Geochemistry of dark-light rhythm sediments of the Japan Sea

Ocean Drilling Program Legs 127 and 128 in the Japan Sea have revealed the existence of numerous dark-light rhythms of remarkable consistency in sediments of late Miocene, latest Pliocene, and especially Pleistocene age. Light-colored units within these rhythms are massive or bioturbated, consist of diatomaceous clays, silty clays, or nannofossil-rich clays, and are generally poor in organic matter. Dark-colored units are homogeneous, laminated, or thinly bedded and include substantial amounts of biogenic material such as well-preserved diatoms, planktonic foraminifers, calcareous nannofossils, and organic matter (maximum 7.4 wt%). The dark-light rhythms show a similar geometrical pattern on three different scales: First-order rhythms consist of a cluster dominated by dark-colored units followed by a cluster dominated by light-colored units (3-5 m). Spectral analysis of a gray-value time series suggests that the frequencies of the first-order rhythms in sediments of latest Pliocene and Pleistocene age correlate to the obliquity and the eccentricity cycles. The second-order dark-light rhythms include a light and a dark-colored unit (10-160 cm). They were formed in time spans of several hundred to several ten thousand years, with variance centering around 10,500 yr. This frequency may correspond to half the precessional cycle. Third-order rhythms appear as laminated or thinly bedded dark-light couplets (2-15 mm) within the dark-colored units of the second-order rhythms and may represent annual frequencies. In interpreting the rhythms, we have to take into account that (1) the occurrence of the first- and second-order rhythms is not necessarily restricted to glacial or interglacial periods as is shown by preliminary stable-isotope analysis and comparison with the published d18O record; (2) they appear to be Milankovitch-controlled; and (3) a significant number of the rhythms are sharply bounded. The origin of the dark-light rhythms is probably related to variations in monsoonal activity in the Japan Sea, which show annual frequencies, but also operates in phase with the orbital cycles.

Tie points and goechemical analysis from different Holes of ODP Site 165-1002

The fine-grained sediments of the Cariaco Basin, Venezuela, of the last 130 ky, whose deposition history is well characterized, were analyzed geochemically in order to test the validity of sediment bulk geochemistry as an indicator of detrital provenance. Several binary and ternary diagrams as well as the chemical index of alteration (CIA) were tested for their capacity to discriminate the poorly contrasted detrital sources to the Cariaco Basin, and to describe the temporal evolution of the contributions of these different sources. Most of the diagrams tested did not allow a good discrimination of sources or, when sources were well discriminated, did not allow an interpretation of the temporal variations consistent with the known history. A relatively good discrimination of sources and a consistent interpretation of temporal variations were however obtained using Hf vs. Th and La/Yb vs. Gd/Yb binary diagrams, as well as Ti-Zr-Th, Ti-Zr-La, and Lu-Hf-Th ternary diagrams. Compared to the previous studies of the detrital content of the Cariaco Basin sediments, the geochemical approach permitted the recognition of a sediment contribution eroded from the Unare platform and Gulf of Cariaco during rapid sea level oscillations, and the contribution of Saharan eolian particles during the Younger Dryas-Preboreal and MIS6-5 transition. The choice of plotted elements was determined after considering carrier minerals, so that different elements may be informative in different sedimentary contexts. Overall, mineral sorting during transport appears as a major limit to quantitative estimation of the different contributions. In particular mineral sorting leads to the selective enrichment of elements associated with clays (Al, Rb, Th and LREE) in sediments deposited in the basin. Unless the geochemical effect of mineral sorting can be measured, it appears that quantitative provenance analysis should be performed on fractions of similar grain size instead of bulk sediment.

Chemical and isotopic compositions of sediments and some minerals from the Derugin Basin, Sea of Okhotsk

The paper reports specific mineralogical and geochemical characteristics of deposits from local depressions of the Derugin Basin. They were formed in an environment with periodic changes from oxic to anoxic conditions and show evidence for presence of hydrogen sulfide in bottom waters. Deposits of this type can be considered as a modern model for ancient ore-bearing black shale associations. Compared with typical metalliferous black shale sequences, which are characterized by high contents of organic matter, the sediments described here are depleted in elements of the organophilic association (Mo, Ni, Cu, Zn, V, and U), but have higher Mn contents.

