ARTICLE IN PRESS Marine and Petroleum Geology 25 (2008) 457–472 www.elsevier.com/locate/marpetgeo Complex plumbing systems in the near subsurface: Geometries of authigenic carbonates from Dolgovskoy Mound (Black Sea) constrained by analogue experiments Adriano Mazzinia,, Michael K. Ivanovb, Anders Nermoena, André Bahrc, Gerhard Bohrmannc, Henrik Svensena, Sverre Plankea,d a Physics of Geological Processes, University of Oslo, P.O. Box 1048, 0364 Oslo, Norway b Moscow State University, Vorobjevy Gory, Moscow 119992, Russia c Research Centre Ocean Margins, University of Bremen, Post Box 330 440, D-28334 Bremen, Germany d Volcanic 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 seeps have been a target of investigation of numerous marine expeditions with the aim of investigating the mechanisms of hydrocarbon-rich fluids seepage (Ivanov et al., 1989; Corresponding author. E-mail address: adriano.mazzini@fys.uio.no (A. Mazzini). 0264-8172/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpetgeo.2007.10.002 Ginsburg et al., 1990; Ivanov et al., 1992; Limonov et al., 1994; Woodside et al., 1997; Ivanov et al., 1998; Bohrmann and Schenck, 2002; Ergun et al., 2002; Kenyon et al., 2002). Differently shaped authigenic carbonates (slabs, chimneys, irregular, blocky) have been observed and sampled from various sites of the Black Sea Basin often associated with microbial colonies (Woodside et al., 1997; Peckmann et al., 2001; Thiel et al., 2001; Michaelis et al., 2002; Mazzini et al., 2004). The precipitation of these carbonates is ARTICLE IN PRESS 458 A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 considered to be the result of coupled sulphate reduction and anaerobic methane oxidation (AOM) operated by consortia 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 a broad variety in shape and mineralogy. This variety is interpreted to be related with a combination of numerous factors; the four main ones include the varying rate and composition of the seeping fluids, the type of sediment where fluid seepage occurs and the type of biota thriving at the seepage sites (Mazzini, 2004). Several authors tried to model the various carbonate shapes based mainly on morphological and petrotraphy studies (e.g. Kulm and Suess, 1990; Michaelis et al., 2002; Diaz-del-Rio et al., 2003; Mazzini et al., 2004, 2006). However a modelling approach trying to combine these disciplines with analogue laboratory modelling has not been investigated in detail yet. In 2005 a joint venture of Training Through Research and METRO Research Programmes (TTR15 cruise), visited the Shatsky Ridge focussing on the study of Dolgovskoy Mound (DM) situated along the northwestern Shatsky Ridge (Fig. 1(A)). This paper reports the data and the observations collected from the DM during the TTR15 cruise (Akhmetzhanov et al., 2007). Petrography and geochemical studies on a unique authigenic carbonate collection were complemented by laboratory modelling studies representing a novel approach for seepage studies. The described multidisciplinary approach, including sandbox laboratory simulations, aims to give new insights into the marine subsurface plumbing system. 2. Geological setting Despite the numerous cruises exploring the Black Sea, little documentation is available from the Shatsky Ridge region that was broadly explored mainly by Russian scientists during the last decade (e.g. Grinko et al., 2004; Afanasenkov et al., 2005a). The Shatsky Ridge is located between the Tuapse Trough and the Eastern Black Sea Basin. The ridge has no bathymetric expression observable on the seafloor due to a thick cover of Cenozoic sediments. The ridge overlies continental crust (Starostenko et al., 2004) and appeared as a positive structure on the seafloor during the Cretaceous separating the deep water basins of the Great Caucasus from the new ‘‘young’’ Eastern Black Sea Basin (Nikishin et al., 2003). Since no deep drilling has ever been conducted in the Eastern Black Sea region, most interpretations are based on the geology of the surrounding coast areas and seismic investigations. Recent seismic investigations (2001–2004) revealed structures, suggesting that a significant portion of the ridge consists of Late Jurassic carbonate build-ups (Afanasenkov et al., 2005a, b). More detailed bathymetric studies were conducted in 1996 by the RV Gelendzik completing a Simrad EM-12S multibeam mosaic along the Shatsky Ridge and the Tuapse Trough (Andreev, 2005). This mosaic combined with the previously acquired seismic data allowed the identification of several new structures (possible mud volcanoes) in these two areas. 