Carbon, boron and oxygen isotope ratios of sediments from the Moresby Seamount

We report results from boron, carbon and oxygen stable isotope analyses of faulted and veined rocks recovered by scientific ocean drilling during ODP Leg 180 in the western Woodlark Basin, off Papua New Guinea. In this area of active continental extension, crustal break-up and incipient seafloor spreading, a shallow-dipping, seismically active detachment fault accommodates strain, defining a zone of mylonites and cataclasites, vein formation and fluid infiltration. Syntectonic microstructures and vein-fill mineralogy suggest frictional heating during slip during extension and exhumation of Moresby Seamount. Low carbon and oxygen isotope ratios of calcite veins indicate precipitation from hydrothermal fluids (delta13C PDB down to -17?; delta18O PDB down to -22?) formed by both dehydration and decarbonation. Boron contents are low (<7 ppm), indicating high-grade metamorphic source rock for the fluids. Some of the delta11B signatures (17-35?; parent solutions to calcite vein fills) are low when compared to deep-seated waters in other tectonic environments, likely reflecting preferential loss of 11B during low-grade metamorphism at depth. Pervasive devolatilization and flux of CO2-rich fluids are evident from similar vein cement geochemistry in the detachment fault zone and splays further updip. Multiple rupture-and-healing history of the veins suggests that precipitation may be an important player in fluid pressure evolution and, hence, seismogenic fault movement.

Geochemistry of tephra layers in ODP Site 121-758

A tephrochronology of the past 5 Ma is constructed with ash layers recovered from Neogene sediments during drilling at ODP Leg 121 Site 758 on northern Ninetyeast Ridge. The several hundred tephra layers observed in the first 80 m of cores range in thickness from a few millimeters to 34 cm. Seventeen tephra layers, at least 1 cm thick, were sampled and analyzed for major elements. Relative ages for the ash layers are estimated from the paleomagnetic and d18O chronostratigraphy. The ash layers comprise about 1.7% by volume of the sediments recovered in the first 72 m. The median grain size of the ashes is about 75 ?m, with a maximum of 150 ?m. The ash consists of rhyolitic bubble junction and pumice glass shards. Blocky and platy shards are in even proportion (10%-30%) and are dominated by bubble wall shards (70%-90%). The crystal content of the layers is always less than 2%, with Plagioclase and alkali feldspar present in nearly every layer. Biotite was observed only in the thickest layers. The major element compositions of glass and feldspar reflect fractionation trends. Three groupings of ash layers suggest different provenances with distinct magmatic systems. Dating by d18O and paleomagnetic reversals suggests major marine ash-layer-producing eruptions (marine tephra layers > 1 cm in thickness) occur roughly every approximately 414,000 yr. This value correlates well with landbased studies and dates of Pleistocene Sumatran tuffs (average 375,000-yr eruptive interval). Residence times of the magmatic systems defined by geochemical trends are 1.583, 2.524, and 1.399 Ma. The longest time interval starts with the least differentiated magma. The Sunda Arc, specifically Sumatra, is inferred to be the source region for the ashes. Four of the youngest five ash layers recovered correlate in time and in major element chemistry to ashes observed on land at the Toba caldera.

Sedimentology, mineral magnetism, andoxygen isotope stratigraphy of ODP Hole 133-819A

