(Table 1) Mineralogical composition of sediments from DSDP Sites 69-504 and 69-505

We discuss the provenance of minerals detected by X-ray-diffraction analyses of sediments of Sites 504 and 505 of Deep Sea Drilling Project Leg 69. These are X-ray-amorphous material, opal-CT, calcite, quartz, feldspar, apatite, smectite, illite, kaolinite, magnetite, maghemite, pyrite, marcasite, barite, sepiolite, and clinoptilolite. Authigenic marcasite and clinoptilolite together with opal-CT are restricted to Site 504, indicating the special diagenetic conditions related to relatively high sediment temperatures at this site. Marcasite formation is likely dependent on the relatively low pH values of <7.1 found in interstitial waters of Site 504 sediments below 50 meters sub-bottom. Clinoptilolite evidently was formed by diagenetic alteration of rhyolitic volcanic glass or smectite plus biogenic silica within the chalk-limestone-chert sequence of Site 504, where opal-CT also reflects a high degree of silica dissolution and reprecipitation. This was a consequence of high temperatures (50-55 °C) at the base of the sediment column.

(Table 1) Water-extractable and acid-extractable carbohydrates in DSDP Leg 65 samples

Selected parts of ten frozen core samples from Holes 482A, 482B, 483A, and 485A, Leg 65 of the Deep Sea Drilling Project (DSDP), were analyzed for residual carbohydrates in order to determine the provenance and history of the organic material in the sediments. The samples, which represented silty-clay, shale, and nannofossil- chalk sediments, were analyzed for water-soluble monosaccharides, acid-soluble monosaccharides, and for starch and cellulose. Most samples yielded positive results for acid-extractable (polymeric) arabinose, fucose, xylose, mannose, galactose, and glucose. Amylose was detected in seven of the samples, whereas cellulose was found in only one. Possible explanations for the relatively high levels of free sugars are suggested in the conclusions to this chapter.

Occurrence and chemistry of microtektites of ODP Site 121-758

The Toba lake event, the Australasian microtektite event, and the Cretaceous/Paleogene boundary were analyzed on the basis of foraminifers, carbonate content, trace elements, and spherules (microtektites). The Toba ash event, recovered in Hole 758C, may have had minor influences on the foraminiferal populations. The Australasian tektite event has probably some influence on foraminiferal ecology, because the larger specimens become scarce just above the microtektite layer. Microtektites recovered from Hole 758B closely resemble spherules recovered from several Cretaceous/Paleogene boundary localities in North America. The Cretaceous/Paleogene spherules, however, are usually larger and are completely altered to goyazite in the terrestrial environment and to smectite in a marine environment. The Cretaceous/Paleogene boundary of Hole 752B does not show obvious anomalous trace-element concentrations, and iridium concentrations are below our detection limits. The trace-element pattern is dominated by the alternation of chalk with volcanic ash layers above the Cretaceous/Paleogene boundary.

Petrographic description and mineral composition of ODP Site 161-975 sediments

Ocean Drilling Program Site 975 is located near the base of the Menorca Rise in the South Balearic Basin of the western Mediterranean Sea. Coring at this site penetrated the Pliocene/Miocene boundary and recovered a sequence of sediments that represent the final stages of salt deposition and the transition from evaporitic to open marine conditions at the end of the Miocene (Messinian). Detailed petrographic observations and bulk mineralogical analyses by X-ray diffraction form the basis for preliminary interpretations of depositional environments for this section. Gypsum is thought to have been deposited in an evaporating basin below wave base. Cycles consisting of a clay layer overlain by gypsiferous chalk, laminated gypsum, and finally pinch-and-swell gypsum suggest upsection increases in salinity. The gypsum section is overlain by two exotic sand layers thought to mark events of fresher water (marine or meteoric) inflow to the basin. Gypsum deposition terminated and was replaced by inorganic precipitation of micritic calcite with periodic, variable dilution by fine-grained terrigenous sediment. The micritic sediments have fine, slightly wavy, laminations indicating either an algal/microbial mat origin, or varve-like fluctuations in deposition, perhaps in a deep basin. The Pliocene/Miocene boundary falls within an interval of banded micritic silty clays that reflect the final environmental fluctuations during the transition to the open marine conditions of the Pliocene.

