Granulometry, mineralogy and geochemistry of sediments from ODP Hole 169-1037B and Site 169-1038

Central Hill is in the northern part of the Escanaba Trough, which is a sediment-filled rift of southern Gorda Ridge. Central Hill is oriented north-south and is associated with extensive sulfide deposits. Hydrothermal alteration of sediment from Site 1038 was studied through analyses of mineralogy and the chemistry and oxygen isotopic compositions of one nearly pure clay sample. In addition, Site 1037 was drilled to establish the character of the unaltered sedimentary sequence away from the hydrothermal centers of the Northern Escanaba Trough Study Area (NESCA). Mineralogy of the clay-size fraction of turbiditic and hemipelagic sediments of Hole 1037B are predominantly quartz, feldspar, pyroxene, illite, chlorite, and smectite, representing continental-derived material. Cores from Hole 1038I, located within the area of Central Hill but away from known active vent areas, recovered minor amounts of chlorite/smectite mixed-layer clay in the fine fraction, indicating a low-temperature hydrothermal alteration. The 137.4-m-thick sediment section of Hole 1038G is located in an area of low-temperature venting. The uppermost sample is classified as chlorite/smectite mixed layer, which is underlain by chlorite as the dominant mineral. The lowermost deposits of Hole 1038G are also characterized by chlorite/smectite mixed-layer clay. In comparison to Hole 1038I, the mineralogic sequence of Hole 1038G reflects increased chloritization. Intensely altered sediment is almost completely replaced by hydrothermal chlorite in subsurface sediments of Hole 1038H. Alteration to chlorite is characterized by depletion in Na, K, Ti, Ca, Sr, Cs, and Tl and enrichment in Ba. Further, Eu depletion reflects a high-temperature plagioclase alteration. A chlorite 18O value of 2.6 indicates formation at a temperature of ~190°C. It is concluded that the authigenic chlorite in Hole 1038H formed by an active high-temperature fluid flow in the shallow subsurface.

d18O, lithologies, mineralogy and determination of temperature and depth of formation of DSDP Site 69-504 siliceous rocks

Seven opal-CT-rich and five quartz-rich porcellanites and cherts from Site 504 have a range in oxygen-isotope values of 24.4 and 29.4 per mil. In opal-CT rocks, d18O becomes larger with sub-bottom depth and with age. Quartz-rich rocks do not show these trends. Boron, in general, increases with decreasing d18O for porcellanites and cherts considered together, supporting the conclusion that boron is incorporated within the quartz crystal structure during precipitation of the SiO2. Silicification of the chalks at Site 504 began 1 m.y. ago - that is, 5 m.y. after sedimentation commenced on the oceanic crust. Temperatures of chert formation determined from oxygen-isotope compositions reflect diagenetic temperatures rather than bottom-water temperatures, and are comparable to temperatures of formation determined by down-hole measurements. Opal-A in the chalks began conversion to opal-CT when a temperature of 50°C was reached in the sediment column. Conversion of opal-CT to quartz started at 55 °C. Silicification occurred over a stratigraphic thickness of about 10 meters when the temperature at the top of the 10 meters reached about 50°C. It took about 250,000 years to complete the silica transformation within each 10-meter interval of sediment at Site 504. Quartz formed over a stratigraphic range of at least 30 meters, at temperatures of about 54 to 60°C. The time and temperatures of silicification of Site 504 rocks are more like those at continental margins than those in deep-sea, open-ocean deposits.

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.

