Composition of hardgrounds and of pore-water parameters in ODP Holes 166-1008 and 166-1009

Mineralogic, petrographic, and geochemical analyses of sediments recovered from two Leg 166 Ocean Drilling Program cores on the western slope of Great Bahama Bank (308 m and 437 m water depth) are used to characterize early marine diagenesis of these shallow-water, periplatform carbonates. The most pronounced diagenetic products are well-lithified intervals found almost exclusively in glacial lowstand deposits and interpreted to have formed at or near the seafloor (i.e., hardgrounds). Hardground cements are composed of high-Mg calcite (~14 mol% MgCO3), and exhibit textures typically associated with seafloor cementation. Geochemically, hardgrounds are characterized by increased d18O and Mg contents and decreased d13C, Sr, and Na contents relative to their less lithified counterparts. Despite being deposited in shallow waters that are supersaturated with the common carbonate minerals, it is clear that these sediments are also undergoing shallow subsurface diagenesis. Calculation of saturation states shows that pore waters become undersaturated with aragonite within the upper 10 m at both sites. Dissolution, and likely recrystallization, of metastable carbonates is manifested by increases in interstitial water Sr and Sr/Ca profiles with depth. We infer that the reduction in mineral saturation states and subsequent dissolution are being driven by the oxidation of organic matter in this Fe-poor carbonate system. Precipitation of burial diagenetic phases is indicated by the down-core appearance of dolomite and corresponding decrease in interstitial water Mg, and the presence of low-Mg calcite cements observed in scanning electron microscope photomicrographs.

Mineral, chemical and isotopic compositions of hydrothermally altered sediments from the Middle Valley (Juan de Fuca Ridge), ODP Site 139-858

Li and Li isotopes have been measured in the clay fraction of sediments recovered from the Middle Valley hydrothermal site on the Juan De Fuca Ridge. The Li content of pure detrital clays is 51 ppm while hydrothermal clays and carbonates have lower Li (22+/-11 ppm). However, there is no clear relationship between the mineralogy of the hydrothermal alteration products and their Li content. The d7Li value of the detrital clays is +5.8?. Hydrothermal clays and carbonates have d7Li in the range of -3.9? to +7.8?; these values do not seem to be dependent on the temperature at which they formed. Modelling of the Li and Li isotope systematics indicates that the fluid from which the alteration products form is significantly enriched in Li (higher than 10000 µmol/kg) relative to pore fluids recovered from within the sediments (up to 589 µmol/kg; [Wheat, C.G., M.J. Mottl, 1994. Data report: trace metal composition of pore water from Sites 855 through 858, Middle valley, Juan De Fuca Ridge. In Mottl, M.J., Davis, E.E., Fisher, A.T., Slack, J.F. (Eds.), Proc. ODP, Sci. Res. 139: 749-755; doi:10.2973/odp.proc.sr.139.269.1994]), and that this Li is derived from sediment. Thus, the alteration products are not in equilibrium with their conjugate pore fluids; rather, the alteration minerals formed at lower water/sediment ratios. This suggests that fluid flow pathways at Middle Valley were more diffuse in the past than they are today.

Chemical and mineral compositions of bottom sediments from the East Pacific Rise near 13°N

During underwater photography and sampling of the rift valley bottom in the axial part of the East Pacific Rise, where water transparency is reduced due to hydrothermal input, ore manifestations have been found. The bottom is covered by them as by a jacket on both sides from the EPR axial zone. However, exposed pillow-lavas and clumpy blocks in rift ledges are covered by a thin metal-bearing film. It is supposed that sedimentation results mainly from hydrothermal input of dissolved chemical elements in seawater, their transformation on the geochemical barrier, and subsequent deposition as particulates. Contents of ore components in metalliferous sediments have been measured by atomic-absorption and X-ray radiometry methods. Sediment age has been determined as Middle Pleistocene - Holocene. Maximal hydrothermal activity was at the beginning of Early Holocene, about 10 Ka. A smoker has been found on the western slope of the rift valley.

