Mineralogy and stable isotopic composition of carbonates and sulfide minerals from ODP Leg 164 sites

During Ocean Drilling Program Leg 164, gas hydrates were recovered in the Blake Ridge where the top of the gas hydrate zone lies at about 200 meters below seafloor (mbsf) and the bottom-simulating reflector (BSR) is located at about 450 mbsf. There is no sedimentological discontinuity crossing the BSR. The BSR is disrupted by the salt piercement of the Cape Fear Diapir. The authigenic carbonates (dolomite and siderite) are always present in small amounts (a few weight percent) in the sediments; they are also concentrated in millimeter- to centimeter-sized nodules and layers composed of dolomite above the top of the gas hydrate reservoir, and of siderite below the BSR. In the Blake Ridge, the dolomite/siderite boundary is located near 140 mbsf. The distribution with depth of the d18O values of dolomite and siderite shows a sharp decrease from high values (maximum 7.5 per mil) in the topmost 50 m, to very low values (minimum -2.7 per mil) at 140 mbsf, and at greater depth increase to positive values within the range of 1.8 per mil to 5.0 per mil. The d13C distribution is marked by the rapid increase with greater depth from low values (-31.3 per mil to -11.4 per mil) near 50 mbsf to positive values at 110 mbsf, which remain in the range of 1.7 to 5.4 down to 700 mbsf. Diagenetic carbonates were precipitated in pore waters in which d18O and d13C values were highly modified by strong fractionation effects, both in the water and in the CO2-CH4 systems associated with the formation and dissociation of gas hydrates.

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.

Methane, helium isotope and hydrogen data from the Nibelungen hydrothermal area, Mid Atlantic Ridge

Hydrothermal emission of mantle helium appears to be directly related to magma production rate, but other processes can generate methane and hydrogen on mid-ocean ridges. In an on-going effort to characterize these processes in the South Atlantic, the flux and distribution of these gases were investigated in the vicinity of a powerful black smoker recently discovered at 8°17.9' S, 13°30.4' W. The vent lies on the shoulder of an oblique offset in the Mid-Atlantic Ridge and discharges high concentrations of methane and hydrogen. Measurements during expeditions in 2004 and 2006 show that the ratio of CH4 to 3He in the neutrally buoyant plume is quite high, 4 x 10**8. The CTD stations were accompanied by velocity measurements with lowered acoustic Doppler current profilers (LADCP), and from these data we estimate the methane transport to have been 0.5 mol/sec in a WSW-trending plume that seems to develop during the ebb tidal phase. This transport is an order of magnitude greater than the source of CH4 calculated from its concentration in the vent fluid and the rise height of the plume. From this range of methane fluxes, the source of 3He is estimated to be between 0.14 and 1.2 nmol/sec. In either case, the 3He source is significantly lower than expected from the spreading rate of the Mid-Atlantic Ridge. From the inventory of methane in the rift valley adjacent to the vent, it appears that the average specific rate of oxidation is 2.6 to 23/yr, corresponding to a turnover time between 140 and 16 days. Vertical profiles of methane in the surrounding region often exhibited Gaussian-like distributions, and the variances appear to increase with distance from the vent. Using a Gaussian plume model, we obtained a range of vertical eddy diffusivities between 0.009 and 0.08 m2m2/sec. These high values may be due to tidally driven internal waves across the promontory on which the vent is located.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Ingestion and clearance rates of Copepods

Feeding activity, selective grazing and the potential grazing impact of two dominant grazers of the Polar Frontal Zone, Calanus simillimus and Rhincalanus gigas, and of copepods < 2 mm were investigated with incubation experiments in the course of an iron fertilized diatom bloom in November 2000. All grazers were already actively feeding in the low chlorophyll waters prior to the onset of the bloom. C. simillimus maintained constant clearance rates and fed predominantly on diatoms. R. gigas and the small copepods strongly increased clearance and ingestion of diatoms in response to their enhanced availability. All grazers preyed on microzooplankton, most steadily on ciliates, confirming the view that pure herbivory appears to be the exception rather than the rule in copepod feeding. The grazers exhibited differences in feeding behavior based on selectivity indices. C. simillimus and R. gigas showed prey switching from dinoflagellates to diatoms in response to the phytoplankton bloom. All grazers most efficiently grazed on large diatoms leading to differences in daily losses for large and small species, e.g. Corethron sp. or Thalassionema nitzschioides. Species-specific diatom mortality rates due to grazing suggest that the high feeding activity of C. simillimus prior to and during the bloom played a role in shaping diatom population dynamics

Geochemistry of hydrothermal solutions, ores, and biota from hydrothermal fields at the East Pacific Rise axis near 9°50'N

