Element stratigraphy across the Cretaceous-Tertiary boundary in ODP Hole 119-738C

Neutron activation analyses of iridium and other chemical elements were performed across a 1-m-thick, partly nonbioturbated, clay-rich interval at the Cretaceous/Tertiary boundary in ODP Hole 738C. The results show that the boundary interval holds one of the highest Ir enrichments (320 ng Ir/cm2) of all known Cretaceous/Tertiary boundary layers. Iridium concentrations are highest (18 ppb Ir, whole-rock samples) a few centimeters above the base of the clayrich interval and gradually tail off upsection. Compared with background levels the most Ir-rich interval also shows strongly enhanced concentrations of Cr (215 ppm) and slightly elevated Co concentrations (13 ppm). The Ir-rich interval shows low As (< 15 ppm) and Sb (<0.8 ppm) concentrations, a fact that is congruent with absence of abundant authigenic sulfides in the sediment. Irregularly distributed Fe enrichments and a greenish gray color of the Fe-rich intervals may indicate the presence of glauconitic clay minerals and suboxic, slightly reducing conditions during deposition. Rare earth element (REE) abundance patterns change considerably across the Cretaceous/Tertiary boundary interval, reflecting either a change in Cretaceous/Tertiary boundary seawater REE composition or the occurrence of different REE fractionation processes due to changing depositional environment. Element-vs.-element ratios of Hf, Ta, Th, U, Cs, and Sc are similar between the most Ir-rich layers of the boundary section and other levels with lower Ir concentrations. This may imply that the clay fraction of the Ir-rich layers of the Cretaceous/Tertiary boundary interval is made up predominantly of locally derived material. Calculated calcite-free abundances of Hf, Ta, Th, U, Cs, and Sc, on the other hand, are reconcilable with an extraneous origin of the bulk of the clay in the most Ir-rich layers. The Ir in the Cretaceous/Tertiary boundary clay-rich zone in Hole 738C is most likely derived from an earth-impacting asteroid; however, the origin of the clay-rich zone remains enigmatic.

Composition of the argillite sequence, continental slope of the Sea of Japan

The argillite sequence located at the base of the sedimentary cover on the continental slope of the Sea of Japan was studied by petrographic, palynological, and X-ray diffraction methods. Two spores-pollen complexes were distinguished in it: the Late Oligocene reflecting cooling and the Early Miocene corresponding to initiated warming. Data obtained indicate that the sequence is composed of terrigenous silty-clayey sediments that accumulated in shallow coastal-marine settings. The global sea-level rise at the Early-Middle Miocene transition, combined with regional tectonic processes, determined basin's deepening, owing to which the argillite sequence was overlain by a thick layer of Middle Miocene diatomaceous-clayey sediments. Due to tectonic movement along existing faults in the terminal Late Miocene, the argillite sequence occurring initially at depths of at least 400-500 m was locally exhumed to the basin bottom.

Chemical composition of basalts from DSDP Hole 46-396B

Samples of crystalline basalt from Site 396 B are all more or less altered, usually in strongly zoned patterns. Evidence has been found for several related or independent alteration stages, including (1) minor localized deuteric (amphibole and mixed clay minerals in miarolitic voids); (2) minor widespread nonoxidizing (pyrite on walls of vugs and cracks); (3) localized diffusion-controlled rug filling ("glauconite" in black halos); (4) pervasive low level oxidizing (transformation of titanomagnetite to cation-deficient titanomaghemite); (5) localized diffusion-controlled strongly oxidizing (breakdown of olivine and titanomaghemite in brown zones). Plagioclase and pyroxene are essentially unaltered. Detailed analyses of gray and brown zones in pillow basalts show that low temperature oxidation has proceeded in a step-wise fashion, with the relative stabilities of the igneous minerals controlling the steps. Secondary minerals that crystallized from pore fluids on to the walls of vugs may or may not be related to local alteration of primary phases. During the most intense stage of alteration, brown oxidation zones grew into basalt fragments behind diffusion controlled fronts. The specific reactions and products of this stage differ among the lithologic units at the site. A model is proposed whereby efficient seawater circulation through the pillow units maintains the pH and the concentrations of Mg2+ and SiO2 dissolved at low levels in pore fluids, so that olivine is replaced by hydrous ferric oxides, and Mg and SiO2 are removed from the system. In the massive basalt unit, circulation is somewhat less effective and Mg and SiO2 are retained in smectites. Deposition of authigenic minerals in the sequence saponite/Fe-Mn oxides/phillipsite/calcite in vugs and cracks may reflect the gradual closing of the systems and probably signals the end of localized oxidation in parts of the core. Mineral compositions indicate that most of these deposits formed from seawater at very low temperature.