To investigate late Quaternary paleoclimatic and paleoceanographic change in the sedimentary record, preserved on the Australian Continental Margin during the late Quaternary, core material was collected from Ocean Drilling Program, Leg 133, Site 819. An expanded sequence of late Quaternary, rhythmically bedded, predominantly hemipelagic sediments were recovered from Hole 819A. The foraminiferal d18O record preserved at Hole 819A suggests that the late Quaternary section is incomplete. Both benthic and planktonic d18O stratigraphies can be traced tentatively downcore to stage 6 at about 32.5 mbsf, where a major hiatus occurs. At this level, a slump detachment surface has been identified (Shipboard Scientific Party, 1991). This slump has removed marine oxygen isotope stages 7 to 13. Below 32.5 mbsf, continuous correlation can be achieved in the planktonic d18O curve, with existing deep-sea foraminiferal oxygen isotope stratigraphies from stage 14 through stage 28. The major hiatus at 32.5 mbsf marks the position of a significant change in the character of the sedimentation at Site 819. Sediments below 32.5 mbsf, relative to those above 32.5 mbsf, are characterized by less variation in mean particle size; lower percentages of carbonate content in the coarse fraction (>63 µm); a stronger relationship between the percentage of fine fraction and magnetic mineral concentration, and lower foraminiferal abundances. Above the hiatus, large fluctuations in mean particle size occurred, which have been interpreted to be the result of high foraminiferal abundances. Early highstands show high terrigenous influx in the fine fraction above the hiatus. This is the opposite of the general idea of high terrigenous influx during lowstands of sea level on siliciclastic dominated continental margins. We are far from understanding the origin of this material and further investigation will be required (see also Glenn et al., this volume). All our records, except the planktonic foraminiferal oxygen isotope record, indicate that the major hiatus marks the position of a significant change in the environment at Site 819. The planktonic foraminiferal d18O record suggests that environmental change occurred prior to the formation of the hiatus (i.e., near the Brunhes/Matuyama [B/M] boundary). The interval between the B/M boundary and the hiatus represents a transitional period between two different patterns of ocean circulation. Throughout most of the lower part of the sequence, Site 819 was at a shallow-water depth and local oceanographic conditions were dominated by sluggish Subtropical Central Water (SCW) flow. However, near the B/M boundary, ocean circulation patterns intensified, reflecting a worldwide change in paleoenvironment. Enhanced ocean circulation patterns were possibly aided by tectonic subsidence. During this period Site 819 became progressively more under the influence of Antarctic Intermediate Water (AAIW), than SCW. In the upper part of the sequence at Hole 819 A, we see a continuation of the pattern of oceanographic reorganization suggested during stages 21 through 14. Intensification of the subsurface oceanographic circulation was also accompanied by the progressive wedging southward of surface waters associated with the East Australian Current (EAC). The change in the nature of the records in the lower and upper parts of the sequence at Site 819 are thought to reflect perturbations by the orbital eccentricity cycle.

Hydrate abundances at the high-flux Batumi seep area in the southeastern Black Sea

Submarine gas hydrates are a major global reservoir of the potent greenhouse gas methane. Since current assessments of worldwide hydrate-bound carbon vary by one order of magnitude, new technical efforts are required for improved and accurate hydrate quantifications. Here we present hydrate abundances determined for surface sediments at the high-flux Batumi seep area in the southeastern Black Sea at 840 m water depth using state-of-the art autoclave technology. Pressure sediment cores of up to 2.65 m in length were recovered with an autoclave piston corer backed by conventional gravity cores. Quantitative core degassing yielded volumetric gas/bulk sediment ratios of up to 20.3 proving hydrate presence. The cores represented late glacial to Holocene hemipelagic sediments with the shallowest hydrates found at 90 cmbsf. Calculated methane concentrations in the different cores surpassed methane equilibrium concentrations in the two lowermost lithological Black Sea units sampled. The results indicated hydrate fractions of 5.2% of pore volume in the sapropelic Unit 2 and mean values of 21% pore volume in the lacustrine Unit 3. We calculate that the studied area of ~ 0.5 km**2 currently contains about 11.3 kt of methane bound in shallow hydrates. Episodic detachment and rafting of such hydrates is suggested by a rugged seafloor topography along with variable thicknesses in lithologies. We propose that sealing by hydrate precipitation in coarse-grained deposits and gas accumulation beneath induces detachment of hydrate/sediment chunks. Floating hydrates will rapidly transport methane into shallower waters and potentially to the sea-atmosphere boundary. In contrast, persistent in situ dissociation of shallow hydrates appears unlikely in the near future as deep water warming by about 1.6 °C and/or decrease in hydrostatic pressure corresponding to a sea level drop of about 130 m would be required. Because hydrate detachment should be primarily controlled by internal factors in this area and in similar hydrated settings, it serves as source of methane in shallow waters and the atmosphere which is mainly decoupled from external forcing.

