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.

Analysis of organic matter from DSDP Leg 81 Holes

Organic geochemical and visual kerogen analyses were carried out on approximately 50 samples from Leg 81 (Rockall Plateau, North Atlantic). The sediments are from four sites (Sites 552-555), Pleistocene to Paleocene in age, and represent significantly different depositional environments and sources of organic matter. The Pleistocene glacial-interglacial cycles show differences in sedimentary organic matter based on Rock-Eval pyrolysis, organic phosphorus, and pyrolysis/mass-spectrometry analyses. Glacial samples contain more organic carbon, with a larger proportion of reworked organic matter. This probably reflects increased erosion of continental and shelf areas as a result of low sea level stands. Inter glacial samples contain a larger proportion of marine organic matter as determined by organic phosphorus and pyrolysis analyses. This immature, highly oxidized marine organic matter may be associated with the skeletal organic matrix of calcareous organisms. In addition, Rock-Eval data indicate no significant inorganic-carbonate contribution to the S3 pyrolysis peak. The Pliocene-Miocene sediments consist of pelagic, biogenic carbonates. The organic matter is similar to that of the Pleistocene interglacial periods; a mixture of oxidized marine organic matter and reworked, terrestrial detritus. The Paleocene-Oligocene organic matter reflects variations in source and depositional factors associated with the isolation of Rockall from Greenland. Paleocene sediments contain primarily terrestrial organic matter with evidence of in situ thermal stress resulting from interbedded lava flows. Late Paleocene and early Eocene organic matter suggests a highly oxidized marine environment, with major periods of deposition of terrestrially derived organic matter. These fluctuations in organic-matter type are probably the result of episodic shallowing and deepening of Rockall Basins. The final stage of Eocene/Oligocene sedimentation records the accelerating subsidence of Rockall and its isolation from terrestrial sources (Rockall and Greenland). This is shown by the increasingly marine character of the organic matter. The petroleum potential of sediments containing more than 0.5% organic carbon is poor because of their thermal immaturity and their highly oxidized and terrestrial organic-matter composition.

Oxygen and carbon isotope composition of Globoquadrina venezuelana and Oridorsalis umbonatus at DSDP Leg 85 Holes

Oxygen and carbon isotope stratigraphies are given for the planktonic foraminifer Globoquadrina venezuelana (a deep-dwelling species) at three DSDP sites located along a north-south transect at approximately 133°W across the Pacific equatorial high-productivity zone. The records obtained at Sites 573 and 574 encompass the lower Miocene. At Site 575 the record includes the middle Miocene and extends into the lowermost lower Miocene. The time resolution of the planktonic foraminifer isotope record varies from 50,000 to 500,000 yr. The benthic foraminifer Oridorsalis umbonatus was analyzed for isotope composition at a few levels of Site 575. Isotope stratigraphies for all three sites are compared with carbonate, foraminifer preservation, and grain size records. We identified a number of chemostratigraphic signals that appear to be synchronous with previously recognized signals in the western equatorial Pacific and the tropical Indian Ocean, and thus provide useful tools for chronostratigraphic correlations. The sedimentary sequence at Site 573 is incomplete and condensed, whereas the sequences from Sites 574 and 575 together provide a complete lower Miocene record. The expanded nature of this record, which was recovered with minimum disturbance and provides excellent calcareous and siliceous biostratigraphic control, offers a unique opportunity to determine the precise timing of early Miocene events. Paleomagnetic data from the hydraulic piston cores at Site 575 for the first time allow late early Miocene paleoceanographic events to be tied directly to the paleomagnetic time scale. The multiple-signal stratigraphies provide clues for paleoceanographic reconstruction during the period of preconditioning before the major middle Miocene cooling. In the lowermost lower Miocene there is a pronounced shift toward greater d13C values (by -1%) within magnetic Chron 16 (between approximately 17.5 and 16.5 Ma). The "Chron 16 Carbon Shift" coincides with the cessation of an early Miocene warming trend visible in the d18O signals. Values of d13C remain high until approximately 15 Ma, then decrease toward initial (early Miocene) values near 13.5 Ma. The broad lower to middle Miocene d13C maximum appears to correlate with the deposition of organic-carbon-rich sediments around the margin of the northern Pacific in the Monterey Formation of California and its lateral equivalents. The sediments rimming the Pacific were probably deposited under coastal upwelling conditions that may have resulted from the development of a strong permanent thermocline. Deposition in the upwelling areas occurred partly under anaerobic conditions, which led to the excess extraction of organic carbon from the ocean. The timing of the middle Miocene cooling, which began after the Chron 16 Carbon Shift, suggests that the extraction of organic carbon preconditioned the ocean-atmosphere system for subsequent cooling. A major carbonate dissolution event in the late early Miocene, starting at approximately 18.7 Ma, is associated with the enrichment in 13C. The maximum dissolution is coeval with the Chron 16 Carbon Shift. It corresponds to a prominent acoustic horizon that can be traced throughout the equatorial Pacific.

