Hydrate, ice and quartz content of eight holes of Leg 204

The state of preservation of natural gas hydrate samples, recovered from 6 sites drilled during ODP Leg 204 at southern summit of Hydrate Ridge, Oregon Margin, has been investigated by X-ray diffraction (XRD) and cryo-scanning-electron-microscopy (cryo-SEM) techniques. A detailed characterization of the state of decomposition of gas hydrates is necessary since no pressurized autoclave tools were used for sampling and partial dissociation must have occurred during recovery prior to the quench and storage in liquid nitrogen. Samples from 16 distinct horizons have been investigated by synchrotron X-ray diffraction measurements at HASYLAB/ Hamburg. A full profile fitting analysis ("Rietveld method") of synchrotron XRD data provides quantitative phase determinations of the major sample constituents such as gas hydrate structure I (sI), hexagonal ice (Ih) and quartz. The ice content (Ih) in each sample is related to frozen water composed of both original existing pore water and the water from decomposed hydrates. Hydrate contents as measured by diffraction vary between 0 and 68 wt.% in the samples we measured. Samples with low hydrate content usually show micro-structural features in cryo-SEM ascribed to extensive decomposition. Comparing the appearance of hydrates at different scales, the grade of preservation seems to be primarily correlated with the contiguous volume of the original existing hydrate; the dissociation front appears to be indicated by micrometer-sized pores in a dense ice matrix.

Sulphur geochemistry of whole-rock samples from ODP Hole 176-735B

Sulfide petrography plus whole rock contents and isotope ratios of sulfur were measured in a 1.5 km section of oceanic gabbros in order to understand the geochemistry of sulfur cycling during low-temperature seawater alteration of the lower oceanic crust, and to test whether microbial effects may be present. Most samples have low SO4/Sum S values (<= 0.15), have retained igneous globules of pyrrhotite ± chalcopyrite ± pentlandite, and host secondary aggregates of pyrrhotite and pyrite laths in smectite ± iron-oxyhydroxide ± magnetite ± calcite pseudomorphs of olivine and clinopyroxene. Compared to fresh gabbro containing 100-1800 ppm sulfur our data indicate an overall addition of sulfide to the lower crust. Selection of samples altered only at temperatures <= 110 °C constrains microbial sulfate reduction as the only viable mechanism for the observed sulfide addition, which may have been enabled by the production of H2 from oxidation of associated olivine and pyroxene. The wide range in d34Ssulfide values (-1.5 to + 16.3 per mil) and variable additions of sulfide are explained by variable epsilon sulfate-sulfide under open system pathways, with a possible progression into closed system pathways. Some samples underwent oxidation related to seawater penetration along permeable fault horizons and have lost sulfur, have high SO4/Sum S (>= 0.46) and variable d34Ssulfide (0.7 to 16.9 per mil). Negative d34Ssulfate-d34Ssulfide values for the majority of samples indicate kinetic isotope fractionation during oxidation of sulfide minerals. Depth trends in sulfide-sulfur contents and sulfide mineral assemblages indicate a late-stage downward penetration of seawater into the lower 1 km of Hole 735B. Our results show that under appropriate temperature conditions, a subsurface biosphere can persist in the lower oceanic crust and alter its geochemistry.

Radionuclides in ice cores I and II from Vernagferner, Austria

Fission product (90Sr-90Y, 137Cs, total beta) and 21OPb-210Po activities were measured in core samples from the temperate vernagtferner (3150 m altitude, Oetztal Alps, Austria). The results show that the investigated fission products are transported with water resulting from melting processes, and are sorbed on dust or dirt horizons. These products are, therefore, not suited for dating temperate glaciers. 210Pb is also transported with water and displaced from its original deposition. However, despite large fluctuations, the specific activity of 210Pb decreases with depth, and can be used to estimate accumulation rates and the age of the ice. The average annual accumulation rate amounts to about 80 cm water equivalent, and the deepest sample (81 m i.e. ab. 65 m w. e.) was deposited in the beginning of this century. These results agree with data obtained from other observations on this glacier and show that the 210Pb_method is suitable to date temperate glaciers, if the ice cores cover a time interval of about 100 years (i.e. ab. 4 half-lives of 210Pb). The surface activity of 210Pb was found to be 5 ± 1 dpm per kg of ice in agreement with other locations in the Alps and with measurements of fresh snow.

