Lithology, stratigraphy, organic carbon content, extract and liquid chromatography yields, and Rock-Eval pyrolysis at DSDP Holes 75-530A and 75-532

Seventeen sediment samples of Albian-Cenomanian to early Pliocene age from DSDP Hole 530A in the Angola Basin and six sediment samples of early Pliocene to late Pleistocene age from the Walvis Ridge were investigated by organic geochemical methods, including organic carbon determination, Rock-Eval pyrolysis, gas chromatography and combined gas chromatography/mass spectrometry of extractable hydrocarbons, and kerogen microscopy. The organic matter in all samples is strongly influenced by a terrigenous component from the nearby continent. The amount of marine organic matter present usually increases with the total organic carbon content, which reaches an extreme value of more than 10% in a Cenomanian black shale from Hole 530A. At Site 530 the extent of preservation of organic matter in the deep sea sediments is related to mass transport down the continental slope, whereas the high organic carbon contents in the sediments from Site 532 reflect both high bioproductivity in the Benguela upwelling regime and considerable supply of terrigenous organic matter. The maturation level of the organic matter is low in all samples.

Geochemistry and petrographic characters at DSDP Leg 58 Holes

Refractive index and chemical composition were determined for glass shards contained in more than 100 tephra layers in DSDP Leg 58 sediment cores collected in the Shikoku Basin, North Philippine Sea. The refractive index is consistent with chemical composition. Refractive index and total iron show a linear relationship. Tephra in Pleistocene and Pliocene sediments is mostly rhyolitic and dacitic (non-alkali), whereas tephra in the Miocene shows wide composition variations in the eastern part of the basin. Basaltic tephra is recognized in Miocene sediments at Sites 443 and 444, but not at Site 442, west of the other two sites. This indicates that the basaltic tephra came from eruption relatively close to those drill sites (perhaps the Kinan Seamounts and the Shichito-Iwo Jima volcanic arc), although the exact source has not been identified.

Geochemistry of serpentine muds of ODP Leg 125 holes

The <63-µm fractions of serpentinite muds from two seamounts on the Mariana and Izu-Bonin forearcs were analyzed for mineral composition by X-ray diffraction and for chemical composition by X-ray fluorescence. The silt fraction of the muds consists predominantly of chrysotile, brucite, and ample amorphous constituents. Chlorite and smectite are less abundant components. Of special interest is the occurrence of iowaite, a brucite-like, Cl-bearing mineral with a layered structure. Iowaite was not found in the samples from the summit site of one of the seamounts drilled; however, it is scattered throughout the strata, composing the flanks of both seamounts investigated. No systematic change of the iowaite abundance with depth was observed. The distribution of iowaite is confined to the surface of the flanks of the seamount. Based on the distribution on the mineral and its chemical composition, we suggest that the iowaite formed by oxidation of some of the ferrous iron in brucite contained in the serpentine mud as it contacted abyssal seawater during protrusion onto the seafloor. The resulting positive charge imparted to the brucite was compensated by the uptake of seawater chloride. Consequently, the formation of iowaite is restricted to the seafloor where oxygen and chloride are available for these reactions. The availability of oxygen is considered the limiting factor. We conclude that iowaite formation cannot be a major cause for the low chlorinity of pore fluids inside the seamounts.

Electrical resistivity, formation factors, and sound velocity at DSDP Holes 75-530A and 75-530B

