Geochemistry at DSDP Leg 75 Holes

Samples of sediments and rocks collected at DSDP Sites 530 and 532 were analyzed for 44 major, minor, and trace elements for the following purposes: (1) to document the downhole variability in geochemistry within and between lithologic units; (2) to document trace-element enrichment, if any, in Cretaceous organic-carbon-rich black shales at Site 530; (3) to document trace-element enrichment, if any, in Neogene organic-carbon-rich sediments at Site 532; (4) to document trace-element enrichment, if any, in red claystone above basalt basement at Site 530 that might be attributed to hydrothermal activity or weathering of basalt. Results of the geochemical analyses showed that there are no significant enrichments of elements in the organic-carbon-rich sediments at Site 532, but a number of elements, notably Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn, are enriched in the Cretaceous black shales. These elements have different concentration gradients within the black-shale section, however, which suggests that there was differential mobility of trace elements during diagenesis of interbedded more-oxidized and less-oxidized sediments. There is little or no enrichment of elements from hydrothermal activity in the red claystone immediately overlying basalt basement at Site 530, but slight enrichments of several elements in the lowest meter of sediment may be related to subsea weathering of basalt

Geochemistry at DSDP Leg 74 Holes

Clay mineralogical and inorganic geochemical data from the Campanian to the Pleistocene provide information bearing on the evolution of both continental and marine paleoenvironments in the Walvis Ridge area. (1) Alteration processes of basalts occurred under subaerial conditions during the Campanian and Maestrichtian and were virtually absent in deeper marine environments. (2) Strong tectonic effects were present during the Campanian and persisted until the early Eocene. (3) Subsidence of this part of the Walvis Ridge became important during the late Maestrichtian and continued into the Paleocene and Eocene. (4) The influence of global climatic cooling was evident from the late Eocene on. (5) Modification of oceanic circulation and the increasing influence of surface and deep water masses on the sedimentation characterized the Cenozoic.

Age models, accumulation rates, sand and carbonates at DSDP Leg 74 holes

Accumulation rates for the five sites drilled during Leg 74 of the Glomar Challenger are presented on a common timescale based on calibration of datum levels to paleomagnetic records in Leg 74 sediments for the Paleogene, and a new compilation by Berggren et al. (1985), for the Neogene, and using the seafloor-spreading magnetic anomaly timescale of Kent (1985). We present data on accumulation of total sediment, of foraminifers, of the noncarbonate portion, and of fish teeth that give a history of productivity, winnowing, carbonate dissolution, and nonbiogenic input to what was then a part of the South Atlantic at about 30 deg S.

Neogene and Quaternary paleoenvironmental history at DSDP Leg 71 Holes

The Neogene and Quaternary sedimentary record of Leg 71 and previously drilled sequences from the Southern Ocean reveal evidence of a major late Miocene change of oceanic and glacial conditions in the southern high latitudes during paleomagnetic Chron 9. The characteristics of late Miocene sedimentation and in particular the study of erosional patterns and ice-rafted debris suggest the following conclusions. 1) In the late Miocene, the Polar Front first migrated to the northern latitudes of the Southern Ocean and surface water temperatures became similar to those of today. 2) Extensive ice shelves or ice tongues were not present along the Antarctic margin until late Chron 9 (about 9.0 Ma). 3) Before Chron 9, West Antarctica was occupied by an archipelago and the West Antarctic Sea. 4) Extensive ice shelves formed in the West Antarctic region, eventually coalescing and thickening to form the grounded West Antarctic ice sheet by Chron 9. 5) The newly formed West Antarctic ice sheet was probably unstable and frequently became an ungrounded ice shelf, thus accounting for the scarcity of late Miocene ice-rafted debris. 6) Extensive erosion or nondeposition of sediment was probably the result of increased Antarctic Bottom Water (AABW) formation in the West Antarctic region during the initial formation of extensive West Antarctic ice shelves and during periods when the West Antarctic ice sheet was ungrounded. 7) In the Southwest Atlantic, AABW velocity waned during the latest Miocene. During the late Gilbert Chron a major and permanent change occurred in the pattern of ice-rafting to the South Atlantic, and after 4.35 Ma the increased IRD accumulation rate and frequency of major episodes of IRD accumulation suggest increased stability of the West Antarctic ice sheet. In addition, radiolarian faunas of Hole 514 record at least eight migrations of the Polar Front to the north of the site during the past 4.07 m.y. An apparent increase in the frequency of Polar Front migrations occurred about 2.7-2.6 Ma, possibly in response to oceanic change induced by fluctuations in glacial conditions of the Northern Hemisphere.