Geochemistry of Neogene-Quaternary sediments in ODP Site 105-645

Subcontinuously cored early(?)-middle Miocene to recently deposited sediments from ODP Site 645 were studied texturally, mineralogically, and geochemically. The entire sequence contains minerals and associated chemical elements that are chiefly of detrital origin. In particular, the clay minerals, which include smectite, kaolinite, chlorite, and illite, are detrital. No obvious evidence of diagenesis with depth, of burial, of volcanism, or of hydrothermal alteration was observed. The sedimentary textures, clay mineralogy, and <2-µm fraction geochemistry of the early middle Miocene sediments (630 to 1147 mbsf) suggest the pronounced but variable influence of a southward bottom current. Two clay facies are defined. The lower one, Cj (780 to 1147 mbsf), is characterized by the great abundance of discrete smectite (with less than 15% illite interlayers), probably detrital in origin, and reworked older, discrete, smectite-rich sediments. The upper clay facies, C2 (630 to 780 mbsf), shows a net decrease of the fully expandable clay abundances, with a great abundance of mixed-layer, illite-smectite clays (60 to 80% of illite interlayers). Such clay assemblages can be inherited from paleosoils or older sedimentary rocks. An important change occurs at 630 mbsf (clay fraction) or 600 mbsf (sedimentary texture), which may be explained by the beginning of continental glaciation (630 mbsf, ~9 Ma) and the onset of ice rafting in Baffin Bay (600 mbsf, ~8 Ma). Above this level, the characteristics and modifications of the clay assemblages are controlled climatically and can be explained by the fluctuations of (1) ice-rafting, (2) speed of weak bottom currents, and (3) some supply by mud turbiditic currents. Three clay facies (C3, C4, and C5) can be defined by the abrupt increases of the inherited chlorite and illite clays.

Grain size and chemical compositions of bottom sediments from the Amur Bay

Composition of clay minerals in the <0.001 mm size fraction from the uppermost layer of bottom sediments in the northern Amur Bay was determined by X-ray powder diffraction analysis, and enrichment of 33 elements in the <0.001 mm and <0.01 mm size fractions of surface sediments from a number of sites at the marginal filter of the Razdol'naya River were studied by ICP-MS. Fe, U, and chalcophile elements occur in the highest concentrations in sediments from all sampling sites within the filter. The bottom sediments are not enriched in trace, alkali, and alkaline earth elements. Maximum concentrations of chemical elements were found in deposits from the brackish part of the marginal filter, perhaps, because of formation of Fe and Mn (Al) hydroxides. Bottom sediments at the boundary between the brackish and marine parts of the filter contain the lowest concentrations of the examined elements.

Mineralogy of ODP Site 105-645

Cores from the upper 70 meters below seafloor (mbsf) (upper Pleistocene) at Ocean Drilling Program (ODP) Site 645 in Baffin Bay show dramatic meter-scale changes in color and mineralogy. Below this interval, mineralogical changes are more gradual to the top of the Miocene at about 550 mbsf. The Pliocene-Pleistocene section can be divided into five facies: Facies 1 - massive, poorly sorted, gravel-bearing muds; Facies 2 - gray silty clays and silty muds; Facies 3 - laminated detricarbonate silty muds; Facies 4 - silty sand and sandy silt; and Facies 5 - poorly sorted muddy sands and silty muds. Facies 4 and 5 are restricted to the Pliocene section below depths of about 275 mbsf. The mineralogical/color cycles in the upper 70 mbsf are the result of alternations between Facies 2 and three lithotypes of Facies 1: lithotype A - tan-colored, carbonate-rich, gravel-bearing mud; lithotype B - weak, red-colored, gravel-bearing mud rich in sedimentary rock fragments; and lithotype C - gray, gravel-bearing mud. A fourth lithotype, D, is restricted to depths of 168-275 mbsf and is dark gray, carbonate-poor, gravel-bearing mud. We believe that all lithotypes of Facies 1 and the sand and gravel fractions of Facies 2 and 3 were deposited by ice rafting. Depositional processes for Facies 4 and 5 probably include ice rafting and bottom- and turbidity-current transport. Data from petrographic analyses of light and heavy sand-sized grains and X-ray analyses of silt- and clay-size fractions suggest that tan-colored sediments (lithotype A of Facies 1; Facies 3) were derived mainly from Paleozoic carbonates of Ellesmere, Devon, and northern Baffin islands. Weak red sediments (lithotype B) contain significant red sedimentary clasts, reworked quartzarenite grains and clasts, and rounded colorless garnets, all derived from Proterozoic sequences of the Borden and Thule basins, and from minor Mesozoic red beds. Other sediments in the upper 335 mbsf at Site 645 contain detritus from a heterogeneous mixture of sources, including Precambrian shield terranes around Baffin Bay. Sediments from 335 to 550 mbsf (Facies 5) are rich in friable sedimentary clasts and detrital micas and contain glauconite and, in a few samples, reworked diatoms. These components suggest derivation from poorly consolidated Mesozoic-Tertiary sediments in coastal outcrops and beneath the modern shelves of northeastern Baffin Island and western Greenland. For the upper Pleistocene section (about 0-100 mbsf), marked mineralogical cyclicity is attributed to fluctuating glacial margins, calving rates, and iceberg melting rates, particularly around the northern end of Baffin Bay. Tan-colored, carbonate-rich units were derived at times of maximum advance of glaciers on Ellesmere and Devon islands, during relatively warm intervals induced by incursion of warm Atlantic surface water into the bay. At the beginning of these warmer episodes, most icebergs were contributed by glaciers near sea level around the Arctic channels, which resulted in deposition of weak red, ice-rafted units rich in Proterozoic sedimentary clasts.

