¼ h/L. The parameter p1is interpreted to be the ratio of the material strength C
and the fluid overpressure across the bed, while p2 is ageometric conversion factor between the sediment heightand the inlet diameter. The dimensionless parameters canalso be written as
vc ¼Ck
mhg
h
L
� �.
The laboratory experiments were performed repro-ducing the simulation varying h and measuring vc asdescribed in Section 4 using a single media. Our results(Fig. 8) show that g(p2) increased with (h/L)2. As g(p2) isapplicable also in natural seepage settings, and as L
represents a parameter that is measurable both inlaboratory and in the field, the width L of the feederchannel could be extrapolated using the physical para-meters existing in natural seepage settings (Table 2).L was found to be in the order of 10�1m. The valueobtained matches the size of the feeder channel observedat the Shatsky Ridge seepage sites and is also typicalfor many other marine locations (e.g. Kulm andSuess, 1990; Michaelis et al., 2002; Diaz-del-Rio et al.,2003).
Further extrapolations from the results summarizedin Fig. 8(B), can be obtained from Fig. 9 that showshow the critical Darcy velocity vc correlates withthe variations of C and k/m. Fig. 9 also indicates thefield of deformation in natural settings (i.e. in clayeysediments and in the close subsurface) where a criticalDarcy velocity is estimated at �10�3m/s, confirmingother estimates (cf. Table 2). Finally the plot can beused to constrain the sediment cohesion in any settingwhere the permeability of the sediment, viscosity ofthe fluid, the feeder width, height from the pressuresource onto the surface and the Darcy velocity aremeasured.
Our results show that analogue experiments representa powerful tool to investigate the mechanisms of fluidsseepage in granular media. This type of calculationrepresents an initial attempt to quantify the geometryand the physical principles of the plumbing system.However, further investigations have to be performedto further corroborate the geological observations inorder to, e.g., prove the scaling dependency of the inletdiameter.
7. Conclusions
Acoustic investigations and ground truthing of the DMrevealed the presence of seeping hydrocarbon-rich fluidsand ongoing AOM resulting in widespread carbonate
precipitation. Based on sample observations combinedwith laboratory experiments, three types of carbonatestructures related to fluid seepage and mineralogicalprecipitation have been identified.
(A)
Slab: Darcian flow of hydrocarbon-rich fluids inducesprecipitation of micritic carbonate cement within thethin sedimentary laminae;(B)
Cavern: thick clayey laminae present inside Unit 1impede sustained seepage of hydrocarbon-richfluids, inducing subsurface deformation and precipita-tion of carbonate cement within the large cavernousfeatures;(C)
Chimneys and tubes: can have vertical or horizontalorientation (tubular structures). Focussed and vigor-ous seepage of fluids from the overpressured cavernousfeatures results in pipe structures where predominantlypyrite precipitation occurs.The data described indicates that fluids seep vigorouslynot only vertically but also migrate horizontally in thesubsurface. The methanogenic origin of the carbonates issupported by stable isotope data (d13C as low as �36.7%)and by the thick microbial mats that thrive profusely at thissite. Mud breccia was not retrieved at any station; thereforethe inferred mud volcanic activity at DM cannot be provenbased on the existing data.Sandbox simulations revealed to be a useful tool to
simulate the seepage of fluids and to understand thedeformation mechanisms occurring in the subsurface.Dimensional analysis shows that the Hele–Shaw experi-ments can provide quantitative information of the naturalseeping systems.
Acknowledgements
This paper is dedicated to the memory of LeonidMazurenko, great friend and scientist. The authors aregrateful to Yuri Podladchikov for his support duringthe preparation of the manuscript and to AndreyAkhmetzhanov and Galen Gisler for their useful com-ments. David Roberts and two anonymous reviewers arethanked for their constructive reviews. We wouldlike to acknowledge the Crew and the Scientific Partyof the TTR-15 Cruise and the UNESCO-MSU Centrefor Marine Geosciences. We gratefully acknowledgeBMBF-funded project METRO which paid ship time ofR/V Professor Logachev and support from a Centre ofExcellence grant to PGP, and a PETROMAKS grantto Anders Malthe-Sørenssen, both from the NorwegianResearch Council.
References
Afanasenkov, A.P., Nikishin, A.M., Obukhov, A.N., 2005a. Geological
history of Eastern Black Sea region and its oil and gas potential.