From 0 to 277 m at Site 530 are found Holocene to Miocene diatom ooze, nannofossil ooze, marl, clay, and debrisflow deposits; from 277 to 467 m are Miocene to Oligocene mud; from 467 to 1103 m are Eocene to late Albian Cenomanian interbedded mudstone, marlstone, chalk, clastic limestone, sandstone, and black shale in the lower portion; from 1103 to 1121 m are basalts. In the interval from 0 to 467 m, in Holocene to Oligocene pelagic oozes, marl, clay, debris flows, and mud, velocities are 1.5 to 1.8 km/s; below 200 m velocities increase irregularly with increasing depth. From 0 to 100 m, in Holocene to Pleistocene diatom and nannofossil oozes (excluding debris flows), velocities are approximately equivalent to that of the interstitial seawater, and thus acoustic reflections in the upper 100 m are primarily caused by variations in density and porosity. Below 100 or 200 m, acoustic reflections are caused by variations in both velocity and density. From 100 to 467 m, in Miocene-Oligocene nannofossil ooze, clay, marl, debris flows, and mud, acoustic anisotropy irregularly increases to 10%, with 2 to 5% being typical. From 467 to 1103 m in Paleocene to late Albian Cenomanian interbedded mudstone, marlstone, chalk, clastic limestone, and black shale in the lower portion of the hole, velocities range from 1.6 to 5.48 km/s, and acoustic anisotropies are as great as 47% (1.0 km/s) faster horizontally. Mudstone and uncemented sandstone have anisotropies which irregularly increase with increasing depth from 5 to 10% (0.2 km/s). Calcareous mudstones have the greatest anisotropies, typically 35% (0.6 km/s). Below 1103 m, basalt velocities ranged from 4.68 to 4.98 km/s. A typical value is about 4.8 km/s. In situ velocities are calculated from velocity data obtained in the laboratory. These are corrected for in situ temperature, hydrostatic pressure, and porosity rebound (expansion when the overburden pressure is released). These corrections do not include rigidity variations caused by overburden pressures. These corrections affect semiconsolidated sedimentary rocks the most (up to 0.25 km/s faster). These laboratory velocities appear to be greater than the velocities from the sonic log. Reflection coefficients derived from the laboratory data, in general, agree with the major features on the seismic profiles. These indicate more potential reflectors than indicated from the reflection coefficients derived using the Gearhart-Owen Sonic Log from 625 to 940 m, because the Sonic Log data average thin beds. Porosity-density data versus depth for mud, mudstone, and pelagic oozes agree with data for similar sediments as summarized in Hamilton (1976). At depths of about 400 m and about 850 m are zones of relatively higher porosity mudstones, which may suggest anomalously high pore pressure; however, they are more probably caused by variations in grain-size distribution and lithology. Electrical resistivity (horizontal) from 625 to 950 m ranged from about 1.0 to 4.0 ohm-m, in Maestrichtian to Santonian- Coniacian mudstone, marlstone, chalk, clastic limestone, and sandstone. An interstitial-water resistivity curve did not indicate any unexpected lithology or unusual fluid or gas in the pores of the rock. These logs were above the black shale beds. From 0 to 100 m at Sites 530 and 532, the vane shear strength on undisturbed samples of Holocene-Pleistocene diatom and nannofossil ooze uniformly increases from about 80 g/cm**2 to about 800 g/cm**2. From 100 to 300 m, vane shear strength of Pleistocene-Miocene nannofossil ooze, clay, and marl are irregular versus depth with a range of 500 to 2300 g/cm**2; and at Site 532 the vane shear strength appears to decrease irregularly and slightly with increasing depth (gassy zone). Vane shear strength values of gassy samples may not be valid, for the samples may be disturbed as gas evolves, and the sediments may not be gassy at in situ depths.

Petrology at DSDP Leg 66 Holes

The sandstone petrology of Leg 66 samples provides insights into changes through time in the geology of the source regions along the Guerrero portion of the Middle America continental margin. This in turn constrains possible models of the evolution of the Middle America Trench (e.g., de Czerna, 1971; Malfait and Dinkleman, 1972; Karig, 1974). Primarily medium-grained sands and sandstones, representing the widest variety available of trench/trench slope settings and ages, were analyzed in both light and heavy mineral studies. Standard techniques were used as much as possible in order to compare results from other margins and from ancient rocks.

Geochemistry at DSDP Leg 70 Holes

The hydrothermal mounds on the southern flank of the Galapagos Spreading Center are characterized by the following main features: 1) They are located over a young basement (0.5 to 0.85 m.y. of age) in a region known for its high sedimentation rate (about 5 cm/10**3 y.) because it is part of the equatorial high biological productivity zone. 2) They are located in a region with generally high heat flow (8 to 10 HFU). The highest heat-flow measurements (up to 10**3 HFU) correspond to mound peaks (Williams et al., 1979), where temperatures up to 15°C were measured during a dive of the submersible Alvin (Corliss et al., 1978). 3) They are often located on small vertical faults which displace the basement by a few meters (Lonsdale, 1977) and affect the 25- to 50-meter-thick sediment cover. Most of these characteristics have also been observed in the other three known cases of hydrothermal deposits with mineral parageneses similar to that of the Galapagos mounds. However, the case of the hydrothermal mounds south of the Galapagos Spreading Center is unique because of the unusual thickness of the hydrothermal deposits present. The mounds are composed of several, up to 4.5-meter-thick, layers of green clays which, in one case (Hole 509B), are overlain by about 1.4 meters of Mn-oxide crust. We suspect that such a large accumulation of hydrothermal products results from the "funnelling" of the hydrothermal solutions exiting from a highly permeable basement along the faults. This chapter reports a preliminary study of those green clays collected by hydraulic piston coring of the Galapagos mounds during Deep Sea Drilling Project (DSDP) Leg 70 of the D/V Glomar Challenger. Green clays have also been reported from three presently or recently active hydrothermal areas in or close to spreading centers.