Active methane seepage in the Southern Ocean, off the sub-Antarctic island of South Georgia

An extensive submarine cold-seep area was discovered on the northern shelf of South Georgia during R/V Polarstern cruise ANT-XXIX/4 in spring 2013. Hydroacoustic surveys documented the presence of 133 gas bubble emissions, which were restricted to glacially-formed fjords and troughs. Video-based sea floor observations confirmed the sea floor origin of the gas emissions and spatially related microbial mats. Effective methane transport from these emissions into the hydrosphere was proven by relative enrichments of dissolved methane in near-bottom waters. Stable carbon isotopic signatures pointed to a predominant microbial methane formation, presumably based on high organic matter sedimentation in this region. Although known from many continental margins in the world's oceans, this is the first report of an active area of methane seepage in the Southern Ocean. Our finding of substantial methane emission related to a trough and fjord system, a topographical setting that exists commonly in glacially-affected areas, opens up the possibility that methane seepage is a more widespread phenomenon in polar and sub-polar regions than previously thought.

Major, trace and rare earth element concentration of ODP Site 210-1277 basalts, Newfoundland margin

Drilling of the distal Newfoundland margin at Ocean Drilling Program Site 1277 recovered part of the transition between exhumed sub-continental mantle lithosphere and normal mid-ocean-ridge basalt (N-MORB) volcanism perhaps related to the initiation of seafloor spreading, which may have occurred near the Aptian/Albian boundary, coincident with the final separation of subcontinental mantle lithosphere. Subcontinental mantle lithosphere was recovered near the crest of a basement high, the Mauzy Ridge. This ridge lies near magnetic Anomaly M1 and is inferred to be of Barremian age. The recovered section is dominated by serpentinized spinel harzburgite, with subordinate dunite and minor gabbroic intrusives, and it includes inferred high-temperature ductile shear zones. The serpentinite is capped by foliated gabbro cataclasite that is interpreted as the product of a major seafloor extensional detachment. The serpentinized harzburgite beneath is highly depleted subcontinental mantle lithosphere that was exhumed to create new seafloor within the ocean-continent transition zone. After inferred removal of overlying brittle crust, the detachment was eroded, producing multiple mass flows that were dominated by clasts of serpentinite and gabbro in a lithoclastic and calcareous matrix. Basaltic lavas were erupted spasmodically, mainly as sheet flows, with subordinate lava breccia, hyaloclastite, and possible pillow lava. The sedimentary-volcanic succession and the exhumed mantle lithosphere experienced later high-angle extensional fracturing and probably faulting. Extensional fissures opened incrementally and were filled with silt-sized carbonate, basalt-derived clastic sediment, and hyaloclastite, forming neptunian dykes and geopetal structures. Chemical analysis of representative basalts for major elements and trace elements were made using a high-precision, high-accuracy X-ray fluorescence method (utilizing increased count times) and by whole-rock inductively coupled plasma-mass spectrometry that yielded additional evidence for rare earth elements. The analyses indicate N-MORB to slightly enriched compositions. The MORB was produced by relatively high degree melting of a fertile mantle source that differed strongly from the cored serpentinized peridotites. The basalts exhibit a distinct negative Nb anomaly on MORB-normalized plots that can be explained by prior extraction of melt from upper mantle that had previously been affected by subduction, possibly during closure of the Iapetus or Rheic oceans. In the proposed interpretation, mantle lithosphere was exhumed to the seafloor and experienced mass wasting to form serpentinite-rich mass flows. The interbedded MORB records the beginning of a transition to "normal" seafloor spreading. This interpretation takes into account drilling results from the Iberia-Galicia margin and the Jurassic Alps-Apennines.

