Oxygen isotope concentrations of minerals from the upper kilometer of the ocean crust, DSDP Hole 504B

DSDP Hole 504B is the deepest basement hole in the oceanic crust, penetrating through a 571.5 m pillow section, a 209 m lithologic transition zone, and 295 m into a sheeted dike complex. An oxygen isotopic profile through the upper crust at Site 504 is similar to that in many ophiolite complexes, where the extrusive section is enriched in 18O relative to unaltered basalts, and the dike section is variably depleted and enriched. Basalts in the pillow section at Site 504 have delta 18O values generally ranging from +6.1 to +8.5? SMOW (mean= +7.0?), although minor zeolite-rich samples range up to 12.7?. Rocks depleted in 18O appear abruptly at 624 m sub-basement in the lithologic transition from 100% pillows to 100% dikes, coinciding with the appearance of greenschist facies minerals in the rocks. Whole-rock values range to as low as +3.6?, but the mean values for the lithologic transition zone and dike section are +5.8 and +5.4?, respectively. Oxygen and carbon isotopic data for secondary vein minerals combined with the whole rock data provide evidence for the former presence of two distinct circulation systems separated by a relatively sharp boundary at the top of the lithologic transition zone. The pillow section reacted with seawater at low temperatures (near 0°C up to a maximum of around 150°C) and relatively high water/rock mass ratios (10-100); water/rock ratios were greater and conditions were more oxidizing during submarine weathering of the uppermost 320 m than deeper in the pillow section. The transition zone and dikes were altered at much higher temperatures (up to about 350°C) and generally low water/rock mass ratios (~1), and hydrothermal fluids probably contained mantle-derived CO2. Mixing of axial hydrothermal fluids upwelling through the dike section with cooler seawater circulating in the overlying pillow section resulted in a steep temperature gradient (~2.5°C/m) across a 70 m interval at the top of the lithologic transition zone. Progressive reaction during axial hydrothermal metamorphism and later off-axis alteration led to the formation of albite- and Ca-zeolite-rich alteration halos around fractures. This enhanced the effects of cooling and 18O enrichment of fluids, resulting in local increases in delta 18O of rocks which had been previously depleted in 18O during prior axial metamorphism.

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.

Debris flow magnitudes: a global catalog

The episodic occurrence of debris flow events in response to stochastic precipitation and wildfire events makes hazard prediction challenging. Previous work has shown that frequency-magnitude distributions of non-fire-related debris flows follow a power law, but less is known about the distribution of post-fire debris flows. As a first step in parameterizing hazard models, we use frequency-magnitude distributions and cumulative distribution functions to compare volumes of post-fire debris flows to non-fire-related debris flows. Due to the large number of events required to parameterize frequency-magnitude distributions, and the relatively small number of post-fire event magnitudes recorded in the literature, we collected data on 73 recent post-fire events in the field. The resulting catalog of 988 debris flow events is presented as an appendix to this article. We found that the empirical cumulative distribution function of post-fire debris flow volumes is composed of smaller events than that of non-fire-related debris flows. In addition, the slope of the frequency-magnitude distribution of post-fire debris flows is steeper than that of non-fire-related debris flows, evidence that differences in the post-fire environment tend to produce a higher proportion of small events. We propose two possible explanations: 1) post-fire events occur on shorter return intervals than debris flows in similar basins that do not experience fire, causing their distribution to shift toward smaller events due to limitations in sediment supply, or 2) fire causes changes in resisting and driving forces on a package of sediment, such that a smaller perturbation of the system is required in order for a debris flow to occur, resulting in smaller event volumes.