Age profiles and isotopes d18O and d13C in Globigerina angiporoides and Oridorsalis umbonatus at DSDP Site 90-593 and Holes 12-111, 29-277 and 90-592

The late Eocene through earliest Miocene stable-isotope composition of southwest Pacific microfossils has been examined in a traverse of high-quality sedimentary sequences ranging from subantarctic (DSDP Site 277) through temperate regions (DSDP Sites 592 and 593). Changes in oxygen-isotope values, measured in benthic and planktonic foraminifers, document the Oligocene development and strengthening of latitudinal thermal zonation from water masses with broad temperature gradients during the Eocene to the steeper gradients and more distinct latitudinally distributed surface water-mass belts of the Neogene. The oxygen-isotope records can be divided into three intervals: late Eocene, early Oligocene, and middle to late Oligocene. Each interval represents a successive stage in the evolution of latitudinal thermal gradients between subantarctic and temperate regions in the Southern Hemisphere. During the late Eocene, oxygen-isotope values at subantarctic Site 277 were similar to those at temperate Sites 592 and 593. The isotope values suggest that, although the inferred paleotemperatures at Site 277 are slightly cooler on average than those at the temperate sites, there is no evidence for a major thermal boundary between the regions at this time. All three sites record the well-known oxygen-isotope enrichment of about 1 per mil in both planktonic and benthic foraminifers in close association with the Eocene/Oligocene boundary. In contrast to the earliest Oligocene enrichments in the planktonic and benthic oxygen-isotope composition at Site 277, more northern Sites 592 and 593 exhibit a depletion through the early-middle Oligocene. This documents the beginning of thermal segregation as subantarctic waters cooled relative to those at temperate latitudes. During the Oligocene, this surface-water differentiation continued, as measured by planktonic d18O values. The oxygen-isotope records of the benthic foraminifers also began to diverge in the earliest Oligocene. The most enriched oxygen-isotope values in all records cluster in the middle Oligocene, marked by oscillating episodes of enrichments >0.5 per mil occurring most prominently in the subantarctic record of Site 277. These values can be interpreted as recording either the coldest oceanic temperatures of the Paleogene and/or accumulations of Antarctic ice. After this interval, latitudinal thermal differentiation developed rapidly during the middle Oligocene, especially in the surface waters which actually warmed in temperate areas. If the enriched Oligocene oxygen-isotope values indicate that ice had accumulated, this ice must have disappeared by the early Miocene, when depleted oxygen-isotope values suggest very warm conditions. The data presented in this chapter document the progressive increase of latitudinal temperature gradients from the late Eocene through the late Oligocene. This pattern of increasing isotopic offset between latitudinally distributed southwest Pacific sites is linked to the establishment and strengthening of the Circum-Antarctic Current, previously considered to have developed during the middle to late Oligocene. The intensification of this current system progressively decoupled the warm subtropical gyres from cool polar circulation, in turn leading to increased Antarctic glaciation.

Geochemical characterizations of the Cretaceous formations at DSDP Holes 93-603B and 11-105

Geochemical characterizations of the Cretaceous formations at Site 603 are quite comparable with those at Site 105. In the Blake-Bahama and the Hatteras formations, the petroleum potential is medium (<5 kg HC/t of rock) to very low (<0.5 kg HC/t of rock), and the organic matter is mainly of type III origin, that is, terrestrial. At the top of the Hatteras Formation, there is a condensed series, which chiefly contains organic matter of type II origin, with up to 20 wt.% total organic carbon content in Core 603B-34 and 25 wt.% in Core 105-9. This accumulation corresponds to the Cenomanian/Turonian boundary event. An examination of dinoflagellates in the kerogen concentration assigns dates to the samples studied by organic geochemistry. The Cenomanian and Turonian age of the organic-matter-rich black claystones indicates a low rate of sedimentation, about 1 m/Ma. Furthermore, the occurrence of type II organic matter indicates an anoxic environment with insufficient oxygen renewal to oxidize the sinking hemipelagic organic matter. This organic enrichment is not related to local phenomena but to sedimentation over an extended area, because deposits are well known in various areas with different paleodepths in the North Atlantic.

