Mineral composition, rare earth elements, and trace elements from samples of the northern Congo deep-sea fan

Authigenic carbonates were collected from methane seeps at Hydrate Hole at 3113 m water depth and Diapir Field at 2417 m water depth on the northern Congo deep-sea fan during RV Meteor cruise M56. The carbonate samples analyzed here are nodules, mainly composed of aragonite and high-Mg calcite. Abundant putative microbial carbonate rods and associated pyrite framboids were recognized within the carbonate matrix. The d13C values of the Hydrate Hole carbonates range from -62.5 permil to -46.3 permil PDB, while the d13C values of the Diapir Field carbonate are somewhat higher, ranging from -40.7 permil to -30.7 permil PDB, indicating that methane is the predominant carbon source at both locations. Relative enrichment of 18O (d18O values as high as 5.2 permil PDB) are probably related to localized destabilization of gas hydrate. The total content of rare earth elements (REE) of 5% HNO3-treated solutions derived from carbonate samples varies from 1.6 ppm to 42.5 ppm. The shale-normalized REE patterns all display positive Ce anomalies (Ce/Ce* > 1.3), revealing that the carbonates precipitated under anoxic conditions. A sample from Hydrate Hole shows a concentric lamination, corresponding to fluctuations in d13C values as well as trace elements contents. These fluctuations are presumed to reflect changes of seepage flux.

(Table T1) Composition of clay minerals from ODP Leg 204 sediments

This report describes the results of semiquantitative analysis of clay mineral composition by X-ray diffraction. The samples consist of hemipelagic mud and mudstone cored from Hydrate Ridge during Leg 204 of the Ocean Drilling Program. We analyzed oriented aggregates of the clay-sized fractions (<2 µm) to estimate relative percentages of smectite, illite, and chlorite (+ kaolinite). For the most part, stratigraphic variations in clay mineral composition are modest and there are no significant differences among the seven sites that were included in the study. On average, early Pleistocene to Holocene trench slope and slope basin deposits contain 29% smectite, 31% illite, and 40% chlorite (+ kaolinite). Late Pliocene to early Pleistocene strata from the underlying accretionary prism contain moderately larger proportions of smectite with average values of 38% smectite, 27% illite, and 35% chlorite (+ kaolinite). There is no evidence of clay mineral diagenesis at the depths sampled. The expandability of smectite is, on average, equal to 64%, and there are no systematic variations in expandability as a function of burial depth or depositional age. The absence of clay mineral diagenesis is consistent with the relatively shallow sample depths and corresponding maximum temperatures of only 24°-33°C.

Distribution of Uvigerina proboscidea in Late Neogene sediments of DSDP Hole 22-214 in the northern Indian Ocean (Table 1)

This study attempts to understand the significance of Uvigerina proboscidea in paleoceanographic reconstructions at the northern (tropical) Indian Ocean DSDP Site 214 from the Late Miocene through the Pleistocene. In this interval at this site, U. proboscidea is the most abundant species of the benthic assemblage and shows abrupt frequency changes (about 1-74%). Based on relative percentages of U. proboscidea calibrated with oxygen and carbon isotope record and the sediment accumulation rates, the modern distribution of the species in the Indian Ocean, and other evidence, the peaks of abundance of U. proboscidea are inferred to represent times of high-surface productivity, This productivity is related to intensified trade winds during strong southwest (SW) Indian monsoons, causing widespread upwelling along equatorial divergemce in the Indian Ocean. The sudden increase of U. proboscidea abundance at approximately 8.5-7.5 Ma reflects significant upwelling at the equatorial divergence. This event corresponds to the permanent build-up of West Antarctic ice sheets, and a major increase in SW Indian monsoons related upwelling in the northwestern Indian Ocean. The Chron-6 carbon shift at approximately 6.2 Ma is marked by another peak of abundance, reflecting widespread ocean fertility. The highest abundances of U. proboscidea and highest sediment accumulation rates occur between 5.8 and 5.1 Ma, which coincidies with the greatest development of Antarctic ice sheets and strong southwest monsoons. The higher percentages at 3.2-3.1 Ma, approximately 2.4 Ma, and 1.6 Ma all represent phases of high productivity at the equatorial divergence.

