(Table 1) Mineralogy of DSDP Leg 65 sediments

During Leg 65, four sites were drilled near the mouth of the Gulf of California where high sedimentation rates made it possible to sample young oceanic crust near the ridge crest. The oldest sediments cored were upper Pliocene siltstones (Site 483); the samples at the other sites (482, 484, and 485) were all Quaternary in age. A series of 80 sediment samples, most of them hemipelagic clays, were examined by semiquantitative X-ray diffraction and Carbonate Bomb techniques to determine their mineralogy and carbonate contents. The results of this study may be used to determine their provenance and diagenesis.

Mössbauer study at DSDP Hole 95-612

57Fe Mössbauer spectra of 15 oceanic sediment samples collected from Site 612 (Deep Sea Drilling Project Leg 95) were recorded. These spectra showed that most of the iron in the sediments was present as high-spin, paramagnetic Fe2+ and Fe3+. The ferrous iron was mainly distributed in terrigenous clays and biogenic carbonates. The variation of the Mössbauer parameters for Fe2+ with sub-bottom depth suggests that the main Fe2+-bearing component changed with geologic time. The amount of iron in each iron-bearing phase as estimated from the corresponding peak areas in the spectra also changed with depth. These variations in the Mössbauer parameters and peak areas are correlated with lithologic changes in the sediment column.

(Table 2) Geochemistry at DSDP Holes 62-464 and 62-465A

Igneous rocks were recovered from three sites on Hess Rise during Deep Sea Drilling Project Leg 62: altered basalt at Site 464, at the northern end of Hess Rise; and altered trachyte from Site 465, and rounded basalt pebbles in upper Albian to middle Miocene sediments from Site 466, both at the southern end of Hess Rise. Major-, minor-, and trace-element data for basalt from Hole 464 are consistent with these rocks being transitional tholeiites that have undergone low-temperature alteration by reaction with sea water. Trachyte from Hole 465A exhibits as many as three generations of plagioclase along with potash feldspar that are flow aligned in groundmasses alterted to smectites and random mixed-layer clays. Textural evidence indicates that these rocks were eruped subaerially. Chemical data show a range of values when plotted on two- and three-component variation diagrams. The observed variations may result in part from differentiation, but they also reflect the high degree of alteration. Several oxides and elements show strong correlation with H2O+: K2O, SiO2, Rb and Lu decrease and MgO increases with increasing H2O+. These trends, except for that of Lu, are consistent with experimentally determined changes in chemistry that accompany alteration. The trend for Lu has not been previously reported; it may result from a more-intense alteration of the HREE-rich mafic minerals than of the LREE-rich feldspars. Despite their alteration, the trachytes compare favorably with alkalic differentiates from oceanic islands. We interpret Hess Rise as a volcanic platform formed by eruption of off-ridge volcanic rocks onto MORB oceanic crust during the Aptian and Albian stages, after the basement had migrated away from the spreading center. By analogy with present oceanic islands, we propose that early tholeiitic basalts were followed by alkalic basalts and their differentiation products (trachytes), producing a volcanic archipelago of islands and seamounts. Subsequent tectonism and subsidence led to the present state of Hess Rise.

(Table 2) Uranium and thorium isotopic composition, activity ratios and ages of bivalvia shells in sediment core GIK14350, northern Germany

A new chemical procedure for cleaning marine carbonates was applied to remove detritus as well as metaloxide contaminations of marine shells from Eemian deposits and adjoining succession of a sediment core from Dagebüll, Schleswig- Holstein. Hence, one can significantly reduce the contamination with detrital uranium and thorium. Thermal ionisation mass spectrometry was applied to determine the uranium and thorium activities used for 230Th/U dating of these shells. At least ten samples of marine bivalves of five different core sections were analysed. Samples located below a five meter thick clay layer at 19-24 m yielded an average age of 132±18 ka. Shells located above the clays at 15-20 m depth were strongly influenced by percolating groundwaters of an open system. Therefore, a reliable dating of these samples was not possible.