Physical properties and sedimentology on core GeoB1510-1

Detailed information about the sediment properties and microstructure can be provided through the analysis of digital ultrasonic P wave seismograms recorded automatically during full waveform core logging. The physical parameter which predominantly affects the elastic wave propagation in water-saturated sediments is the P wave attenuation coefficient. The related sedimentological parameter is the grain size distribution. A set of high-resolution ultrasonic transmission seismograms (ca. 50-500 kHz), which indicate downcore variations in the grain size by their signal shape and frequency content, are presented. Layers of coarse-grained foraminiferal ooze can be identified by highly attenuated P waves, whereas almost unattenuated waves are recorded in fine-grained areas of nannofossil ooze. Color-encoded pixel graphics of the seismograms and instantaneous frequencies present full waveform images of the lithology and attenuation. A modified spectral difference method is introduced to determine the attenuation coefficient and its power law a = kfn. Applied to synthetic seismograms derived using a "constant Q" model, even low attenuation coefficients can be quantified. A downcore analysis gives an attenuation log which ranges from ca. 700 dB/m at 400 kHz and a power of n = 1-2 in coarse-grained sands to few decibels per meter and n ? 0.5 in fine-grained clays. A least squares fit of a second degree polynomial describes the mutual relationship between the mean grain size and the attenuation coefficient. When it is used to predict the mean grain size, an almost perfect coincidence with the values derived from sedimentological measurements is achieved.

Chemical composition of upper Cenozoic at DSDP Leg 70 Holes

The hydrothermal deposits that we analyzed from Leg 70 are composed of ferruginous green clays and fragments of manganese-hydroxide crust. Data from X-ray diffraction, IR-spectroscopy, electron diffraction, and chemical analyses indicate that the hydrothermal green clays are composed of disordered mixed-layer phases of celadonite-nontronite. Electron diffraction shows that the parameters of the unit cells and the degree of three-dimensional ordering of mixed-layer phases with 80% celadonite interlayers are very close to Fe-micas of polymorphic modification IM-celadonite. In some sections, there is a tendency for the number of celadonite layers to increase with depth. The manganese-hydroxide crust fragments are predominantly composed of todorokite (buserite). An essential feature of hydrothermal accumulation is the sharp separation of Fe and Mn. Ba/Ti and Ba/Sr ratios are typical indicators of hydrothermal deposits. Sediments composing the hydrothermal mounds were deposited from moderately heated waters, which had extracted the components from solid basalts in environments where there were considerable gradients of temperature, eH, and pH. The main masses of Fe and Mn were deposited in the late Pleistocene. Postsedimentary alteration of deposited hydrothermal sediments led to their slight recrystallization and, in the green clays, to celadonitization. Further, factor analysis (by Varentsov) of chemical components from these hydrothermal deposits revealed paragenetic assemblages. Green clays corresponding to a definite factor assemblage were formed during the main stage of hydrothermal mineral formation. Manganese hydroxide and associated components were largely accumulated during an early stage and at the end of the main stage.

Geochemistry of middle Eocene-lower Oligocene pelagic sediments of ODP Hole 105-647A

Geochemical analyses of the middle Eocene through lower Oligocene lithologic Unit IIIC (260-518 meters below seafloor [mbsf]) indicate a relatively constant geochemical composition of the detrital fraction throughout this depositional interval at Ocean Drilling Program (ODP) Site 647 in the southern Labrador Sea. The main variability occurs in redox-sensitive elements (e.g., iron, manganese, and phosphorus), which may be related to early diagenetic mobility in anaerobic pore waters during bacterial decomposition of organic matter. Initial preservation of organic matter was mediated by high sedimentation rates (36 m/m.y.). High iron (Fe) and manganese (Mn) contents are associated with carbonate concretions of siderite, manganosiderite, and rhodochrosite. These concretions probably formed in response to elevated pore-water alkalinity and total dissolved carbon dioxide (CO2) concentrations resulting from bacterial sulfate reduction, as indicated by nodule stable-isotope compositions and pore-water geochemistry. These nodules differ from those found in upper Cenozoic hemipelagic sequences in that they are not associated with methanogenesis. Phosphate minerals (carbonate-fluorapatite) precipitated in some intervals, probably as the result of desorption of phosphorus from iron and manganese during reduction. The bulk chemical composition of the sediments differs little from that of North Atlantic Quaternary abyssal red clays, but may contain a minor hydrothermal component. The silicon/ aluminum (Si/Al) ratio, however, is high and variable and probably reflects original variations in biogenic opal, much of which is now altered to smectite and/or opal CT. An increase in the sodium/potassium (Na/K) ratio in the upper Eocene corresponds to the beginning of coarsergrained feldspar flux to the site, possibly marking the onset of more vigorous deep currents. Although the Site 647 cores provide a nearly complete high-resolution, high-latitude Eocene-Oligocene record, the high sedimentation rate and somewhat unusual diagenetic conditions have led to variable alteration of benthic foraminifers and fine-fraction carbonate and have overprinted the original stable-isotope records. Planktonic foraminifers are less altered, but on the whole, there is little chance of sorting out the nature and timing of environmental change on the basis of our stable-isotope analyses.