Oxygen and sulfur isotopes of peridotite and gabbro from the Mid-Atlantic Ridge

Whole rock sulfur and oxygen isotope compositions of altered peridotites and gabbros from near the 15°20'N Fracture Zone on the Mid-Atlantic Ridge were analyzed to investigate hydrothermal alteration processes and test for a subsurface biosphere in oceanic basement. Three processes are identified. (1) High-temperature hydrothermal alteration (~250-350°C) at Sites 1268 and 1271 is characterized by 18O depletion (2.6-4.4 per mil), elevated sulfide-S, and high delta34S (up to ~2 wt% and 4.4-10.8 per mil). Fluids were derived from high-temperature (>350°C) reaction of seawater with gabbro at depth. These cores contain gabbroic rocks, suggesting that associated heat may influence serpentinization. (2) Low-temperature (<150°C) serpentinization at Sites 1272 and 1274 is characterized by elevated delta18O (up to 8.1 per mil), high sulfide-S (up to ~3000 ppm), and negative delta34S (to -32.1 per mil) that reflect microbial reduction of seawater sulfate. These holes penetrate faults at depth, suggesting links between faulting and temperatures of serpentinization. (3) Late low-temperature oxidation of sulfide minerals caused loss of sulfur from rocks close to the seafloor. Sulfate at all sites contains a component of oxidized sulfide minerals. Low delta34S of sulfate may result from kinetic isotope fractionation during oxidation or may indicate readily oxidized low-delta34S sulfide derived from microbial sulfate reduction. Results show that peridotite alteration may be commonly affected by fluids +/- heat derived from mafic intrusions and that microbial sulfate reduction is widespread in mantle exposed at the seafloor.

Nature, chemistry, and origin of late Cenozoic megascopic tephras in Legs 89 and 90 Cores from the Southwest Pacific

Several thin (1-10 cm) megascopic vitric tephras occur in the late Cenozoic calcareous oozes on Lord Howe Rise in the Tasman Sea and off eastern South Island, New Zealand. Of the 18 tephras analyzed 15 are silicic (75-78% SiO2) with abundant clear glass shards and a biotite ± hypersthene ± green hornblende ferromagnesian mineralogy. The Neogene silicic tephras were derived from the now-extinct Coromandel volcanic area in New Zealand, and the Quaternary ones from the presently active Central Volcanic Region of New Zealand. On the basis of glass chemistry and age, several of the Quaternary tephras are probably correlatives, and at least two can be matched to the major on-land Mt. Curl tephra (-0.25 m.y.). The occurrence of correlative silicic tephras both northwest and southeast of New Zealand may result from particularly violent eruptions, the ash below and above an altitude of -20 km being dispersed in opposite directions toward the Pacific Ocean and Tasman Sea, respectively. Ash drifting eastward into the southeasterly trade wind belt off northeastern New Zealand could also be carried into the central and northern Tasman Sea. Three megascopic tephras consist of altered basic shards and common labradorite crystals. They record Neogene explosive basaltic to andesitic activity from nearby ocean island or ridge sources in the Ontong-Java Plateau and Vanuatu regions. The megascopic tephras are a very incomplete and biased record of late Cenozoic explosive volcanism in the southwest Pacific because the innumerable, thin, green argillaceous layers in the cores (Gardner et al., this volume) probably represent devitrified intermediate to basic tephras derived mainly from oceanic arc volcanism along the Pacific/Australia plate boundary. In contrast to the New Zealand-derived silicic glass shards, the preservation potential of these more basic shards in Leg 90 calcareous sediments was low.

