Carbonate fraction, magnesium and strontium concentration, oxygen and carbon isotopes at DSDP Hole 92-600C

Strontium, magnesium, oxygen, and carbon isotope profiles of the carbonate fraction of Hole 600C sediments support the lithologic and petrographic observations of extensive CaCO3 dissolution and recrystallization in the Pliocene basal section. Convective fluid flow through the sediments during the first 1 to 1.5 m.y. of the sedimentary history of these sediments may explain these observations.

Methane and sulfide fluxes in permanent anoxia: in situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV), located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea), was visited during the M72/2 cruise with the RV Meteor to investigate the methane and sulfide release from mud volcanoes into the Black Sea hydrosphere. We studied benthic fluxes of methane and sulfide, and the factors controlling transport, consumption and production of both compounds within the sediment. The pie shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at a small elevation north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was excluded from this zone due to fluid-flow induced sulfate limitation and a fresh mud flow and consequently methane escaped into the water column with a rate of 0.46 mol/m**2/d. In the outer center of the mud volcano fluid flow and total methane flux were decreased, correlating with an increase in sulfate penetration into the sediment, and with higher SR and AOM rates. Here between 50-70% of the methane flux (0.07-0.1 mol/m**2/d) was consumed within the upper 10 cm of the sediment. Also at the edge of the mud volcano fluid flow and rates of methane and sulfate turnover were substantial. The overall amount of dissolved methane released from the mud volcano into the water column was significant with a discharge of 1.4x10**7 mol/yr. The DMV maintains also high areal rates of methane-fueled sulfide production of on average 0.05 mol/m**2/d. However, we concluded that sulfide and methane emission into the hydrosphere from deep water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.

Permeability measurements on sheared and unsheared samples from different IODP Holes of Leg 316 and from IODP Hole 315-C0001E and ODP Hole 190-1174B

At subduction zones, the permeability of major fault zones influences pore pressure generation, controls fluid flow pathways and rates, and affects fault slip behavior and mechanical strength by mediating effective normal stress. Therefore, there is a need for detailed and systematic permeability measurements of natural materials from fault systems, particularly measurements that allow direct comparison between the permeability of sheared and unsheared samples from the same host rock or sediment. We conducted laboratory experiments to compare the permeability of sheared and uniaxially consolidated (unsheared) marine sediments sampled during IODP Expedition 316 and ODP Leg 190 to the Nankai Trough offshore Japan. These samples were retrieved from: (1) The décollement zone and incoming trench fill offshore Shikoku Island (the Muroto transect); (2) Slope sediments sampled offshore SW Honshu (the Kumano transect) ~ 25 km landward of the trench, including material overriden by a major out-of-sequence thrust fault, termed the "megasplay"; and (3) A region of diffuse thrust faulting near the toe of the accretionary prism along the Kumano transect. Our results show that shearing reduces fault-normal permeability by up to 1 order of magnitude, and this reduction is largest for shallow (< 500 mbsf) samples. Shearing-induced permeability reduction is smaller in samples from greater depth, where pre-existing fabric from compaction and lithification may be better developed. Our results indicate that localized shearing in fault zones should result in heterogeneous permeability in the uppermost few kilometers in accretionary prisms, which favors both the trapping of fluids beneath and within major faults, and the channeling of flow parallel to fault structure. These low permeabilities promote the development of elevated pore fluid pressures during accretion and underthrusting, and will also facilitate dynamic hydrologic processes within shear zones including dilatancy hardening and thermal pressurization.