Chemical composition of DSDP cherts and associated host sediments

Chert and associated host sediments from Monterey Formation and Deep Sea Drilling Project (DSDP) sequences were analyzed in order to assess chemical behavior during diagenesis of biogenic sediments. The primary compositional contrast between chert and host sediment is a greater absolute SiO2 concentration in chert, often with final SiO2 >=98 wt%. This contrast in SiO2 (and Si/Al) potentially reflects precursor sediment heterogeneity, diagenetic chemical fractionation, or both. SiO2 concentrations and Si/Al ratios in chert are far greater than in modern siliceous oozes, however and often exceed values in acid-cleaned diatom tests. Compositional contrasts between chert and host sediment are also orders-of-magnitude greater than between multiple samples of the host sediment. Calculations based on the initial composition of adjacent host, observed porosity reductions from host to chert and a postulated influx of pure SiO2, construct a chert composition which is essentially identical to observed SiO2 values in chert. Thus, precursor heterogeneity does not seem to be the dominant factor influencing the current chert composition for the key elements of interest. In order to assess the extent of chemical fractionation during diagenesis, we approximate the precursor composition by analyzing host sediments adjacent to the chert. The SiO2 concentration contrast seems caused by biogenic SiO2 dissolution and transport from the local adjacent host sediment and subsequent SiO2 reprecipitation in the chert. Along with SiO2, other elements are often added (with respect to Al) to Monterey and DSDP chert during silicification, although absolute concentrations decrease. The two Monterey quartz chert nodules investigated, in contrast to the opal-CT and quartz chert lenses, formed primarily by extreme removal of carbonate and phosphate, thereby increasing relative SiO2 concentrations. DSDP chert formed by both carbonate/phosphate dissolution and SiO2 addition from the host. Manganese is fractionated during chert formation, resulting in MnO/Al2O3 ratios that no longer record the depositional signal of the precursor sediment. REE data indicate only subtle diagenetic fractionation across the rare earth series. Ce/Ce* values do not change significantly during diagenesis of either Monterey or DSDP chert. Eu/Eu* decreases slightly during formation of DSDP chert. Normative La/Yb is affected only minimally as well. During formation of one Monterey opal-CT chert lens, REE/Al ratios show subtle distribution changes at Gd and to a lesser extent near Nd and Ho. REE compositional contrasts between diagenetic states of siliceous sediment and chert are of a vastly smaller scale than has been noted between different depositional environments of marine sediment, indicating that the paleoenvironmental REE signature is not obscured by diagenetic overprinting.

Vertical distribution of relative numbers of the main groups of sound-scattering fishes in the Central Indian Ocean

Findings made in 31 catches with an Isaacs-Kidd midwater trawl in the light (09.00-16.00) and dark (21.00-04.00) periods of a day within a survey area of about 100 sq. miles with approximate center coordinates of 13°S and 78°E have been used to investigate vertical distribution of the main groups of sound-scattering fishes (35 species of the family Myctophidae and 16 species of other families). It has been shown that during daylight hours all fishes sink to depths deeper than 400 m. Data are presented concerning the fish population of night-time sound-scattering layers at depths of 70-150 m and about 400 m and of the daytime ones at depths of about 450 m.

Relative abundance and isotopic composition of calcite, dolomite and siderite from ODP Leg 164 sites

Authigenic carbonate mineral distributions are compared to pore-water geochemical profiles and used to evaluate diagenesis within sedimentary sections containing gas hydrates on the Blake Ridge (Ocean Drilling Program Sites 994, 995, and 997). Carbonate mineral distributions reveal three distinct diagenetic zones. (1) Carbonate minerals in the upper 20 m are primarily biogenic and show no evidence of diagenesis. The d13C and d18O values of calcite within this zone reflects marine carbonate (~0 per mil Peedee belemnite [PDB]) formed in equilibrium with seawater. (2) Between 20 and 100 mbsf, calcite d13C values are distinctly negative (as low as -7.0 per mil), and authigenic dolomite is common (~2-40 wt%) with d13C values between -3.6 per mil and 13.7 per mil. (3) Below 100 mbsf, dolomite abundance decreases to trace amounts, and disseminated siderite becomes the pervasive (~2-30 wt%) authigenic carbonate. Both siderite textures and stable isotope values indicate direct precipitation from pore fluids rather than dolomite replacement. The d13C and d18O values of siderite vary from 5.0 per mil to 10.9 per mil and 2.9 per mil to 7.6 per mil, respectively. Comparisons between the d13C profiles of dissolved inorganic carbon (DIC) and pore-water concentration gradients, with the d13C and d18O values of authigenic carbonates, delineate a distinct depth zonation for authigenic carbonate mineral formation. Coincidence of the most negative d13CDIC values (<=-38 per mil) and negative d13C values of both calcite and dolomite, with pore-water alkalinity increases, sulfate depletion, and decreases in interstitial Ca2+ and Mg2+ concentrations at and below 20 mbsf, suggests that authigenic calcite and dolomite formation is initiated at the base of the sulfate reduction zone (~21 mbsf) and occurs down to ~100 mbsf. Siderite formation apparently occurs between 120 and 450 mbsf; within, and above, the gas hydrate-bearing section of the sediment column (~200-450 mbsf). Siderite d13C and d18O values are nearly uniform from their shallowest occurrence to the bottom of the sedimentary section. However, present-day pore-water d13CDIC values are only similar to siderite d13C values between ~100 and 450 mbsf. Furthermore, calculated equilibrium d18O values of siderite match the measured 18O values of siderite between 120 and 450 mbsf. This interval is characterized by high alkalinity (40-120 mM) and low Ca2+ and Mg2+ concentrations, conditions that are consistent with siderite formation.