Geochemistry of Atlantis Massif serpentinites

The Lost City hydrothermal system at the southern Atlantis Massif (Mid-Atlantic Ridge, 30°N) provides a natural laboratory for studying serpentinization processes, the temporal evolution of ultramafic-hosted hydrothermal systems, and alteration conditions during formation and emplacement of an oceanic core complex. Here we present B, O, and Sr isotope data to investigate fluid/rock interaction and mass transfer during detachment faulting and exhumation of lithospheric sequences within the Atlantis Massif. Our data indicate that extensive serpentinization was a seawater-dominated process that occurred predominately at temperatures of 150-250 °C and at high integrated W/R ratios that led to a marked boron enrichment (34-91 ppm). Boron removal from seawater during serpentinization is positively correlated with changes in d11B (11-16 per mil) but shows no correlation with O-isotope composition. Modeling indicates that B concentrations and isotope values of the serpentinites are controlled by transient temperature-pH conditions. In contrast to prior studies, we conclude that low-temperature marine weathering processes are insignificant for boron geochemistry of the Atlantis Massif serpentinites. Talc- and amphibole-rich fault rocks formed within a zone of detachment faulting at temperatures of approximately 270-350 °C and at low W/R ratios. Talc formation in ultramafic domains in the massif was subsequent to an early stage of serpentinization and was controlled by the access of Si-rich fluids derived through seawater-gabbro interactions. Replacement of serpentine by talc resulted in boron loss and significant lowering of d11B values (9-10 per mil), which we model as the product of progressive extraction of boron. Our study provides new constraints on the boron geochemical cycle at oceanic spreading ridges and suggests that serpentinization associated with ultramafic-hosted hydrothermal systems may have important implications for the behavior of boron in subduction zone settings.

Description and geochemical composition of tephra layers from ODP Hole 186-1150A and Site 186-1151

The sediments collected at Sites 1150 and 1151 during Leg 186 included many tephra layers and volcaniclastic detritus. In order to identify these tephras, the major oxide compositions of individual glass shards were determined by electron probe microanalyzer. The uppermost four tephras in sediments from Hole 1150A are correlated with the Towada-Hachinohe tephra (To-H; Tohoku district), Shikotsu Daiichi (1st) tephra (Spfa-1; Hokkaido district), Narugo-Yanagisawa tephra (Nr-Y; Tohoku district), and Aso-4 tephra (Kyushu district), respectively. The uppermost tephra in Hole 1151C is correlated with To-H tephra. To-H, Spfa-1, and Aso-4 tephras are also present in piston core KH94-3, LM-8, collected between Sites 1150 and 1151. Eruptive ages of To-H and Spfa-1 estimated from the oxygen isotopic Stages of core KH94-3, LM-8 are between 14.9-15.3 and 39.5-40.1 ka.

Gridded bathymetry from multibeam echosounder EM122 data of the cruise M84/2, off Eregli (2011)

We investigated gas bubble emissions at the Don-Kuban paleo-fan in the northeastern Black Sea regarding their geological setting, quantities as well as spatial and temporal variabilities during three ship expeditions between 2007 and 2011. About 600 bubble-induced hydroacoustic anomalies in the water column (flares) originating from the seafloor above the gas hydrate stability zone (GHSZ) at ~700 m water depth were found. At about 890 m water depth a hydrocarbon seep area named "Kerch seep area" was newly discovered within the GHSZ. We propose locally domed sediments ('mounds') discovered during ultra-high resolution bathymetric mapping with an autonomous underwater vehicle (AUV) to result from gas hydrate accumulation at shallow depths. In situ measurements indicated spatially limited temperature elevations in the shallow sediment likely induced by upward fluid flow which may confine the local GHSZ to a few meters below the seafloor. As a result, gas bubbles are suspected to migrate into near-surface sediments and to escape the seafloor through small-scale faults. Hydroacoustic surveys revealed that several flares originated from a seafloor area of about 1 km**2 in size. The highest flare disappeared in about 350 m water depth, suggesting that the released methane remains in the water column. A methane flux estimate, combining data from visual quantifications during dives with a remotely operated vehicle (ROV) with results from ship-based hydroacoustic surveys and gas analysis revealed that between 2 and 87 x 10**6 mol CH4 yr-1 escaped into the water column above the Kerch seep area. Our results show that the finding of the Kerch seep area represents a so far underestimated type of hydrocarbon seep, which has to be considered in methane budget calculations.