Methane discharge in sediments of the Dvurechenskii mud volcano

During the MARGASCH cruise M52/1 in 2001 with RV Meteor we sampled surface sediments from three stations in the crater of the Dvurechenskii mud volcano (DMV, located in the Sorokin Trough of the Black Sea) and one reference station situated 15 km to the northeast of the DMV. We analysed the pore water for sulphide, methane, alkalinity, sulphate, and chloride concentrations and determined the concentrations of particulate organic carbon, carbonate and sulphur in surface sediments. Rates of anaerobic oxidation of methane (AOM) were determined using a radiotracer (14CH4) incubation method. Numerical transport-reaction models were applied to derive the velocity of upward fluid flow through the quiescently dewatering DMV, to calculate rates of AOM in surface sediments, and to determine methane fluxes into the overlying water column. According to the model, AOM consumes 79% of the average methane flux from depth (8.9 x 10**+ 6 mol a**-1), such that the resulting dissolved methane emission from the volcano into the overlying bottom water can be determined as 1.9 x 10**+ 6 mol a**-1. If it is assumed that all submarine mud volcanoes (SMVs) in the Black Sea are at an activity level like the DMV, the resulting seepage represents less than 0.1% of the total methane flux into this anoxic marginal sea. The new data from the DMV and previously published studies indicate that an average SMV emits about 2.0 x 10**+ 6 mol a**-1 into the ocean via quiescent dewatering. The global flux of dissolved methane from SMVs into the ocean is estimated to fall into the order of 10**+10 mol a**-1. Additional methane fluxes arise during periods of active mud expulsion and gas bubbling occurring episodically at the DMV and other SMVs.

Gridded bathymetry from multibeam echosounder EM12S data of the cruise TTR6/2 (1996)

Bathymetry based on data recorded during TTR6 between 05.07.1996 and 20.08.1996 in the Black Sea. In the central Black Sea, the aim of TTR-6 the investigation was a bathymetric map of a field of mud volcanoes known from the previous TTR cruises, during transit. In the Sorokin Trough, where gas hydrates were earlier obtained from sea bottom sediments the primary goals concerned the elucidation of the structure of clay diapiric folds and the searching for mud volcanoes and other evidence for fluid flux through the seafloor. The task of looking for the seafloor manifestation of deep fluid emanation was set in the Pallas Uplift area. The EM12s surveying on the Caucasian margin was aimed at the construction of the first detailed bathymetric map of this area.

Ocean bottom seismometer sgy-files of refraction seismic profiles from Professor Logachev cruise TTR16/3

Over the last decade pockmarks have proven to be important seabed features that provide information about fluid flow on continental margins. Their formation and dynamics are still poorly constrained due to the lack of proper three dimensional imaging of their internal structure. Numerous fluid escape features provide evidence for an active fluid-flow system on the Norwegian margin, specifically in the Nyegga region. In June-July 2006 a high-resolution seismic experiment using Ocean Bottom Seismometers (OBS) was carried out to investigate the detailed 3D structure of a pockmark named G11 in the region. An array of 14 OBS was deployed across the pockmark with 1 m location accuracy. Shots fired from surface towed mini GI guns were also recorded on a near surface hydrophone streamer. Several reflectors of high amplitude and reverse polarity are observed on the profiles indicating the presence of gas. Gas hydrates were recovered with gravity cores from less than a meter below the seafloor during the cruise. Indications of gas at shallow depths in the hydrate stability field show that methane is able to escape through the water-saturated sediments in the chimney without being entirely converted into gas hydrate. An initial 2D raytraced forward model of some of the P wave data along a line running NE-SW across the G11 pockmark shows, a gradual increase in velocity between the seafloor and a gas charged zone lying at ~300 m depth below the seabed. The traveltime fit is improved if the pockmark is underlain by velocities higher than in the surrounding layer corresponding to a pipe which ascends from the gas zone, to where it terminates in the pockmark as seen in the reflection profiles. This could be due to the presence of hydrates or carbonates within the sediments.

(Table 2) Composition of the deapest pore fluids from ODP Holes 168-1030B and 168-1031A