Sediment description, CaCO3, density and porosity at DSDP Site 89-585

Siliceous sediments and sedimentary rocks occur as chert and silicified chalk, limestone, and claystone in Site 585 lower Miocene to Campanian sediments, with one older occurrence of chert near the Cenomanian/Turonian boundary. The recovered drill breccia in the Miocene to middle Eocene interval is dominated by bright red, orange, yellow, and brown chips and fragments of chert. In early Eocene and older sediments gray silicified limestone and yellowish brown chert fragments predominate. Recovery is poor in cores with chert because chert tends to fracture into smaller pieces that escape the drill and because the hard chert fragments grind away other sediments during rotary drilling. Thin-section and hand-sample studies show complex diagenetic histories of silicification (silica pore infill) and chertification (silica replacement of host rock). Multiple events of silicification can occur in the same rocks, producing chert from silicified limestone. Despite some prior silicification, silicified limestone is porous enough to provide conduits for dissolved silica-charged pore waters. Silicification and chert are more abundant in the coarser parts of the sedimentary section. These factors reflect the importance of porosity and permeability as well as chemical and lithologic controls in the process of silica diagenesis.

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.

Calcareous nannofossils of ODP Leg 101 holes

Leg 101 of the Ocean Drilling Program drilled 19 holes at 11 sites to investigate the geology of the Straits of Florida and the northern Bahamas. Drilling at Site 626 indicated that the Gulf Stream has had significant flow through the Straits of Florida for at least the last 24 million years. Winnowed, foraminiferal grainstones and packstones with sparse nannofossil assemblages and the reworking of older nannofossils suggest strong bottom-current activity throughout this interval. Drilling north of Little Bahama Bank and in Exuma Sound documents the growth of platform slopes during the late Cenozoic. Nannofossil biostratigraphy of the upper Cenozoic sediments from the Little Bahama Bank and Exuma Sound slope transects indicates relatively continuous deposition, with only short breaks in the periplatform ooze and/or calciturbidite accumulation during the late Pliocene. These unconformities may be linked to sea-level lowstands. Nannofossil assemblages are generally poorly preserved owing to accelerated diagenesis caused by high aragonite and high magnesium calcite contents of bank-derived material. High rates of influx of bank-derived materials appear to coincide with highstands of sea level. Periplatform sediments are largely limited to the upper Cenozoic at Little Bahama Bank. Pelagic and/or hemipelagic conditions existed during the Late Cretaceous and Paleogene. A relatively complete, continuous section of Oligocene is present in the Little Bahama Bank area, although the rest of the Paleogene is thin. Paleogene material is also present in Northeast Providence Channel, although its thickness is uncertain. A thick upper Campanian chalk sequence with abundant, moderately to well-preserved nannofossils occurs in the Little Bahama Bank area. Hemipelagic nannofossil marls and marly chalks at Little Bahama Bank contain an excellent nannofossil record, which indicates a continuous lowermost to middle Cenomanian sequence overlying the upper Albian drowned platform. These hemipelagic sediments are significantly younger than the organic-rich, middle Albian limestones in Northeast Providence Channel. The latter indicate that a deep-water channel was already well established by the middle Albian.

Composition of Cretaceous basalts from DSDP Hole 16-163

Basalt underlying early Campanian chalk at Deep Sea Drilling Project (DSDP) Site 163 is divided into seven extrusive cooling units bounded by glassy margins. The margins have dips of 15° to 70°, suggestive of pillow flows rather than tabular flows. The margins are fresh sideromelane (glass) grading inward to opaque and reddish-brown globules containing microcrystalline material with radial, undulose extinction. Relative to adjacent sideromelane, the reddish-brown globules are enriched in sodium and calcium, whereas the opaque globules are depleted in these elements and enriched in iron and magnesium. It appears that basalt just inside the pillow margins has differentiated in place into globules of two distinct compositions. This globule zone grades inward to less rapidly cooled pyroxene varioles and intergrowths of plagioclase and opaque minerals. In the center of the thicker cooling units, the texture is diabasic. Alteration and calcite vein abundance are greatest at pillow margins and decrease inward; the interior of the thickest cooling unit is only slightly altered, and calcite veins are absent. Chemical analysis of whole rock by atomic absorption spectrophotometry, and of sideromelane by electron microprobe, indicates that the rock is a slightly weathered tholeiite. The atomic absorption analyses, except the one nearest the top of the basalt, are relatively uniform and similar to the sideromelane microprobe analyses, including those near the top of the basalt. This suggests that deep penetration is not necessary to get through the severely altered layer at the basalt surface, and that within this altered layer, analyses of sideromelane may be more representative of crustal composition than analyses of whole rock.

