Lead and strontium isotopic composition of some metalliferous and pelagic sediments and basalts at DSDP Leg 70 Holes

In recent years, metalliferous sediments have been discovered overlying newly generated oceanic crust in the East Pacific, North Atlantic, Indian Ocean, Red Sea, Gulf of Aden, and elsewhere (e.g., Boström, 1973; Lalou et al., 1977; Bischoff, 1969; Boström and Fisher, 1971; Cann et al., 1977, respectively). Such material has also been recovered by drilling from sediments lying upon older oceanic crust (Boström et al., 1972, 1976; Horowitz and Cronan, 1976). Hydrothermal circulation of seawater at a spreading ridge results in the leaching of Fe, Mn, and possibly other elements from the basaltic volcanic layer and their transport and discharge into ocean bottom waters, whereupon fine-grained Fe-Mn-rich precipitates form and settle into the ambient sediment (cf. Corliss, 1971; Dasch et al., 1971; Spooner and Fyfe, 1973; Bischoff and Dickson, 1975; Heath and Dymond, 1977; Corliss et al., 1979, Edmond et al., 1979). Mn-rich crusts have also been recovered from active ridges and are inferred to have formed in the vicinity of hydrothermal discharge areas (Scott et al., 1974; Moore and Vogt, 1976; Corliss et al., 1978; Hoffert et al., 1978). The source of the trace elements in the metalliferous deposits is generally not clear. They may be derived from seawater by adsorption onto the precipitates or crusts, or from hydrothermal solutions which have leached them from the basalts. Pb, however, can be used as a geochemical tracer because of the known isotopic compositional differences between oceanic basalts and seawater. Isotopic investigations of Pb in ferruginous sediments from the East Pacific have shown that it has been derived partly or mostly from a basaltic source (Bender et al., 1971; Dasch et al., 1971; Dymond et al., 1973). In the present study, Pb isotopic analyses have been made of a suite of metalliferous sediments (nontronite, Mn-oxide crust, Mn-Fe-oxide mud), pelagic sediments, and basalts from the Galapagos mounds area. The main purposes of the Pb study were to determine the source or sources of Pb in the metalliferous sediments, and whether or not stratigraphic variations exist in the isòtopic composition of Pb in the sediments.

Magnetic properties and heavy metals at DSDP Hole 83-504B

We report measurements of magnetic intensity, inclination, initial susceptibility, Koenigsberger's ratio, saturation magnetization, and Curie temperatures of 68 basalt samples from the Leg 83 section of Hole 504B. As in the upper part of the hole, reversely magnetized units predominate. Intensities of natural remanent magnetization vary widely, but the range of variation is an order of magnitude less than in the upper part of the hole. This and the other properties measured indicate that the magnetic characteristics of basalts from Hole 504B have been strongly affected by hydrothermal alteration, particularly in the deeper, Leg 83 section. The alteration states of the magnetic samples were studies using Xray diffraction, electron microprobe, X-ray fluorescence, and ion coupled plasma. Our results suggest three alteration zones in Hole 504B: a low-temperature zone (274.5-890 m) and two high-temperature zones (890-1050 m and 1050- 1350 m), differing in the number of veins observed in the samples and presumably differing in the volumes of hydrothermal fluids which reacted with the basalts.

Preliminary ichthyolith biostratigraphy and age profiles at DSDP Sites 91-595 and 91-596

Seventy meters of Cenozoic and Mesozoic pelagic clay cored at DSDP Sites 595 and 596 provide the basis for a preliminary analysis of ichthyolith biostratigraphy in the southwest Pacific. A most likely order of the more reliable ichthyolith events is compared with a synthesis of ichthyolith biostratigraphy in the North Pacific and with dated composite ranges. The resultant preliminary ichthyolith stratigraphy suggests that the Cenozoic is represented by the upper 20 m at Site 596 and 16 to 22 m at Site 595. Mixing of taxa precludes a clear recognition of the Cretaceous/Tertiary boundary at Site 595. The occurrence of 13 newly described subtypes is recorded in Mesozoic sediments at Sites 595 and 596. These new subtypes and previously described Mesozoic forms may be useful for recognizing Mesozoic subdivisions when their occurrences in sequences dated by other microfossils are investigated.