Whole-rock geochemistry of amphibolites and metagabbros from ODP Holes 173-1067A and 173-1068A

The Leg 173 Site 1067 and 1068 amphibolites and metagabbros from the west Iberia margin exhibit variable whole-rock compositions from primitive to more evolved (Mg numbers = 49-71) that are generally incompatible trace and rare earth element enriched (light rare earth element [LREE] = 11-89 x chondrite). The Site 1067 amphibolites are compositionally similar to the basalts reported at Site 899 from this same region, based on trace and rare earth element contents. The Site 1068 amphibolites and metagabbros are similar to the Site 899 diabases but are more LREE enriched. However, the Sites 1067 and 1068 amphibolites and metagabbros are not compositionally similar to the Site 900 metagabbros, which are from the same structural high as the Leg 173 samples. The Leg 173 protoliths may be represented by basalts, diabases, and/or fine-grained gabbros that formed from incompatible trace element-enriched liquids.

Permeability measurements on sheared and unsheared samples from different IODP Holes of Leg 316 and from IODP Hole 315-C0001E and ODP Hole 190-1174B

At subduction zones, the permeability of major fault zones influences pore pressure generation, controls fluid flow pathways and rates, and affects fault slip behavior and mechanical strength by mediating effective normal stress. Therefore, there is a need for detailed and systematic permeability measurements of natural materials from fault systems, particularly measurements that allow direct comparison between the permeability of sheared and unsheared samples from the same host rock or sediment. We conducted laboratory experiments to compare the permeability of sheared and uniaxially consolidated (unsheared) marine sediments sampled during IODP Expedition 316 and ODP Leg 190 to the Nankai Trough offshore Japan. These samples were retrieved from: (1) The décollement zone and incoming trench fill offshore Shikoku Island (the Muroto transect); (2) Slope sediments sampled offshore SW Honshu (the Kumano transect) ~ 25 km landward of the trench, including material overriden by a major out-of-sequence thrust fault, termed the "megasplay"; and (3) A region of diffuse thrust faulting near the toe of the accretionary prism along the Kumano transect. Our results show that shearing reduces fault-normal permeability by up to 1 order of magnitude, and this reduction is largest for shallow (< 500 mbsf) samples. Shearing-induced permeability reduction is smaller in samples from greater depth, where pre-existing fabric from compaction and lithification may be better developed. Our results indicate that localized shearing in fault zones should result in heterogeneous permeability in the uppermost few kilometers in accretionary prisms, which favors both the trapping of fluids beneath and within major faults, and the channeling of flow parallel to fault structure. These low permeabilities promote the development of elevated pore fluid pressures during accretion and underthrusting, and will also facilitate dynamic hydrologic processes within shear zones including dilatancy hardening and thermal pressurization.

Amino acids from ODP Holes 117-722B and 177-724C

Sedimentary d15N records are valuable archives of ocean history but they are often modified during early diagenesis. Here we quantify the effect of early diagenetic enrichment on sedimentary N-isotope composition in order to obtain the pristine signal of reactive N assimilated in the euphotic zone. This is possible by using paired data of d15N and amino acid composition of sediment samples, which can be applied to estimate the degree of organic matter degradation. We determined d15N and amino acid composition in coeval sediments from Ocean Drilling Program (ODP) Hole 772 B in the central Arabian Sea and from Hole 724 C situated on the Oman Margin in the western Arabian Sea coastal upwelling area. The records span the last 130 kyr and include two glacial-interglacial cycles. These new data are used in conjunction with data available for surface sediments that cover a wide range of organic matter degradation states, and with other cores from the northern and eastern Arabian Sea to explore spatial variations in the isotopic signal. In order to reconstruct pristine N values we apply the relationship between organic matter degradation and 15N enrichment in surface sediments to correct the core records for early diagenetic enrichment. Reconstructed d15N values suggest a significant role of N2-fixation during glacial stages. An evaluation of two preservation indices based on amino acid composition (Reactivity Index, RI; Jennerjahn and Ittekkot, 1997; and the Degradation Index, DI; Dauwe et al., 1999) in both recent sediments and core samples suggests that the RI is more suitable than the DI in correcting Arabian Sea d15N records for early diagenetic enrichment.

