(Table 1) Compressional- and share-wave velocieties at elevated confining pressure of ODP Holes 136-842C and 136-843A

Identification of a sediment/basement contact using seismic reflection recordings has proven to be extremely difficult in wide areas of the North Pacific Ocean owing to the presence of massive, highly reflective chert layers within the sediment column. Leg 136 of the Ocean Drilling Program recovered coherent pieces of chert of sufficient size for the first comprehensive laboratory measurements of the seismic properties of this material. Compressional-wave velocities of six samples at 40-MPa confining pressure averaged 5.33 km/s, whereas shear-wave velocities at the same pressure averaged 3.48 km/s. Velocities were independent of porosity, which ranged from 5% to 13%, suggesting that pores within the samples were mostly high aspect ratio vugs as opposed to low aspect ratio cracks. Back-scattered electron images made with a scanning electron microscope confirmed this observation. Acoustic impedances were calculated for the chert samples and from shipboard measurements of the red clay sediment overlying the chert layers. An extremely large compressional-wave reflection coefficient (0.73) characterized the interface between the two lithologies. A synthetic seismogram was calculated using chert and typical pelagic carbonate properties to illustrate the influence of chert layers on a marine seismic-reflection section. Compressional-wave to shear-wave velocity ratios of the chert samples (Vp/Vs =1.53) are close to that of single-crystal quartz in spite of variable porosity. Shear-wave reflection coefficients are estimated to be approximately 0.94. A compressional-wave reflection coefficient for a basement/sediment (carbonate) interface is estimated to be approximately 0.50, significantly less than that of sediment/chert.

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.

Mineralogy and geochemistry of Mg-phyllosilicates from Middle Valley, northern Juan de Fuca Ridge

We present results of a detailed mineralogical and geochemical study of the progressive hydrothermal alteration of clastic sediments recovered at ODP Site 858 in an area of active hydrothermal venting at the sedimented, axial rift valley of Middle Valley (northern Juan de Fuca Ridge). These results allow a characterization of newly formed phyllosilicates and provide constraints on the mechanisms of clay formation and controls of mineral reactions on the chemical and isotopic composition of hydrothermal fluids. Hydrothermal alteration at Site 858 is characterized by a progressive change in phyllosilicate assemblages with depth. In the immediate vent area, at Hole 858B, detrital layers are intercalated with pure hydrothermal precipitates at the top of the section, with a predominance of hydrothermal phases at depth. Sequentially downhole in Hole 858B, the clay fraction of the pure hydrothermal layers changes from smectite to corrensite to swelling chlorite and finally to chlorite. In three pure hydrothermal layers in the deepest part of Hole 858B, the clay minerals coexist with neoformed quartz. Neoformed and detrital components are clearly distinguished on the basis of morphology, as seen by SEM and TEM, and by their chemical and stable isotope compositions. Corrensite is characterized by a 24 Å stacking sequence and high Si- and Mg-contents, with Fe/(Fe+Mg) ratio of = 0.08. We propose that corrensite is a unique, possibly metastable, mineralogical phase and was precipitated directly from seawater-dominated hydrothermal fluids. Hydrothermal chlorite in Hole 858B has a stacking sequence of 14 Å with Fe/(Fe+Mg) ratios of ? 0.35. The chemistry and structure of swelling chlorite suggest that it is a corrensiteychlorite mixed-layer phase. The mineralogical zonation in Hole 858B is accompanied by a systematic decrease in d18O, reflecting both the high thermal gradients that prevail at Site 858 and extensive sediment-fluid interaction. Precipitation of the Mg-phyllosilicates in the vent region directly controls the chemical and isotopic compositions of the pore fluids. This is particularly evident by decreases in Mg and enrichments in deuterium and salinity in the pore fluids at depths at which corrensite and chlorite are formed. Structural formulae calculated from TEM-EDX analyses were used to construct clay-H2O oxygen isotope fractionation curves based on oxygen bond models. Our results suggest isotopic disequilibrium conditions for corrensite-quartz and swelling chlorite-quartz precipitation, but yield an equilibrium temperature of 300° C ± 30° for chlorite-quartz at 32 m below the surface. This estimate is consistent with independent estimates and indicates steep thermal gradients of 10-11°/m in the vent region.

Geochemistry at DSDP Leg 70 Holes

The hydrothermal mounds on the southern flank of the Galapagos Spreading Center are characterized by the following main features: 1) They are located over a young basement (0.5 to 0.85 m.y. of age) in a region known for its high sedimentation rate (about 5 cm/10**3 y.) because it is part of the equatorial high biological productivity zone. 2) They are located in a region with generally high heat flow (8 to 10 HFU). The highest heat-flow measurements (up to 10**3 HFU) correspond to mound peaks (Williams et al., 1979), where temperatures up to 15°C were measured during a dive of the submersible Alvin (Corliss et al., 1978). 3) They are often located on small vertical faults which displace the basement by a few meters (Lonsdale, 1977) and affect the 25- to 50-meter-thick sediment cover. Most of these characteristics have also been observed in the other three known cases of hydrothermal deposits with mineral parageneses similar to that of the Galapagos mounds. However, the case of the hydrothermal mounds south of the Galapagos Spreading Center is unique because of the unusual thickness of the hydrothermal deposits present. The mounds are composed of several, up to 4.5-meter-thick, layers of green clays which, in one case (Hole 509B), are overlain by about 1.4 meters of Mn-oxide crust. We suspect that such a large accumulation of hydrothermal products results from the "funnelling" of the hydrothermal solutions exiting from a highly permeable basement along the faults. This chapter reports a preliminary study of those green clays collected by hydraulic piston coring of the Galapagos mounds during Deep Sea Drilling Project (DSDP) Leg 70 of the D/V Glomar Challenger. Green clays have also been reported from three presently or recently active hydrothermal areas in or close to spreading centers.

