Trace and rare elements and factors at DSDP Hole 71-511

The distribution of paragenetic assemblages of trace and rare elements, as revealed by factor analysis (R-mode, Q-mode), the ratios of elements to Zr and the interpretation of these data in the context of the known mineralogy, lithology, and geology of the region, provide the bases for the outline of the geochemical history of sedimentation in the study area that forms the subject of this chapter. Two stages may be discerned. 1. Late-Middle Jurassic-Early Cretaceous (160-106? Ma). The sediments that accumulated in relatively shallow water (shelf) were predominantly clay, with dispersed sapropelic organic matter, plant fragments, pyrite, admixtures of acid-medium volcanic glass, and epigenetic crystals of gypsum. The bottom water layers of the basin are notably stagnant. The sediments are characterized by higher amounts of V, Zn, Cu, Cr, Rb, and Be associated with organic matter. Lower Cretaceous sediments, separated from those of the Upper Jurassic by a hiatus, accumulated in a deepened and enlarging basin. These Lower Cretaceous deposits are chemically similar to those of the Upper Jurassic, but contain diagenetic concentrations of Zn, Ni, and La. 2. Early-middle Albian (Unit 5)-middle Maestrichtian (1067-66.6Ma). The prevailing regime was that of an open ocean basin that tended to expand and deepen. During the second half of the early-middle Albian, the biogenic components Ba, Sr, and CaCO3 accumulated. By the end of this interval, Ti/Zr values had increased. In conjunction data on mineral composition, they testify to an outburst of basaltoid volcanism related to tectonic activity before an erosional hiatus (late Albian-Cenomanian). At the end of the Cenomanian-Turonian, residual deposits of predominantly clay sediments with relatively high amounts of Ti and Zr and associated rare alkalis (Li, Rb) accumulated. Clay sediments deposited during the Coniacian-Santonian were characterized by higher concentrations of Ti, Zr, Li, and Rb, by diagenetic carbonate phases of Ni, Zn, and La, and by sulphides and Fe-oxides with an admixture of Ni and Co. The latter half of the interval saw the deposition of fine basaltoid volcanoclastic material, diagenetically altered by zeolitization and carbonatization and enriched with Se, Pb, Ti, Sr, Ba, Y, and Yb. Sediments with a similar chemistry accumulated in the Campanian-middle Maestrichtian. Strong current activity preceding a global hiatus at the Mesozoic/Cenozoic boundary is reflected in both lower sedimentation rates and the presence of higher residual concentrations of Ti, Zr, Ba, Sr, and other elements studied in this chapter.

(Table 1) Lead isotopic compositions of basalts from DSDP Hole 81-553

The passive continental margin south-west of Rockall Plateau is characterized by a thick sequence of oceanward-dipping seismic reflectors. During Leg 81 of the Deep Sea Drilling Project, these reflectors were sampled at Site 553 and proved to consist almost exclusively of basalt. Here we present lead isotope data which indicate that these basalts may have been contaminated by ancient uranium-depleted continental crust, or alternatively, derived from a sub-continental lithospheric mantle source. In either case, the implications are that the basalts of the south-west Rockall Plateau formed by eruption through and onto continental basement, not by 'subaerial seafloor spreading'. This conclusion is in accord with gravity models of the area, which predict stretched continental crust beneath the dipping reflector sequence.