Diffusion transport of water in basalts

Studying diffusive transport in porous rocks is of fundamental importance in understanding a variety of geochemical processes including: element transfer, primary mineral dissolution kinetics and precipitation of secondary phases. Here we report new findings on the relationship between diffusive transport and textural characteristics of the pore systems on the example of mid-oceanic ridge basalts having different degree of alteration but very similar bulk pore volume. Diffusion processes in porous basalts were studied in situ using H2O -> D2O exchange experiments. The effective diffusion coefficients of water molecules increase systematically from 5.05*10**-11 to 1.19*10**-10 m**2/s for fresh and moderately altered basalts and from 2.40*10**-11 to 6.72*10**-11 m**2/s for completely altered basalt as temperature increases from 5 to 50 °C. The activation energy of the diffusion process increases from 12.29 ± 0.71 kJ/mol for fresh and moderately altered basalts to 14.3 ± 1.33 kJ/mol for completely altered basalt. The results indicate that neither the bulk porosity nor the degree of alteration can be used as proxies for the efficiency of element transport during MORB-water interaction. The formation of secondary phases that replace primary minerals and fill the pore space in the rock leads to the formation of tiny pores and phases with large specific surface area. These factors might have a dominant control on the transport properties of altered basaltic rocks.

Mineral and oxygen isotopic compositions in a profile through the altered lower oceanic crust, ODP Hole 176-735B

ODP Hole 735B located on the Southwest Indian Ridge at 57°E is an in situ sampled long, continuous section of lower oceanic crust. Oxygen isotope compositions of constituent minerals of Leg 176 gabbros have been measured by UV-laser oxygen isotope microprobe. Together with existing data from Leg 118, a complete oxygen isotope profile through the lower oceanic crust has been obtained. Most clinopyroxenes and olivines have normal mantle values of ~5.5 per mil and ~5.2 per mil, respectively, while plagioclases show slight d18O enrichment relative to its mantle value of 6.1per mil. Down-hole variations of Hole 735B gabbro indicate a downward decreasing d18O profile, with a kink at a depth of about 800 m below sea floor. Above this depth, gabbros are depleted in 18O relative to unaltered basalts, while below ~800 m they show nearly unmodified d18O values. Abundant seawater penetration appears to be limited to the upper part of the lower crust at ODP site 735 (~800 m into the gabbroic layer and ~2-2.5 km into the oceanic crust from the top of pillow basalts). Mass balance calculations show that the lower crust formed under this ultra-slow-spreading ridge has an average d18O value of 5.5 per mil. The whole crust at Site 735 has an overall 18O enrichment with d18O values of 6.0 per mil to 7.8 per mil, depending on the possible variation of the d18O values of the upper pillow basalts and sheeted dykes. The apparent difference in oxygen isotope compositions of ocean crusts formed with different spreading rates has important implications on the buffering of ocean water over geological time, as well as on the oxygen recycling between crust and mantle through subduction. The difference of seawater penetration between fast- and slow-spreading ridges could be related to their particular magmatic-tectonic history during the formation and aging of the crust. However, more analyses on continuous sections through oceanic and ophiolitic crust in different tectonic settings are required to derive any predictive models.

Biogenic and mineral composition and foraminiferal stratigraphy of sediment cores obtained in northern Germany

