Chemical and Sr isotopic compositions and timing of carbonate mineral precipitation, ODP Leg 115

The strontium isotope ratios of authigenic carbonates from Indian Ocean sea-floor basalts have been used to determine the timing of carbonate mineral precipitation and fluid flow. The samples include calcites from 57.2 Ma crust from Ocean Drilling Project (ODP) Site 715, and calcites, aragonites, and siderites from 63.7 Ma crust from ODP Site 707. At Site 715, calcite precipitation may have begun at any time after the basalts cooled, and it continued until approximately 31 Ma, or 26 m.y. after basalt eruption. At Site 707, aragonite and siderite did not begin to precipitate until about 36 Ma, almost 30 m.y. after basalt eruption, and continued to precipitate until at least 30 and 28 Ma, respectively. Calcite precipitation began at approximately 32 Ma and continued until 22 Ma. These ages suggest that vein mineral deposition and low-temperature fluid circulation in the ocean crust may continue for much longer periods of time than previously observed.

Geochemistry of the sheeted dike complex at Pito Deep

Alteration of sheeted dikes exposed along submarine escarpments at the Pito Deep Rift (NE edge of the Easter microplate) provides constraints on the crustal component of axial hydrothermal systems at fast spreading mid-ocean ridges. Samples from vertical transects through the upper crust constrain the temporal and spatial scales of hydrothermal fluid flow and fluid-rock reaction. The dikes are relatively fresh (average extent of alteration is 27%), with the extent of alteration ranging from 0 to >80%. Alteration is heterogeneous on scales of tens to hundreds of meters and displays few systematic spatial trends. Background alteration is amphibole-dominated, with chlorite-rich dikes sporadically distributed throughout the dike complex, indicating that peak temperatures ranged from <300°C to >450°C and did not vary systematically with depth. Dikes locally show substantial metal mobility, with Zn and Cu depletion and Mn enrichment. Amphibole and chlorite fill fractures throughout the dike complex, whereas quartz-filled fractures and faults are only locally present. Regional variability in alteration characteristics is found on a scale of <1-2 km, illustrating the diversity of fluid-rock interaction that can be expected in fast spreading crust. We propose that much of the alteration in sheeted dike complexes develops within broad, hot upwelling zones, as the inferred conditions of alteration cannot be achieved in downwelling zones, particularly in the shallow dikes. Migration of circulating cells along rides axes and local evolution of fluid compositions produce sections of the upper crust with a distinctive character of alteration, on a scale of <1-2 km and <5-20 ka.

Strontium and rubidium isotopes in serpentinites from ODP Site 195-1200

Subduction of the Pacific plate beneath the Mariana forearc releases fluids to the overlying mantle wedge that ascend, producing serpentinite "mud" that discharges on the ocean floor. As part of Leg 195 of the Ocean Drilling Program cores were obtained from drill-holes into the mud volcanoes. We report the isotopic composition of Sr in water squeezed from intervals of the cores, in the serpentinite mud, in leaches of the serpentinite mud, and in entrained small harzburgitic clasts. Except in the upper few meters below the seawater-mud interface, where pore water approaches seawater Sr concentration and isotopic ratio, Sr concentration and isotopic composition remain constant at 3-6 µmol/kg and ~0.7054. Because the elemental chemistry of the pore water is unlike seawater, this isotopic composition reflects fluids derived from the subducted slab, probably modified by reaction with mantle material during ascent. Higher Sr isotopic ratios, up to 0.7087, - but not with higher Sr concentrations in pore water - occur superimposed on an advection profile at 13-16 mbsf surrounding a thin layer of foraminiferal sand. Since the upward seepage velocity of slab fluids in the mud volcano vents is a few cm/yr, exchange of Sr between these carbonates and the rising fluids must have occurred within a maximum of a few hundred years, essentially instantaneously given the millions, or tens of millions, of years the mud volcanoes have been in existence. In contrast, the strontium isotopic compositions of leached serpentinite mud, and of small harzburgite clasts entrained in the mud, are always significantly greater than that of the pore water. In small harzburgite clasts the ratio reaches 0.7088, almost as high as the seawater value of 0.7092 and much higher than the value of typical mantle-derived strontium of ~0.704. The serpentinite muds and harzburgite clasts clearly equilibrated with seawater Sr when they were initially deposited at the surface of the seamount, but following burial they have not fully equilibrated with strontium in the pore water now discharging through the vents. These variations in the strontium isotopic composition of solids and pore waters are more consistent with episodic expulsion of fluids in the subduction zone than steady state flow. Whereas strontium in carbonates equilibrates isotopically within a few hundred years, strontium in buried harzburgite clasts does not equilibrate in the same time, assuming steady state rates of upward fluid flow. By inference, the harzburgite clasts and associated serpentinite mud must have been near the seafloor, unburied, for a yet undetermined but much longer period of time to have equilibrated from ~0.704 to 0.709 prior to subsequent burial. It may be possible to characterize at least the periodicity of fluid release in the mud volcano setting by investigating the zonation of strontium isotopic composition of hartzburgite clasts throughout the 60-meter deep composite cores.