Vestnik MGU, Series 4, Geology 5, 3–13 (in Russian).
ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 471
Afanasenkov, A.P., Nikishin, A.M., Obukhov, A.N., 2005b. The System
of Late Jurassic carbonate buildups in the northern Shatsky Swell
(Black Sea). Doklady Akademii Nauk 403 (2), 216–219.
Akhmetzhanov, A.M., Ivanov, M.K., Kenyon, N., Mazzini, A. (Eds.),
2007. Deep-water cold seeps, sedimentary environments and echosys-
tems of the Black and Tyrrhenian Seas and the Gulf of Cadiz. IOC
Technical Series No. 72, UNESCO, 140pp.
Andreev, V.M., 2005. Mud volcanoes and oil evidence in the Tuapse
Trough and the Shatsky Ridge (Black Sea). Doklady Akademii Nauk
402 (3), 362–365.
Andrusov, N.I., 1890. Preliminary account of participation in the Black
Sea deep-water expedition of 1980. Izvestija Vsesoyuznogo Geogra-
ficheskogo Obshchestva 26, 380–409 (in Russian).
Bahr, A., Pape, T., Bohrmann, G., Mazzini, A., Haeckel, M., Reitz, A.,
Ivanov, M., 2007. Authigenic carbonate precipitates from the NE
Black Sea: a mineralogical, geochemical and lipid biomarker study.
International Journal of Earth Sciences, in press.
Boetius, A., Suess, E., 2004. Hydrate Ridge: a natural laboratory for the
study of microbial life fueled by methane from near-surface gas
hydrates. Chemical Geology 205 (3–4), 291–310.
Boetius, A., Ravenschlag, K., Schubert, C.J., Rickert, D., Widdel, F.,
Gieseke, A., Amann, R., Jorgensen, B.B., Witte, U., Pfannkuche, O.,
2000. A marine microbial consortium apparently mediating anaerobic
oxidation of methane. Nature 407, 623–625.
Bohrmann, G., Schenck, S. (Eds.), 2002. Marine gas hydrates of the
Black Sea (Margasch): R/V Meteor cruise report M52/1, Istanbul
(January 2–February 1, 2002). GEOMAR Report 108, 191pp.
Braeck, S., Podladchikov, Y.Y., 2007. Spontaneous thermal runaway as
an ultimate failure mechanism of materials. Physical Review Letters 98
(9), 095504-1-4.
Calvert, S.E., Vogel, J.S., Southon, J.R., 1987. Carbon accumulation rates
and the origin of the Holocene sapropel in the Black Sea. Geology 15,
918–921.
Degens, E.T., Ross, D.A., 1972. Chronology of the Black Sea over the last
25,000 years. Chemical Geology 10, 1–16.
Degens, E.T., Stoffers, P., Golubic, S., Dickman, M.D., 1978. Varve
chronology: estimated rates of sedimentation in the Black Sea
deep basin. Initial Reports of the Deep Sea Drilling Project 42,
pp. 499–508.
Diaz-del-Rio, V., Somoza, L., Martinez-Frias, J., Mata, M.P., Delgado,
A., Hernandez-Molina, F.J., Lunar, R., Martin-Rubi, J.A., Maestro,
A., Fernandez-Puga, M.C., 2003. Vast fields of hydrocarbon-derived
carbonate chimneys related to the accretionary wedge/olistostrome of
the Gulf of Cadiz. Marine Geology 195 (1–4), 177–200.
Ergun, M., Dondurur, D., Cifci, G., 2002. Acoustic evidence for shallow
gas accumulations in the sediments of the Eastern Black Sea. Terra
Nova 14 (5), 313–320.
Friedman, I., O’Neil, J.R., 1977. Compilation of stable isotope fractiona-
tion factors of geochemical interest. In: Fleisher, M. (Ed.), Data of
Geochemistry, sixth ed. USGS Prof. Paper, 12pp.
Gidaspow, D., 1994. Multiphase Flow and Fluidization. Academic Press
Inc., Harcourt Brace & Company, 457pp.
Ginsburg, G.D., Kremlev, A.N., Grigor’ev, M.N., Larkin, G.V.,
Pavlenkin, A.D., Saltykova, N.A., 1990. Filtrogenic gas hydrates in
the Black Sea (21 voyage of the research vessel ‘‘Evpatoriya’’). Soviet
Geology and Geophysics (Geologiya i Geofizika) 31 (3), 8–16
(in Russian).