Stable isotope record of the Okhotsk Sea

Stable isotope data on benthic foraminifera from more than 30 cores on the northern Emperor Seamounts and in the Okhotsk Sea are synthesized in paleohydrographic profiles spanning the depth range 1000-4000 m. Holocene (core-top) benthic foraminiferal d18O and d13C data are calibrated to modern hydrographic properties through measurements of d13C of SumCO2 and d18O of seawater. Cibicidoides stable isotope ratios are close to the d13C and equilibrium d18O of seawater, whereas Uvigerina d18O and d13C are variably offset from Cibicidoides. Glacial maximum d13C of Cibicidoides displays a different vertical profile than that of the Holocene. When results are adjusted by +0.32 per mil to account for the secular change in d13C during the last glacial maximum, the data coincide with the modern seawater and foraminiferal curves deeper than ~2 km. However, at shallower depths d13C gradually increases by as much as 1 per mil above the modern value. Furthermore, above 2 km the benthic d18O decreases by ~0.5 per mil. These results are consistent with a benthic front at ~2 km in the North Pacific (see Herguera et al., 1992), but they differ from interpretations based on trace metal data which indicate a source of nutrient-depleted deep water during glaciation. The isotopic data suggest that during glaciation there was a better ventilated watermass at intermediate depths in the far northwestern Pacific, it was relatively fresher than deep waters there, and deep waters were as nutrient-rich as today.

Stable carbon isotopes, Methane Index, and distributions of different GDGTs

Gas hydrates represent one of the largest pools of readily exchangeable carbon on Earth's surface. Releases of the greenhouse gas methane from hydrates are proposed to be responsible for climate change at numerous events in geological history. Many of these inferred events, however, were based on carbonate carbon isotopes which are susceptible to diagenetic alterations. Here we propose a molecular fossil proxy, i.e., the "Methane Index (MI)", to detect and document the destabilization and dissociation of marine gas hydrates. MI consists of the relative distribution of glycerol dibiphytanyl glycerol tetraethers (GDGTs), the core membrane lipids of archaea. The rational behind MI is that in hydrate-impacted environments, the pool of archaeal tetraether lipids is dominated by GDGT-1, -2 and -3 due to the large contribution of signals from the methanotrophic archaeal community. Our study in the Gulf of Mexico cold-seep sediments demonstrates a correlation between MI and the compound-specific carbon isotope of GDGTs, which is strong evidence supporting the MI-methane consumption relationship. Preliminary applications of MI in a number of hydrate-impacted and/or methane-rich environments show diagnostic MI values, corroborating the idea that MI may serve as a robust indicator for hydrate dissociation that is useful for studies of global carbon cycling and paleoclimate change.

Geochemistry of Neogene volcanic ashs in ODP Leg 124 holes

Mineralogical and geochemical analyses were performed on 40 ash layers of Pleistocene to late Miocene age, recovered during Leg 124 in the Celebes and Sulu Seas (Sites 767, 768, and 769). They provide information on alteration processes related to burial diagenesis. The zonal distribution of secondary volcanic products emphasizes a major diagenetic change, characterized by the complete replacement of volcanic glass by an authigenic smectite-phillipsite assemblage, in tephra layers dated at 3.5-4 Ma. This diagenetic "event" occurs simultaneously in the two basins, and, on the basis of isotopic data, under low-temperature conditions. It is independent of distinct sedimentation rates and related to a relative quiescence of on-land volcanic activity. This period suggests a more uniform paleooceanographic situation having tectonic significance, and probably reflects a kinetic and environmental control of diagenetic reactions.