Gas emissions and ROV survey tracks of the Regab pockmark (Northern Congo Fan)

Pockmarks are seafloor depressions commonly associated with fluid escape from the seabed and are believed to contribute noticeably to the transfer of methane into the ocean and ultimately into the atmosphere. They occur in many different areas and geological contexts, and vary greatly in size and shape. Nevertheless, the mechanisms of pockmark growth are still largely unclear. Still, seabed methane emissions contribute to the global carbon budget, and understanding such processes is critical to constrain future quantifications of seabed methane release at local and global scales. The giant Regab pockmark (9°42.6' E, 5°47.8' S), located at 3160 m water depth near the Congo deep-sea channel (offshore southwestern Africa), was investigated with state-of-the-art mapping devices mounted on IFREMER's (French Research Institute for Exploitation of the Sea) remotely operated vehicle (ROV) Victor 6000. ROV-borne micro-bathymetry and backscatter data of the entire structure, a high-resolution photo-mosaic covering 105,000 m2 of the most active area, sidescan mapping of gas emissions, and maps of faunal distribution as well as of carbonate crust occurrence are combined to provide an unprecedented detailed view of a giant pockmark. All data sets suggest that the pockmark is composed of two very distinctive zones in terms of seepage intensity. We postulate that these zones are the surface expression of two fluid flow regimes in the subsurface: focused flow through a fractured medium and diffuse flow through a porous medium. We conclude that the growth of giant pockmarks is controlled by self-sealing processes and lateral spreading of rising fluids. In particular, partial redirection of fluids through fractures in the sediments can drive the pockmark growth in preferential directions.

Chemistry of low-temperature hydrothermal altered basement of ODP Site 129-801

Low-temperature hydrothermal alteration of basement from Site 801 was studied through analyses of the mineralogy, chemistry, and oxygen isotopic compositions of the rocks. The more than 100-m section of 170-Ma basement consists of 60 m of tholeiitic basalt separated from the overlying 60 m of alkalic basalts by a >3-m-thick Fe-Si hydrothermal deposit. Four alteration types were distinguished in the basalts: (1) saponite-type (Mg-smectite) rocks are generally slightly altered, exhibiting small increases in H2O, d18O, and oxidation; (2) celadonite-type rocks are also slightly altered, but exhibit uptake of alkalis in addition to hydration and oxidation, reflecting somewhat greater seawater/rock ratios than the saponite type; (3) Al-saponite-type alteration resulted in oxidation, hydration, and alkali and 18O uptake and losses of Ca and Na due to the breakdown of plagioclase and clinopyroxene; and (4) blue-green rocks exhibit the greatest chemical changes, including oxidation, hydration, alkali uptake, and loss of Ca, Na, and Mg due to the complete breakdown of plagioclase and olivine to K-feldspar and phyllosilicates. Saponite- and celadonite-type alteration of the tholeiite section occurred at a normal mid-ocean ridge basalt spreading center at temperatures <20°C. Near- or off-axis intrusion of an alkali basalt magma at depth reinitiated hydrothermal circulation, and the Fe-Si hydrothermal deposit formed from cool (<60°C) distal hydrothermal fluids. Focusing of fluid flow in the rocks immediately underlying the deposit resulted in the extensive alteration of the blue-green rocks at similar temperatures. Al-saponite alteration of the subsequent alkali basalts overlying the deposit occurred at relatively high water/rock ratios as part of the same low-temperature circulation system that formed the hydrothermal deposit. Abundant calcite formed in the rocks during progressive "aging" of the crust during its long history away from the spreading center.

