Stable isotope and geochemical record of sediments from the Bering Sea

here is controversy over the role of marine methane hydrates in atmospheric methane concentrations and climate change during the last glacial period. In this study of two sediment cores from the southeast Bering Sea (700 m and 1467 m water depth), we identify multiple episodes during the last glacial period of intense methane flux reaching the seafloor. Within the uncertainty of the radiocarbon age model, the episodes are contemporaneous in the two cores and have similar timing and duration as Dansgaard-Oeschger events. The episodes are marked by horizons of sediment containing 13C-depleted authigenic carbonate minerals; 13C-depleted archaeal and bacterial lipids, which resemble those found in ANME-1 type anaerobic methane oxidizing microbial consortia; and changes in the abundance and species distribution of benthic foraminifera. The similar timing and isotopic composition of the authigenic carbonates in the two cores is consistent with a region-wide increase in the upward flux of methane bearing fluids. This study is the first observation outside Santa Barbara Basin of pervasive, repeated methane flux in glacial sediments. However, contrary to the "Clathrate Gun Hypothesis" (Kennett et al., 2003), these coring sites are too deep for methane hydrate destabilization to be the cause, implying that a much larger part of the ocean's sedimentary methane may participate in climate or carbon cycle feedback at millennial timescales. We speculate that pulses of methane in these opal-rich sediments could be caused by the sudden release of overpressure in pore fluids that builds up gradually with silica diagenesis. The release could be triggered by seismic shaking on the Aleutian subduction zone caused by hydrostatic pressure increase associated with sea level rise at the start of interstadials.

Granulometry, mineralogy and geochemistry of sediments from ODP Hole 169-1037B and Site 169-1038

Central Hill is in the northern part of the Escanaba Trough, which is a sediment-filled rift of southern Gorda Ridge. Central Hill is oriented north-south and is associated with extensive sulfide deposits. Hydrothermal alteration of sediment from Site 1038 was studied through analyses of mineralogy and the chemistry and oxygen isotopic compositions of one nearly pure clay sample. In addition, Site 1037 was drilled to establish the character of the unaltered sedimentary sequence away from the hydrothermal centers of the Northern Escanaba Trough Study Area (NESCA). Mineralogy of the clay-size fraction of turbiditic and hemipelagic sediments of Hole 1037B are predominantly quartz, feldspar, pyroxene, illite, chlorite, and smectite, representing continental-derived material. Cores from Hole 1038I, located within the area of Central Hill but away from known active vent areas, recovered minor amounts of chlorite/smectite mixed-layer clay in the fine fraction, indicating a low-temperature hydrothermal alteration. The 137.4-m-thick sediment section of Hole 1038G is located in an area of low-temperature venting. The uppermost sample is classified as chlorite/smectite mixed layer, which is underlain by chlorite as the dominant mineral. The lowermost deposits of Hole 1038G are also characterized by chlorite/smectite mixed-layer clay. In comparison to Hole 1038I, the mineralogic sequence of Hole 1038G reflects increased chloritization. Intensely altered sediment is almost completely replaced by hydrothermal chlorite in subsurface sediments of Hole 1038H. Alteration to chlorite is characterized by depletion in Na, K, Ti, Ca, Sr, Cs, and Tl and enrichment in Ba. Further, Eu depletion reflects a high-temperature plagioclase alteration. A chlorite 18O value of 2.6 indicates formation at a temperature of ~190°C. It is concluded that the authigenic chlorite in Hole 1038H formed by an active high-temperature fluid flow in the shallow subsurface.

