Geochemistry and fluxes at DSDP Hole 83-504B

This chapter documents the chemical changes produced by hydrothermal alteration of basalts drilled on Leg 83, in Hole 504B. It interprets these chemical changes in terms of mineralogical changes and alteration processes and discusses implications for geochemical cycling. Alteration of Leg 83 basalts is characterized by nonequilibrium and is heterogeneous on a scale of centimeters to tens or hundreds of meters. The basalts exhibit trends toward losses of SiO2, CaO, TiO2; decreases in density; gains of MnO, Na2O, CO2, H2O+ , S; slight gains of MgO; increased oxidation of Fe; and variable changes in A12O3. Some mobility of rare earth elements (REE) also occurred, especially the light REE and Eu. The basalts have lost Ca in excess of Mg + Na gains. Variations in chemical trends are due to differing water/rock ratios, substrate control of secondary mineralogy, and superimposition of greenschist and zeolite facies mineralogies. Zeolitization resulted in uptake of Ca and H2O and losses of Si, Al, and Na. These effects are different from the Na uptake observed in other altered basalts from the seafloor attributed to the zeolite facies and are probably due to higher temperatures of alteration of Leg 83 basalts. Basalts from the transition zone are enriched in Mn, S, and CO2 relative to the pillow and dike sections and contain a metal-sulfide-rich stockwork zone, suggesting that they once were located within or near a hydrothermal upflow zone. Samples from the bottom of the dike section are extensively fractured and recrystallized indicating that alteration was significantly affected by local variations in permeability.

Occurrence and estimated abundance of planktonic foraminifers at DSDP Leg 85 holes

Tropical planktonic foraminifers occur throughout the sequences at all sites of Leg 85, and the standard planktonic foraminiferal zonation of Blow (1969) is applicable to most of the recovered sequences. However, the abundance and state of preservation of foraminifers decline markedly in certain intervals because of the effects of dissolution. Although siliceous microfossils studied on this leg indicate recovery of nearly complete records for the Pleistocene to Oligocene interval, the planktonic foraminiferal biostratigraphy is interrupted by strongly dissolved sections at all sites. Particularly, faunas assignable to Zone N7 (early Miocene) and Zone N15-16 (early late Miocene) are almost totally unrecognizable throughout the eastern equatorial Pacific. Well-preserved and diverse planktonic foraminifers occur in the lower middle Miocene, where the evolutionary developments of Orbulina universa d'Orbigny and Globorotalia fohsi Cushman and Ellisor are well represented. The Orbulina first appearance datum is observed to be nearly coincident with the last occurrence level of the diatom Annellus californicus Tempère, thus .establishing an age of 15 Ma for this datum by using the paleomagnetic calibration of the diatom datum. Moderately well-preserved late Eocene planktonic foraminifers occur in the carbonate sediments immediately overlying the basalt basement at Sites 573 and 574. The Eocene-Oligocene faunal transition, however, is masked at both sites by an intercalation of metalliferous layers containing no planktonic foraminifers.

A sedimentological, faunal, and isotopic record of the middle-to-late Pliocene transition at DSDP Hole 80-548

Hydraulic piston coring at DSDP Site 548, on the upper continental slope southwest of Ireland, recovered a nearly complete Pliocene section spanning 103 m of sediment. The sediments are greenish gray carbonate-rich hemipelagites containing abundant nannofossils and foraminifers. Grain-size analysis demonstrates that the texture of the section is fairly constant, with most of the variation occurring in 63- to 32-µm and < 2-µm fractions. Previous research has shown that the middle-to-late Pliocene transition in the North Atlantic was marked by the appearance of the planktonic foraminiferal species Globorotalia inflata and by the first occurrence of significant quantities of ice-rafted sediment grains in deep-sea sediments. The latter is taken to represent the first important development of Northern Hemisphere glaciation. The first appearance of G. inflata is carefully documented for Site 548 and is demonstrated to be an evolutionary datum at this site, rather than an ecologically controlled first appearance. Surface ocean conditions represented in the sediment section spanning the appearance of G. inflata were strongly cyclic, resulting in large periodic changes in the abundances of Globorotalia puncticulata and N. acostaensis. The benthic foraminiferal population was studied in detail over the middle-to-upper Pliocene transition to establish the nature and behavior of the intermediate-depth water mass in the northeastern Atlantic at the time of ice-sheet growth in the Northern Hemisphere. This water mass is presently warm and saline, having its source in the Mediterranean Sea. The benthic data show that the intermediate-depth water mass was undergoing a series of progressive changes over the interval including the first appearance of G. inflata. These changes are particularly reflected in the relative abundances of Globocassidulina subglobosa (Brady), Uvigerina, and Ehrenbergina. Also, the mean size of individuals in the G. subglobosa populations shows systematic variation, indicating changing intermediate-depth water properties. Oxygen-isotope analyses show that the intermediate-depth water mass was cold during the middle-to-late Pliocene transition. This interpretation is supported by the relative abundances of benthic foraminiferal species. Hence, the intermediate-depth northeastern Atlantic water mass of the middle to late Pliocene was considerably different from the intermediate-depth water mass of the present.