Carbonate minerals, uranium and thorium concentration and U-Th ages of sediments from ODP Leg 166 sites

We have performed U-Th isotope analyses on pure aragonite samples from the upper sections of Leg 166 cores to assign each aragonite-rich sediment package to the correct sea-level highstand. The uppermost sediment package from each of the four sites investigated (Sites 1003, 1005, 1006, and 1007) yielded a Holocene U-Th age. Sediment packages from deeper in the cores have suffered diagenesis. This diagenesis consists of significant U loss (up to 40%) in the site nearest the platform (Site 1005), slight U gain in sites further from the platform, and continuous loss of pure 234U caused by alpha recoil at all sites. The difference in diagenesis between the sites can be explained by the different fluid-flow histories they have experienced. Site 1005 is sufficiently close to the platform to have probably experienced a change in flow direction whenever the banks have flooded or become exposed. Other sites have probably experienced continuous flow into the sediment. Although diagenesis prevents assignment of accurate ages, it is sufficiently systematic that it can be corrected for and each aragonite-rich package assigned to a unique highstand interval. Site 1005 has sediment packages from highstands associated with marine isotope Stages 1, 5, 7, 9, and 11. Site 1006 is similar, except that the Stage 7 highstand is missing, at least in Hole 1006A. Site 1003 has sediment only from Stage 1 and 11 highstands within the U-Th age range. And Site 1007 has sediment only from the stage 1 highstand. This information will allow the construction of better age models for these sites. No high-aragonite sediments are seen for Stage 3 or Substages 5a and 5c. Unless rather unusual erosion has occurred, this indicates that the banks did not flood during these periods. If true, this would require the sea level for Substages 5a and 5c to have remained at least ~10 m lower than today.

Artificial oxygen fluxes measured by the eddy correlation method using stirring-sensitive oxygen microsensor and oxygen optodes in a flume experiment

In the last decade, the aquatic eddy correlation (EC) technique has proven to be a powerful approach for non-invasive measurements of oxygen fluxes across the sediment water interface. Fundamental to the EC approach is the correlation of turbulent velocity and oxygen concentration fluctuations measured with high frequencies in the same sampling volume. Oxygen concentrations are commonly measured with fast responding electrochemical microsensors. However, due to their own oxygen consumption, electrochemical microsensors are sensitive to changes of the diffusive boundary layer surrounding the probe and thus to changes in the ambient flow velocity. The so-called stirring sensitivity of microsensors constitutes an inherent correlation of flow velocity and oxygen sensing and thus an artificial flux which can confound the benthic flux determination. To assess the artificial flux we measured the correlation between the turbulent flow velocity and the signal of oxygen microsensors in a sealed annular flume without any oxygen sinks and sources. Experiments revealed significant correlations, even for sensors designed to have low stirring sensitivities of ~0.7%. The artificial fluxes depended on ambient flow conditions and, counter intuitively, increased at higher velocities because of the nonlinear contribution of turbulent velocity fluctuations. The measured artificial fluxes ranged from 2 - 70 mmol m**-2 d**-1 for weak and very strong turbulent flow, respectively. Further, the stirring sensitivity depended on the sensor orientation towards the flow. Optical microsensors (optodes) that should not exhibit a stirring sensitivity were tested in parallel and did not show any significant correlation between O2 signals and turbulent flow. In conclusion, EC data obtained with electrochemical sensors can be affected by artificial flux and we recommend using optical microsensors in future EC-studies. Flume experiments were conducted in February 2013 at the Institute for Environmental Sciences, University of Koblenz-Landau Landau. Experiments were performed in a closed oval-shaped acrylic glass flume with cross-sectional width of 4 cm and height of 10 cm and total length of 54 cm. The fluid flow was induced by a propeller driven by a motor and mean flow velocities of up to 20 cm s-1 were generated by applying voltages between 0 V and 4 V DC. The flume was completely sealed with an acrylic glass cover. Oxygen sensors were inserted through rubber seal fittings and allowed positioning the sensors with inclinations to the main flow direction of ~60°, ~95° and ~135°. A Clark type electrochemical O2 microsensor with a low stirring sensitivity (0.7%) was tested and a fast-responding needle-type O2 optode (PyroScience GmbH, Germany) was used as reference as optodes should not be stirring sensitive. Instantaneous three-dimensional flow velocities were measured at 7.4 Hz using stereoscopic particle image velocimetry (PIV). The velocity at the sensor tip was extracted. The correlation of the fluctuating O2 sensor signals and the fluctuating velocities was quantified with a cross-correlation analysis. A significant cross-correlation is equivalent to a significant artificial flux. For a total of 18 experiments the flow velocity was adjusted between 1.7 and 19.2 cm s**-1, and 3 different orientations of the electrochemical sensor were tested with inclination angles of ~60°, ~95° and ~135° with respect to the main flow direction. In experiments 16-18, wavelike flow was induced, whereas in all other experiments the motor was driven by constant voltages. In 7 experiments, O2 was additionally measured by optodes. Although performed simultaneously with the electrochemical sensor, optode measurements are listed as separate experiments (denoted by the attached 'op' in the filename), because the velocity time series was extracted at the optode tip, located at a different position in the flume.