On the eastern flank of the Juan de Fuca Ridge, reaction between upwelling basement fluid and sediment alters hydrothermal fluxes of Ca, SiO2(aq), SO4, PO4, NH4, and alkalinity. We used the Global Implicit Multicomponent Reactive Transport (GIMRT) code to model the processes occurring in the sediment column (diagenesis, sediment burial, fluid advection, and multicomponent diffusion) and to estimate net seafloor fluxes of solutes. Within the sediment section, the reactions controlling the concentrations of the solutes listed above are organic matter degradation via SO4 reduction, dissolution of amorphous silica, reductive dissolution of amorphous Fe(III)-(hydr)oxide, and precipitation of calcite, carbonate fluorapatite, and amorphous Fe(II)-sulfide. Rates of specific discharge estimated from pore-water Mg profiles are 2 to 3 mm/yr. At this site the basement hydrothermal system is a source of NH4, SiO2(aq), and Ca, and a sink of SO4, PO4, and alkalinity. Reaction within the sediment column increases the hydrothermal sources of NH4 and SiO2(aq), increases the hydrothermal sinks of SO4 and PO4, and decreases the hydrothermal source of Ca. Reaction within the sediment column has a spatially variable effect on the hydrothermal flux of alkalinity. Because the model we used was capable of simulating the observed pore-water chemistry by using mechanistic descriptions of the biogeochemical processes occurring in the sediment column, it could be used to examine the physical controls on hydrothermal fluxes of solutes in this setting. Two series of simulations in which we varied fluid flow rate (1 to 100 mm/yr) and sediment thickness (10 to 100 m) predict that given the reactions modeled in this study, the sediment section will contribute most significantly to fluxes of SO4 and NH4 at slow flow rates and intermediate sediment thickness and to fluxes of SiO2(aq) at slow flow rates and large sediment thickness. Reaction within the sediment section could approximately double the hydrothermal sink of PO4 over a range of flow rates and sediment thickness, and could slightly decrease (by

Boron contents and boron, carbon, and oxygen isotope data for ODP Sites 160-970 and 160-971

Products of two mud volcanoes from the distal part of the Mediterranean Ridge accretionary complex have been investigated regarding their B, C, and O stable isotope signatures. The mud breccias have been divided into mud matrix, lithified clasts, biogenic deposits, and authigenic cements and crusts related to fluid flow and cementation. Isotope geochemistry is used to evaluate the depth of mobilization of each phase in the subduction zone. B contents and isotope ratios of the mud and mud clasts show a general trend of B enrichment and decreasing d11B values with increasing consolidation (i.e., depth). However, the majority of the clast and matrix samples relate to moderate depths of mobilization within the wedge (1-2 km below seafloor). The carbonate cements of most of these clasts as well as the authigenic crusts, however, provide evidence for a deep fluid influence, probably associated with the décollement at 5-6 km depth. This interpretation is supported by d13C ratios of the crust, which indicate precipitation of C from thermogenic methane, and by the d11B ratios of pore-water samples of mud-breccia drill cores. Clams (Vesicomya sp.) living adjacent to fluid vents have d11B and d18O values corresponding to brines known in the area, which acted as the parent solution for shell precipitation. Such brines are most likely Miocene pore waters trapped at deep levels within the backstop to the accretionary prism, probably prior to desiccation of the Mediterranean in the Messinian (6-5 Ma). Combining all results, deep fluid circulation and expulsion are identified as the main processes triggering mud liquefaction and extrusion, whereas brines contribute only locally. Given the high B contents, mud extrusion has to be considered a major backflux mechanism of B into the hydrosphere.

Geochemistry of pore fluids from ODP Leg 134 sites

Depending on the temperature and the extent of diagenetic alteration of fluid chemistry, fluid flow at convergent margins may transfer important quantities of heat and mass between the crust and seawater, thereby influencing global mass, isotopic and heat budgets. In the North Aoba Basin, an intra-arc basin located at the New Hebrides Island Arc, alteration of volcanic ash to clay minerals and zeolites forms a CaCl2 brine, perhaps in less than 1 to 3 m.y. The brine results from an exchange of Ca for Na, K, and Mg, and an increase in Cl concentrations to a maximum of 1241 mM. The Cl increase is partly due to the transfer of H2O from the pore fluid into authigenic minerals, but water mass balances, d18O-Cl correlations, and Br/Cl ratios suggest that there is a source of Cl in the sediments. Concentration profiles indicate that Li is transferred from the fluid to solid phase at depths <300 meters below seafloor (mbsf), but at greater depths it is transferred from the solid to fluid phase, at temperatures possibly as low as 25°C. In the accretionary wedge extensive fluid flow appears to be confined to highly faulted regions. Although Cl concentrations less than seawater value are common at convergent margins, the New Hebrides margin contains little low-Cl fluid. Br/Cl ratios suggest the low-Cl fluid is from dilution, and d18O values indicate the water may be derived from mineral dehydration and mixing with meteoric water. The New Hebrides margin exhibits few surface manifestations of venting (e.g., sulfide-oxidizing benthic biological communities, carbonate crusts, mud volcanoes) and thus fluid fluxes may be smaller than at many other margins.