3. Sedimentary units and authigenic carbonates from the Black Sea A common pattern of three distinct modern sedimentary units characterize most of the deep water areas of the Black Sea (Andrusov, 1890; Degens and Ross, 1972; Ross and Degens, 1974; Shimkus et al., 1975). Below the seafloor, the typical 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 reach several centimetres. At seepage locations, Unit 1 (and sometimes Unit 2) can be interbedded by exotic centimetre thick structureless and light coloured clayey layers. The origin of these so called ‘‘Degens layers’’ has been discussed for long since their first discovery and several hypotheses have 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 by Kempe et al. (2001) that suggested the localized expulsion of fluidized and overpressured clayey sediments on the seafloor. (b) Unit 2 consists of thin laminations of sapropel; (c) Unit 3, interpreted to be lacustrine facies, consists of laminations of terrigenous (silty–clayey) sediment, commonly containing hydrotroilite layers. These units reach their maximum thickness in the central part of the Black Sea; Units 1 and 2 are on average 30 cm thick, while Unit 3 can reach several metres in thickness (Ross and Degens, 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 of layered slabs of carbonate cemented clayey and coccolith ooze laminae from Unit 1); Type U2 (consisting of layered slabs of carbonate cemented sapropelic Unit 2), Type U3 (layered carbonate cemented Unit 3), Type MSa (structureless micrite-cemented clay) usually forming laterally extensive pavements at the seafloor or within Unit 1. This type of slabs possibly represents the carbonate cementation of the described ‘‘Degens layers.’’ Carbonate types U1 and MSa were sampled from the study area described in this paper. 4. Methods and experimental setup The marine expedition was conducted with the RV Professor Logachev equipped with the long range sidescan sonar OKEAN, single channel seismic system, MAK-1 M 35°0'E 30' 36°0'E 30' 37°0'E 30' 38°0'E 30' 36° 40.5'E 39°0'E 36° 41'E 36° 41.5'E 36° 42'E 44° 1.5'N 30' A 20 45°0'N B 30' 10 MAK 58BS 45°0'N 50 100 200 12 8 00 00 400 1400 600 30' BS347G 100 0 30' 1600 1800 Tu aps eT rou gh 2000 BS348G BS349Gr 44°0'N Dolgovskoy 44° 1'N Sh ats ky Rid ge 30' 30' 30' 36°0'E 30' 37°0'E 30' 38°0'E 30' 39°0'E 500 C 500 1970 m SE acoustic shadows NW 2020 m 2070 m 20:30 20:00 19:00 18:00 17:00 459 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. ARTICLE IN PRESS 35°0'E A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 44°0'N BS346Gr ARTICLE IN PRESS A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 460 deep towed high resolution 100 kHz sidescan sonar system and 5 kHz subbottom profiler, with a TV remote controlled grab, and a 1.5 tonnes gravity coring device that sampled the targeted locations. The samples collected were described and selected for further analyses. Thin sections of carbonate samples were studied using both optical and electronic microscopes. X-ray diffraction (XRD) analyses were performed on bulk carbonate samples to determine the dominant carbonate phase. Carbon and oxygen isotopic analyses were completed on bulk carbonate samples at the Institute for Energy Technology at Kjeller, Norway. Carbonate cements were ground and digested with a 0.1 ml 100% H3PO4 solution for 2 h at 30.0 1C in a vacuumed environment. The released CO2 was transferred to a Finnigan MAT DeltaXP isotope ratio mass spectrometer (IRMS), for determination of d13C and d18O. Results are reported in % relative to the VPDB standard (Table 1). The precision for d13C is 70.1% and 70.2% for d18O. Sandbox experiments on granular media (Gidaspow, 1994; Jaeger et al., 1996) were conducted at the Physics of Geological Processes Laboratory (University of Oslo) on a quasi two dimensional Hele–Shaw cell (e.g. Woolsey et al., 1975; Tanaka and Toyokumi, 1991; Nichols et al., 1994) consisting of two 600 600 12 mm3 glass plates 8 mm distant from each other. Several set-ups and tests have been collected before selecting the ideal parameters where the subsurface deformation in fluid flushed discontinuous media are best observable. The cell was filled with an 18 cm thick interval of spherical Beijer glass beads (ø ¼ 420–840 mm) interbedded by a 0.3 mm thick layer of devolite (china clay) in the upper part. Air was used as the analogue fluid to induce overpressure in the media. Air was flushed in the system through an inlet with inner diameter of 3.8 mm, placed 6.3 cm into the cell in order to prevent preferential flow along the bottom and edges of the cell. Air flux and pressure data (i.e. monotonic increase of air flow and pressure drops across the sedimentary media) were collected in real time by an Omega pressure sensor and Omega FV-135 flow meter. The pressure sensors were placed by the air inlet and at the top of the bed. Pictures were taken during the experiment using a high resolution digital camera at a rate of 10 images per second. Experiments were performed in a two dimensional set-up and the quantitative measurements of the pressure and flow velocity are thus not directly applicable to a three dimensional setting. The walls of the Hele–Shaw cell set definite limits on the deformation of the top layer. Furthermore there exists friction between the walls and the flowing grains that does not occur in natural systems (Mourgues and Cobbold, 2003). Nevertheless, adding a third dimension does not introduce any new physical effects in the processes of interest. The