Uranium concentrations and isotope ratios Bahamas seawater and ODP holes pore-water

The geometry, timing, and rate of fluid-flow through carbonate margins and platforms is not well constrained. In this study, we use U concentrations and isotope ratios measured on small volumes of pore-water from Bahamas slope sediment, coupled with existing chlorinity data, to place constraints on the fluid-flow in this region and, by implication, other carbonate platforms. These data also allow an assessment of the behaviour of U isotopes in an unusually well constrained water-rock system. We report pore-water U concentrations which are controlled by dissolution of high-U organic material at shallow depths in the sediment and by reduction of U to its insoluble 4+ state at greater depths. The dominant process influencing pore-water (234U/238U) is alpha recoil. In Holocene sediments, the increase of pore-water (234U/238U) due to recoil provides an estimate of the horizontal flow rate of 11 cm/year, but with considerable uncertainty. At depths in the sediment where conditions are reducing, features in the U concentration and (234U/238U) profiles are offset from one another which constrains the effective diffusivity for U in these sediments to be c. 1-2 * 10**-8 cm**2/s. At depths between the Holocene and these reducing sediments, pore-water (234U/238U) values are unusually low due to a recent increase in the dissolution rate of grain surfaces. This suggests a strengthening of fluid flow, probably due to the flooding of the banks at the last deglaciation and the re-initiation of thermally-driven venting of fluid on the bank top and accompanying recharge on the slopes. Interpretation of existing chlorinity data, in the light of this change in flow rate, constrain the recent horizontal flow rate to be 10.6 ( 3.4) cm/year. Estimates of flow rate from (234U/238U) and Cl[-] are therefore in agreement and suggest flow rates close to those predicted by thermally-driven models of fluid flow. This agreement supports the idea that flow within the Bahamas Banks is mostly thermally driven and suggests that flow rates on the order of 10 cm/year are typical for carbonate platforms where such flow occurs.

Pore-water chemistry of ODP Sites 124-767 and 124-768

The combination of multiple sediment sources and varying rates of sediment accumulation in the Celebes and Sulu seas have had significant impact on the processes of diagenesis, mineralization, and pore-fluid flow. Isotopic and mass-balance calculations help elucidate the various reactions taking place in these western Pacific basins, where ash alteration and basalt-seawater interactions are superimposed on the effects of sulfate oxidation of organic carbon and biogenic methane and of dolomitization of biogenic carbonates. Based on the shape of the calcium and magnesium depth profiles, two major reactive zones have been identified. The first is located near the zone of sulfate depletion and is characterized by carbonate recrystallization, dolomitization and ash alteration reactions at both Ocean Drilling Program Sites 767 and 768. The second reactive zone corresponds to the bottom of the sedimentary sequence and is characterized by alteration reactions in the basement (Site 767) and in the pyroclastic deposits beneath the sediment column (Site 768).

(Appendix) Petrographic information, trace element and Sr isotope ratios of Pito Deep samples

Fluid flow through the axial hydrothermal system at fast spreading ridges is investigated using the Sr-isotopic composition of upper crustal samples recovered from a tectonic window at Pito Deep (NE Easter microplate). Samples from the sheeted dike complex collected away from macroscopic evidence of channelized fluid flow, such as faults and centimeter-scale hydrothermal veins, show a range of 87Sr/86Sr from 0.7025 to 0.7030 averaging 0.70276 relative to a protolith with 87Sr/86Sr of ~0.7024. There is no systematic variation in 87Sr/86Sr with depth in the sheeted dike complex. Comparison of these new data with the two other localities that similar data sets exist for (ODP Hole 504B and the Hess Deep tectonic window) reveals that the extent of Sr-isotope exchange is similar in all of these locations. Models that assume that fluid-rock reaction occurs during one-dimensional (recharge) flow lead to significant decreases in the predicted extent of isotopic modification of the rock with depth in the crust. These model results show systematic misfits when compared with the data that can only be avoided if the fluid flow is assumed to be focused in isolated channels with very slow fluid-rock exchange. In this scenario the fluid at the base of the crust is little modified in 87Sr/86Sr from seawater and thus unlike vent fluids. Additionally, this model predicts that some rocks should show no change from the fresh-rock 87Sr/86Sr, but this is not observed. Alternatively, models in which fluid-rock reaction occurs during upflow (discharge) as well as downflow, or in which fluids are recirculated within the hydrothermal system, can reproduce the observed lack of variation in 87Sr/86Sr with depth in the crust. Minimum time-integrated fluid fluxes, calculated from mass balance, are between 1.5 and 2.6 * 10**6 kg/m**2 for all areas studied to date. However, new evidence from both the rocks and a compilation of vent fluid compositions demonstrates that some Sr is leached from the crust. Because this leaching lowers the fluid 87Sr/86Sr without changing the rock 87Sr/86Sr, these mass balance models must underestimate the time-integrated fluid flux. Additionally, these values do not account for fluid flow that is channelized within the crust.