Strontium, oxygen and hydrogen isotope ratios of basalts from DSDP Hole 504B

DSDP Hole 504B was drilled into 6 Ma crust, about 200 km south of the Costa Rica Rift, Galapagos Spreading Center, penetrating 1.35 km into a section that can be divided into four zones-Zone I: oxic submarine weathering; Zone II: anoxic alteration; Zones III and IV: hydrothermal alteration to greenschist facies. In Zone III there is intense veining of pillow basalts. Zone IV consists of altered sheeted dikes. Isotopic geochemical signatures in relation to the alteration zones are recorded in Hole 504B, as follows: Zone Depth(m) Average87Sr/86Sr Average delta18O (?) Average deltaD (?) I 275-550 0.7032 7.3 -63 II 550-890 0.7029 6.5 -45 III 890-1050 0.7035 5.6 -31 IV 1050-1350 0.7032 5.5 -36 Alteration temperatures are as low as 10°C in Zones I and II based on oxygen isotope fractionation. Strontium isotopic data indicate that a circulation of seawater is much more restricted in Zone II than in Zone I. Fluid inclusion measurements of vein quartz indicate the alteration temperature was mainly 300 +/- 20°C in Zones III and IV, which is consistent with secondary mineral assemblages. The strontium, oxygen, and hydrogen isotopic compositions of hydrothermal fluids which were responsible for the greenschist facies alteration in Zones III and IV are estimated to be 0.7037, 2?, and 3?, respectively. Strontium and oxygen isotope data indicate that completely altered portions of greenstones and vein minerals were in equilibrium with modified seawater under low water/rock ratios (in weight) of about 1.6. This value is close to that of the end-member hydrothermal fluids issuing at 21°N EPR. Basement rocks are not completely hydrothermally altered. About 32% of the greenstones in Zones III and IV have escaped alteration. Thus 1 g of fresh basalt including the 32% unaltered portion are required in order to make 1 g of end-member solution from fresh seawater in water-rock reactions.

Mineral composition of sediments from ODP Leg 190 sites and DSDP Hole 31-297

This data report documents the acquisition of two new sets of normalization factors for semiquantitative X-ray diffraction analyses. One set of factors is for bulk sediment powders, and the other applies to oriented aggregates of clay-sized fractions (<2 µm). We analyzed mixtures of standard minerals with known weight percentages of each component and solved for the normalization factors using matrix singular value decomposition. The components in bulk powders include total clay minerals (a mixture of smectite, illite, and chlorite), quartz, plagioclase, and calcite. For clay-sized fractions, the minerals are smectite, illite, chlorite, and quartz. We tested the utility of the method by analyzing natural mudstone specimens from Site 297 of the Deep Sea Drilling Project, which is located in the Shikoku Basin south of Site 1177 of the Ocean Drilling Program (Ashizuri transect).