Geochemistry of basalts at DSDP Leg 73 Holes

During Deep Sea Drilling Project Leg 73 (South Atlantic), basaltic pillow lava, flows, and sills were encountered in Holes 519A, 520, 522B, and 524. Paleomagnetic data indicate that the basalts from Holes 519A (magnetic Anomaly 51) and 522B (Anomaly 16) have ages of about 12 m.y. and about 38 m.y., respectively. The major- and trace- (including rare-earth-) element characteristics of the Hole 519A basalts (a total of 27 m) demonstrate that these basalts are typical normal-type mid-ocean-ridge basalts (N-type MORB). In composition the basalts overlap olivine tholeiites from other normal Mid-Atlantic Ridge segments. Both the spectra of incompatible, or less-hygromagmatophile elements (such as Ti, V, Y, and Zr) and REE abundances indicate that these basalts are the result of a low-pressure fractionation of olivine, spinel, and Plagioclase prior to eruption. In Hole 520 only 1.7 m of basalt were recovered from a total drilling depth of 10.5 m. These pillow basalts crystallized from fairly evolved (N-type MORB) tholeiitic melts. In total, 19 m of basaltic pillow lavas and flows were penetrated in Hole 522B. Thirteen cooling units were distinguished on the basis of glassy margins and fine quench textures. In contrast to Holes 519A and 520, the basalts of the Hole 522B ridge section can be divided into two major groups of tholeiites: (1) Cooling Units 1 through 12 and (2) Cooling Unit 13. The basalts in this ridge section are also N-type MORBs but are generally more differentiated than those of Holes 519A and 520. The lowermost basalts (Cooling Unit 13) have the most primitive composition and make up a compositional group distinct from the more evolved basalts in the twelve units above it. Hole 524 was drilled on the south flank of the Walvis Ridge and thus provided samples from a more complex part of the South Atlantic seafloor. Three different basaltic rock suites, interlayered with volcanic detrital sediments, were encountered. The rock suites are, from top to bottom, an alkali basaltic pillow lava; a 16-m-thick alkaline diabase sill with an age of about 65 m.y. (according to K-Ar dating and planktonic foraminifers); and a second sill that is approximately 9 m thick, about 74 m.y. in age, and tholeiitic in composition, thus contrasting strongly with the overlying alkaline rocks. The alkali basalts of Hole 524 show chemical characteristics that are very similar to the basaltic lavas of the Tristan da Cunha group volcanoes, which are located approximately 400 km east of the Mid-Atlantic Ridge crest. Thus, the Walvis Ridge may plausibly be interpreted as a line of hot-spot alkaline volcanoes.

Oxygen and carbon isotopes for foraminifers at DSDP Leg 73 Holes

We carried out oxygen and carbon isotope studies on monospecific foraminifer samples from DSDP Sites 522, 523, and 524 of Leg 73 in the central South Atlantic Ocean. The oxygen isotope ratios show a warming of 2 to 3 °C in bottom water and 5°C in surface water during the Paleocene and early Eocene. The carbon isotope values indicate strong upwelling during the early Eocene. The 1% increase in the d18O values of benthic and planktonic foraminifers at Site 523 in the later middle Eocene we ascribe to changes in the pattern of the evaporation and precipitation. The changes may be due to the worldwide Lutetian transgression. The oxygen ratios for the benthic and planktonic foraminifers indicate a cooling at the Eocene/Oligocene transition. The maximum temperature drop (5°C for benthic and 3°C for planktonic foraminifers) is recorded slightly beyond the Eocene/Oligocene boundary and took place over an interval of about 100,000 yr. The pattern of currents in the Southern Hemisphere was mainly structured by a precursor of the subtropical convergence during the Paleocene to late Eocene. The cooling at the Eocene/Oligocene transition led to drastic changes in the circulation pattern, and a precursor of the Antarctic convergence evolved.

Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.

Numerical ages of magnetostratigraphically calibrated biostratigraphic zones at DSDP Leg 73 Holes