Barents and Kara Seas oceanographic data base (BarKode)

Oceanographic data collected by ocean research organisations in Russia, the USA, the United Kingdom, Germany, Norway, and Poland for the Barents, Kara and White Seas region are presented in this atlas. Recently declassified naval data from Norway, the USA, and the UK are also included. More than 1,000,000 oceanographic stations containing temperature and/or sea-water salinity data were originally selected. After correcting errors and eliminating duplicates, data from 206,300 checked stations were placed on CD-ROM, together with many figures describing the characteristics of both the single-input and combined data set. In addition, temperature and salinity measurements were interpolated to the following standard horizons: 0, 25, 50, 100, 150, 200, 250, 300 m, and bottom. This atlas covers the 100-year period 1898 to 1998 and is, to date, the most complete oceanographic data collection for these Arctic shelf seas. This data set is complemented by more than 9,000 measurements of sea surface temperature, which were recently digitized from ships' logbooks. They cover the same geographical area within the time period 1867-1912.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Drained thaw-lake basin soil characteristics of cores from Barrow, Alaska

Arctic soils contain a large fraction of Earth's stored carbon. Temperature increases in the Arctic may enhance decomposition of this stored carbon, shifting the role of Arctic soils from a net sink to a new source of atmospheric CO2. Predicting the impact of Arctic warming on soil carbon reserves requires knowledge of the composition of the stored organic matter. Here, we employ solid state 13C nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared-photoacoustic spectroscopy (FTIR-PAS) to investigate the chemical composition of soil organic matter collected from drained thaw-lake basins ranging in age from 0 to 5500 years before present (y BP). The 13C NMR and FTIR-PAS data were largely congruent. Surface horizons contain relatively large amounts of O-alkyl carbon, suggesting that the soil organic matter is rich in labile constituents. Soil organic matter decreases with depth with the relative amounts of O-alkyl carbon decreasing and aromatic carbon increasing. These data indicate that lower horizons are in a more advanced stage of decomposition than upper horizons. Nonetheless, a substantial fraction of carbon in lower horizons, even for ancient thaw-lake basins (2000-5500 y BP), is present as O-alkyl carbon reflecting the preservation of intrinsically labile organic matter constituents. Climate change-induced increases in the depth of the soil active layer are expected to accelerate the depletion of this carbon.

Isotopic ratios, concentration of noble gases and mineral and bulk composition of extraterrestrial dust particles in Dome Fuji ice core, East Antarctica

Two silicate-rich dust layers were found in the Dome Fuji ice core in East Antarctica, at Marine Isotope Stages 12 and 13. Morphologies, textures, and chemical compositions of constituent particles reveal that they are high-temperature melting products and are of extraterrestrial origin. Because similar layers were found ~2000 km east of Dome Fuji, at EPICA (European Project for Ice Coring in Antarctica)-Dome C, particles must have rained down over a wide area 434 and 481 ka. The strewn fields occurred over an area of at least 3 × 10**6 km**2. Chemical compositions of constituent phases and oxygen isotopic composition of olivines suggest that the upper dust layer was produced by a high-temperature interaction between silicate-rich melt and water vapor due to an impact explosion or an aerial burst of a chondritic meteoroid on the inland East Antarctic ice sheet. An estimated total mass of the impactor, on the basis of particle flux and distribution area, is at least 3 × 10**9 kg. A possible parent material of the lower dust layer is a fragment of friable primitive asteroid or comet. A hypervelocity impact of asteroidal/cometary material on the upper atmosphere and an explosion might have produced aggregates of sub-µm to µm-sized spherules. Total mass of the parent material of the lower layer must exceed 1 × 10**9 kg. The two extraterrestrial horizons, each a few millimeters in thickness, represent regional or global meteoritic events not identified previously in the Southern Hemisphere.