Hydrocarbon concentrations from pressurized cores in the northern Gulf of Mexico

Two newly developed coring devices, the Multi-Autoclave-Corer and the Dynamic Autoclave Piston Corer were deployed in shallow gas hydrate-bearing sediments in the northern Gulf of Mexico during research cruise SO174 (Oct-Nov 2003). For the first time, they enable the retrieval of near-surface sediment cores under ambient pressure. This enables the determination of in situ methane concentrations and amounts of gas hydrate in sediment depths where bottom water temperature and pressure changes most strongly influence gas/hydrate relationships. At seep sites of GC185 (Bush Hill) and the newly discovered sites at GC415, we determined the volume of low-weight hydrocarbons (C1 through C5) from nine pressurized cores via controlled degassing. The resulting in situ methane concentrations vary by two orders of magnitudes between 0.031 and 0.985 mol kg**-1 pore water below the zone of sulfate depletion. This includes dissolved, free, and hydrate-bound CH4. Combined with results from conventional cores, this establishes a variability of methane concentrations in close proximity to seep sites of five orders of magnitude. In total four out of nine pressure cores had CH4 concentrations above equilibrium with gas hydrates. Two of them contain gas hydrate volumes of 15% (GC185) and 18% (GC415) of pore space. The measurements prove that the highest methane concentrations are not necessarily related to the highest advection rates. Brine advection inhibits gas hydrate stability a few centimeters below the sediment surface at the depth of anaerobic oxidation of methane and thus inhibits the storage of enhanced methane volumes. Here, computerized tomography (CT) of the pressure cores detected small amounts of free gas. This finding has major implications for methane distribution, possible consumption, and escape into the bottom water in fluid flow systems related to halokinesis.

Pore pressure measurements on IODP Exp308 sites

Overpressures measured with pore pressure penetrometers during Integrated Ocean Drilling Program (IODP) Expedition 308 reach 70% and 60% of the hydrostatic effective stress (View the MathML source) in the first 200 meters below sea floor (mbsf) at Sites U1322 and U1324, respectively, in the deepwater Gulf of Mexico, offshore Louisiana. High overpressures are present within low permeability mudstones where there have been multiple, very large, submarine landslides during the Pleistocene. Beneath 200 mbsf at Site U1324, pore pressures drop significantly: there are no submarine landslides in this mixture of mudstone, siltstone, and sandstone. The penetrometer measurements did not reach the in situ pressure at the end of the deployment. We used a soil model to determine that an extrapolation approach based on the inverse of square route of time (View the MathML source) requires much less decay time to achieve a desirable accuracy than an inverse time (1/t) extrapolation. Expedition 308 examined how rapid and asymmetric sedimentation above a permeable aquifer drives lateral fluid flow, extreme pore pressures, and submarine landslides. We interpret that the high overpressures observed are driven by rapid sedimentation of low permeability material from the ancestral Mississippi River. Reduced overpressure at depth at Site U1324 suggests lateral flow (drainage) whereas high overpressure at Site U1322 requires inflow from below: lateral flow in the underlying permeable aquifer provides one mechanism for these observations. High overpressure near the seafloor reduces slope stability and provides a mechanism for the large submarine landslides and low regional gradient (2°) offshore from the Mississippi delta.

Eruption of the Håkon Mosby mud volcano recorded by the long-term observatory on mud-volcano eruptions (LOOME) between 2009 and 2010

Submarine mud volcanoes are considered an important source of methane to the water column. However, the temporal variability of their fluid transport including mud and methane emissions is largely unknown. Assuming that this transport was continuous and at steady state, methane emissions were previously proposed to result from a dynamic equilibrium between upward migration and consumption at the seabed by methane-consuming microbes. Here we have investigated non-steady state situations of vigorous mud movements and their reflection in fluid flow, seabed temperature and bathymetry. Time series of pressure, temperature, pH and seafloor photography were collected by a benthic observatory (LOOME) for 431 days at the active Håkon Mosby mud volcano. These new data document eruptions, which were accompanied by pulses of hot subsurface fluids and triggered rapid sediment uplift and lateral movement, as well as emissions of free gas.