Corrected ICESat altimetry data, surface mass balance, and firn elevation change on Antarctic ice shelves

Accurate prediction of global sea-level rise requires that we understand the cause of recent, widespread and intensifying glacier acceleration along Antarctic ice-sheet coastal margins. Floating ice shelves buttress the flow of grounded tributary glaciers and their thickness and extent are particularly susceptible to changes in both climate and ocean forcing. Recent ice-shelf collapse led to retreat and acceleration of several glaciers on the Antarctic Peninsula. However, the extent and magnitude of ice-shelf thickness change, its causes and its link to glacier flow rate are so poorly understood that its influence on the future of the ice sheets cannot yet be predicted. Here we use satellite laser altimetry and modelling of the surface firn layer to reveal for the first time the circum-Antarctic pattern of ice-shelf thinning through increased basal melt. We deduce that this increased melt is the primary driver of Antarctic ice-sheet loss, through a reduction in buttressing of the adjacent ice sheet that has led to accelerated glacier flow. The highest thinning rates (~7 m/a) occur where warm water at depth can access thick ice shelves via submarine troughs crossing the continental shelf. Wind forcing could explain the dominant patterns of both basal melting and the surface melting and collapse of Antarctic ice shelves, through ocean upwelling in the Amundsen and Bellingshausen Seas and atmospheric warming on the Antarctic Peninsula. This implies that climate forcing through changing winds influences Antarctic Ice Sheet mass balance, and hence global sea-level, on annual to decadal timescales.

Chemical composition and description of a ferromanganese crust, sample 89D, obtained during R/V Capricorne cruise ARCANTE 1

A manganese oxide encrustation (2.5 kg) was dredged, in an island arc setting, downslope of Bertrand bank, a seamount culminating at 70-m depth and located NNE of Grande-Terre, Guadeloupe, and SE of Antigua, West Indies. A thorough texturai analysis indicated a rhythmic precipitation and growth polarity as well as mineralogical ( 10 A tektomanganate) and geochemical (low concentrations of Ni, Cu, Co, Zn, Pb and REE) criteria, point to a submarine hydrothermal origin for most of the sample. The crust was coated with a fine ferromanganese oxide cortex deposited iii a "normal" oceanic environment; it also included micritic fillings, a main pyroclastic zone near the top of the crust, and a Mg-Al sulphate deposit. Planktonic foraminifera coeval with the precipitation of the manganese oxide indicate an age of ca. 3 m. y. (upper Pliocene); i.e., more than 20 m. y. after the cessation of the volcanic activity of the Lesser Antilles outer arc that was responsible for the buildup of the Bertrand seamount. Furthermore, the genesis of the crust is not linked to the activity of the contemporaneous inner arc (Miocene to Present), particularly of its nearmost segment (Basse Terre, Guadeloupe-Montserrat) located about 50 km to the West. The authors suggest that the manganese oxide is the result of convective circulation of sea water through a faulted system occurring in an area of intense seismic activity. The remobilization of chemical elements (Mn, S, etc.) within the seamount volcanic core bas probably affected a substratum that was still hydrothermally altered during the previous volcanic activity of the outer arc. The authors insist on the interest in using texturai analysis for Fe/Mn oxide investigations.

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.

Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

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.

Bulk stable carbon and oxygen isotopes from ODP Site 1258, and Fe intensities from ODP Site 1262, and minimal tuning age model options for ODP Site 1258 and 1262

Timing is crucial to understanding the causes and consequences of events in Earth history. The calibration of geological time relies heavily on the accuracy of radioisotopic and astronomical dating. Uncertainties in the computations of Earth's orbital parameters and in radioisotopic dating have hampered the construction of a reliable astronomically calibrated time scale beyond 40 Ma. Attempts to construct a robust astronomically tuned time scale for the early Paleogene by integrating radioisotopic and astronomical dating are only partially consistent. Here, using the new La2010 and La2011 orbital solutions, we present the first accurate astronomically calibrated time scale for the early Paleogene (47-65 Ma) uniquely based on astronomical tuning and thus independent of the radioisotopic determination of the Fish Canyon standard. Comparison with geological data confirms the stability of the new La2011 solution back to ~54 Ma. Subsequent anchoring of floating chronologies to the La2011 solution using the very long eccentricity nodes provides an absolute age of 55.530 {plus minus} 0.05 Ma for the onset of the Paleocene/Eocene Thermal Maximum (PETM), 54.850 {plus minus} 0.05 Ma for the early Eocene ash -17, and 65.250 {plus minus} 0.06 Ma for the K/Pg boundary. The new astrochronology presented here indicates that the intercalibration and synchronization of U/Pb and 40Ar/39Ar radiometric geochronology is much more challenging than previously thought.