Age determination of sediment cores from the northern Mid-Atlantic Ridge

We construct age models for a suite of cores from the northeast Atlantic Ocean by means of accelerator mass spectrometer dating of a key core, BOFS 5K, and correlation with the rest of the suite. The effects of bioturbation and foraminiferal species abundance gradients upon the age record are modeled using a simple equation. The degree of bioturbation is estimated by comparing modeled profiles with dispersal of the Vedde Ash layer in core 5K, and we find a mixing depth of roughly 8 cm for sand-sized material. Using this value, we estimate that age offsets between unbioturbated sediment and some foraminifera species after mixing may be up to 2500 years, with lesser effect on fine carbonate (< 10 µm) ages. The bioturbation model illustrates problems associated with the dating of 'instantaneous' events such as ash layers and the 'Heinrich' peaks of ice-rafted detritus. Correlations between core 5K and the other cores from the BOFS suite are made on the basis of similarities in the downcore profiles of oxygen and carbon isotopes, magnetic susceptibility, water and carbonate content, and via marker horizons in X radiographs and ash beds.

Composition of Fe-Mn micronodules, nodules and host bottom sediments from the Northeast Pacific Basin

Authigenic ferromanganese manifestations in bottom sediments from two horizons (0-10 and 240-250 cm) located in the low/high bioproductive transitional zone of the Pacific Ocean were studied. In addition two compositionally different types of micronodules, crusts and ferromanganese nodules were detected in the surface horizon (0-1 cm). Three size fractions (50-100, 100-250, and 250-500 µm) of manganese micronodules were investigated. In terms of surface morphology, color, and shape, the micronodules are divided into dull round (MN1) and angular lustrous (MN2) varieties with different mineral and chemical compositions. MN1 are enriched in Mn and depleted in Fe as compared with MN2. Mn/Fe ratio in MN1 varies from 13 to 14. Asbolane-buserite and birnessite are the major manganese minerals in them. MN2 is mainly composed of vernadite with Mn/Fe ratio from 4.3 to 4.8. Relative to MN1, fraction 50-100 µm of MN2 is enriched in Fe (2.6 times), W (1.8), Mo (3.2), Th (2.3), Ce (5.8), and REE (from 1.2 to 1.8). Relative to counterparts from MN1, separate fractions of MN2 are characterized by greater compositional difference. For example, increase in size of micronodules leads to decrease in contents of Fe (by 10 rel. %), Ce (2 times), W (2.1 times), Mo (2.2 times), and Co (1.5 times). At the same time one can see increase in contents of other elements: Th and Cu (2.1 times), Ni (1.9 times), and REE (from 1.2 to 1.6 times). Differences in chemical and mineral compositions of MN1 and MN2 fractions can be related to alternation of oxidative and suboxidative conditions in the sediments owing to input of labile organic matter, which acts as the major reducer, and allochthonous genesis of MN2.

Distribution of polycyclic aromatic hydrocarbons in eolian and eolian-deluvial sediments from the North Iceland

This work considers results of a study of Holocene cover sediments in Iceland. They are largely composed of wind-transported palagonitized hyaloclastite particles and coeval horizons of acid and basic tephras. It is established that polyciclic aromatic hydrocarbons (PAH) are released from basaltic glass in natural environments only in case of intense physicochemical alteration and destruction of its structure. This process does not influence PAH composition and their quantitative proportions. No new PAH formed during several thousands of years in Holocene section. Hydrocarbons are transferred from fixed state in basaltic glass into free state in palagonites practically without any changes. PAH were mainly redeposited by winds, derived together with palagonite from weathered hyaloclastites, and precipitated from atmosphere with tephra during eruptions.

