Strontium and neodymium isotope data for barite separates and pore waters, and isotope and concentration data for foraminifera and fish teeth from DSDP Leg 85 sediments

Strontium and neodymium isotopic data are reported for barite samples chemically separated from Late Miocene to Pliocene sediments from the eastern equatorial Pacific. At a site within a region of very high productivity close to the equator, 87Sr/86Sr ratios in the barite separates are indistinguishable from those of foraminifera and fish teeth from the same samples. However, at two sites north of the productivity maximum barite separates have slightly, but consistently lower (averaging 0.000062) ratios than the coexisting phases, although values still fall within the total range of published values for the contemporaneous seawater strontium isotope curve. We examine possible causes for this offset including recrystallization of the foraminifera, fish teeth or barite, the presence of non-barite contaminants, or incorporation of older, reworked deep-sea barite; the inclusion of a small amount of hydrothermal barite in the sediments seems most consistent with our data, although there are difficulties associated with adequate production and transportation of this phase. Barite is unlikely to replace calcite as a preferred tracer of seawater strontium isotopes in carbonate-rich sediments, but may prove a useful substitute in cases where calcite is rare or strongly affected by diagenesis. In contrast to the case for strontium, neodymium isotopic ratios in the barite separates are far from expected values for contemporary seawater, and appear to be dominated by an (unobserved) eolian component with high neodymium concentration and low 143Nd/144Nd. These results suggest that the true potential of barite as an indicator of paleocean neodymium isotopic ratios and REE patterns will be realized only when a more selective separation procedure is developed.

Accumulation rate, carbon geochemistry and clay mineralogy of ODP Site 181-1123 sediments, southwest Pacific

Site 1123 is located on the northeastern flank of the Chatham Rise. Sedimentological and clay mineralogical analyses indicate a very fine grained carbonate-rich sediment. Smectite and illite are the main constituents of the clay mineral assemblage. High smectite values in the Eocene decrease in younger sediment sequences. Illite and chlorite concentrations increase in younger sediments with significant steps at 13.5, 9, and 6.4 Ma. The kaolinite content is near the detection limit and not significant. We observed only small fluctuations of the clay mineral composition, which indicates a uniform sedimentation process, probably driven by long-term processes. Good correspondence is shown between increasing illite and chlorite values and the tectonic uplift history of the Southern Alps.

Composition of bottom sediments from the Campeche Bank

A complete section of an unconsolidated sedimentary sequence about 5 m thick was sampled in the western margin of the Campeche Bank with use of gravity cores. The sequence forms a flat sea bottom at depth of 51-53 m and rests on a consolidated basement composed of coral limestones and carbonate sandstones. Initiation of deposition of unconsolidated sediments in this area is related to a sea transgression caused by sea level rise that followed the Würm glaciation stage about 10-11 ky ago. Analysis of grain size and chemical compositions of sediments and study of biogenic carbonate remains made it possible to outline environmental changes in this region during the last 10 ky.

Sediments in Arctic sea ice

Despite the Arctic sea ice cover's recognized sensitivity to environmental change, the role of sediment inclusions in lowering ice albedo and affecting ice ablation is poorly understood. Sea ice sediment inclusions were studied in the central Arctic Ocean during the Arctic 91 expedition and in the Laptev Sea (East Siberian Arctic Region Expedition 1992). Results from these investigations are here combined with previous studies performed in major areas of ice ablation and the southern central Arctic Ocean. This study documents the regional distribution and composition of particle-laden ice, investigates and evaluates processes by which sediment is incorporated into the ice cover, and identifies transport paths and probable depositional centers for the released sediment. In April 1992, sea ice in the Laptev Sea was relatively clean. The sediment occasionally observed was distributed diffusely over the entire ice column, forming turbid ice. Observations indicate that frazil and anchor ice formation occurring in a large coastal polynya provide a main mechanism for sediment entrainment. In the central Arctic Ocean sediments are concentrated in layers within or at the surface of ice floes due to melting and refreezing processes. The surface sediment accumulation in central Arctic multi-year sea ice exceeds by far the amounts observed in first-year ice from the Laptev Sea in April 1992. Sea ice sediments are generally fine grained, although coarse sediments and stones up to 5 cm in diameter are observed. Component analysis indicates that quartz and clay minerals are the main terrigenous sediment particles. The biogenous components, namely shells of pelecypods and benthic foraminiferal tests, point to a shallow, benthic, marine source area. Apparently, sediment inclusions were resuspended from shelf areas before and incorporated into the sea ice by suspension freezing. Clay mineralogy of ice-rafted sediments provides information on potential source areas. A smectite maximum in sea ice sediment samples repeatedly occurred between 81°N and 83°N along the Arctic 91 transect, indicating a rather stable and narrow smectite rich ice drift stream of the Transpolar Drift. The smectite concentrations are comparable to those found in both Laptev Sea shelf sediments and anchor ice sediments, pointing to this sea as a potential source area for sea ice sediments. In the central Arctic Ocean sea ice clay mineralogy is significantly different from deep-sea clay mineral distribution patterns. The contribution of sea ice sediments to the deep sea is apparently diluted by sedimentary material provided by other transport mechanisms.