main processes of interests (i.e. Darcy flow in porous media and deformation) and their scaling are independent of the number of spatial dimensions (Gidaspow, 1994). Therefore two dimensional experiments capture the same physical processes as in a three dimensional setting. Further experiments were done in order to constrain the parameters controlling the deformation of the media. This was achieved using Beijer glass beads as single media and varying its thickness h (Fig. 8(A)) from the major permeability contrast (i.e. here represented by the interface between the inlet and the glass beads) to the surface. In this way the deformation observed on the contact between the inlet and the Beijer glass beads follows the same principles of the deformation occurring between the glass beads and the impermeable clayey layer as the abrupt permeability contrast (from higher to lower Table 1 Summary of sampling points described and main petrographic, morphological and geochemical characteristicsa Sample number Structure d13C% (VPDB) d18O% (VPDB) XRD analyses %a Comments BS346–2.1 Vertical chimney – – Py ¼ 100 BS346–2.2 Vertical chimney – – Py ¼ 100 BS346–2.3 Cavernous 27.4 0.8 CC ¼ 100 BS346–2.4 Slab 36.7 0.2 CC ¼ 100 BS346–2.5 Cavernous 36.4 0.4 CC ¼ 100 BS346–2.6 Horizontal tube 33.5 0.1 Py ¼ 100 BS346–2.7 Slab 33.5 0.0 MgCC ¼ 37, CC ¼ 37, Qz ¼ 26 Black iron rich mineral (pyrite) from central part of seepage pipes Black iron rich mineral (pyrite) from central part of seepage pipes White calcite minerals associated with bacterial mats Carbonate cement from laminated slab Type U1 White calcite minerals close to pyrite deposits Carbonate crystals (isotopes analyses) close to black iron-rich mineral (XRD analyses) from tubular shaped precipitate White slab Type MSa capping Type U1 crust Pv ¼ pyrite, MgCC ¼ Mg calcite, CC ¼ calcite, Qz ¼ quartz. a Average estimates. ARTICLE IN PRESS A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 permeability) generates a zone of overpressured fluids. This set-up allowed us to acquire a significant amount of data simply by changing the thickness h of the single granular media. 5. Results 5.1. Acoustic survey: the structure of the mound A sidescan sonar survey was conducted in order to select the primary targets for further sampling. Sidescan sonar line MAK58BS was acquired in a NW–SE direction along the Shatsky ridge (Fig. 1(C)). The acoustic image shows that the mound has a subcircular shape with a diameter of approximately 900 m and a height of more than 70 m (Fig. 1(B) and (C)). The mound is highly asymmetric and shows at least three sharp positive features on its top part. The northwestern (and probably southern) slope is steep and slump deposits (possibly representing mud breccia) are observed 461 at its foot. The south-eastern slope is gentler and is interrupted by a sharp step in its middle part. A moat frames the foot of this slope. Backscatter record appears patchy throughout the structure, revealing areas with stronger reflection where carbonate crusts and/or coarser sediment deposits (e.g. mud breccia) are inferred. Strong backscatter is not observed in the central part of the structure. The record of weak and medium backscattering signal between time marks 18:31–18:37 is associated with partial recording error when the fish was rapidly pulled up along 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 the Black Sea. Usually sonar images are characterized by weak grey monotonous backscatter, and profiler displays flat relief and relatively deep penetration of the acoustic signal through the stratified Quaternary deposits. The images recorded around the DM show the opposite. The sonar image shows a complex backscatter consisting of patches of different size and shape while the profiler reveals irregular 5 cm d l d l d l 500 m 200 Fig. 2. Slab shaped carbonates. (A) Seafloor image showing laterally extensive carbonate slabs; image view approximately 1.2 m; (B) hand specimen of finely laminated and carbonate cemented sedimentary Unit 1; note some small degassing vesicles on the upper surface filled by microbial colonies (arrowed); (C) thin section image perpendicular to lamination showing layering of alternated coccolith-rich and clay-rich layers; (D) detail of area framed in image (C) showing alternations of darker pyrite-organic-calcite-rich layers (d) and lighter coloured clay-rich layers (l). ARTICLE IN PRESS 462 A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 8 cm 5 cm 2 cm 500 μm Fig. 3. Cavernous shaped carbonate. (A) Seafloor image showing irregular morphology; image view approximately 1.2 m; (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. ARTICLE IN PRESS A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 morphology with numerous positive shapes a few meters in height and with no layering of sedimentary units. Numerous subcircular depressions up to tens of meters in size were also observed through the sonar record. Some of these features resemble the pockmarks observed in other settings. Areas with very strong backscatter are