Rare earth elements of modern seeps from the Gulf of Mexico, the Black Sea, and the Congo Fan

At marine seeps, methane is microbially oxidized resulting in the precipitation of carbonates close to the seafloor. Methane oxidation leads to sulfate depletion in sediment pore water, which induces a change in redox conditions. Rare earth element (REE) patterns of authigenic carbonate phases collected from modern seeps of the Gulf of Mexico, the Black Sea, and the Congo Fan were analyzed. Different carbonate minerals including aragonite and calcite with different crystal habits have been selected for analysis. Total REE content (SumREE) of seep carbonates varies widely, from 0.1 ppm to 42.5 ppm, but a common trend is that the SumREE in microcrystalline phases is higher than that of the associated later phases including micospar, sparite and blocky cement, suggesting that SumREE may be a function of diagenesis. The shale-normalized REE patterns of the seep carbonates often show different Ce anomalies even in samples from a specific site, suggesting that the formation conditions of seep carbonates are variable and complex. Overall, our results show that apart from anoxic, oxic conditions are at least temporarily common in seep environments.

Composition of sediment pore water and isotopes in carbonate and benthic foraminifera at DSDP Holes 68-501, 69-505 and Site 69-504

Two sites on the southern flank of the Costa Rica Rift were drilled on DSDP Legs 68 and 69, one on crust 3.9 m.y. old and the other on crust 5.9 m.y. old. The basement of the younger site is effectively cooled by the circulation of seawater. The basement of the older site has been sealed by sediment, and an interval in the uppermost 560 meters of basement recently reheated to temperatures of 60 to 120°C. Although the thickness of the sediments at the two sites is similar (150-240 m versus 270 m), the much rougher basement topography at the younger Site 505 produces occasional basement outcrops, through which 80 to 90% of the total heat loss apparently occurs by advection of warm seawater. This seawater has been heated only slightly, however; the temperature at the base of the sediments is only 9°C. Changes in its composition due to reaction with the basement basalts are negligible, as indicated by profiles of sediment pore water chemistry. Bacterial sulfate reduction in the sediments produces a decrease in SO4 (and Ca) and an increase in alkalinity (and Sr and NH3) as depth increases to an intermediate level, but at deeper levels these trends reverse, and all of these species plus Mg, K, Na, and chlorinity approach seawater values near basement. Si, however, is higher, and Li may be lower. At the older site, Site 501/504, where heat loss is entirely by conduction, the temperature at the sediment/basement contact is 59°C. Sediment pore water chemistry is heavily affected by reaction with the basaltic basement, as indicated by large decreases in d18O, Mg, alkalinity, Na, and K and an increase in Ca with increasing depth. The size of the changes in d18O, Mg, alkalinity, Ca, Sr, and SO4 varies laterally over 500 meters, indicating lateral gradients in pore water chemistry that are nearly as large as the vertical gradients. The lateral gradients are believed to result from similar lateral gradients in the composition of the basement formation water, which propagate upward through the sediments by diffusion. A model of the d18O profile suggests that the basement at Site 501/504 was sealed off from advection about 1 m.y. ago, so that reaction rates began to dominate the basement pore water chemistry. A limestone-chert diagenetic front began to move upward through the lower sediments less than 200,000 yr. ago.

Mineral composition of altered felsic volcanic rocks from ODP Site 193-1188 and Hole 193-1189A, PACMANUS field

This report presents short-wave infrared spectroscopic data acquired from both core and powdered samples collected during Ocean Drilling Program Leg 193, from Holes 1188A, 1188F, and 1189A, using a Portable Infrared Mineral Analyzer reflectance spectrometer. The distribution of alteration minerals detected using this method for each site is presented.