Sediment wave layer summary in ODP Site 172-1062

Abyssal mud waves (or fine-grained sediment waves) are often cited as evidence for deep current activity because subbottom profiles show that the wave form has migrated with time. The migration history of a fine-grained sediment wave on the Blake-Bahama Outer Ridge (ODP Site 1062) has been studied through the analysis of multiple ODP holes spaced across the wave. Additional information about wave migration patterns comes from 3.5-kHz records and watergun seismic profiles. These data suggest that wave migration has varied during the last not, vert, similar ~10 Myr, although the only sediments sampled are younger than 4.8 Ma. Seismic profiles suggest wave migration was initiated about 8-10 Ma, and wave migration was pronounced from about 5 Ma to about 1 Ma (with an episode of wave reorganization about 4.5 Ma). Analysis of ODP cores suggests that migration rates have been somewhat lower and more variable during the last 1 Myr. Intervals of no wave migration are observed for several time intervals and appear to characterize deglaciations, especially during the last 500 kyr. Comparisons between seismic profiles and the core record show that most of the seismic horizons correlate closely with time horizons, and thus that the seismic profiles give a reasonable representation of sediment wave migration. Models suggest that wave migration is more pronounced during periods of higher bottom current flow and less pronounced during periods of lower current flow. Thus the migration record is consistent with generally higher bottom flow speeds at this site prior to 1 Ma and lower bottom flow speeds after 1 Ma. The Mid-Pleistocene Transition from a dominant climatic periodicity of 40 kyr to a dominant climatic periodicity of 100 kyr starts at about this time, suggesting an overall reduction in bottom flow speed at this site coincident with changing climate patterns. These changes in flow speed could be related to changes in the depth of the Western Boundary Undercurrent as well as to changes in the speed of thermohaline circulation.

Rare earth and other element contents and speciations in samples from Core AKO26-35, Pacific Ocean, Southwest Basin

Ferromanganese micro- and macronodules in eupelagic clays at Site AKO26-35 in the Southwest Pacific Basin were studied in order to check REE distribution during ferromanganese ore formation in non-productive zones of the Pacific Ocean. Host sediments and their labile fraction, ferromanganese micronodules (in size fractions 50-100, 100-250, 250-500, and >500 ?m) from eupelagic clays (horizons 37-10, 105-110, 165-175, and 189-190 cm), and buried ferromanganese micronodules (horizons 64-68, 158-159, and 165-166 cm) were under study. Based on partition analysis data anomalous REE enrichment in eupelagic clays from Site AKO26-35 is related to accumulation of rare earth elements in iron hydroxophosphates. Concentration of Ce generally bound with manganese oxyhydroxides is governed by oxidation of Mn and Ce in ocean surface waters. Micronodules (with Mn/Fe from 0.7 to 1.6) inherit compositional features of the labile fraction of bottom sediments. Concentrations of Ce, Co, and Th depend on micronodule sizes. Enrichment of micronodules in hydrogenic or hydrothermal matter is governed by their sizes and by a dominant source of suspended oxyhydroxide material. The study of buried ferromanganese micronodules revealed general regularities in compositional evolution of oxyhydroxide matrices of ferromanganese micro- and macronodules. Compositional variation of micro- and macronodules relative to the labile fraction of sediments in the Pacific non-productive zone dramatically differs from the pattern in bioproductive zones where micronodule compositions in coarser fractions are similar to those in associated macronodules and labile fractions of host sediments due to more intense suboxidative diagenesis.

Chemical element concentrations in sediments from DSDP Holes 60-458 and 60-459

The development of laser ablation-inductively coupled plasma-mass spectrometry has revolutionized the analysis of tephras by providing (1) an efficient and precise method for determining abundances of a wide variety of trace elements at low concentrations in individual glass shards and (2) assessment of geochemical heterogeneities within individual ash horizons. This development is important for petrogenetic studies of intraoceanic arc systems, where tephras provide the most complete temporal record of magmatism. Results from the Izu-Bonin and Mariana arc systems indicate that despite close geographical proximity and similar tectonic evolution, they contrast strongly in terms of geochemical evolution since 35 Ma. Whereas the Mariana tephras have exceptional compositional diversity, ranging from low-K (Oligocene), to high-K (Miocene), and subsequently medium-K compositions (Pliocene-Quaternary), the Izu-Bonin arc has been dominated by low-K compositions throughout. The Mariana increases in K are paralleled by increases in abundances of incompatible trace elements and by increased values of diagnostic ratios (e.g., Nb/yb and Th/yb) regarded as monitors of potential mantle-source fertility. The relative uniformity of Nb/yb and Nb/Zr ratios in Izu-Bonin tephras indicates that cyclic processes of backarc basin development and mantle depletion do not necessarily induce large-scale temporal geochemical variations in the associated arc. Temporal variability within the Mariana arc, and its divergence from the Izu-Bonin arc ca. 13 Ma, can be traced to a major injection of subducted sediment in the Mariana system at this time.