Most Cenozoic nannofossil and many foraminiferal zonal boundaries have been accurately determined and magnetostratigraphically calibrated at five Leg 73 boreholes. The numerical ages of the boundaries were computed by assuming a linear seafloor spreading rate and a radiometric age of 66.5 m.y. for the Cretaceous/Tertiary boundary. Alternative magnetostratigraphic ages (given below in parentheses) were obtained by adopting a 63.5 m.y. age for the Cenozoic. Our data confirm previous determinations of the Pleistocene/Pliocene boundary at 1.8 (1.7) m.y. and of the Pliocene/ Miocene boundary at 5.1 (5.0) m.y. The Miocene/Oligocene boundary is placed within Chron C-6C and has a magnetostratigraphic age of 23.8 to 24.0 (22.7 to 22.9) m.y. The Oligocene/Eocene boundary is also very precisely located within Chron C-13-R, with a magnetostratigraphic age of 37.1 to 37.2 (35.5 to 35.6) m.y. The Eocene/Paleocene boundary should be located within an uncored interval of Chron C-24 and have a magnetostratigraphic age of 59.0 (55.4) +/- 0.2 m.y. The general accord of the magnetostratigraphic and radiometric ages supports the hypothesis that the seafloor spreading rate was linear during the Cenozoic. Two possible exceptions are noted: the middle Miocene radiometric ages are a few million years older, and the early Eocene radiometric ages are several million years younger, than the corresponding magnetostratigraphic ages.

Mid-Pliocene deep-sea bottom water temperatures based on ostracode Mg/Ca ratios

We studied magnesium:calcium (Mg/Ca) ratios in shells of the deep-sea ostracode genus Krithe from a short interval in the middle Pliocene between 3.29 and 2.97 Ma using deep-sea drilling sites in the North and South Atlantic in order to estimate bottom water temperatures (BWT) during a period of climatic warmth. Results from DSDP and ODP Sites 552A, 610A, 607, 658A, 659A, 661A and 704 for the period Ma reveal both depth and latitudinal gradients of mean Mg/Ca values. Shallower sites (552A, 610A and 607) have higher mean Mg/Ca ratios (10.3, 9.7, 10.1 mmol/mol) than deeper sites (661A, 6.3 mmol/mol), and high latitude North Atlantic sites (552A, 610 and 607) have higher Mg/Ca ratios than low latitude (658A: 9.8 mmol/mol, 659A: 7.7 mmol/mol, 661A: 6.3 mmol/mol) and Southern Ocean (704: 8.0 mmol/mol) sites. Converting Mg/Ca ratios into estimated temperatures using the calibration of Dwyer et al. (1995) [Dwyer, G.S., Cronin, T.M., Baker, P.A., Raymo, M.E., Buzas, J.S., Corrège, T., 1995. North Atlantic deepwater temperature change during late Pliocene and late Quaternary climatic cycles. Science 270, 1347-1351] suggests that mean middle Pliocene bottom water temperatures at the study sites in the deep Atlantic were about the same as modern temperatures. However, brief pulses of elevated BWT occurred several times between 3.29 and 2.97 Ma in both the North and South Atlantic Ocean suggesting short-term changes in deep ocean circulation.

Stable isotopic and carbonate cyclicity in deep sea sediments from different DSDP Holes

Oxygen and carbon isotopic variability of the dominant (<38 µm) carbonate fraction within bedded, organic-carbon rich Lower Cretaceous sediment intervals from various DSDP sites are closely correlated with preservational changes in the carbonates. Isotopic fluctuations are absent where carbonate contents vary little and where the carbonate fraction is dominated by biogenic phytoplankton remains. Within each of the studied intervals oxygen and carbon isotopic ratios become increasingly more negative in samples with carbonate contents higher than about 60% in which the proportion of diagenetic microcarbonate increases rapidly. Carbon isotopic ratios show a trend towards positive values in samples with carbonate contents of less than 40% and strong signs of dissolution. The taxonomic composition of nannofossil assemblages varies little within single intervals, despite significant differential diagenesis among individual beds; this points towards ecological stability of oceanic surface waters during the deposition of alternating beds. Bedding is, however, closely related to changing bioturbation intensity, indicating repeated fluctuations of the deep-water renewal rates and oxygen supply. Various microbial decomposition processes of organic matter leading to bed-specific differential carbonate diagenesis resulted in an amplification of primary bedding features and are considered responsible for most of the observed fluctuations in the stable isotopic ratios and carbonate contents.