Calcareous nannofossils of the Soithern Coral Sea

Leg 90 of the Deep Sea Drilling Project drilled 18 holes at eight sites (Sites 587-594) on several shallow-water platforms in the southern Coral Sea, Tasman Sea, and southwestern Pacific Ocean. The results from an additional hole (Hole 586B) drilled at Site 586 during Leg 89 are included in this report. Together, these sites form a latitudinal traverse which extends from the equator (Site 586) to 45°S (Site 594) and includes all the major water masses from tropical to subantarctic. Samples recovered at these sites range in age from middle Eocene to late Quaternary. The calcareous nannoplankton biostratigraphy for Leg 90 has divided into two parts: part 1, the Neogene and Quaternary of Sites 586-594. (this chapter); and part 2, the Paleogene of Sites 588, 592, and 593 (Martini, 1986). A slightly modified version of the Martini (1971) standard Tertiary and Quaternary zonation scheme was used to make age determinations on over 700 samples. All of the relevant Neogene and Quaternary zone-defining nannoplankton are present at Sites 586-591 (0°-30°S) but become increasingly rare or are absent at Sites 592-594 (35°-45°S). Species diversity increases southward from the equator (Site 586) and reaches a peak at 20°S (Site 587). A decrease at 25°S (Site 588) and 30°S (Sites 589-591) is followed by an increase in species diversity at 35°S (Site 592). South of 35°S, species diversity again decreases and reaches a low at 45 °S (Site 594). Species diversity for all sites as a group generally increases through the early, middle, and late Miocene, reaches a peak in the early Pliocene, then gradually decreases through the late Pliocene and Quaternary

Late Cretaceous-Cenozoic magnetostratigraphic and biostratigraphic correlation of DSDP Hole 73-519 in the South Atlantic

DSDP Leg 73 sediment cores allow direct calibrations of magnetostratigraphy and biostratigraphy for much of the latest Cretaceous to Cenozoic in the mid-latitude South Atlantic Ocean. A complete record of the Cenozoic was not obtained, however, because strong dissolution, poor core recovery and intense core disturbance have masked the biostratigraphy or magnetostratigraphy over some intervals of all recovered sections. DSDP Leg 73 results show the following correlations: Early/middle Miocene in Chron 16 Oligocene/Miocene within Subchron C6CN Eocene/Oligocene within Subchron C13R Middle/late Eocene top of Chron C17 Early/late Paleocene top of Subchron C27N Cretaceous/Tertiary within Subchron C29R

Porosity, permeability, trace elements, and carbon-oxygen isotopes at DSDP Hole 77-536

Talus deposits recovered from Site 536 show evidence of aragonite dissolution, secondary porosity development, and calcite cementation. Although freshwater diagenesis could account for the petrographic features of the altered talus deposits, it does not uniquely account for isotopic or trace-element characteristics. Also, the hydrologic setting required for freshwater alteration is not easily demonstrated for the Campeche Bank. A mixing-zone model does not account for the available trace-element data, but does require somewhat less drastic assumptions about the size of the freshwater lens. Although a seawater (bottom-water) alteration model requires no hydrologic difficulties, unusual circumstances are required to account for the geochemical characteristics of the talus deposits using this model.

Planktonic foraminifers from Oligocene to Pleistocene sediments of DSDP Leg 92 sites

Leg 92 of the Deep Sea Drilling Project cored sediments containing calcareous microfossils at six sites along 19°S latitude in the South Pacific Ocean. Shipboard examination of these sediments revealed planktonic foraminifers of uppermost Oligocene through Pleistocene age that were identified and assigned to biostratigraphic zones according to the tropical zonation scheme of Blow (1969). Preservation of planktonic foraminifers in the sites from Leg 92 has been affected by the position of each site with respect to the lysocline and calcium carbonate compensation depth (CCD) at the time of deposition, depth of burial, and sediment accumulation rate (rate of burial). An additional factor may also be important, especially in the sediments deposited immediately above basement. Evidence of poor preservation in basal sediments of Holes 600C and 601, which have always been shallower than both the lysocline and the CCD, suggests that hydrothermal solutions circulating within young oceanic crust may penetrate the overlying sediments and affect the preservation of calcareous microfossils deposited there.