Organic chemistry of sediments of the Peru margin

Organic-carbon-rich anoxic sediments from the continental shelf (Site 680) and the lower continental slope (Site 688) off Peru were studied to determine factors controlling the accumulation of reduced sulfur. High concentrations of organic matter in diatomaceous muds, its thermal immaturity, and the presence of abundant hydrogen-containing organic compounds lead to the conclusion that organic matter is not limiting for reduced sulfur formation. Rather, high degrees of iron pyritization at Site 680 limit pyrite accumulation in sediments from this shelf site. The low degree of iron pyritization and nearly complete reduction of dissolved sulfate at Site 688 suggest that a lack of interstitial sulfate is limiting pyrite formation there. Although factors that limit the formation of sedimentary iron sulfide are different at each site, the resulting average reduced-sulfur concentrations are remarkably similar (0.85 wt.% at Site 680 and 0.86 wt.% at Site 688). Carbon to sulfur (C/S) ratios are higher in samples containing in excess of 3 wt.% organic carbon than the average of 2.8 in normal marine sediments and have been primarily influenced by variations in organic matter concentrations.

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.

Descriptions, isotopes and minerals of sediments at DSDP Leg 64 Holes

Mineralogical and oxygen isotopic analyses of samples from Deep Sea Drilling Project Sites 477, 481, and 477 in the Guaymas Basin indicate the existence of two distinct hydrothermal systems. In the first, at Sites 481 and 478, hot dolerite sills intruded into highly porous hemipelagic siliceous mudstones that were moderately rich in organic matter, thermally altered the adjacent sediments, and expelled hydrothermal pore fluids. The second, at Site 477 and active at present, is most probably caused by a recent igneous intrusion forming a magma chamber at shallow depth. In the first hydrothermal system, the main thermal reactions above and below the sills are dissolution of opal-A and formation of quartz, either directly or through opal-CT; formation of smectite; formation of analcime only above the sills; dissolution and recrystallization of calcite and occasional formation of dolomite or protodolomite. The d18O values of the hydrothermally altered sediments range from 9.9 to 12.2 per mil (SMOW). The d18O values of recrystallized calcites above the first sill complex, Site 481, indicate temperatures of 140° to 170°C. No fluid recharge is required in this system. The thickness of the sill complexes and the sequence and depth of intrusion into the sediment column determine the thickness of the alteration zones, which ranges from 2 or 3 to approximately 50 meters. Generally, the hydrothermally altered zone is thicker above than below the sill. In the second type, the sediments are extensively recrystallized. The characteristic greenschist-facies mineral assemblage of quartz-albite-chlorite-epidote predominates. Considerable amounts of pyrite, pyrrhotite, and sphene are also present. The lowest d18O value of the greenschist facies rocks is 6.6 per mil, and the highest d18O value of the associated pore fluids is +1.38 per mil (SMOW). The paragenesis and the oxygen isotopes of individual phases indicate alteration temperatures of 300 ± 50°C. On the basis of the oxygen isotopes of the solids and associated fluids, it is concluded that recharge of fluids is required. The water/rock ratio in wt.% is moderate, approximately 2/1 to 3/1 - higher than the calculated water/rock ratio of the hydrothermal system at the East Pacific Rise, 21 °N.

Stable isotope composition of early Danian sediments from the Atlantic Ocean

A long-standing question in Paleogene climate concerns the frequency and mechanism of transient greenhouse gas-driven climate shifts (hyperthermals). The discovery of the greenhouse gas-driven Paleocene-Eocene Thermal Maximum (PETM; ~55 Ma) has spawned a search for analogous events in other parts of the Paleogene record. On the basis of high-resolution bulk sediment and foraminiferal stable isotope analyses performed on three lower Danian sections of the Atlantic Ocean, we report the discovery of a possible greenhouse gas-driven climatic event in the earliest Paleogene. This event - that we term the Dan-C2 event - is characterized by a conspicuous double negative excursion in delta13C and delta18O, associated with a double spike in increased clay content and decreased carbonate content. This suggests a double period of transient greenhouse gas-driven warming and dissolution of carbonates on the seafloor analogous to the PETMin the early Paleocene at ~65.2 Ma. However, the shape of the two negative carbon isotope excursions that make up the Dan-C2 event is different from the PETM carbon isotope profile. In the Dan-C2 event, these excursions are fairly symmetrical and each persisted for about ~40 ky and are separated by a short plateau that brings the combined duration to ~100 ky, suggesting a possible orbital control on the event. Because of the absence of a long recovery phase, we interpret the Dan-C2 event to have been associated with a redistribution of carbon that was already in the biosphere. The Dan-C2 event and other early Paleogene hyperthermals such as the short-lived early Eocene ELMO eventmay reflect amplification of a regular cycle in the size and productivity of the marine biosphere and the balance between burial of organic and carbonate carbon.