Hydrothermal solutions were examined in a circulation system that started to develop after the 1991 volcanic eruption in the axial segment of the EPR between 9°45'N and 9°52'N. Within twelve years after this eruption, diffusion outflow of hot fluid from fractures in basaltic lavas gave way to focused seeps of hot solutions through channels of hydrothermal sulfide edifices. An example of the field Q demonstrates that from 1991 to 2003 H2S concentrations decreased from 86 to 1 mM/kg, and the Fe/H2S ratio simultaneously increased by factor 1.7. This fact can explain disappearance of microbial mats that were widespread within the fields before 1991. S isotopic composition of H2S does not depend on H2S concentration. This fact testifies rapid evolution of the hydrothermal system in the early years of its evolution. Carbon in CH4 from hot fluid sampled in 2003 is richer in 12C isotope than carbon in fluid from the hydrothermal field at 21°N EPR. It suggests that methane comes to the Q field from more than one source. Composition of particulate matter in hydrothermal solutions indicates that it was contributed by biological material. Experimental solutions with labeled substrates (t<70°C) show evidence of active processes of methane oxidation and sulfate reduction. Our results indicate that, during 12-year evolution of the hydrothermal system, composition of its solutions evolved and approached compositions of solutions in mature hydrothermal systems of the EPR.

Geological, geochemical and biogeochemical data on boundary zones of the Atlantic Ocean

Results of studies in two biogeochemically active zones of the Atlantic Ocean (the Benguela upwelling waters and the region influenced by the Congo River run-off) are reported in the book. A multidisciplinary approach included studies of the major elements of the ocean ecosystem: sea water, plankton, suspended matter, bottom sediments, interstitial waters, aerosols, as well as a wide complex of oceanographic studies carried out under a common program. Such an approach, as well as a use of new methodical solutions led to obtaining principally new information on different aspects of oceanology.

Geochemistry of sediment cores GeoB13820-1 and GeoB13863-1 from the western South Atlantic

Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere.

Anaerobic oxidation of methane and sulphate reduction rates, hydrocarbons, sulphate and sulphide concentrations of sediment cores from the Larsen B embayment at the eastern site of the Antarctic Peninsula

First videographic indication of an Antarctic cold seep ecosystem was recently obtained from the collapsed Larsen B ice shelf, western Weddell Sea (Domack et al., 2005). Within the framework of the R/V Polarstern expedition ANTXXIII-8, we revisited this area for geochemical, microbiological and further videographical examinations. During two dives with ROV Cherokee (MARUM, Bremen), several bivalve shell agglomerations of the seep-associated, chemosynthetic clam Calyptogena sp. were found in the trough of the Crane and Evans glacier. The absence of living clam specimens indicates that the flux of sulphide and hence the seepage activity is diminished at present. This impression was further substantiated by our geochemical observations. Concentrations of thermogenic methane were moderately elevated with 2 µM in surface sediments of a clam patch, increasing up to 9 µM at a sediment depth of about 1 m in the bottom sections of the sediment cores. This correlated with a moderate decrease in sulphate from about 28 mM at the surface down to 23.4 mM, an increase in sulphide to up to 1.43 mM and elevated rates of the anaerobic oxidation of methane (AOM) of up to 600 pmol cm**-3 d**-1 at about 1 m below the seafloor. Molecular analyses indicate that methanotrophic archaea related to ANME-3 are the most likely candidates mediating AOM in sediments of the Larsen B seep.

Chemical and isotopic compositions of samples from the Haakon Mosby mud volcano and nearby

Authigenic carbonates in the caldera of an Arctic (72°N) submarine mud volcano with active methane-bearing fluid discharge are formed at the bottom surface during anaerobic microbial methane oxidation. The microbial community consists of specific methane-producing bacteria, which act as methanotrophic ones in conditions of excess methane, and sulfate reducers developing on hydrogen, which is an intermediate product of microbial CH4 oxidation. Isotopically light carbon (aver. d13C = -28.9 per mil) of CO2 produced during CH4 oxidation is the main carbonate carbon source. Heavy oxygen isotope ratio (aver. d18O = 5 per mil) in carbonates is inherited from seawater sulfate. Rapid sulfate reduction (up to 12 mg S/dm**3/day) results in total exhausting of sulfate ion in the upper sediment layer (10 cm). Because of this carbonates can only be formed in surface sediments near the water-bottom interface. Salinity as well as CO3/Ca and Mg/Ca ratios correspond to the field of non-magnesian calcium carbonate precipitation. Calcite is the dominant carbonate mineral in the methane seep caldera, where it occurs in the paragenetic association with barite. Radiocarbon age of carbonates is about 10 Ka.

Molecular and isotopic properties of gases from ODP Holes of ODP Leg 204

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C2+ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO2 and H2S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.

Hydrocarbon contents and carbon isotope composition of organic matter from holes of DSDP Legs 50 and 64

The book is devoted to fundamental problems of organic geochemistry of ocean sediments. It is based on materials of organic matter and gas studies in cores from DSDP Legs 50 and 64. Experimental results obtained in the Laboratory of Carbon Geochemistry (V.I. Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow) take the main part of the book. Evolution of organic matter in specific environment of deep ocean sediments, sources of organic matter in the ocean and methods of their identification based on isotopic analysis and other methods are under discussion. Gas geochemistry in normal conditions of diagenesis, and in conditions under intense heating is studied.

Pore water and solid phase sulfur, carbon and iron data from samples collected in the Argentine Basin during expedition M78

Sulfur phases in the Argentine Basin.