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.

Chemistry of magmatic samples of ODP Holes 134-832B and 134-833B

New petrographic and compositional data were reported for 143 samples of core recovered from Sites 832 and 833 during Ocean Drilling Program (ODP) Leg 134. Site 832 is located in the center and Site 833 is on the eastern edge of the North Aoba Basin, in the central part of the New Hebrides Island Arc. This basin is bounded on the east (Espiritu Santo and Malakula islands) and west (Pentecost and Maewo islands) by uplifted volcano-sedimentary ridges associated with collision of the d'Entrecasteaux Zone west of the arc. The currently active Central Belt volcanic front extends through the center of this basin and includes the shield volcanoes of Aoba, Ambrym, and Santa Maria islands. The oldest rocks recovered by drilling are the lithostratigraphic Unit VII Middle Miocene volcanic breccias in Hole 832B. Lava clasts are basaltic to andesitic, and the dominant phenocryst assemblage is plagioclase + augite + orthopyroxene + olivine. These clasts characteristically contain orthopyroxene, and show a low to medium K calc-alkaline differentiation trend. They are tentatively correlated with poorly documented Miocene calc-alkaline lavas and intrusives on adjacent Espiritu Santo Island, although this correlation demands that the measured K-Ar of 5.66 Ma for one clast is too young, due to alteration and Ar loss. Lava clasts in the Hole 832B Pliocene-Pleistocene sequence are mainly ankaramite or augite-rich basalt and basaltic andesite; two of the most evolved andesites have hornblende phenocrysts. These lavas vary from medium- to high-K compositions and are derived from a spectrum of parental magmas for which their LILE and HFSE contents show a broad inverse correlation with SiO2 contents. We hypothesize that this spectrum results from partial melting of an essentially similar mantle source, with the low-SiO2 high HFSE melts derived by lower degrees of partial melting probably at higher pressures than the high SiO2, low HFSE magmas. This same spectrum of compositions occurs on the adjacent Central Chain volcanoes of Aoba and Santa Maria, although the relatively high-HFSE series is known only from Aoba. Late Pliocene to Pleistocene lava breccias in Hole 833B contain volcanic clasts including ankaramite and augite + olivine + plagioclase-phyric basalt and rare hornblende andesite. These clasts are low-K compositions with flat REE patterns and have geochemical affinities quite different from those recovered from the central part of the basin (Hole 832B). Compositionally very similar lavas occur on Merelava volcano, 80 km north of Site 833, which sits on the edge of the juvenile Northern (Jean Charcot) Trough backarc basin that has been rifting the northern part of the New Hebrides Island Arc since 2-3 Ma. The basal sedimentary rocks in Hole 833B are intruded by a series of Middle Pliocene plagioclase + augite +/- olivine-phyric sills with characteristically high-K evolved basalt to andesite compositions, transitional to shoshonite. These are compositionally correlated with, though ~3 m.y. older than, the high-HFSE series described from Aoba. The calc-alkaline clasts in Unit VII of Hole 832B, correlated with similar lavas of Espiritu Santo Island further west, presumably were erupted before subduction polarity reversal perhaps 6-10 Ma. All other samples are younger than subduction reversal and were generated above the currently subduction slab. The preponderance in the North Aoba Basin and adjacent Central Chain islands of relatively high-K basaltic samples, some with transitional alkaline compositions, may reflect a response to collision of the d'Entrecasteaux Zone with the arc some 2-4 Ma. This may have modified the thermal structure of the subduction zone, driving magma generation processes to deeper levels than are present normally along the reminder of the New Hebrides Island Arc.

Thecosomata in late Quternary deposits of ODP Holes 134-830A and 134-831A

We undertook a quantitative study of Thecosomata shells (pelagic gastropods) and their remains in Quaternary foraminiferal oozes deposited on the tilted calcareous platform of the Bougainville Guyot (Hole 831 A), and in the late Quaternary volcanic siltstones, claystones and sandy interbeds on the upper forearc slope of the central New Hebrides Island Arc (Hole 830A). The distribution of the species is based on the identification of adult shells, juvenile stages, protoconchs, and characteristic shell fragments. By studying thecosomatous shells using a scanning electron microscope (SEM), we were able to specify the fine microstructure of the coiled Limacina inflata and compare it with the rod-type crossed-lamellar structure of some other Limacina species, as well as with the helical structure of the Cavoliniidae.