Lithology, stage, organic carbon, d13C, hydrocarbons and fatty acids at DSDP Hole 93-603B

Organic-matter-rich Upper Cretaceous claystones from DSDP Hole 603B, lower continental rise, had organic carbon values ranging from 1.7 to 13.7%, C/N ratios from 32 to 72, and d13C values from -23.5 to -27.1 per mil. Lipid class maxima for the unbound alkanes (C29 and C31), unbound fatty acids (C28 and C30), and bound fatty acids (C24, C26 , and C28) and the strong odd-carbon and even-carbon preferences, respectively, suggested that the organic matter in these sediments was partially the result of input from continental plant waxes. Transport of the organic-matter-rich sediments to the deep sea from the near-shore environment probably resulted from turbiditic flow under oxygen-stressed conditions.

Mud, sand, heavy and light minerals composition in lower Cretaceous at DSDP Hole 93-603B

During the drilling of Hole 603B on Deep Sea Drilling Project Leg 93, an unexpected series of sand-, silt-, and claystone turbidites was encountered from Cores 603B-45 through -76 (1224-1512 m sub-bottom depth). Complete and truncated Bouma sequences were observed, some indicating deposition by debris flows. Sand emplacement culminated with the deposition of a 30-m-thick, unconsolidated sand unit (Cores 603B-48 through -45). The purpose of this preliminary study is to determine the nature of the heavy mineral suites of this sediment in order to make tentative correlations with onshore equivalents. The heavy mineralogy of Lower Cretaceous North American mid-Atlantic coastal plain sediment has been extensively studied. This sediment is classified as the Potomac Group, which has a varied heavy mineral suite in its lower part (Patuxent Formation), and a limited suite in its upper part (Patapsco Formation). The results of this study reveal a similar trend in the heavy mineral suites of sediment in Hole 603B. Hauterivian through lower Barremian sediment has a heavy mineral suite that is dominated by zircon, apatite, and garnet, with minor amounts of staurolite and kyanite. Beginning in the mid-Barremian, a new source of sediment becomes dominant, one which supplies an epidote-rich heavy mineral suite. The results of the textural analyses show that average grain size of the light mineral fraction increases upsection, whereas sorting decreases. The epidote-rich source may have delivered sediment with a slightly coarser mean grain size. This sediment may represent a more direct continental input at times of maximum turbidite activity (mid-Barremian) and during deposition of the upper, unconsolidated sand unit.

Epoch, organic carbon and compounds at DSDP Holes 93-605 and 95-613

Twenty-four sediment samples from DSDP Holes 605 (Leg 93) and 613 (Leg 95) on the New Jersey continental rise were analyzed by pyrolysis-gas chromatography. Twelve of these samples were also analyzed by pyrolysis-gas chromatography/mass spectrometry. The degree of preservation of sediment organic matter, as determined by these techniques, helped to distinguish slumped sediments from sediments that have not moved from their original place of deposition. Total levels of pyrolyzable organic material, as determined from pyrolysis-gas chromatography, were low in sediments that were not slumped, indicating that the organic material is highly degraded. Nitrogen- and oxygen-containing compounds were the primary compounds detected by gas chromatography/mass spectrometry (GCMS) analysis of the pyrolyzate of non-slumped sediments. Smaller amounts of aromatic compounds and branched alkanes were also present in some of these samples. In contrast, slumped sediments showed larger amounts of pyrolyzable organic matter, as determined from pyrolysis-gas chromatography, and better preservation of alkyl chains in the sediment organic matter, as suggested by the presence of n-alkanes in GCMS analysis of the pyrolyzate. Better preservation of the organic matter in slumped sediments can be attributed to more moderate bioturbation by bottom-dwelling organisms at the original deposition site.

Nature, chemistry, and origin of late Cenozoic megascopic tephras in Legs 89 and 90 Cores from the Southwest Pacific