present between time mark 16:20–16:40 and 17:10–17:20 starboard side. This type of backscatter is not associated with sharp relief and is interpreted as (a) lithological heterogeneity due to deposits from the distal part of the Kerchensky Fan or (b) associated with localized hydrocarbon-rich fluids seepage (e.g. authigenic carbonate). However, in case of the section from 19:20 to 20:20 we can observe clear topographic image with strong backscatter towards the sidescan and accompanied by acoustic shadow. The apparent subcircular form of this feature might be interpreted as the existence of a mud volcano with crater walls (?). A similar kind of buried mud volcanoes or large collapse structures have been observed previously in the 463 Sorokin Through (Ivanov et al., 1998) and Mediterranean Ridge (Ivanov et al., 1996). An alternative interpretation suggests that these features could represent the remains of the channel-levee system recorded in SE part of this line. The acoustic reflectivity of the bottom deposits are changing 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 selected based on the acquired sidescan sonar images. A preliminary report of the seafloor sampling and observations with a discussion of the results was initially given by Mazzini et al. (2007). The TV record revealed the presence of numerous escarpments (up to 1–2 m high), differently shaped carbonate deposits and localized microbial mats. The three gravity core sampling stations retrieved ordinary hemipelagic sequences, showing distinct carbonate cemented Fig. 4. ‘‘Chimney-like’’ carbonates. (A) Image showing chimney-like carbonates rising from the seafloor (framed on dashed line); image view approximately 1.2 m; (B) hand specimen showing sections of chimneys entirely cemented by framboidal pyrite; (C) details of internal part of the chimney (framed in image B) entirely consisting of black framboidal pyrite, the reddish colour represents the oxidation that appeared the day after the sampling and (D) thin section image of pyrite framboid aggregates. ARTICLE IN PRESS A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 layers (Type U1 and Type MS) and sandy-silty intervals. Spectacular samples were recovered from the topmost part of DM (station BS346Gr, 1965 m water depth) were the sidescan sonar record had high backscatter and where the TV images showed an irregular seafloor. Using a TV remote controlled grab, a large collection of authigenic carbonates (up to 60 cm wide) was retrieved onboard. The recovery revealed that these carbonates have a complex geometry in the subsurface. Analyses and observations (Table 1) distinguished three main shapes of carbonate features: (a) slab, (b) cavernous and (c) chimney-like and tubular. The slab type carbonates appear laterally extensive on the seafloor (Fig. 2(A)) and mainly consists of carbonate cemented Unit 1 sometimes capped or interbedded by a layer of carbonate Type MSa (cf. Section 3). The thickness of these slabs can vary from a few centimetres up to 10–15 cm (Fig. 2). Microbial colonies were observed thriving as a thin dark biofilm on the interface between the carbonate cemented sedimentary layers. Thin section observations are identical to the one described by Mazzini et al. (2004) showing the fine laminations of alternated clay- and coccolith-rich layers. Microscopy also shows that carbonate precipitation occurs prevalently along the coccolith-rich layers where pyrite framboids and microbial remains 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 and stacked carbonate cemented sedimentary intervals (Unit 1) that encase carbonate-coated cavernous structures (up to 25–30 cm2 in size, Figs. 3(B) and (D)). These cavities are cemented by carbonate Type U1 occasionally interbedded by Type MS (high magnesium calcite). Approaching the thick microbial mats in the internal part, the low magnesium carbonate Type U1 is much better crystallized. The internal part of these large voids is commonly coated by light coloured sparitic calcite and by several centimetres thick microbial colonies of differing colours (i.e. mainly pinkish, but also whitish and yellowish, Figs. 3(D) and (E)). Within these thick mats, millimetre scaled layers of calcite were observed forming distinct horizons. XRD analyses and thin section images of the carbonate coating the subsurface chambers and growing within the microbial mats show sparitic low magnesium calcite devoid of any siliciclastic admixture (Fig. 3(F)). Several types of ‘‘chimney-like’’ and tubular carbonate samples are associated with these cavernous structures. δ18O (%o V-PDB) -2 -1 0 1 2 -10 -15 NIOZ MV Odessa MV -20 δ13C (%o V-PDB) 464 Dolgovskoy M -25 -30 -35 -40 -45 -50 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). Chimneys erect vertically in the water column (Fig. 4(A)). At these sites the carbonate thickness and vertical deformation is prominent and a positive relief with high concentrations of microbial mats are observed. The internal part of these chimneys is often completely filled by framboidal pyrite, but it is not uncommon to observe a central void conduit that pierces the whole chimney (Figs. 4(B) and (C)). XRD analyses and thin section images confirm the sole presence of pyrite aggregates together with microbial remains. Tubular features (up to 5 cm in diameter) can also branch off from the lower part of the cavernous structures, forming a network that extends horizontally in the subsurface (e.g. Fig. 3(C)). 