Sedimentary cycles on the Exmouth Plateau

Sedimentary cycles are observed in the nearly complete Lower Cretaceous to Eocene pelagic carbonates at Site 762 on the Exmouth Plateau off northwest Australia. The high-frequency cycles of variable clay and foraminifers in nannofossil chalk appear as color cycles repeating on a scale of centimeters to meters in thickness. Measured cycle thickness indicate that the dominant cycles appear to be related to the precession and obliquity periods. To evaluate the high-frequency variance observed on the gamma-ray curve, spectral analysis of the log was performed on two intervals: 260 to 365 mbsf in the Cenozoic, and 555 to 685 mbsf in the Mesozoic. Average Cenozoic sedimentation rates of 10.5 m/m.y. are high enough to show that variance is present in the full suite of eccentricity bands (413-123-95 k.y.). Spectral analysis of the Mesozoic section failed to produce dominant peaks that could be correlated to predicted orbital periods. The bioturbation observed in the cores in this interval may be responsible for diluting the signal and producing high-frequency noise, which is manifested in the spectra as low, broad amplitude peaks. Orbital forcing may be affecting sedimentation on the Exmouth Plateau by influencing cycles of increased carbonate production or dissolution. Alternatively, clay abundance cycles may be related to eolian deposition during cycles of increased aridity in western Australia. Four low-frequency events were also identified at Site 762 from the core and log data. The duration of these events is approximately 13 m.y., and the conformable boundaries of these sedimentary cycles correlate with observed nondepositional surfaces in other wells in western Australia. The causal mechanism for the onset of these events may be eustatic, but alternatively may be regional tectonism with associated circulation pattern changes.

Mineralogy, lithology and stable isotope composition of diagenetic siliceous rocks from ODP Leg 129 sites

Ocean Drilling Program Leg 129 recovered chert, porcellanite, and radiolarite from Middle Jurassic to lower Miocene strata from the western Pacific that formed by different processes and within distinct host rocks. These cherts and porcellanites formed by (1) replacement of chalk or limestone, (2) silicification and in-situ silica phase-transformation of bedded clay-bearing biosiliceous deposits, (3) high-temperature silicification adjacent to volcanic flows or sills, and (4) silica phase-transformation of mixed biosiliceous-volcaniclastic sediments. Petrologic and O-isotopic studies highlight the key importance of permeability and time in controlling the formation of dense cherts and porcellanites. The formation of dense, vitreous cherts apparently requires the local addition and concentration of silica. The influence of permeability is shown by two examples, in which: (1) fragments of originally identical radiolarite that were differentially isolated from pore-water circulation by cement-filled fractures were silicified to different degrees, and (2) by the development of secondary porosity during the opal-CT to quartz inversion within conditions of negligible permeability. The importance of time is shown by the presence of quartz chert below, but not above, a Paleogene hiatus at Site 802, indicating that between 30 and 52 m.y. was required for the formation of quartz chert within calcareous-siliceous sediments. The oxygen-isotopic composition for all Leg 129 carbonate- and Fe/Mn-oxide-free whole-rock samples of chert and porcellanite range widely from d18O = 27.8 per mil to 39.8 per mil vs. V-SMOW. Opal-CT samples are consistently richer in 18O (34.1 per mil to 39.3 per mil) than quartz subsamples (27.8 per mil to 35.7 per mil). Using the O-isotopic fractionation expression for quartz-water of Knauth and Epstein (1976) and assuming d18Opore water = -1.0 per mil, model temperatures of formation are 7°-26°C for carbonate-replacement quartz cherts, 22°-25°C for bedded quartz cherts, and 32°-34°C for thermal quartz cherts. Large variations in O-isotopic composition exist at the same burial depth between co-existing silica phases in the same sample and within the same phase in adjacent lithologies. For example, quartz has a wide range of isotopic compositions within a single breccia sample; d18O = 33.4 per mil and 28.0 per mil for early and late stages of fracture-filling cementation, and 31.6 per mil and 30.2 per mil for microcrystalline quartz precipitation within enclosed chert and radiolarite fragments. Similarly, opal-CT d101 spacing varies across lithologic or diagenetic boundaries within single samples. Co-occurring opal-CT and chalcedonic quartz in shallowly buried chert and porcellanite from Sites 800 and 801 have an 8.7 per mil difference in d18O, suggesting that pore waters in the Pigafetta Basin underwent a Tertiary shift to strongly 18O-depleted values due to alteration of underlying Aptian to Albian-Cenomanian volcaniclastic deposits after opal-CT precipitation, but prior to precipitation of microfossil-filling chalcedony.