Quaternary radiolarian counts from Site 181-1123

In the present work Quaternary radiolarian assemblages from the Southwest Pacific were investigated due to their importance for correlation and identification of climatic changes. The studied Ocean Drilling Program (ODP) Site 1123 (Leg 181) is situated on the northern flanks of the Chatham Rise, 1100 kilometres offshore eastern New Zealand and in a water depth o f 3290 metres. It is situated just north of the Subtropical Convergence (STC) in temperate climatic conditions, influenced by the cold deep Deep Western Boundary Current (DWBC) and by the subtropical East Cape Current (ECC) in shallow water depths. A continuous record of 79 sediment samples from this site with a temporal resolution of ~15,000 years provided a medium-resolution record of radiolarian assemblages through the Quaternary. This allowed investigations on how radiolarian assemblages are influenced by climatic variations at obliquity and eccentricity bandwidth, with periodic variations of 40,000, 100,000 and 400,000 years, respectively. Emphasis was given to changes in radiolarian assemblages through the Mid-Pleistocene climate transition (MPT) that marks a fundamental reorganisation in Earth's climate system by change from 40,000 to 100,000 year cycles. Glacial and interglacial variations in oceanography were investigated. Especially the influence of the DWBC was examined due to its input of deep and cold waters to the Pacific Ocean, which plays an important role in Earth's climate system. 167 radiolarian counting groups were examined concerning variations in radiolarian abundance, preservation, diversity, the relative abundance of orders, families, and selected species in order to detect influences of past climatic variations in the Southwest Pacific. No significant changes in radiolarian assemblages were found in coincidence with the onset of the MPT. Investigations led to the recognition of four characteristic phases within the last 1.2 million years. Within one of these phases (Phase Ill), about 160,000 years after the onset of the MPT, fundamental changes in radiolarian assemblages occurred. Investigations yielded highest diversity and highest numbers of nassellarians in abundant samples, whereas sparse samples were mostly poorly preserved and were dominated by spumellarians. Abundance of certain radiolarian families in interglacials or glacials indicated their usefulness as indicators for climatic conditions at Site 1123. Trends o f selected taxa within these families supported the significance of warm- or cool-water preference of these families. Use of 67 radiolarian species as climate indicators showed abundance of warm-water assemblages within interglacials, whereas abundance of cool-water species was increased within glacials. Depth distributional patterns of 52 radiolarian species indicated a strong influence of shallow waters, possibly the EEC, within interglacials and increased influence of deep and intermediate waters, possibly of southern-sourced character and the DWBC in glacial stages.

Clay mineralogy of ODP Site 188-1165

The Ocean Drilling Program Leg 188 Site 1165 was drilled on the Wild Drift on the Continental Rise off Prydz Bay, East Antarctica to a total depth of 999.1 meters below seafloor (mbsf). It recovered an extensive suite of terrigenous and hemipelagic sediments of early Miocene to Pleistocene age. Of special interest in this study is the sediment column between 0 and 50 mbsf, which consists of a well-preserved section of Pliocene-Pleistocene-age sediments that was sampled at 10-cm intervals. Multiproxy study of this interval could show possible intervals of expansions of the ice-sheet across the continental shelves and express the climatic evolution in Antarctica, particularly during the 'middle' Pliocene warm period (3.15 to 2.85 Ma) which may provide an indication of how the Earth responds to a rise of its surface temperature. According to the existing age model, the upper 50 mbsf stratigraphic sequence of Site 1165 reaches back to ~4.9 Ma. Throughout this interval, the clay-mineral content is characterized by fluctuations of individual clay minerals, particularly smectite and chlorite. The smectite concentration varies mainly between 0% and 30%. Illite fluctuates less between 50% and 80%, and kaolinite varies mainly between 10% and 20%. Chlorite concentrations are mainly 0% to 10%. There is also a noticeable change in magnetic susceptibility at ~34 mbsf that is clearly indicated in the composition of the clay-mineral suite. At this level, smectite decreases and illite, kaolinite and chlorite show some variability. In particular, there is a slight but persistent increase in chlorite. The results from the Plio-Pleistocene transition, with evenly fluctuating smectite and illite contents and the gradually increasing chlorite content, may indicate cooler conditions compared to the mid-Pliocene conditions. Slight increase in illite content and decrease in smectite content towards Pleistocene supports the previous assumption. The results from the mid-Pliocene with the increasing smectite content and decreasing illite content may indicate warmer and possibly interglacial conditions.