5.3. Geochemical analyses Carbon stable isotope measurements on the authigenic carbonates (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 observed in carbonate measured from the different samples. The lightest carbon values are observed in carbonates Fig. 6. Hele–Shaw sandbox analogue simulation of fluid induced deformation of an heterogeneous sedimentary package. (A) Initial experimental conditions: the porous granular media (dark grey) is interlaid in the top part of the box by a impermeable thin layer of clay (black); the air inlet is indicated by an arrow; (B) At P ¼ 2276 Pa diffusive air seepage through the porous granular media; once the air reaches the impermeable clayey layer the diffused seepage is impeded and when the required overpressure is reached, a displacement occurs on the interface between the two media; (C, D) deformation occurs when the overpressured fluids are gathered underneath the impermeable clayey layer; the deformation increases with pressure (pressure varies from 3530 to 3632 Pa); (E) the deformation persists and fluids continue to seep laterally. Microfractures and sediment unconformities develop, allowing part of the fluid to breach the impermeable clayey media in the extensional zones (P ¼ 3415 Pa); (F) vertical seepage towards the open surface cannot cope with the amount of fluids seeping from depth and is coupled with lateral seepage deformation; pressure drops to P ¼ 2960 Pa and (G) diagram showing pressure reading and flow velocity of the fluid during the experiment. Corresponding figures are indicated by arrows. ARTICLE IN PRESS A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 465 ARTICLE IN PRESS 466 A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 precipitating close to the microbial mats. To our knowledge no other stable isotope data from authigenic carbonates from the Shatsky Ridge has been documented. 5.4. Hele–Shaw sandbox simulation As previously described (cf. Section 3) localized variations and discontinuities exist in the thickness of the clayey layers present in Unit 1. The working hypothesis is that since some of the described impermeable clayey laminae have thickness greater than centimetre scale, they can impede more efficiently the seepage of fluids, hence creating overpressure in the subsurface and further deformation. This hypothesis was tested with the Hele– Shaw sandbox experiment aiming to observe the fluid behaviours through overpressured lithologically discontinuous units (Fig. 6(A)). Hence particularly significant were the deformations occurring on the interface between the granular and clayey media. Constant monitoring of the pressure drop and the flow velocity during the experiment (Fig. 6(G)) allowed to couple visual observations with these physical parameters. The sequence of images shows that at low air fluxes and at pressure drop of 2276 Pa, the fluid seeps with a Darcian flow distributing evenly through the permeable granular media lying underneath the low permeability clayey layer (Fig. 6(B)). The laterally continuous impermeable clayey layer cannot accommodate the flow and impedes the seepage of fluids towards the surface. As the fluid flux increases, overpressure on the interface between the granular and the clayey media is sufficient (i.e. pressure ¼ 3530 Pa) to gradually lift vertically and deform the top layers (Fig. 6(C)). As the overpressure build-up increases, the bulging becomes more prominent as well as the lateral seepage 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 occurs on the top part of the bulge and extension along the lower flanks where weakness spots become more distinct (Fig. 6(E)). To this abrupt fracturing corresponds a sudden irreversible pressure drop (3415 Pa). This extension allows the fracturing and thus the seepage of fluids through the clayey layer, forming a subvertical conduit (Fig. 6(F)). At this 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 the acoustic data. Sampling showed that a complex plumbing system exists in the subsurface of the study area. The carbonate 13C depletion revealed by stable isotope analyses supports the idea that the extended microbial colonies mediate the oxidation of hydrocarbon-rich fluid, resulting in carbonate precipitation. This is also supported by stable carbon isotopic analyses (d13 CCH4 as low as 75.1%) of free gas collected from the sediments in the TV grab (V. Blinova, pers. comm.). The three described carbonate types are interpreted as the result of three different mechanisms of fluid seepage and carbonate precipitation. Striking mineralogical differences have been described between the chimney features (entirely coated by framboidal pyrite) and