Coccoliths and carbonate grain-size compositions in sediment samples from the Mid-Atlantic Ridge

This study presents a differentiated carbonate budget for marine surface sediments from the Mid-Atlantic Ridge of the South Atlantic, with results based on carbonate grain-size composition. Upon separation into sand, silt, and clay sub-fractions, the silt grain-size distribution was measured using a SediGraph 5100. We found regionally characteristic grain-size distributions with an overall minimum at 8 µm equivalent spherical diameter (ESD). SEM observations reveal that the coarse particles (>8 µm ESD) are attributed to planktic foraminifers and their fragments, and the fine particles (<8 µm ESD) to coccoliths. On the basis of this division, the regional variation of the contribution of foraminifers and coccoliths to the carbonate budget of the sediments are calculated. Foraminifer carbonate dominates the sediments in mesotropic regions whereas coccoliths contribute most carbonate in oligotrophic regions. The grain size of the coccolith share is constant over water depth, indicating a lower susceptibility for carbonate dissolution compared to foraminifers. Finally, the characteristic grain-size distribution in fine silt (<8 µm ESD) is set into context with the coccolith assemblage counted and biometrically measured using a SEM. The coccoliths present in the silt fraction are predominantly large species (length > 4 µm). Smaller species (length < 4 µm) belong to the clay fraction (<2 µm ESD). The average length of most frequent coccolith species is connected to prominent peaks in grain-size distributions (ESD) with a shape factor. The area below Gaussian distributions fitted to these peaks is suggested as a way to quantitatively estimate the carbonate contribution of single coccolith species more precisely compared to conventional volume estimates. The quantitative division of carbonate into the fraction produced by coccoliths and that secreted by foraminifers enables a more precise estimate for source/sink relations of consumed and released CO2 in the carbon cycle. The allocation of coccolith length and grain size (ESD) suggests size windows for the separation or accumulation of distinct coccolith species in investigations that depend on non to slightly-mixed signals (e.g., isotopic studies).

Alkenones and coccolithophorids in late Quaternary sediments from the Walvis Ridge

Sea surface temperatures (SSTs) derived from the alkenone UK'37) record of Quaternary sediments may be subject to bias if algae with different temperature sensitivities have contributed to the sedimentary alkenone record. The alkenone-derived SST records are usually based on a UK'37-temperature relationship which was measured in culture experiments using the coccolithophorid Emiliania huxleyi (F.G. Prahl, L.A. Muehlhausen and D.L. Zahnle, 1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochim. Cosmochim. Acta 52, 2303-2310). To assess possible effects of past species changes on the UK'37-temperature signal, we have analyzed long-chain alkenones and coccolithophorids in a late Quaternary sediment core from the Walvis Ridge and compared the results to SST estimates extracted from the d18O record of the planktonic foraminifer Globigerinoides ruber. Alkenones and isotopes were determined over the entire 400-kyr core record while the coccolithophorid study was confined to the last 200 kyr when the most pronounced changes in alkenone content occurred. Throughout oxygen-isotope stages 6 and 5, species of the genus Gephyrocapsa were the predominating coccolithophorids. E. huxleyi began to increase systematically in relative abundance since the stage 5/4 transition, became dominant over Gephyrocapsa spp. during stage 3 and reached the highest abundances in the Holocene. Carbon-normalized alkenone concentrations are inversely related to the relative abundances of E. huxleyi, and directly related to that of Gephyrocapsa spp., suggesting that species of this genus were the principal alkenone contributors to the sediments. Nevertheless, SST values obtained from the UK'37-temperature relationship for E. huxleyi compare favourably to the isotope-derived temperatures. The recently reported UK'37-temperature relationship for a single strain of Gephyrocapsa oceanica (J.K. Volkman. S.M. Barrett, S.I. Blackburn and E.L. Sikes, 1995. Alkenones in Gephyrocapsa oceanica: Implications for studies of paleoclimate. Geochim. Cosmochim. Acta 59, 513-520) produces unrealistically high SST values indicating that the temperature response of the examined strain is not typical for the genus Gephyrocapsa. This is supported by the C37:C38, alkenone ratios of the sediments which are comparable to average ratios reported for E. huxleyi, but significantly higher than for the G. oceanica strain. Most notably, the general accordance of the alkenone characteristics between sediments and E. huxleyi persists through stages 8 to 5 and even in times that predate the first appearance of this species (268 ka; H.R. Thierstein, K.R. Geitzenauer and B. Molfino, 1977. Global synchroneity of late Quaternary coccolith datum levels: Validation by oxygen isotopes. Geology 5, 400-404). Our results suggest that UK'37-temperature relationships based on E. huxleyi produce reasonable paleo-SST estimates even for late Quaternary periods when this species was scarce or absent because other alkenone-synthesizing algae, e.g. of the genus Gephyrocapsa.

Thecosomata in late Quternary deposits of ODP Holes 134-830A and 134-831A

We undertook a quantitative study of Thecosomata shells (pelagic gastropods) and their remains in Quaternary foraminiferal oozes deposited on the tilted calcareous platform of the Bougainville Guyot (Hole 831 A), and in the late Quaternary volcanic siltstones, claystones and sandy interbeds on the upper forearc slope of the central New Hebrides Island Arc (Hole 830A). The distribution of the species is based on the identification of adult shells, juvenile stages, protoconchs, and characteristic shell fragments. By studying thecosomatous shells using a scanning electron microscope (SEM), we were able to specify the fine microstructure of the coiled Limacina inflata and compare it with the rod-type crossed-lamellar structure of some other Limacina species, as well as with the helical structure of the Cavoliniidae.