Sedimentary facies and clay mineralogy of ODP Site 105-646

The grain-size study and analyses of bulk sediment and clay mineral composition of samples collected from the dominant lithologies recovered at ODP Site 646, located on the northern flank of the Eirik Ridge (Labrador Sea), show variations indicating that contour-following currents, linked to Norwegian Sea Overflow Water (NSOW), have controlled sedimentation since the early Pliocene. These currents were influential until the early Pleistocene, despite the onset of major ice-rafting at about 2.5 Ma. A major mineralogical change occurred during the late Miocene: a decrease in the smectite to illite and chlorite ratio and a decrease of the crystallinity of smectites. This change indicates a renewing of the source rocks, which could result from an important hydrological change at this time. This change also is depicted by grain-size data that suggest the bottom current influence should be set earlier than the Pliocene.

Stable isotopes, sedimentology and geochemical analyses of Middle Eocene to early Miocene sediments of ODP Site 177-1090

During Leg 177 of the Ocean Drilling Program (ODP), a well-preserved middle Eocene to lower Miocene sediment record was recovered at Site 1090 on the Agulhas Ridge in the Atlantic sector of the Southern Ocean. This new sediment record shows evidence of a hitherto unknown late Eocene opal pulse. Lithological variations, compositional data, mass-accumulation rates of biogenic and lithogenic sediment constituents, grain-size distributions, geochemistry, and clay mineralogy are used to gain insights into mid-Cenozoic environmental changes and to explore the circumstances of the late Eocene opal pulse in terms of reorganizations in ocean circulation. The base of the section is composed of middle Eocene nannofossil oozes mixed with red clays enriched in authigenic clinoptilolite and smectite, deposited at low sedimentation rates (LE 2 cm/ka). It indicates reduced terrigenous sediment input and moderate biological productivity during this preglacial warm climatic stage. The basal strata are overlain by an extended succession (100 m, 4 cm/ka) of biosiliceous oozes and muds, comprising the upper middle Eocene, the entire late Eocene, and the lowermost early Oligocene. The opal pulse occurred between 37.5 and 33.5 Ma and documents the development of upwelling cells along topographic highs, and the utilization of a marine nutrient- and silica reservoir established during the pre-late Eocene through enhanced submarine hydrothermal activity and the introduction of terrigenous solutions from chemical weathering on adjacent continents. This palaeoceanographic overturn probably was initiated through the onset of increased meridional ocean circulation, caused by the diversion of the Indian equatorial current to the south. The opal pulse was accompanied by increased influxes of terrigenous detritus from southern African sources (illite), mediated by enhanced ocean particle advection in response to modified ocean circulation. The opal pulse ended because of frontal shifts to the south around the Eocene/Oligocene boundary, possibly in response to the opening of the Drake Passage and the incipient establishment of the Antarctic Circumpolar Current. Condensed sediments and a hiatus within the early Oligocene part of the section possibly point to an invigoration of the deep-reaching Antarctic Circumpolar Current. The mid-Oligocene to lower Miocene section on long time scale exhibits less pronounced lithological variations than the older section and points to relatively stable palaeoceanographic conditions after the dramatic changes in the late Eocene to early Oligocene.

Mineral XRD peak areas and ratios of ODP Site 184-1146 clays, South China Sea

Site 1146 (19°27.40'N, 116°16.37'E) was drilled in ~2092 m water depth in a rift basin on the continental slope of the South China Sea. A total of 607 m of sediment was cored in Hole 1146A, and a composite section from three holes extends down to 640 meters composite depth (mcd). Three stratigraphic sedimentary units were recognized at this site: late Pliocene to Pleistocene nannofossil clay (Unit I), middle Miocene to late Pliocene foraminifer and nannofossil clay mixed sediment (Unit II), and early to middle Miocene nannofossil clay (Unit III). This study reports the mineralogy from the late Miocene through early Pleistocene, 150-440 mcd.