the internal part of the cavernous features (sparitic calcite). As already documented by other authors these two minerals are, respectively, the by-product of sulphate 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) completed detailed lipid biomarker analyses on the thick microbial colonies in the cavernous features, detecting the presence of SRB and MOAs. Our visual and petrography observations could suggest that SRB thrive more abundantly in the chimney and tubular features where focussed fluid seepage occurs, while preferentially MO flourish where no sustained seepage occurs, forming thick mats and inducing Fig. 7. Conceptual evolutionary cartoon of fluids seepage and carbonate precipitation in the subsurface. (A) Fluids rising from greater depth reach the near subsurface moving by Darcian flow through parallel layered sediment deposits; (B) details from area framed in image A. When more sustained fluid seepage occurs and when the seeping fluids reach thicker clayey layers, their rise is impeded and deform the soft sediment creating chambers where gas is accumulated and (C) microbial colonies grow in the internal part of these chambers (pink framing line) and precipitation of authigenic carbonate occurs. The overpressured fluids continue to move laterally, forming a network of pipes and tubular features that extends horizontally through the soft sediment. Note: the fish has a purely cosmetic purpose for the cartoon, as we are considering anoxic conditions (i.e. water depth 2000 m). ARTICLE IN PRESS A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 467 6.2. Gas hydrates fuelling from the subsurface? precipitation of calcite (i.e. in the large voids in the subsurface). However this is a speculative suggestion since comparative analyses from the microbial colonies thriving in the pyrite-rich chimneys are currently not available. DM lies in the gas hydrate stability field. The hypothesis that significant deposits of gas hydrates were present at this P2 Glass beads h L P1 Inlet L=0.8 cm Flow meter Flow control 2500 π1 = vc μh / (Ck), [1] 2000 1500 Deformation 1000 Static bed 500 0 0 10 20 30 40 π2 = h / L, [1] 50 60 70 80 Fig. 8. (A) Schematic drawing of the experimental set-up. The air is injected through the vertical pipe into the bed. The critical Darcy velocity vc and pressure P ¼ P1–P2 is measured with sensors. The height h is measured from the surface down to the permeability contrast at which the sediment deformation occurs. In the development of the phase diagram h is measured from the top of the inlet to the surface. In the experiment represented by the pictures in Fig. 6, the main permeability contrast is between the surface and the bottom of the clay layer where the deformation occurs. (B) Dimensionless phase diagram marking the onset of the fluid-induced deformation. The diamonds show the measurements of the normalized critical Darcy velocities, the solid line shows the best fit to the measured values; g(p2) can be extrapolated and applied to similar cohesion controlled settings, such as the Dolgovskoy Mound. ARTICLE IN PRESS A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 468 location is certainly fascinating and could perfectly fit with the morphology of the described features. The subsurface cavities could represent the volume occupied by former gas hydrate deposits that were subjected to dissociation. Nevertheless this possibility might be ruled out since the observed oxygen isotopic values are not consistent with cements 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 a fluid in isotopic equilibrium with the seafloor temperature that averages around 9 1C (Friedman and O’Neil, 1977; Swart, 1991). This is consistent with the absence of typical features of gas hydrate dissociation in the grab retrieved onboard. 6.3. The subsurface plumbing system: mechanisms of fluids seepage and carbonate precipitation Based on the observations and experimental results, and taking into account the previously published data, the following section suggests conceptual models of authigenic carbonate formation and fluid seepage for the study area. The Hele–Shaw sandbox simulation may decipher some of the mechanisms of fluid seepage-induced matrix deformation. Where local fluid seepage is not sustained, Darcian flow processes prevail and the formation of slab features occurs (Fig. 7(A)). During this type of microseepage no significant deformation occurs as observed on the carbonate cemented slabs and during the sandbox experiments (Figs. 2 and 6(B)). The cementation process of almost identical slabs has been studied in detail by Mazzini et al. (2004, Fig. 12) after comparing a large collection of carbonate cemented sedimentary units from different regions of the Black Sea. The petrography observations presented in this paper also confirm that the vertical seepage of hydrocarbon-rich fluids is impeded by clayey layers. At this interface microbial colonies thrive and induce precipitation of micritic carbonate cement that extends within the more porous coccolith-rich layers. This