Several thin (1-10 cm) megascopic vitric tephras occur in the late Cenozoic calcareous oozes on Lord Howe Rise in the Tasman Sea and off eastern South Island, New Zealand. Of the 18 tephras analyzed 15 are silicic (75-78% SiO2) with abundant clear glass shards and a biotite ± hypersthene ± green hornblende ferromagnesian mineralogy. The Neogene silicic tephras were derived from the now-extinct Coromandel volcanic area in New Zealand, and the Quaternary ones from the presently active Central Volcanic Region of New Zealand. On the basis of glass chemistry and age, several of the Quaternary tephras are probably correlatives, and at least two can be matched to the major on-land Mt. Curl tephra (-0.25 m.y.). The occurrence of correlative silicic tephras both northwest and southeast of New Zealand may result from particularly violent eruptions, the ash below and above an altitude of -20 km being dispersed in opposite directions toward the Pacific Ocean and Tasman Sea, respectively. Ash drifting eastward into the southeasterly trade wind belt off northeastern New Zealand could also be carried into the central and northern Tasman Sea. Three megascopic tephras consist of altered basic shards and common labradorite crystals. They record Neogene explosive basaltic to andesitic activity from nearby ocean island or ridge sources in the Ontong-Java Plateau and Vanuatu regions. The megascopic tephras are a very incomplete and biased record of late Cenozoic explosive volcanism in the southwest Pacific because the innumerable, thin, green argillaceous layers in the cores (Gardner et al., this volume) probably represent devitrified intermediate to basic tephras derived mainly from oceanic arc volcanism along the Pacific/Australia plate boundary. In contrast to the New Zealand-derived silicic glass shards, the preservation potential of these more basic shards in Leg 90 calcareous sediments was low.

Geochemistry of DSDP Leg 91 basalts

Basalts recovered from Sites 595 and 596 on Mesozoic crust in the southwest Pacific range from olivine-bearing tholeiites to ferrobasalts. Despite having undergone extensive low-grade alteration, which has raised K and Rb abundances, the basalts have consistent interelement ratios of Ti, Zr, Hf, rare-earth elements, Y, Th, Ik, and Nb. La/Ta (-18), Lan/Ybn (0.6), Ti/Zr (115), Zr/Nb (20), and Th/Hf (0.08) ratios all fall within the range of N-type mid-ocean-ridge basalt. The basalts from Sites 595 and 596 indicate that the Mesozoic Pacific crust was derived from a mantle source by processes similar to those operating at the present-day East Pacific Rise.

Physical properties of sediments at DSDP Sites 93-603, 93-604, and 93-605

On Leg 93, physical properties measurements were made of vertical and horizontal sonic velocity, acoustic impedance, vane shear strength, and penetrometer strength, using procedures discussed in Boyce (1973, 1976, 1984). Gravimetric procedures were used to determine wet-bulk density, grain density, porosity, and water content, using either the chunk method or the cylinder method. Calcium carbonate content of Leg 93 sediments was determined by the carbonate.

Sulfur isotopic variations in nodular and disseminated pyrite at DSDP Hole 93-603B

Analyses of modern marine sediments have suggested that availability and type of organic matter, sedimentation rate, and openness of the sulfate system influence the degree of isotopic fractionation between seawater sulfate and sedimentary iron sulfides. Isotopic studies of ancient sulfides should, therefore, provide insights into conditions of deposition and early diagenesis. Analysis of d34S of disseminated pyrite from Cretaceous sediments of Hole 603B yielded fractionations relative to coeval seawater sulfate ranging from 40 to 55 per mil, which are within the range for modern oxic marine sediments reported by others. Sulfur/carbon ratios are similar to those found from modern marine sediments and suggest that disseminated pyrite formation was dependent upon available organic carbon. These results imply that depositional and early diagenetic conditions during the Cretaceous in Hole 603B were similar to those occurring in initially oxic marine environments today. Macroscopic (nodular) pyrite from Hole 603B is isotopically variable (d34S values = - 48 to + 33 per mil), but generally more positive than disseminated pyrite. The isotopic evidence suggests that macroscopic pyrite formed during late stages of sulfate reduction in a system closed with respect to sulfate. However, detailed analyses of large pyrite nodules did not yield a consistent pattern of isotopic variation from center to rim.

C1-C8 hydrocarbons at DSDP Site 93-603

Small amounts of C1-C8 hydrocarbons were detected in continental rise sediments from DSDP Site 603. Organiccarbon- lean sections contained only C1-C3 compounds believed to have migrated from organic-carbon-rich sections. Heavier (C4-C8) hydrocarbons were found only in organic-carbon-rich sections. Restricted and sporadic distribution of C4-C6 compounds in 0-1100 m sub-bottom sediments suggest low-temperature (<20°C) biological/chemical generation processes. Increased C4-C8 concentrations and complexity, including unusually high levels of xylene, were detected in two deeper Cretaceous sections (603-34-2, 134 cm and 603-81-3, 120 cm). This behavior, which was not observed in 17 other samples from sub-bottom depths greater than 1100 m, is similar to that observed in immature surface sediments from the geothermally active Guaymas Basin (Gulf of California) area.