Petrology and carbon and oxygen stable isotopic composition of macrofossils and sediments from the Blake-Bahama Formation, DSDP Hole 93-603B

Strata that record the evolutionary history of the North American continental margin in a region that serves as the basin margin interface between allochthonous sedimentation from the continent and pelagic sedimentation from the oceanic realm were recovered at Deep Sea Drilling Project Site 603, on the lower continental rise. The lowermost unit recovered at this site is composed of upper Berriasian-Aptian interbedded laminated limestone and bioturbated limestone with sandstone to claystone turbidites. This unit can be correlated with the Blake-Bahama Formation in the western North Atlantic. Studies of the laminated and bioturbated limestones were used to determine the depositional environment. Geochemical and petrographic studies suggest that the laminated limestones were deposited from the suspended particulate loads of the nepheloid layer associated with weak bottom-current activity as well as moderate to poorly oxygenated bottom-water conditions. Fragments of macrofossils are also found in the Blake-Bahama Formation drilled at Site 603. Twelve specimens and their host sediment were analyzed for their carbon and oxygen isotopic composition. The macrofossil samples chosen for analysis consist of nine samples of Inoceramus, two ammonite aptychi, and one belemnite sample. Depletion in 18O is observed in recrystallized specimens. The ammonite aptychi have been diagenetically altered and/or exhibit evidence of isotopic fractionation by the organism. Oxygen isotope paleotemperatures obtained from five well-preserved specimens - four of Inoceramus and one of a belemnite - suggest that bottom-water temperatures in the North Atlantic Basin during the Early Cretaceous were very warm, at least 11°C.

Composition of Messinian sediments from the Tyrrhenian Sea

The data base for this study is represented by essentially nonevaporitic Messinian sediments recovered at ODP Sites 654, 653, 652, and 656 along the eastern Sardinian margin, and of the overlying early Pliocene oozes. Grain-size distribution, carbonate content, and microscopic observation of the sand size fractions were investigated. Messinian paleoenvironments, documented in the western Tyrrhenian Sea (ODP Sites 654 and 653), provide additional evidence supporting the deep basin desiccation model. A sharp lithologic contrast between early Pliocene pelagic oozes and latest Messinian conformable gypsiferous silts supports this model. The "lago-mare" biofacies was only occasionally observed in the shallowest site and is limited to the topmost part of the Messinian. Sites 652 and 656, lying in the deeper part of the Tyrrhenian and located on the downthrown side of an important eastward dipping fault system known as "Faglia centrale" are characterized by terrigenous sedimentation, with partly recycled minor evaporites. Of special interest is Site 652, where the thickness of the (probable) Messinian is 530 m. Sedimentary characters indicate a permanently subaqueous but nonmarine environment, with turbidites accumulating in a rapidly subsiding basin. According to the model proposed, this basin was fed by continental waters during times of maximum evaporitic draw-down, with temporary marine incursions from the west or southwest when the water level was higher. A basement ridge separated the evaporating pond from this endoreic lake located on the opposite (eastern) margin of the Tyrrhenian Basin, which was then limited to its western part. Post-Messinian reactivation of the "Faglia centrale" is necessary to account for the inversion of the relief.

Geochemistry of altered phases, basalts and sediments of ODP Site 136-843

40Ar-39Ar incremental heating experiments on a relatively unaltered basalt from Site 843 yield a crystallization age of 110 ± 2 Ma for the central Pacific Ocean igneous basement near Hawaii. Previous estimates of the age of the basement inferred by indirect methods and from radiometric dates of the South Hawaiian Seamounts are too young by 20-30 m.y. Phyllosilicate alteration minerals from veins in the Site 843 basalts define a Rb/Sr isochron with an age of 94.5 ± 0.5 Ma. The isochron records the last equilibration of the phyllosilicate minerals with a hydrothermal fluid at about 16 m.y. after the formation of the igneous basement. The last event recorded by calcite veins is the sealing of the crust by a sufficient thickness of sediment to impede the free circulation of seawater into the crust. The chemistry of the alteration minerals indicates the rare earth elements in the hydrothermal solutions were derived from alteration of the basalts and, furthermore, were transported in solution as metal species and carbonate complexes. Calcite with approximately seawater 87Sr/86Sr, but Sr contents too low to precipitate directly from seawater, is suggested to have formed at a late stage in the alteration history of the crust by the reaction of seawater with calcite precipitated earlier from basalt-dominated hydrothermal fluids.