model is also strongly supported by microbial mats observed thriving preferentially underneath thicker clayey intervals. The seepage of fluids continues vertically through microfractures and microvesicles (see Fig. 5(D) in Mazzini et al., 2004) until another clayey layer will halt the fluid rise, initiating new AOM and carbonate precipitation. The thickness of the carbonate cemented slabs depends on the duration of the fluid flow seepage and on local variations in the clayey layer thickness. A different mechanism involving a significant amount of free gas seepage is necessary to explain the carbonatecemented decimetre scaled cavities and tubular features. At these locations the thicker and more impermeable clayey layers within Unit 1 (including also the Degens layers) impede the immediate release of a more sustained seepage of hydrocarbon-rich fluids (Fig. 7(B)). The gas saturated fluids entrapped in the subsurface deform the soft sedimentary layers, forming large, laterally elongated void areas (Fig. 3). A similar behaviour is observed in the Hele–Shaw experiment when sufficient overpressure is accumulated to initiate the deformation (Fig. 6(C)). Below the seafloor, microbial colonies grow inside these cavities, inducing the precipitation of carbonate minerals via AOM. Once the system reaches these conditions if more fluids are provided (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 the cavernous features (Fig. 4). As carbonate and pyrite precipitation continues, a solid cage inside and around the cavernous structure forms, preventing further deformation of the sedimentary layers and, of course, further reducing permeability of the seeping fluids. Additionally, a progressive decrease of the chimney’s diameter (due to continuous precipitation of authigenic minerals) induces new internal overpressure. Since seepage of fluids at the seafloor cannot cope with the amount of gas rising from depth, the subsurface plumbing system has to further adjust, forming complex networks of tubes, pipes and cavernous structures that extend laterally (Figs. 7(C) and 3(C)). The described model is reproducible at various depths (e.g. where the thicker clayey layers occur) and can explain the presence of the superposed cavernous structures collected from Unit 1. 6.4. Dimensional analysis from the Hele–Shaw sandbox experiments Numerous landers have been distributed at several offshore seepage and venting sites with the aim to complete long-term measurements of the seeping fluids (e.g. Leifer et al., 2004; Marinaro et al., 2006; Person et al., 2006). A problem with this type of monitoring is that it cannot take into account the subsurface deformations or consider Table 2 Physical parameters used in the Hele–Shaw sandbox and existing in natural seepage environments Setting C (Pa) K (m2) L (m) m (Pa s) h (m) vc (m/s) Hele–Shaw Offshore seepsa 102 106 1.33 109 1013 3.8 103 L 17.6 106 104 h 101 vc 103 a Average estimates. ARTICLE IN PRESS A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 469 h/L=10 000 12 0 Ultimate strength of materials −2 log 10 (C), [Pa] 8 −3 Static bed −4 6 −5 −6 4 −7 −8 2 −9 Deformation 0 −18 −16 log10 of critical Darcy velocity [m/s] −1 C* 10 1m/s −14 −12 −10 −8 −6 −4 −10 1mm/yr 2 log 10 (k/μ), [m /Pas] h/L=10 12 0 Ultimate strength of materials C* −1 −2 Static bed log 10 (C), [Pa] 8 −3 −4 deformation on offshore seeps 6 −5 −6 4 −7 Deformation log10 of critical Darcy velocity [m/s] 10 1m/s −8 2 −9 0 −18 −16 −14 −12 −10 −8 −6 −4 −10 1mm/yr log (k/μ ), [m 2 /Pas] 10 Fig. 9. Plots showing how the sediment cohesion C, which is the least constrained parameter, depends on sediment permeability over fluid viscosity k/m when 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. the rheology of the sediments during the fluid seepage. Sandbox experiments could provide further information in order to quantify the mechanism of fluid seepage. In order to estimate if the Hele–Shaw technique has relevance also for natural seepage systems, we have used a quantitative approach to the data collected. In cohesion controlled systems the weight of the overburden can be neglected, when looking at the top surface sediments (e.g. the topmost layers in marine seepages). For this reason our analysis focused on five dimensional parameters: the critical fluid Darcy velocity vc (m/s) at which the deformation of the sediment occurs; ARTICLE IN PRESS 470 A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 the cohesion C (Pa); the permeability of the bed over the viscosity of the fluid k/m (m2/Pa s); the inlet diameter L (m) and the depth of the permeability contrast at which deformation occurs h (m). When using dimensional analysis, the problem is reduced to two dimensionless parameters p1 ¼ Ck/mhvc and p2 ¼ h/L. The parameter p1 is interpreted to be the ratio of the material strength C and the fluid overpressure across the bed, while p2 is a geometric conversion factor between the sediment height and the inlet diameter. The dimensionless parameters can also be written as Ck h g vc ¼ . mh L The laboratory experiments