Stable isotope and trace element geochemistry of carbonate sediments at DSDP Holes 87-577 and 6-47.2

Detailed analyses of well-preserved carbonate samples from across the Cretaceous/Tertiary boundary in Hole 577 have revealed a significant decline in the d13C values of calcareous nannoplankton from the Maestrichtian to the Danian Age accompanied by a substantial reduction in carbonate accumulation rates. Benthic foraminifers, however, do not exhibit a shift in carbon composition similar to that recorded by the calcareous nannoplankton, but actually increase slightly over the same time interval. These results are similar to the earlier findings at two North Pacific Deep Sea Drilling Project locations, Sites 47.2 and 465, and are considered to represent a dramatic decrease in oceanic phytoplankton production associated with the catastrophic Cretaceous/Tertiary boundary extinctions. In addition, the change in carbon composition of calcareous nannoplankton across the Cretaceous/Tertiary boundary at Hole 577 is accompanied by only minor changes in the oxygen isotope trends of both calcareous nannoplankton and benthic foraminifers, suggesting that temperature variations in the North Pacific from the late Maestrichtian to the early Danian Age were insignificant.

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.

Inorganic geochemistry, epoch and water content in sediments at DSDP Hole 91-595A

This chapter summarizes the principal results of drilling at Deep Sea Drilling Project (DSDP) Site 595, where the Ngendei Seismic Experiment and the emplacement of DARPA's Marine Seismic System (MSS) were carried out. Background and objectives for this work are presented in the introductory chapter to this volume. Interpretation of the seismic experiment and drilling results are presented in subsequent parts of this volume. The chapter also provides a detailed operational summary of the successful deployment of the MSS during Leg 91.

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.

Geochemistry of carbon at DSDP Hole 61-462

Seven quartered sections of Pliocene to Mesozoic (Cenomanian) cores from the Nauru Basin contain primarily marine organic matter admixed with detectable amounts of terrigenous organic matter. The mixture is immature with respect to organic genesis. Chemical properties of this organic matter are compared with properties of other deep-ocean cores from DSDP sites in the central Pacific.

Geochemistry of DSDP Holes 60-453 and 60-454A

Pliocene and Pleistocene volcanic glass fragments from Mariana Trough sediments at Sites 453 (16 samples) and 454 (4 samples), located near the western edge of the trough and just west of the spreading axis, respectively, have been analyzed for major elements with an electron microprobe. They derive from volcanic activity on the present Mariana active arc. The glasses from Site 453 are all tholeiitic with a wide range of SiO2 contents. Those less than 2 m.y. old have slightly lower TiO2 and higher K2O contents than the older ones. The glasses from Site 454 are all Pleistocene and resemble the younger glasses at Site 453. Major element compositions of the older basaltic glasses at Site 453 are similar to those of the Mariana Trough basalts drilled on Leg 60. Both older and younger suites of glasses differ from the composition of rocks exposed on the active arc, which are assumed to be younger than any of the samples studied (i.e., about 200,000 y.). A third suite is represented by the arc rocks exposed on the volcanic islands. These have a smaller range of SiO2 contents and contain more A12O3 but less K2O, TiO2, and FeO1 (total Fe as FeO) than the sediment glasses studied. Further, a plot of FeO1 against MgO for the arc rocks does not follow the island arc tholeiite trend of the trough sediment glasses. Using the major element compositions of the arc rocks and sediment glasses, we can recognize three phases of volcanic activity, as indicated. The first evidence of the oldest phase of activity occurs 5 Ma, about 4.5 m.y. after the trough started to form. The second commenced about 2 Ma, and the last, including present-day activity, began within the last 200,000 y. Initially the rocks had major element affinities with the tholeiitic Mariana Trough seafloor, but this influence declined as the trough widened.