(Table 1) Clay minerals at DSDP Hole 93-603B

Cretaceous sediments encountered in Hole 603B contain a 17 Å smectite as the principal clay mineral, with lesser amounts of illite, kaolinite, and randomly interstratified illite/smectite (I/S). No evidence of smectite to I/S transformation with depth is seen in the interval between 1040 and 1570 m below the sediment surface. Although the presence of some volcanic ash suggests a volcanic origin for the smectite, the nature of associated organic matter together with prevailing sedimentological models for Cretaceous sedimentation on the lower continental rise argue more strongly for a dominantly terrestrial origin for the clays.

Eolian mass-accumulation rates and grain size at DSDP Sites 86-576 and 86-578

The mass-accumulation rate and grain size of the total eolian component of North Pacific pelagic clays at Deep Sea Drilling Project Sites 576 and 578 have been used to evaluate changes in eolian sedimentation and the intensity of atmospheric circulation that have occurred during the past 70 m.y. Eolian deposition, an indicator of source area aridity, was low in the Paleocene, Eocene, and Oligocene, apparently reflecting the humid environments of that time as well as the lack of glacial erosion products. A general increase in eoiian accumulation in the Miocene apparently reflects the relative increase in global aridity during the latter part of the Cenozoic. A dramatic increase in eolian accumulation rates in the Pliocene reflects the increased aridity and availability of glacial erosion products associated with Northern Hemisphere glaciation 2.5 m.y. ago. Eolian grain size, an indicator of wind intensity, suggests that Late Cretaceous wind strength was comparable to present-day wind strength. A sharp decrease in eolian grain size across the Paleocene/Eocene boundary is not readily interpreted, but may indicate a significant reduction in the intensity of atmospheric circulation at that time. Fine eolian grain size and low accumulation rates in the Eocene and early Oligocene are in agreement with low early Tertiary thermal gradients and less vigorous atmospheric circulation. Large increases in grain size during the Oligocene, mid-to-late Miocene, and Pliocene appear to be a response to steepening thermal gradients resulting from increasing polar isolation.

Grain sizes, carbon content and clay minerals of sediments obtained from north Germany and the Baltic Sea

Clay mineralogy and geotechnical properties of Tarras clay, basin clays and tills from some parts of Schleswig-Holstein: Tarras clay of lower Eocene age, Quaternary till containing various admixtures of Tarras clay as well as basin clay and varve-clay from Schleswig-Holstein were investigated. Grain size distribution and soil mechanic characteristics were determined, which indicated different geotechnical properties for each sediment type.

(Table T1) Abundance of silicoflagellates in sediments of ODP Hole 199-1219A

Silicoflagellates ranging from middle Eocene to middle Miocene in age are present in Ocean Drilling Program Hole 1219A. The hole was drilled 250.8 meters below seafloor of which an ~120 m section primarily composed of nannofossil ooze with variable radiolarian and clay content is early Miocene and Oligocene in age, and a 95-m section is Eocene radiolarian and zeolithic clays, radiolarian and diatom oozes, and nannofossil oozes and chalks. A total of 150 samples were studied at a sample interval of one per section. Diversity of silicoflagellates is moderate, and the preservation is good. Abundance is generally low, with many samples barren of silicoflagellates, but 31 species and subspecies were identified. One new species, Naviculopsis trigeminus, is described.