Stable oxygen isotopes of calcite veins in ODP Site 146-892

In situ secondary ionization mass spectrometry (SIMS) analyses of oxygen isotopes in authigenic calcite veins were obtained from an active thrust fault system drilled at Ocean Drilling Program (ODP) Site 892 (44°40.4'N, 125°07.1'W) along the Cascadia subduction margin. The average d18OPDB value of all samples is -9.9 per mil and the values are the lowest of any measured in active accretionary prisms. Ranges in individual veins can be as much as 19.6 per mil. There is an isotopic stratigraphy related to the structural stratigraphy. Mean isotope values in the hanging wall, thrust, and footwall are -14.4 per mil, -9.5 per mil, and -5.2 per mil, respectively. Several veins and crosscutting vein sequences show a general trend from lower to higher d18O values over time. Isotopic and textural data indicate several veins formed by a crack-seal mechanism and growth into open fractures. The best explanation for the strong 18O depletions is periodic rapid flow from 2-3 km deeper in the prism. Relatively narrow isotopic ranges for most veins suggest that fluids were derived from a similar source depth for each episode of fluid pulse and calcite crystallization. Structural and mass balance considerations are consistent with a record preserved in the veins of ten to hundreds of thousands of years. The fluid pulses may relate to periodic large earthquake events such as those recognized in the paleoseismicity records from the Cascadia margin.

(Table 1) Characteristics of silicified sediments at DSDP Site 61-462 according to host-rock lithology, opal-CT-to-quartz ratio, and the origin of the quartz phase

This study deals with the mineralogical variability of siliceous and zeolitic sediments, porcellanites, and cherts at small intervals in the continuously cored sequence of Deep Sea Drilling Project Site 462. Skeletal opal is preserved down to a maximum burial depth of 390 meters (middle Eocene). Below this level, the tests are totally dissolved or replaced and filled by opal-CT, quartz, clinoptilolite, and calcite. Etching of opaline tests does not increase continously with deeper burial. Opal solution accompanied by a conspicuous formation of authigenic clinoptilolite has a local maximum in Core 16 (150 m). A causal relationship with the lower Miocene hiatus at this level is highly probable. Oligocene to Cenomanian sediments represent an intermediate stage of silica diagenesis: the opal-CT/quartz ratios of the silicified rocks are frequently greater than 1, and quartz filling pores or replacing foraminifer tests is more widespread than quartz which converted from an opal-CT precursor. As at other sites, there is a marked discontinuity of the transitions from biogenic opal via opal-CT to quartz with increasing depth of burial. Layers with unaltered opal-A alternate with porcellanite beds; the intensity of the opal-CT-to-quartz transformation changes very rapidly from horizon to horizon and obviously is not correlated with lithologic parameters. The silica for authigenic clinoptilolite was derived from biogenic opal and decaying volcanic components.

Paleomagnetism at DSDP Sites 86-576 and 86-578

The upper sections of Deep Sea Drilling Project Sites 576 (32°21.4'N, 164°16.5'E) and 578 (33°55.6'N, 151°37.7'E) both have stable detrital remanence that can be correlated with the standard reversal stratigraphy. Site 576 contains all reversals above the base of the Gilbert Epoch (5 m.y.) at about 25 m, whereas Site 578 contains a remarkable section of about 60 reversals extending to Anomaly 5B (15 m.y.) at about 150 m sub-bottom depth. In both cases, the paleomagnetic stratigraphy breaks down when accumulation rates drop below 2 m/m.y. At both sites, authigenic manganiferous clays deposited from 70 to 16 m.y. ago accumulated at about 0.4 m/m.y. Similarly, at both sites, the Pleistocene pulse of eolian debris increased accumulation rates by about 6 m/m.y.**2. From 16 to 2 m.y. ago, however, sediment accumulated at Site 578 about five times as rapidly as at Site 576, apparently because of augmented input to the western site by bottom currents.

Geochemistry of pore water and sediments from ODP Leg 136 sites

During Leg 136 drilling was conducted at two sites in pelagic sediments of the north central Pacific Ocean. In this report, pore-water analyses for major seawater constituents, alkalinity, ammonia, nitrate, phosphate, silica, Ba, Fe, Li, Mn, and Sr are presented. Although concentration gradients are generally weak, resulting from slow sedimentation and concomitant diffusive communication with overlying water, there is evidence of sediment/pore-water interactions, associated sediment diagenesis, and formation of authigenic minerals. Bulk major and trace element compositions of the sediments are consistent with reactions inferred to occur within the sediments and with the lithology and mineralogy. Elemental compositions of the sediments are not strongly affected by diagenesis and are primarily related to the dominant mineralogy. Sediments are typical of deep ocean pelagic settings with a significant contribution from the alteration of volcanic ash and the formation of zeolites. Sedimentary rare earth element patterns also provide evidence of active scavenging processes by Mn and Fe oxide phases in the deeper sediments at Site 842.