Chemistry of hydrothermal clasy and sulfides of ODP Site 106-649

Several meters of unconsolidated hydrothermal sediment were recovered from the Snake Pit hydrothermal field during ODP Leg 106. Polymetallic sulfides comprise most of the sediment with minor fragments of massive sulfide, organic debris, clay minerals, and fresh glass shards. Trace element and Sr-isotope contents of hydrothermal clays and sulfides from Holes 649B and 649G indicate that these minerals precipitated from a mixed hydrothermal fluid-seawater solution. Evaluation of the REE mineral data and the Snake Pit hydrothermal fluids shows that the REE distribution coefficients between the hydrothermal fluids and clay-sulfide mixes range from 100-500. This indicates that hydrothermal fluids originating in the root-zone of the Snake Pit hydrothermal system may be modified by the precipitation of hydrothermal minerals, either in the shallow subsurface or within chimney structures. Contrasting REE profiles of clay-sulfide aggregates and massive sulfides from Holes 649B and 649G may be accounted for by spatial and/or temporal variations in redox conditions in the plumbing system.

Consolidation tests of ODP Leg 113 samples

Examination of the geotechnical characteristics of Weddell Sea, Maud Rise, and South Orkney microcontinental margin sediments recovered during ODP Leg 113 reveals that the reduction in porosity (consolidation) of the siliciclastic, calcareous, and diatomaceous sediments is primarily a process governed by vertical stresses created by overburden. The initial porosity of the sediments in these areas is governed by the amount of diatoms present. The more diatoms, the higher the porosity. Surficial diatom-rich sediments are everywhere overconsolidated. This is attributed to the strong microfabric created by the diatoms, calcareous and clay particles. The deeper diatom-free sediments of Maud Rise range from slightly underconsolidated to normally consolidated. The silty clays and clays of the Weddell Sea and South Orkney margin are underconsolidated. The degree of underconsolidation of these sediments is similar to that determined in a number of different locations throughout the world's oceans. The very low permeability of the Weddell Sea and South Orkney margin sediments appears to account for this underconsolidation.

Mineral composition and experimental results from XRD analyses of sediments from ODP Leg 190 sites

X-ray diffraction analyses of the clay-sized fraction of sediments from the Nankai Trough and Shikoku Basin (Sites 1173, 1174, and 1177 of the Ocean Drilling Program) reveal spatial and temporal trends in clay minerals and diagenesis. More detrital smectite was transported into the Shikoku Basin during the early-middle Miocene than what we observe today, and smectite input decreased progressively through the late Miocene and Pliocene. Volcanic ash has been altered to dioctahedral smectite in the upper Shikoku Basin facies at Site 1173; the ash alteration front shifts upsection to the outer trench-wedge facies at Site 1174. At greater depths (lower Shikoku Basin facies), smectite alters to illite/smectite mixed-layer clay, but reaction progress is incomplete. Using ambient geothermal conditions, a kinetic model overpredicts the amount of illite in illite/smectite clays by 15%-20% at Site 1174. Numerical simulations come closer to observations if the concentration of potassium in pore water is reduced or the time of burial is shortened. Model results match X-ray diffraction results fairly well at Site 1173. The geothermal gradient at Site 1177 is substantially lower than at Sites 1173 and 1174; consequently, volcanic ash alters to smectite in lower Shikoku Basin deposits but smectite-illite diagenesis has not started. The absolute abundance of smectite in mudstones from Site 1177 is sufficient (30-60 wt%) to influence the strata's shear strength and hydrogeology as they subduct along the Ashizuri Transect.

Geochemistry at DSDP Holes 80-550 amd 80-548

At Sites 548 and 550 of DSDP Leg 80 several condensed sedimentary sections contain various types of polymetallic crusts. The relationships between mineralogic and geochemical data in the sections have been studied in the context of the biostratigraphic and sedimentologic results. The diagenetic evolution during periods of low accumulation rate varies according to depth and sedimentary environment. At Site 548 on the continental margin, the phosphatic and manganiferous crusts are similar to those related to upwelling influences before Late Cretaceous deposition. At Site 550 the upper Paleocene cherts, deposited directly on oceanic crust, are overlain by pelagic brown clays containing diagenetic manganiferous concretions characterized by very high Sr and Ba contents. The origin of these small nodules is probably related to the authigenesis of fecal pellets. The upper Eocene indurated section is made up of authigenic zeolites, clays, and Fe-Mn phases and is similar to the volcanic-sedimentary deposits described in deep basins and seamounts of the Pacific. These crusts and a polynucleated nodule within the overlying sediments have geochemical characteristics (high Ni, Co, and Cu contents) similar to those formed in the deep ocean under volcanic influences during periods of low sedimentation rates or sedimentary hiatuses. Volcaniclastic material is ubiquitous and peculiarly abundant in Eocene sections and can be related to the volcanic formation of Iceland in the North Atlantic.

Rare earth elements in standard samples of ocean Fe-Mn nodules and crusts

Contents of rare earth elements (REE) in standard samples of Fe-Mn nodules (SDO-5, 6), Fe-Mn crust (SDO-7), and red clay (SDO-9) have been determined by ICP-MS and instrumental neutron activation analysis. Reproducibility of ICP-MS was 5-6%. These results are discussed and compared with other data. It has been found that distribution of REE in the standard samples of ocean Fe-Mn ores and red clay is highly homogenous.