Migration of C1 to C8 volatile organic compounds in sediments at DSDP Hole 75-530A

The distribution of C1 to C8 hydrocarbons in sediment samples from DSDP Leg 75, Hole 530A, indicates that significant amounts of methane and ethane have migrated from organic-rich to organic-lean shales in close proximity. Most compounds larger than ethane are not migrating out of black shales, where they occur in high concentrations. These results lead to a general model for assessing migration. In addition, three shale types are identified on the basis of organic carbon and pyrolysis products and patterns.

Hydrous and anhydrous pyrolysis of DSDP Leg 75 kerogens

The aliphatic hydrocarbon distributions obtained from the natural bitumens of three Leg 75 sediments were compared using computerised gas chromatography-mass spectrometry (C-GC-MS). The kerogens isolated from these sediments were heated in sealed tubes at 330°C using the techniques of hydrous (i.e. heating kerogen in the presence of water) and anhydrous pyrolysis (i.e. heating dry kerogen alone). These experiments were then repeated at a lower temperature (280°C). At 330°C, under anhydrous conditions, considerable destruction of biomarkers in the ancient kerogens (i.e. pre-Tertiary) occurred, whereas with water present significant amounts of hopanes were obtained. However, with more recent kerogens (which contain larger amounts of chemically bound water), both anhydrous and hydrous pyrolysis gave a similar suite of biological markers, in which long chain acyclic isoprenoids (C40) are significant components. Lowering the temperature of pyrolysis to 280°C yielded biological markers under both hydrous and anhydrous conditions for all kerogens. n-Alkenes were not detected in any of the pyrolysates; however, a single unknown triterpene was discovered in several of the hydrous and anhydrous pyrolysates. The results tentatively indicate that the chief value to petroleum research of kerogen hydrous pyrolysis lies in its ability to increase the yield of pyrolysate. High temperature hydrous pyrolysis (280-330°C), under high pressure (2000 psi), does not appear to mimic natural conditions of oil generation. However, this study does not take into account whole rock pyrolysis.

Stable isotope record of Cibicidoides spp. from Late Miocene sediments of the Southern Ocean

Deepwater circulation plays an important role in climate modulation through its redistribution of heat and salt and its control of atmospheric CO2. Oppo and Fairbanks (1987, doi:10.1016/0012-821X(87)90183-X) showed that the Southern Ocean is an excellent monitor of deepwater circulation changes for two reasons: (1) the Southern Ocean is a mixing reservoir for incoming North Atlantic Deep Water and recirculated water from the Pacific and Indian oceans; and (2) the nutrient/delta13C tracers of deepwater are not significantly changed by surficial processes within the Southern Ocean. We can extend these principles to the late Miocene because tectonic changes in the Oligocene and early and middle Miocene developed near-modern basinal configurations. However, on these time scales, changes in the oceanic carbon reservoir and mean ocean nutrient levels also affect the delta13C differences between ocean basins. From 9.8 to 9.3 Ma, Southern Ocean delta13C values oscillated between high North Atlantic values and low Pacific values. The Southern Ocean recorded delta13C values similar to Pacific values from 9.2 to 8.9 Ma, reflecting a low contribution of Northern Component Water (NCW). The delta13C differences between the NCW and Pacific Outflow Water (POW) end-members were low from 8.9 to 8.0 Ma, making it difficult to discern circulation patterns. NCW production may have completely shutdown at 8.6 Ma, allowing Southern Component Water (SCW) to fill the North Atlantic and causing the delta13C values in the North Atlantic, Pacific, and Southern oceans to converge. Deepwater delta13C patterns resembling the modern distributions evolved by 7.0 Ma: delta13C values were near 1.0 per mil in the North Atlantic; 0.0 per mil in the Pacific; and 0.5 per mil in the Southern Ocean. Development of near-modern delta13C distributions by 7.0 Ma resulted not only from an increase in NCW flux but also from an increase in deepwater nutrient levels. Both of these processes increased the delta13C difference between the North Atlantic and Pacific oceans. Deepwater circulation patterns similar to today's operated as early as 9.8 Ma, but were masked by the lower nutrient/delta13C differences. During the late Miocene, 'interglacial' intervals prevailed during intervals of NCW production, while 'glacial' intervals occurred during low NCW production.