Mineralogical and stable isotope analyses of carbonates from the eastern Black Sea

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area ("Batumi seep area") located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in d18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Chemical and isotopic compositions of altered MORB from ODP Holes 187-1154A, 187-1155B, and 187-1160B

Boron and Pb isotopic compositions together with B-U-Th-Pb concentrations were determined for Pacific and Indian mantle-type mid-ocean ridge basalts (MORB) obtained from shallow drill holes near the Australian Antarctic Discordance (AAD). Boron contents in the altered samples range from 29.7 to 69.6 ppm and are extremely enriched relative to fresh MORB glass with 0.4-0.6 ppm B. Similarly the d11B values range from 5.5? to 15.9? in the altered basalts and require interaction with a d11B enriched fluid similar to seawater ~39.5? and/or boron isotope fractionation during the formation of secondary clays. Positive correlations between B concentrations and other chemical indices of alteration such as H2O CO2, K2O, P2O5, U and 87Sr/86Sr indicate that B is progressively enriched in the basalts as they become more altered. Interestingly, d11B shows the largest isotopic shift to +16? in the least altered basalts, followed by a continual decrease to +5-6? in the most altered basalts. These observations may indicate a change from an early seawater dominated fluid towards a sediment-dominated fluid as a result of an increase in sediment cover with increasing age of the seafloor. The progression from heavy d11B towards lighter values with increasing degrees of alteration may also reflect increased formation of clay minerals (e.g., saponite). A comparison of 238U/204Pb and 206Pb/204Pb in fresh glass and variably altered basalt from Site 1160B shows extreme variations that are caused by secondary U enrichment during low temperature alteration. Modeling of the U-Pb isotope system confirms that some alteration events occurred early in the 21.5 Ma history of these rocks, even though a significant second pulse of alteration happened at ~12 Ma after formation of the crust. The U-Pb systematics of co-genetic basaltic glass and variably low temperature altered basaltic whole rocks are thus a potential tool to place age constraints on the timing of alteration and fluid flow in the ocean crust.

Sulphate concentrations and sulphur isotopic composition in pore fluids from ODP Leg 168 sites

A numerical model of sulfate reduction and isotopic fractionation has been applied to pore fluid SO4**2- and d34S data from four sites drilled during Ocean Drilling Program (ODP) Leg 168 in the Cascadia Basin at 48°N, where basement temperatures reach up to 62°C. There is a source of sulfate both at the top and the bottom of the sediment column due to the presence of basement fluid flow, which promotes bacterial sulfate reduction below the sulfate minimum zone at elevated temperatures. Pore fluid d34S data show the highest values (135 per mil) yet found in the marine environment. The bacterial sulfur isotopic fractionation factor, a, is severely underestimated if the pore fluids of anoxic marine sediments are assumed to be closed systems and Rayleigh fractionation plots yield erroneous values for a by as much as 15 per mil in diffusive and advective pore fluid regimes. Model results are consistent with a = 1.077+/-0.007 with no temperature effect over the range 1.8 to 62°C and no effect of sulfate reduction rate over the range 2 to 10 pmol/ccm/day. The reason for this large isotopic fractionation is unknown, but one difference with previous studies is the very low sulfate reduction rates recorded, about two orders of magnitude lower than literature values that are in the range of µmol/ccm/day to tens of nmol/ccm/day. In general, the greatest 34S depletions are associated with the lowest sulfate reduction rates and vice versa, and it is possible that such extreme fractionation is a characteristic of open systems with low sulfate reduction rates.