were performed reproducing the simulation varying h and measuring vc as described in Section 4 using a single media. Our results (Fig. 8) show that g(p2) increased with (h/L)2. As g(p2) is applicable also in natural seepage settings, and as L represents a parameter that is measurable both in laboratory and in the field, the width L of the feeder channel could be extrapolated using the physical parameters existing in natural seepage settings (Table 2). L was found to be in the order of 101 m. The value obtained matches the size of the feeder channel observed at the Shatsky Ridge seepage sites and is also typical for many other marine locations (e.g. Kulm and Suess, 1990; Michaelis et al., 2002; Diaz-del-Rio et al., 2003). Further extrapolations from the results summarized in Fig. 8(B), can be obtained from Fig. 9 that shows how the critical Darcy velocity vc correlates with the variations of C and k/m. Fig. 9 also indicates the field of deformation in natural settings (i.e. in clayey sediments and in the close subsurface) where a critical Darcy velocity is estimated at 103 m/s, confirming other estimates (cf. Table 2). Finally the plot can be used to constrain the sediment cohesion in any setting where the permeability of the sediment, viscosity of the fluid, the feeder width, height from the pressure source onto the surface and the Darcy velocity are measured. Our results show that analogue experiments represent a powerful tool to investigate the mechanisms of fluids seepage in granular media. This type of calculation represents an initial attempt to quantify the geometry and the physical principles of the plumbing system. However, further investigations have to be performed to further corroborate the geological observations in order to, e.g., prove the scaling dependency of the inlet diameter. 7. Conclusions Acoustic investigations and ground truthing of the DM revealed the presence of seeping hydrocarbon-rich fluids and ongoing AOM resulting in widespread carbonate precipitation. Based on sample observations combined with laboratory experiments, three types of carbonate structures related to fluid seepage and mineralogical precipitation have been identified. (A) Slab: Darcian flow of hydrocarbon-rich fluids induces precipitation of micritic carbonate cement within the thin sedimentary laminae; (B) Cavern: thick clayey laminae present inside Unit 1 impede sustained seepage of hydrocarbon-rich fluids, inducing subsurface deformation and precipitation of carbonate cement within the large cavernous features; (C) Chimneys and tubes: can have vertical or horizontal orientation (tubular structures). Focussed and vigorous seepage of fluids from the overpressured cavernous features results in pipe structures where predominantly pyrite precipitation occurs. The data described indicates that fluids seep vigorously not only vertically but also migrate horizontally in the subsurface. The methanogenic origin of the carbonates is supported by stable isotope data (d13C as low as 36.7%) and by the thick microbial mats that thrive profusely at this site. Mud breccia was not retrieved at any station; therefore the inferred mud volcanic activity at DM cannot be proven based on the existing data. Sandbox simulations revealed to be a useful tool to simulate the seepage of fluids and to understand the deformation mechanisms occurring in the subsurface. Dimensional analysis shows that the Hele–Shaw experiments can provide quantitative information of the natural seeping systems. Acknowledgements This paper is dedicated to the memory of Leonid Mazurenko, great friend and scientist. The authors are grateful to Yuri Podladchikov for his support during the preparation of the manuscript and to Andrey Akhmetzhanov and Galen Gisler for their useful comments. David Roberts and two anonymous reviewers are thanked for their constructive reviews. We would like to acknowledge the Crew and the Scientific Party of the TTR-15 Cruise and the UNESCO-MSU Centre for Marine Geosciences. We gratefully acknowledge BMBF-funded project METRO which paid ship time of R/V Professor Logachev and support from a Centre of Excellence grant to PGP, and a PETROMAKS grant to Anders Malthe-Sørenssen, both from the Norwegian Research 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 PRESS A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 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 echosystems 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 Geograficheskogo 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 fractionation 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). 471 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. Methanerelated 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., Blumenberg, 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 PRESS 472 A. Mazzini et al. / Marine and Petroleum Geology 25 (2008) 457–472 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 Mediterranean and Black Sea. Technical Series, Intergovernmental Oceanographic 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.