The Ratekau boring ended in clays of the so-called Asterigerina-Zone; these clays have shallow-water features in the uppermost samples. The clays are overlain by deep-water clays with pteropods; this formation is split into two parts by a shallow-water deposit. The fossiliferous series ends upward in sandy deposits with shallow-water fossils. The question is raised whether the two deep-water deposits might correspond to the Lower Doberg Beds (Eochattian) and the Upper Doberg Beds (Neochattian) at the Doberg hill, closer to the rim of the basin. All fossiliferous samples from this boring are thought to be of Late Oligocene age; the boundary towards the Middle Oligocene, however, could not be ascertained. The Vaale boring ended in rather typical Septaria clay of the Middle Oligocene. This clay is capped by some metres of unfossiliferous glauconite clays, which in turn are overlain by silts and silty clays with planktonic fossils identical to those found at Dingden locality. These deposits are tentatively dated as Early Miocene. The next higher series of samples consists of sands and clays deposited in shallower waters. They contain a rich fauna of benthic molluscs, which, according to the current notion in stratigraphy, would have a Reinbek Age. In addition, they contain a set of planktonic fossils which differs from the 'Lower Miocene' assemblages. These sands and clays are overlain by a thick series of marine sands very poor in fossils. Finally, four metres of clay with foraminifera, having Younger Miocene affinities, form the top of the fossiliferous sequence. The borings at Wulksfelde and Langenhorn were not far apart and their sediments are easily correlated. Both wells start below in continental 'Lignite Sands' and contain overlying shallow water sands and clays. These yielded Hemmoor benthic mollusca, supposed to indicate Lower Miocene in the relevant literature; however, we encountered their planktonic foraminifera in the uppermost Miocene as well. The same planktonic species were found in all samples of both borings. These deposits under discussion furthermore contain a particular pteropod species. They are overlain by a thick series of gypsiferous clays, with scarce fossils. The uppermost fossiliferous clays (probably Langenfelde Age) contain another pteropod species, not met with in other samples. The discrepancies between the plankton zonation and the traditional subdivision according to benthic molluscs in the borings of Vaale, Wulksfelde and Langenhorn (and in samples from Twistringen, Dingden and Antwerp localities as well) renders the time-stratigraphic value of the denominations Reinbek and Hemmoor rather doubtful. The samples of the Westerland boring can be placed in the Gram and Sylt stages of local chronostratigraphy on the strength of the Astarte series established by HINSCH. The Gram samples contain a typical pteropod species; both groups of samples contain the same planktonic foraminifera as the borings Wulksfelde and Langenhorn. Our material did not bring the problem of the Miocene-Pliocene boundary in this region any closer to a solution. In conclusion, it can be claimed that this investigation provides strong arguments that the usual recognition of Hemmoor and Reinbek does not correspond to well-defined chronostratigraphical units. A better chronostratigraphic subdivision has to be based on the examination of many more samples, and on a better understanding of the paleoecology of the fossils involved.

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.

Physical properties, mineral and chemical compositions, and accumulation rates of Holocene and Upper Pleistocene bottom sediments from the Sea of Okhotsk

Mineral and chemical compositions and physical properties of diatomaceous clayey-siliceous sediments from the Sea of Okhotsk are studied. Accumulation rates of silica are determined. Their compositional model based on silica content is similar to that of Late Jurassic and Olenekian-Middle Anisian cherts from the Sikhote Alin region. Thickness of Holocene siliceous unit and accumulation rates of siliceous deposits depended on bioproductivity in the upper water layer and seafloor topography. Accumulation rates of amorphous SiO2 (0.05-5.7 g/cm**2/ka) and free SiO2 (0.5-11.6 g/cm**2/ka) are minimal on seamounts and maximal in depressions near foothills. These values match accumulation rates of free SiO2 in Triassic and Late Jurassic basins of the Sikhote Alin region (0.33-3 g/cm**2/ka). Comparison of composition and accumulation rates of silica shows that Triassic and Late Jurassic siliceous sequences of Sikhote Alin could accumulate in a marginal marine basin near a continent.

Sediment geochemistry and water trace metal concentration in Potter Cove

Recent rapid climate warming at the western Antarctic Peninsula (WAP) results in elevated glacial melting, enhanced sedimentary run-off, increased turbidity and impact of ice-scouring in shallow coastal areas. Discharge of mineral suspension from volcanic bedrock ablation and chronic physical disturbance is expected to influence sessile filter feeders such as the Antarctic soft shell clam Laternula elliptica ( King and Broderip, 1832). We investigated effects of sedimentary run-off on the accumulation of trace metals, and together with physical disturbance, the cumulative effect on oxidative stress parameters in younger and older L. elliptica from two stations in Potter Cove (King George Island, Antarctica) which are distinctly impacted by turbidity and ice-scouring. Fe, Mn, Sr, V and Zn concentrations were slightly higher in sediments of the station receiving more sediment run-off, but not enriched in bivalves of this station. The only element that increased in bivalves experimentally exposed to sediment suspension for 28 days was Mn. Concentration of the waste accumulation biomarker lipofuscin in nervous tissue was higher in L. elliptica from the "exposed" compared to the "less exposed" site, whereas protein carbonyl levels in bivalve mantle tissue were higher at the less sediment impacted site. Tissue metal content and lipofuscin in nervous tissue were generally higher in older compared to younger individuals from both field stations. We conclude that elevated sediment ablation does not per se result in higher metal accumulation in L. elliptica. Instead of direct absorbance from sediment particles, metal accumulation in gills seems to indicate uptake of compounds dissolved in the water column, whereas metals in digestive gland appear to originate from enriched planktonic or detritic food. Accumulation of cellular waste products and potentially reactive metals over lifetime presumably alters L. elliptica physiological performance with age and may contribute to higher stress susceptibility in older animals.