Texture analyses of ODP Site 131-808 sediments

The microfabric of 11 mudrock specimens from ODP Site 808 (Nankai accretionary prism) was quantitatively analyzed using X-ray texture goniometry and optical petrography. The objectives of the study were to learn about rock strain and to detect a component of bulk lateral shortening in the deformation of the mudstones. Strain evaluation is based on the predictions of March theory, and on distortions of initially homogeneous marker particle distributions (the Fry technique). The main results are as follows. The specimens underwent a strain path of progressive flattening, which is closely related to loss of pore space by vertical loading. A component of bulk lateral shortening is detectable in the top 550 mbsf at Site 808, but compared with the amount of uniaxial vertical shortening, its relative magnitude is probably small. Moreover, it cannot be said with confidence whether this is caused by toe contraction of the accretionary wedge or by gravitationally induced downslope movement of the sediment pile. The mudstones examined were deposited in a marine environment with an oxic bottom water column. Micropore collapse is an important fabric building mechanism, but below 400 mbsf its effects are at least partly overridden by recrystallization of smectite. We conclude that mud microfabrics are not very precise deformation gauges, but can be used for rough estimations of strain.

Mineralogy micromorphology, and geochemistry at DSDP Site 89-585

At Site 585 of Deep Sea Drilling Project Leg 89 more than 500 m of volcaniclastic to argillaceous middle-Late Cretaceous sediments were recovered. Analyses by X-ray diffraction (bulk sediment and clay fraction), transmission electron microscopy, molecular and atomic absorption, and electron microprobe were done on Site 585 samples. We identify four successive stages and interpret them as the expression of environments evolving under successive influences: Stage 1, late Aptian to early Albian - subaerial and proximal volcanism, chiefly expressed by the presence of augite, analcite, olivine, celadonite, small and well-shaped transparent trioctahedral saponite, Al hydroxides, Na, Fe, Mg, and various trace elements (Mn, Ni, Cr, Co, Pb, V, Zn, Ti). Stage 2, early to middle Albian - submarine and less proximal volcanic influence, characterized by dioctahedral and hairy Mg-beidellites, a paucity of analcite and pyroxenes, the presence of Mg and K, and local alteration of Mg-smectites to Mg-chlorites. Stage 3, middle Albian to middle Campanian - early marine diagenesis, marked by the development of recrystallization from fleecy smectites to lathed ones (all of alkaline Si-rich Fe-beidellite types), by the development of opal CT and clinoptilolite, and by proximal to distal volcanic influences (Na parallel to Ti, K). Local events consist of the supply of reworked palygorskite during the Albian-Cenomanian, and the recurrence of proximal volcanic activity during the early Campanian. Stage 4, late Campanian to Maestrichtian - development of terrigenous supply resulting from the submersion of topographic barriers; this terrigenous supply is associated with minor diagenetic effects and is marked by a clay diversification (beidellite, illite, kaolinite, palygorskite), the rareness of clay recrystallizations, and the disappearance of volcanic markers.

Mineralogy, grain size composition, bulk carbonate isotopic ratios and ages of ODP Site 182-1128 sediments

This report presents mineralogic and geochemical data from Ocean Drilling Program Leg 182 Site 1128 in the Great Australian Bight. Clay mineralogy is dominated by mixed-layer illite-smectite, followed by minor amounts of kaolinite and illite, with intervals of pure smectite. Carbonate mineralogy is exclusively low-Mg calcite, except for one interval of dolomite in lower Oligocene sediments. Carbonate increases significantly in upper Eocene sediments, decreases through the lower Oligocene, then increases again in the Neogene. Quartz is present as a minor component that covaries inversely with carbonate. High-resolution sampling associated with Chron 13 normal (early Oligocene) reveals high-frequency (~23 k.y.) fluctuations in clay mineralogy and carbonate abundance and a positive oxygen and carbon isotope excursion (in bulk carbonates) related to Antarctic glaciation.