Grinko, B.N., Kovachev, S.A., Khortov, A.B., 2004. The Shatsky Ridge
strucuture (Black Sea) based on OBS regional investigations. Bulletin
of the MOIP, otd. Geology 79 (3), 3–7 (in Russian).
Hovland, M., Talbot, M.R., Olaussen, S., Aasberg, L., 1985. Recently
formed methane-derived carbonates from the North Sea floor.
In: Thomas, B.M. (Ed.), Petroleum Geochemistry in Exploration of
the Norwegian Shelf. Norwegian Petroleum Soc., Graham & Trotman,
pp. 263–266.
Ivanov, M.K., Konyukhov, A.U., Kulnitskii, L.M., Musatov, A.A., 1989.
Mud volcanoes in deep part of the Black Sea. Vestnik MGU, Series
Geology 3, 21–31 (in Russian).
Ivanov, M.K., Limonov, A.F., Woodside, J. (Ed.), 1992. Geological and
geophysical investigations in the Mediterranean and the Black Sea.
UNESCO Reports in Marine Science 56, 208pp.
Ivanov, M.K., Limonov, A.F., van Weering, T.C.E., 1996. Comparative
characteristics of the Black Sea and Mediterranean Ridge mud
volcanoes. Marine Geology 132 (1-4), 253–271.
Ivanov, M.K., Limonov, A.F., Woodside, J.M., 1998. Extensive deep fluid
flux through the sea floor on the Crimean continental margin
(Black Sea). In: Henriet, J.P., Mienert, J. (Eds.), Gas Hydrates:
Relevance to World Margin Stability and Climate Change. Geological
Society, London, Special Publication, pp. 195–214.
Jaeger, H.M., Nagel, S.R., Behringer, R.P., 1996. Granular liquids, solids
and gases. Reviews of Modern Physics 68 (4), 1259–1273.
Kempe, S., Liebezeit, G., Duman, M., Asper, V., 2001. Extrusion: the
formation mechanism for the presumed ‘Turbidites’ of the deep Black
Sea? Senckenbergiana maritima 31 (1), 11–16.
Kenyon, N.H., Ivanov, M.K., Akhmetzhanov, A.M., Akhmanov, G.G.
(Eds.), 2002. Geological Processes in the Mediterranean and Black
Seas and North East Atlantic. Technical Series, Intergovernmental
Oceanographic Commission, 62, 123pp.
Kulm, L.D., Suess, E., 1990. Relationship between carbonate deposits and
fluid venting: Oregon accretionary prism. Journal of Geophysical
Research 95, 8899–8915.
Leifer, I., Boles, J.R., Luyendik, B.P., Clark, J.F., 2004. Transient
discharges from marine hydrocarbon seeps: spatial and temporal
variability. Environnmental Geology 46, 1038–1052.
Limonov, A.F., Woodside, J., Ivanov, M.K. (Eds.), 1994. Mud volcanism
in the Mediterranean and Black Sea and shallow structure of the
Eratostene seamount. UNESCO Reports in Marine Science 64, 173pp.
Marinaro, G., Etiope, G., Lo Bue, N., Favali, P., Papatheodorou, G.,
Christodoulou, D., Furlan, F., Gasparoni, F., Ferentinos, G., Masson,
M., 2006. Monitoring of a methane-seeping pockmark by cabled
benthic observatory (Patras Gulf, Greece). Geo-Marine Letters 26 (5),
297–302.
Mazzini, A., 2004. Methane-related authigenic carbonates: implications
for seeps and hydrocarbon plumbing systems. Ph.D. Thesis, University
of Aberdeen, 437pp.
Mazzini, A., Ivanov, M.K., Parnell, J., Stadnitskaia, A., Cronin, B.T.,
Poludetkina, E., Mazurenko, L., van Weering, T.C.E., 2004. Methane-
related authigenic carbonates from the Black Sea: geochemical
characterisation and relation to seeping fluids. Marine Geology 212
(1–4), 153–181.
Mazzini, A., Svensen, H., Hovland, M., Planke, S., 2006. Comparison and
implications from strikingly different authigenic carbonates in a
Nyegga complex pockmark, G11, Norwegian Sea. Marine Geology
231, 89–102.