Dinoflagellate cysts of ODP Leg 101 holes

The Albian-Cenomanian sediments in Holes 627B and 635B contain diverse dinoflagellate-cyst assemblages, which show affinities with coeval assemblages from offshore Morocco and northwest Europe. A total of 34 samples were analyzed from the shallow-water platform sediments and neritic marly chalk of Hole 627B and from the argillaceous chalk and limestone of Hole 635B. Dinoflagellate cysts indicate that the top of the shallow-water platform drilled at Hole 627B must be attributed to the late Albian. Dinocysts also date the drowning of the carbonate platform of the Blake Plateau. This drowning started in the latest Albian (Vraconian) and continued into the Cenomanian. The site area changed from an inner to intermediate or outer(?) neritic environment. The area around Hole 635B from the late Albian appears to have been situated in a deeper environment than the area around Hole 627B during the same period. The new dinoflagellate-cyst species Compositosphaeridiuml bahamaensis n. sp., Maghrebinia breviornata n. sp., and Subtilisphaeral habibi n. sp. are described, and Pervosphaeridium truncatum is emended. Additional taxonomic remarks about other species are included.

(Table 3) Stable isotope record of Cretaceous foraminifera from DSDP Hole 44-392A

Mid-Cretaceous (Barremian-Turonian) plankton preserved in deep-sea marl, organic-rich shale, and pelagic carbonate hold an important record of how the marine biosphere responded to short- and long-term changes in the ocean-climate system. Oceanic anoxic events (OAEs) were short-lived episodes of organic carbon burial that are distinguished by their widespread distribution as discrete beds of black shale and/or pronounced carbon isotopic excursions. OAE1a in the early Aptian (~120.5 Ma) and OAE2 at the Cenomanian/Turonian boundary (~93.5 Ma) were global in their distribution and associated with heightened marine productivity. OAE1b spans the Aptian/Albian boundary (~113-109 Ma) and represents a protracted interval of dysoxia with multiple discrete black shales across parts of Tethys (including Mexico), while OAE1d developed across eastern and western Tethys and in other locales during the latest Albian (~99.5 Ma). Mineralized plankton experienced accelerated rates of speciation and extinction at or near the major Cretaceous OAEs, and strontium isotopic evidence suggests a possible link to times of rapid oceanic plateau formation and/or increased rates of ridge crest volcanism. Elevated levels of trace metals in OAE1a and OAE2 strata suggest that marine productivity may have been facilitated by increased availability of dissolved iron. The association of plankton turnover and carbon isotopic excursions with each of the major OAEs, despite the variable geographic distribution of black shale accumulation, points to widespread changes in the ocean-climate system. Ocean crust production and hydrothermal activity increased in the late Aptian. Faster spreading rates [and/or increased ridge length] drove a long-term (Albian-early Turonian) rise in sea level and CO2-induced global warming. Changes in ocean circulation, water column stratification, and nutrient partitioning lead to a reorganization of plankton community structure and widespread carbonate (chalk) deposition during the Late Cretaceous. We conclude that there were important linkages between submarine volcanism, plankton evolution, and the cycling of carbon through the marine biosphere.

Chemical and mineral compositions of recent and ancient sediments and sedimentary rocks from the Mariana Trench

On the bed and on the ocean slope of the southern latitudinal part of the Mariana Trench ancient sediments, as well as sedimentary and igneous rocks are exposed. In the lower part of the sampled part of the studied section Late Oligocene to Early Miocene chalk-like limestones and marls occur. Upward marly tuffites and tuffs (apparently alternating with carbonate rocks) occur. These rocks are overlain by Early Miocene tuffaceous clays and siliceous-clayey muds. In the upper part of the section there are Pleistocene pelagic clays and ethmodiscus oozes.