Element contents, sulfur and oxygen isotopes, and molecular biomarkers of phosphatic crust samples from the Chimbote Platform of the shelf off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10°01' S and 10°24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS2) and sphalerite (ZnS). Low d34Spyrite values (average -28.8 per mill) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C15:0, i/ai-C17:0 and 10MeC16:0) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

(Table 1) Stable isotope data of chemoherm carbonates at Hydrate Ridge on the Cascadia continental margin

Two active chemoherm build-ups growing freely up into the oceanic water column, the Pinnacle and the South East-Knoll Chemoherms, have been discovered at Hydrate Ridge on the Cascadia continental margin. These microbially-mediated carbonate formations rise above the seafloor by several tens of meters and display a pinnacle-shaped morphology with steep flanks. The recovered rocks are pure carbonates dominated by aragonite. Based on fabric and mineralogic composition different varieties of authigenic aragonite can be distinguished. Detailed visual and petrographic investigations unambiguously reveal the involvement of microbes during the formation of the carbonates. The fabric of the cryptocrystalline and fibrous aragonite can be described as thrombolitic. Fossilized microbial filaments in the microcrystalline aragonite indicate the intimate relationship between microbes and carbonates. The strongly 13C-depleted carbon isotope values of the samples (as low as -48.1 per mill PDB) are characteristic of methane as the major carbon source for the carbonate formation. The methane-rich fluids from which the carbonates are precipitated originate most probably from a gas reservoir below the bottom-simulating reflector (BSR) and rise through fault systems. The d18O values of the aragonitic chemoherm carbonates are substantially higher (as high as 5.0 per mill PDB) than the expected equilibrium value for an aragonite forming from ambient seawater (3.5 per mill PDB). As a first approximation this indicates formation from glacial ocean water but other factors are considered as well. A conceptual model is presented for the precipitation of these chemoherm carbonates based on in situ observations and the detailed petrographic investigation of the carbonates. This model explains the function of the consortium of archaea and sulfate-reducing bacteria that grows on the carbonates performing anaerobic oxidation of methane (AOM) and enabling the precipitation of the chemoherms above the seafloor surrounded by oxic seawater. Beggiatoa mats growing on the surface of the chemoherms oxidize the sulfide provided by sulfate-dependent anaerobic oxidation of methane within an oxic environment. The contact between Beggiatoa and the underlying microbial consortium represents the interface between the overlying oxic water column and an anoxic micro-environment where carbonate formation takes place.

Geochemistry of phosphatic crusts from the shelf off Peru

Authigenic phosphorite crusts from the shelf off Peru (9°40°S to 13°30°S) consist of a facies with phosphatic coated grains covered by younger phosphatic laminite. The crusts are composed of carbonate fluorapatite, which probably formed via an amorphous precursor close to the sediment water interface as indicated by low F/P2O5 ratios, Sr and Ca isotopes, as well as rare earth element patterns agreeing with seawater-dominated fluids. Small negative Ce anomalies and U enrichment in the laminite suggest suboxic conditions close to the sediment-water interface during its formation. Increased contents of chalcophilic elements and abundant sulfide minerals in the facies with phosphatic coated grains as well as in the laminite denote sulfate reduction and, consequently, point to episodical development of anoxic conditions during phosphogenesis. The Peruvian phosphorites formed episodically over an extended period of time lasting from Middle Miocene to Pleistocene. Individual phosphatic coated grains show a succession of phosphatic layers with varying contents of organic matter and sulfide-rich phosphatic layers. Coated grains supposedly formed as a result of episodic suspension caused by high turbulence and shifting redox conditions. Episodic anoxia in the pore water induced pyritization in the outermost carbonate fluorapatite layer. Phosphatic coated grains were later transported to the place of crust formation, where subsequent laminite formation was favored under lower energy conditions. A similar succession of phosphatic layers with varying contents of organic matter and sulfide-rich layers in the laminite suggests a formation mechanism analogous to that of individual coated grains.