Mineral quantification of a Jordan Cretaceous outcrop (Section GM3, Ghawr Al Mazar, Ghor al Mazrar)

Cyclic fluctuations in global sea level during epochs of warm greenhouse climate have remained enigmatic, because absence or subordinate presence of polar ice during these periods precludes an explanation by glacio-eustatic forcing. An alternative concept suggests that the water-bearing potential of groundwater aquifers is equal to that of ice caps and that changes in the dynamic balance of aquifer charge versus discharge, as a function of the temperature-related intensity of the hydrological cycle, may have driven eustasy during warm climates. However, this idea has long been neglected for two reasons: 1) the large storage potential of subsurface aquifers was confused with the much smaller capacity of rivers and lakes and 2) empirical data were missing that document past variations in the hydrological cycle in relation to eustasy. In the present study we present the first empirical evidence for changes in precipitation, continental weathering intensity and evaporation that correlate with astronomically (long obliquity) forced sea-level cycles during the warmest period of the Cretaceous (Cenomanian-Turonian). We compare sequence-stratigraphic data with changes in the terrigenous mineral assemblage in a low-latitude marine sedimentary sequence from the equatorial humid belt at the South-Tethyan margin (Levant carbonate platform, Jordan), thereby avoiding uncertainties from land-ocean correlations. Our data indicate covariance between cycles in weathering and sea level: predominantly chemical weathering under wet climate conditions is reflected by dominance of weathering products (clays) in deposits that represent sea-level fall (aquifer charge > discharge). Conversely, preservation of weathering-sensitive minerals (feldspars, epidote and pyroxenes) in transgressive sediments reflects decreased continental weathering due to dryer climate (aquifer discharge > charge). Based on our results we suggest that aquifer-eustasy represents a viable alternative to glacio-eustasy as a driver of cyclic 3rd-order sea-level fluctuations during the middle Cretaceous greenhouse climate, and it may have been a pervasive process throughout Earth history.

Geochemistry of primary and secondary mineral phases in ODP Leg 209 sediments

Primary and secondary mineral phases from Holes 1268A (11 samples), 1272A (9 samples), and 1274A (12 samples) were analyzed by electron microprobe in Bonn and Cologne (Germany). Bulk rock powders of these samples were also analyzed geochemically, including major and trace elements (Paulick et al., 2006, doi:10.1016/j.chemgeo.2006.04.011). Ocean Drilling Program (ODP) Leg 209 Holes 1268A, 1272A, and 1274A differ remarkably in alteration intensity and mineralogy, and details regarding their lithologic characteristics are presented in Bach et al. (2004, doi:10.1029/2004GC000744) and Shipboard Scientific Party (2004, doi:10.2973/odp.proc.ir.209.101.2004). Because of the least altered character of peridotite in Hole 1274A, abundant clinopyroxene, orthopyroxene, olivine, and spinel were analyzed at this site. In Hole 1272A, primary silicates are rare and analyses were restricted to some samples that contain traces of olivine and orthopyroxene. Because of the intensity of alteration, Hole 1268A is devoid of primary phases except spinel. Commonly, alteration is pseudomorphic and serpentinization of olivine and orthopyroxene can be distinguished. Accordingly, compositional variations of the alteration minerals with regard to the precursor minerals are one of the issues investigated in this data report.

Chemical and mineral compositions of bottom sediments from the Sea of Japan

Physical properties (water content, bulk density, magnetic susceptibility, natural remanent magnetization, nature of magnetization, and composition of ferromagnetic fraction), chemical, and (optionally) mineral composition of bottom sediments from the north-west Sea of Japan have been studied. Their stratigraphic subdivision based on composition of diatoms has been carried out. Obtained data have allowed to find out some aspects of influence of paleogeographic conditions and diagenetic processes on change of physical properties of the sediments, as well as on their composition in Holocene and Late Pleistocene.