Diatom abundance in middle-to-late Pleistocene sediments of IODP Site 303-U1304

We examined diatom assemblages in a series of remarkable laminated diatomaceous ooze (LDO) horizons in the marine sediments from Integrated Ocean Drilling Program (IODP) Site U1304 to reconstruct the middle-to-late Pleistocene paleoceanographic evolution of the northern North Atlantic Ocean. Four confirmed diatom biohorizons combined with calcareous nannofossil and paleomagnetic stratigraphies established the chronological framework for the material. The planktonic, araphid, needle-like species Thalassiothrix longissima was the greatest contributor to the LDO facies. From the results of a principal component analysis using the percent abundances of 65 significant (p = 5%) diatom taxa, except for Tx. longissima, which was extremely dominant in almost all horizons observed, we identified two principal component (PC) axes. Taxa probably associated with the stratigraphic distribution of the major zonal marker Neodenticula seminae (ranging from 1.26 to 0.84 Ma in this ocean) loaded on PC1 with a high value. PC2 was related to the ocean surface temperature. The stratigraphic variability of the PC2 score indicated that switching between warm- and cold-water assemblages occurred concurrently with LDO deposition (or extreme Tx. longissima dominance) episodes in several horizons (particularly after 0.84 Ma), suggesting that the Subarctic Convergence (SAC) oceanic front passed over Site U1304 during Pleistocene glacial/interglacial cycles. Our floral evidence supports the model of nearly monospecific LDO formation caused by the enhanced physical accumulation of particular diatoms such as Tx. longissima. On the other hand, Nd. seminae, which probably contributes to spring phytoplankton blooms in the modern ocean, was present only between 1.26 and 0.84 Ma in this area. Thus, we infer that the main contributor of export flux in the regional annual primary production cycle would have shifted drastically from one of a spring phytoplankton bloom leader (Nd. seminae) to minor but mass dump assemblages (Tx. longissima etc.) in the mid-Pleistocene.

Chronostratigraphy of sediments from the Bahamas

Continuous cores drilled during the Bahamas Drilling Project (BDP) and the Ocean Drilling Program (ODP) Leg 166 along a transect from the top of Great Bahama Bank to the basin in the Straits of Florida provide a unique data set to test the assumption in seismic stratigraphy that seismic reflections are time lines and, thus, have a chronostratigraphic significance. Seismic reflections that are identified as seismic sequence boundaries (SSBs) were dated by means of biostratigraphy in the five ODP sites and by a combination of biostratigraphy, magnetostratigraphy and Sr isotope stratigraphy in the two BDP sites. The seismic reflection horizons are carried across a variety of facies belts from shallow-water carbonates over slope carbonates to drift deposits in the Straits of Florida. Within this system 17 SSBs were identified and dated. Despite the fact that the seismic reflections cross several facies belts, their ages remain remarkably constant. The average offset in all sites is 0.38 Myr. In no cases do the seismic reflections cut across time lines. The age differences are the combined result of the biostratigraphic sampling frequency, the spacing of marker species that required extrapolation of ages, and the resolution of the seismic data. In addition, uncertainties of age determination in the proximal sites where age-diagnostic fauna are rare add to the age differences between sites. Therefore, it can be concluded that the seismic reflections, which mark the SSBs along the Bahamas Transect, are time lines and can be used as stratigraphic markers. This finding implies that depositional surfaces are preferentially imaged by reflected seismic waves and that an impedance contrast exists across these surfaces. Facies successions across the sequence boundaries indicate that the sequence boundaries coincide with the change of deposition from times of high to low sea level. In the carbonate setting of Great Bahama Bank, sea-level changes produce changes in sediment composition, sedimentation rate and diagenesis from the platform top to the basin. The combination of these factors generates differences in sonic velocity and, thus, in impedance that cause the seismic reflection. The impedance contrasts decrease from the proximal to the distal sites, which is reflected in the seismic data by a decrease of the seismic amplitude in the basinal area.