Middle Eocene bulk sediment, benthic and planktic foraminiferal stable isotope values, and relative weight percent CaCO3 content from ODP Site 207-1260

Major ice sheets were permanently established on Antarctica approximately 34 million years ago, close to the Eocene/ Oligocene boundary, at the same time as a permanent deepening of the calcite compensation depth in the world's oceans. Until recently, it was thought that Northern Hemisphere glaciation began much later, between 11 and 5million years ago. This view has been challenged, however, by records of ice rafting at high northern latitudes during the Eocene epoch and by estimates of global ice volume that exceed the storage capacity of Antarctica at the same time as a temporary deepening of the calcite compensation depth 41.6 million years ago. Here we test the hypothesis that large ice sheets were present in both hemispheres 41.6 million years ago using marine sediment records of oxygen and carbon isotope values and of calcium carbonate content from the equatorial Atlantic Ocean. These records allow, at most, an ice budget that can easily be accommodated on Antarctica, indicating that large ice sheets were not present in the Northern Hemisphere. The records also reveal a brief interval shortly before the temporary deepening of the calcite compensation depth during which the calcite compensation depth shoaled, ocean temperatures increased and carbon isotope values decreased in the equatorial Atlantic. The nature of these changes around 41.6 million years ago implies common links, in terms of carbon cycling, with events at the Eocene/Oligocene boundary and with the 'hyperthermals' of the Early Eocene climate optimum. Our findings help to resolve the apparent discrepancy between the geological records of Northern Hemisphere glaciation and model results that indicate that the threshold for continental glaciation was crossed earlier in the Southern Hemisphere than in the Northern Hemisphere.

Relative abundance of planktonic foraminifera in Pliocene and Pleistocene sediments of DSDP Hole 32-310 from Hess Rise, Central North Pacific (Table II)

Late Neogene planktonic foraminifera have been examined at Site 310 in the Central North Pacific and their stratigraphic ranges and frequencies are presented here. Blow's (1969) zonation developed for tropical regions has been applied where applicable. Where tropical index taxa are rare or absent in this temperate region, Globorotalia crassaformis, and the evolutionary bioseries G. conoidea - G. conomiozea and G. puncticulata - G. inflata have been found useful for zonal subdivisions. A correlation between stratigraphic ranges and frequency distributions of these species at Site 310 in the Central North Pacific, and Site 284 in the Southwest Pacific indicates that these species are relatively consistent biostratigraphic markers in temperate regions of both the North and South Pacific Oceans. An informal zonation for temperate latitudes of the Southwest Pacific has been established by Kennett (1973) and a similar zonal subdivision can be made at Site 310. Paleoclimatic/paleoceanographic interpretations based on coiling ratios, percent abundance, and phenotypic variations of Neogloboquadrina pachyderma indicate four major cold events during early, middle, and late Pliocene, and early Pleistocene. Faunal correlations of these events with similar events elsewhere in the Northeast and Southwest Pacific which have been paleomagnetically dated indicate the following approximate ages for these cold events: 4.7 Ma, 3.0 Ma, 2.6-1.8 Ma, and 1.2 Ma. Faunal assemblages have been divided into three groups representing cool, intermediate, and warmer water assemblages. Cool water assemblages are dominated by ~60% N. pachyderma; intermediate temperature faunas are dominated by species of Globigerina and Globigerinita and contain between 20% and 30% N. pachyderma. Warmer water assemblages are dominated by species of Globorotalia and contain <10% N. pachyderma. Frequency oscillations within these groups, in addition to paleotemperature parameters evident in N. pachyderma, afford refined paleoclimatic/paleoceanographic interpretations.