Stable isotope record of Cibicidoides spp. from early and middle Miocene sediments

The middle Miocene delta18O increase represents a fundamental change in the ocean-atmosphere system which, like late Pleistocene climates, may be related to deepwater circulation patterns. There has been some debate concerning the early to early middle Miocene deepwater circulation patterns. Specifically, recent discussions have focused on the relative roles of Northern Component Water (NCW) production and warm, saline deep water originating in the eastern Tethys. Our time series and time slice reconstructions indicate that NCW and Tethyan outflow water, two relatively warm deepwater masses, were produced from ~20 to 16 Ma. NCW was produced again from 12.5 to 10.5 Ma. Another feature of the early and middle Miocene oceans was the presence of a high delta13C intermediate water mass in the southern hemisphere, which apparently originated in the Southern Ocean. Miocene climates appear to be related directly to deepwater circulation changes. Deep-waters warmed in the early Miocene by ~3°C (?20 to 16 Ma) and cooled by a similar amount during the middle Miocene delta18O increase (14.8 to 12.6 Ma), corresponding to the increase (?20 Ma) and subsequent decrease (~16 Ma) in the production of NCW and Tethyan outflow water. Large (>0.6 per mil), relatively rapid (~0.5 m.y.) delta18O increases in both benthic and planktonic foraminifera (i.e., the Mi zones of Miller et al. (1991a) and Wright and Miller (1992a)) were superimposed in the long-term deepwater temperature changes; they are interpreted as reflecting continental ice growth events. Seven of these m.y. glacial/interglacial cycles have been recognized in the early to middle Miocene. Two of these glacial/interglacial cycles (Mi3 and Mi4) combined with a 2° to 3°C decrease in deepwater temperatures to produce the middle Miocene delta18O shift.

Geochemistry of Walvis Ridge basalts

The proposed origins for the Enriched Mantle I component are many and various and some require an arbitrary addition of an exotic component, be it pure sediment or an enriched melt from the subcontinental lithosphere. With Pitcairn, Walvis Ridge is the 'type-locality' for the Enriched Mantle I (EMI) component. We analyzed basalts from DSDP Site 525A, Site 527 and Site 528 on the Walvis Ridge with the aim to constrain the history of its source. The isotopic compositions we measured for the three sites overlap with the values obtained by Richardson et al. (1982a) and extend towards less radiogenic Sr and more radiogenic Pb and Nd isotopic compositions. We used our new trace element and radiogenic isotope (Hf, Nd, Pb and Sr) characterization in combination with the literature data to produce the simplest possible model that satisfies the trace element and isotopic constraints. Although the elevated 207Pb/204Pb with respect to 206Pb/204Pb predicts an ancient origin for EMI, none of the proposed origins had modeled it as such. The data is consistent with the EMI composition being formed by the addition of a melt to a mantle with bulk Earth-like composition followed by melt extraction of a low degree melt. The timing of these two events is such that the metasomatism has to have taken place prior to 4 Ga and the subsequent melt removal before 3.5 Ga. This confirms the expectation of an ancient character for the EMI component. The Walvis Ridge data shows two distinct two component mixing trends: one formed by the less enriched Site 527 and Site 528 basalts and one formed by the Site 525A basalts. The two trends have the EMI endmember in common. The less depleted end of the Site 527-Site 528 basalts is FOZO-like and can be explained by the addition of a recycled component (basaltic oceanic crust plus sediment). This recycled component was altered during subduction. The sense and magnitude of the chemical fractionation resulting from the subduction alteration are in agreement with dehydration experiments on basalts and sediment. Compared to other EMI like basalts the Walvis Ridge basalts have flatter REE patterns and show less fractionation between large ion lithophile and heavy REE elements. Using the isotopic compositions as constrains for the parent-daughter ratios we were able to model the trace element patterns of the basalts as melting between 5 and 10% for Site 525A and between 10 and 15% for the depleted end of the Site 528-Site 527 array. In all cases a significant portion of melting takes place in the garnet stability field.