Mineralogy and pyrolysis at DSDP Hole 62-463

A 15-meter sequence of early Aptian organic-matter-rich sediments, cored at Deep Sea Drilling Project Site 463 (western Mid-Pacific Mountains) has been submitted for detailed mineralogical studies (XRD, SEM) and organiccarbon characterization. Although intense diagenesis has obscured the sedimentary record of depositional conditions, the history has been tentatively reconstructed. Through sustained volcanic activity and alteration processes on the archipelago, large amounts of silica were released into the sea water, resulting in a "bloom" of radiolarians. Hard parts settled in large amounts, yielding a hypersiliceous sediment; amorphous silica was diagenetically transformed into chalcedony, opal-CT and clinoptilolite through dissolution and recrystallization. Oxidization of part of the radiolarian soft parts (1) depleted the sea water in dissolved oxygen, allowing the burial of organic matter, and (2) generated carbon dioxide which led to dissolution of most of the calcareous tests. Moderate depositional depth and a high sedimentation rate are though to have prevailed during this episode. An immature stage of evolution is assigned to the studied organic matter, which is of two origins: autochthonous marine material, and allochthonous humic compounds and plant debris. Rhythmic sedimentation characterizes the distribution of the organic matter; each sequence shows (1) an upward progressive increase in organic-carbon content, and (2) an upward enrichment in marine organic matter.

Chemical composition of sediments from DSDP Site 223, Indian Ocean

Detailed major- and trace-element chemistry is presented for 41 sediment samples from DSDP Site-223 borehole cores. A marked change in chemical (and mineralogical) character is shown at the end of the Early Miocene Epoch which relates to tectonic events and associated changes in sedimentary regime. Enrichment in the contents of such elements as Mg, Cr and Ni compared with average values for fine-grained sediments occurs throughout the sequence and is particularly marked in the upper group of samples. A basic-ultrabasic provenance is suggested - the Oman ophiolites. Leaching with combined acid-reducing agent indicated typical lithogenous-character ordering for the elements and emphasised the enrichment of Mg, Cr, Ni (and Li, Cu, Zn, Pb, Fe and Ti) over values for near-shore muds and terrigenous material. Factor analysis on the bulk chemical data identifies the main lithogenous and biogenous components, subdividing the latter. It separates the upper and lower group of chemically dissimilar sediments and delineates a Mn-hydroxide phase. It also shows the essentially independent roles of Na, Ba and P.

Magnetostratigraphy of DSDP Leg 73 in the South Atlantic

The main objective of DSDP Leg 73 was to obtain high-quality records of major paleooceanographic events in the South Atlantic. This was achieved by coring six sites on the African plate. The sediments thus recovered span the Cenozoic and five of the six sites proved ideally suited for magnetostratigraphic analysis. The results presented in this paper and elsewhere in this volume constitute the first opportunity to extend the direct correlation of the magnetostratigraphic and biostratigraphic time-scales into the Paleogene in deep-sea cores. The magnetostratigraphic analyses from DSDP Leg 73 sediments are presented in this paper. The correlation of the magnetostratigraphy to the magnetic polarity time-scale provides tight age-depth control for the five sites analyzed, allowing the accurate calculation of sediment accumulation rates. The data presented here represent a remarkable record of the fine-scale polarity history of the Earth's magnetic field. These data place constraints on the interpretation of smallscale marine magnetic anomalies which are modelled equally effectively by field intensity fluctuations as polarity reversals. At least some of the "tiny wiggles" correspond to very short polarity units in the magnetostratigraphic record. By assuming an axial geocentric dipole, the inclination of the time-averaged magnetic field recorded in the sediments can be used to calculate the paleolatitude at which the sediments were deposited. Combining the age and average inclination information available from the magnetostratigraphy, we present paleolatitudes versus time for the Leg 73 drill sites.