Mazzini, A., Kozlova, E., Blinova, V., Ovsyannikov, A., Korost, D.,
Nadezkin, D., Sharapova, A., Belova, A., Malykh, Y., 2007. Easter
Black Sea: bottom sampling in the Trakya Area, Shatsky Ridge,
Tuapse Trough, and Georgian Margin. In: Akhmetjanov, A.M.,
Ivanov, M.K., Kenyon, N., Mazzini, A. (Eds.), Deep-Water Cold
Seeps, Sedimentary Environments and Echosystems of the Black and
Tyrrhenian Seas and the Gulf of Cadiz. IOC Technical Series No. 72,
UNESCO, pp. 30–47 (English).
Michaelis, W., Seifert, R., Nauhaus, K., Treude, T., Thiel, V., Blumen-
berg, M., Knittel, K., Gieseke, A., Peterknecht, K., Pape, T., Boetius,
A., Amann, R., Jørgensen, B., Widdel, F., Peckmann, J., Pimenov,
N.V., Gulin, M.B., 2002. Microbial reefs in the Black Sea fueled by
anaerobic oxidation of methane. Science 297, 1013–1015.
Mourgues, R., Cobbold, P.R., 2003. Some tectonic consequences of fluid
overpressures and seepage forces as demonstrated by sandbox
modeling. Tectonophysics 376, 75–97.
Nichols, R.J., Sparks, R.S.J., Wilson, C.J.N., 1994. Experimental studies
of the fluidization of layered sediments and the formation of fluid
escape structures. Sedimentology 41, 233–253.
Nikishin, A.M., Korotaev, M.V., Ershov, A.V., Brunet, M.-F., 2003. The
Black Sea basin: tectonic history and Neogene–Quaternary rapid
subsidence modelling. Sedimentary Geology 156 (1–4), 149–168.
ARTICLE IN PRESSA. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472472
Peckmann, J., Reimer, A., Luth, U., Luth, C., Hansen, B.T., Heinicke, C.,
Hoefs, J., Reitner, J., 2001. Methane-derived carbonates and
authigenic pyrite from the northwestern Black Sea. Marine Geology
177 (1–2), 129–150.
Person, R., Aoustin, Y., Blandin, J., Marvaldi, J., Rolin, J., 2006. From
bottom landers to observatory networks. Annals of Geophysics 49
(2/3), 351–393.
Ritger, S., Carson, B., Suess, E., 1987. Methane-derived authigenic
carbonates formed by subduction-induced pore-water expulsion along
the Oregon/Washington margin. Geological Society of America
Bulletin 98, 147–156.
Ross, D.A., Degens, E.T., 1974. Recent sediments of Black Sea. In:
Degens, E.T., Ross, D.A. (Eds.), The Black Sea—Geology, Chemistry
and Biology. American Association of Petroleum Geologists Memoir,
20, pp. 183–199.
Shimkus, K.M., Emelianov, E.M., Trimonis, E.S., 1975. Stratigraphy
of the deep-water Black Sea sediments and sedimentation rate.
Investigation of Chemical, Physical and other Processes. Information
Bulletin of the CMEA 3, 156–158 (in Russian).
Starostenko, V., Buryanov, V., Makarenko, I., 2004. Topography of the
crust–mantle boundary beneath the Black Sea Basin. Tectonophysics
381, 211–213.
Swart, P.K., 1991. The oxygen and hydrogen isotopic composition of the
Black Sea. Deep-Sea Research 38 (Suppl. 2), S761–S772.
Tanaka, T., Toyokumi, E., 1991. Seepage failure experiments on multi
layered sand columns. Soil and Foundations 31 (4), 13–36.
Thiel, V., Peckmann, J., Richnow, H.H., Luth, U., Reitner, J., Michaelis, W.,
2001. Molecular signals for anaerobic methane oxidation in Black Sea
seep carbonates and a microbial mat. Marine Chemistry 73 (2), 97–112.
Valentine, D.L., Reeburgh, W.S., 2000. New perspectives on anaerobic
methane oxidation. Environmental Microbiology 2 (5), 477–484.
Woodside, J., Ivanov, M.K., Limonov, A.F. (Eds.), 1997. Neotectonics
and fluid flow through seafloor sediments in the Eastern Mediterra-
nean and Black Sea. Technical Series, Intergovernmental Oceano-
graphic Commission, 48, p. 226.
Woolsey, T.S., McCallum, M.E., Schumm, S.A., 1975. Modeling diatreme
emplacement by fluidization. Physics and Chemistry of Earth’s Interior
9, 29–42.