Calcareous nannofossil stratigraphy and key biohorizons of ODP Leg 173 sites

Six sites were drilled on the southern Iberia Abyssal Plain during Ocean Drilling Program (ODP) Leg 173. Three holes (1067A, 1068A, and 1069A) recovered Eocene sediments consisting of thinly bedded turbidite deposits with interbedded hemipelagic sediments (Bouma sequence Te) deposited near the calcite compensation depth. The hemipelagic sediments are barren of nannofossils, necessitating the use of the turbidite deposits to erect an Eocene biostratigraphy for these holes. Moderately preserved, diverse assemblages of nannofossils were recovered from silty clays (Bouma sequence Td) and poorly preserved, less diverse assemblages were recovered from sandy/silty clays (Bouma sequence Tc). Hole 1067A has a continuous record of sedimentation (Subzones CP9a-CP14a) and Holes 1068A and 1069A have similar continuous records (Subzones CP9a-CP12a), although all holes contain barren intervals. Holes 1067A, 1068A, 1069A, 900A (ODP Leg 149), and 398D (Deep Sea Drilling Project Leg 47B) display a similar increase in mass accumulation rates in the lowermost middle Eocene. A reliable Eocene biostratigraphy has been erected using nannofossil data from turbidite sequences, allowing for correlation between Iberia Abyssal Plain sites.

Agglutinated benthic foraminifera of the Upper Cretaceous

A reexamination of the agglutinated benthic foraminiferal microfaunas found in the Upper Cretaceous red and brown clays of DSDP Hole 603B and ODP Holes 640A and 641A allows us to refine the initial shipboard biostratigraphic interpretation and to propose a fourfold zonation that can be used with some precautions in the oceanic realm. By means of various calibrations, an attempt is also made to integrate this zonation in a worldwide chronostratigraphic framework. The resulting chronologic control permits us to discern large differences in the rhythm of red clay deposition on either side of the North Atlantic Ocean.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

Ge/Si ratios in marine siliceous microfossils

A procedure is presented to separate diatoms and radiolaria from marine sediments and from each other, to purify them of elements associated with other phases, and to dissolve them to determine their elemental composition. The cleaning procedure eliminates artifacts due to the presence of detrital clays and the high sorption capacity of hydrated silica. The concentration of trace elements (Al, Fe, Mg, and Ba) that we find in alkaline dissolutions of clean diatoms are at least an order of magnitude lower than previously reported. The overall long-term precision in the determination of Ge/Si in a sub-standard of clean diatoms is ±0.024 * 10**-6 (1 sigma). Ge/Si measured in diatoms and radiolaria from core tops indicates that high-latitude Holocene diatoms accurately record the present-day oceanic Ge/Si, while radiolarian ratios are systematically lower and display more scatter. Evaluation of Ge/Si in diatoms and radiolaria from Hole DSDP 265 (Plio-Pleistocene) suggests that post-depositional alteration of the ratio does not occur at this site, but the average ratio carried by diatoms over this time interval was lower than that in the present ocean.

(Table 1) Carbohydrates in different sediment types of the Central Pacific

Total contents of carbohydrates were determined in samples of natural sediments of various genetic types. Analyses were made on board. Deep-sea pelagic sediments (red clays of various types including zeolite clays, and also radiolarian and carbonate oozes) were the main types of sediments studied. Contents of carbohydrates in pelagic oozes of the Central Pacific ranged from 214 to 1605 ppm, averaging 602 ppm of air-dried sediment. Organic matter of the group studied is a diagenetically stable complex, with polysaccharides apparently predominating.

Observation of ferromanganese deposits in the Baltic Sea

Baltic sediments have been studied by Behrens, Munthe, Küppers, Spethmann, Apstein, Sjöstedt, Pratje and the writer. The following types of sediments have been observed: varved and non-varved late-glacial clays, gray and black, post-glacial muds, and sands. The organic content of late-glacial clays ordinarily is less than 1.3 per cent, and of post-glacial muds more than 3 per cent. Sediments containing intermediate quantities are scarce. This can be explained as a result of the changed balance between organic and inorganic sedimentation when the glacial period ended; the abundance of fresh detritus then suddenly ceased and inorganic sedimentation became very much slower than before; consequently, the relative amount of organic detritus increased. As most of the material was not subjected to biological analysis, it has not been possible to distinguish different ages among post-glacial sediments.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.