Upper Cretaceous sediments of ODP Hole 122-762C

Well-developed Campanian to Maestrichtian pelagic cyclic sediments were recovered from Hole 762C on the Exmouth Plateau, off northwest Australia, during Ocean Drilling Program Leg 122. The cycles consist of nannofossil chalk (light beds) and clayey nannofossil chalk (dark beds). Both light and dark beds are strongly to moderately bioturbated, alternate on a decimeter scale, and exhibit gradual boundaries. Bioturbation introduces materials from a bed of one color into an underlying bed of another color, indicating that diagenesis is not responsible for the cyclicity. Differences in composition between the light and dark beds, revealed by calcium carbonate measurement and X-ray diffraction analysis, together with trace fossil evidence, indicate that the cycles in the sediments are a depositional feature. Diagenetic processes may have intensified the appearance of the cycles. Spectral analysis was applied to the upper Campanian to lower Maestrichtian cyclic sediments to examine the regularity of the cycles. Power spectra were calculated from time series using Walsh spectral analysis. The most predominant wavelengths of the color cycles are 34-41 cm and 71-84 cm. With an average sedimentation rate of 1.82 cm/k.y. in this interval, we found the time durations of the cycles to be around 41 k.y. and 21 k.y., respectively, comparable to the obliquity and precession periods of the Earth's rotation, which strongly suggests an orbital origin for the cycles. On the basis of sedimentological evidence and plate tectonic reconstruction, we propose the following mechanism for the formation of the cyclic sediments from Hole 762C. During the Late Cretaceous, when there was no large-scale continental glaciation, the cyclic variations in insolation, in response to cyclic orbital changes, controlled the alternation of two prevailing climates in the area. During the wetter, equable, and warmer climatic phases under high insolation, more clay minerals and other terrestrial materials were produced on land and supplied by higher runoff to a low bioproductivity ocean, and the dark clayey beds were deposited. During the drier and colder climatic phases under low insolation, fewer clay minerals were produced and put into the ocean, where bioproductivity was increased and the light beds were deposited.

Magnesium isotope ratios of pore-fluids and dolomites

Magnesium concentrations in deep-sea sediment pore-fluids typically decrease down core due to net precipitation of dolomite or clay minerals in the sediments or underlying crust. To better characterize and differentiate these processes, we have measured magnesium isotopes in pore-fluids and sediment samples from Ocean Drilling Program sites (1082, 1086, 1012, 984, 1219, and 925) that span a range of oceanographic settings. At all sites, magnesium concentrations decrease with depth. At sites where diagenetic reactions are dominated by the respiration of organic carbon, pore-fluid d26Mg values increase with depth by as much as 2 per mil. Because carbonates preferentially incorporate 24Mg (low d26Mg), the increase in pore-fluid d26Mg values at these sites is consistent with the removal of magnesium in Mg-carbonate (dolomite). In contrast, at sites where the respiration of organic carbon is not important and/or weatherable minerals are abundant, pore-fluid d26Mg values decrease with depth by up to 2 per mil. The decline in pore-fluid d26Mg at these sites is consistent with a magnesium sink that is isotopically enriched relative to the pore-fluid. The identity of this enriched magnesium sink is likely clay minerals. Using a simple 1D diffusion-advection-reaction model of pore-fluid magnesium, we estimate rates of net magnesium uptake/removal and associated net magnesium isotope fractionation factors for sources and sinks at all sites. Independent estimates of magnesium isotope fractionation during dolomite precipitation from measured d26Mg values of dolomite samples from sites 1082 and 1012 are very similar to modeled net fractionation factors at these sites, suggesting that local exchange of magnesium between sediment and pore-fluid at these sites can be neglected. Our results indicate that the magnesium incorporated in dolomite is 2.0-2.7 per mil depleted in d26Mg relative to the precipitating fluid. Assuming local exchange of magnesium is minor at the rest of the studied sites, our results suggest that magnesium incorporated into clay minerals is enriched in d26Mg by 0 per mil to +1.25 per mil relative to the precipitating fluid. This work demonstrates the utility of magnesium isotopes as a tracer for magnesium sources/sinks in low-temperature aqueous systems.

Effective stress, porosity, p-wave velocity and mineral composition of ODP Hole 174A-1073A sediments

Porosity, permeability, and compressional (P-wave) velocity were measured as a function of stress on sediments from Ocean Drilling Program Site 1073, U.S. Mid-Atlantic continental slope. Thin sections, scanning electron microscopy, and X-ray diffraction analyses provided mineralogical characteristics of the samples. Uniaxial strain boundary conditions were imposed on the samples during consolidation tests with the maximum effective axial stress reaching 13 MPa. The maximum effective radial stress necessary to maintain uniaxial strain was 7.6 MPa. Over an effective axial stress interval of 0 to 5.2 MPa, Sample 174A-1073A-26X-2, 82-89 cm (226.65 meters below seafloor [mbsf]), exhibited the largest decrease in porosity (51% to 41%), whereas Sample 71X-1, 2-8 cm (644.70 mbsf), exhibited the smallest decrease in porosity (48% to 45%). All samples showed negligible porosity increases during unloading. The permeability (on the order of 1 x 10-17 m**2) of Sample 174A-1073A-71X-1, 2-8 cm, was twice that measured on Sample 8H-1, 23-26 cm (63.75 mbsf), even though the former was considerably deeper and older. The differences in porosity-stress behavior and permeability between shallow and deep samples is related to lithologic, mineralogic, and diagenetic differences between the sediments above and below the Pliocene-Pleistocene to Miocene unconformity. P-wave velocity for Samples 174A-1073A-41X-5, 97-103 cm (372.35 mbsf), and 71X-1, 2-8 cm, increased with decreasing porosity, but did not change significantly during unloading.