Lithologic correlation of ODP Leg 115 holes

Whole-core (WC) measurements of low-field magnetic susceptibility (MS) provide an extremely simple, rapid, and nondestructive technique for high-resolution core logging and lithostratigraphic correlation between subsidiary holes at Ocean Drilling Program (ODP) sites. This is particularly useful for reconstructing composite, stratigraphically continuous sequences for individual ODP sites by splicing the uninterrupted records obtained from subsections of offset cores recovered from adjacent holes. Correlation between the WCMS profiles of holes drilled at different sites is also possible in some instances, especially when lithologic variations at each site are controlled by regional paleoceanographic or global (i.e., orbitally forced) paleoclimatic changes. In such circumstances, WCMS may also be used as a proxy paleoclimatic indicator, duly assisting climatostratigraphic zonation of the recovered sequence by more conventional microfossil and isotopic techniques. High-resolution WCMS profiles are also useful in detecting intervals of the recovered sequence affected by drilling disturbance, in the form of contamination by pipe rust or similar metallic artifacts as well as discontinuities related to repenetration of the corer or loss of material between successively cored intervals. Stratigraphic intervals that have been affected by early (suboxic) diagenesis resulting from a high initial organic matter content of the sediment are also readily identified by WCMS logging. The MS signal of horizons affected by suboxic diagensis is typically degraded in proportion to the duration and intensity (related to initial Corg concentration) of organic matter remineralization. The lowering of MS values during suboxic diagenesis results from "dissolution" (bacterially mediated ionic dissociation) of magnetic iron and manganese oxides and oxyhydroxides in the sediment. It is to be hoped that, on future ODP (or similar) cruises, WCMS logging will cease to be regarded as a mere adjunct to paleomagnetic measurements, but rather as a simple, yet powerful, lithostratigraphic tool, directly analogous to downhole geophysical logging tools, and complimentary to shipboard techniques for whole-core measurements of physical properties (e.g., P-wave logging, GRAPE, etc.).

(Table 1) Sulfur isotopes, total sulfur, and degree of oxidation of basalt samples from DSDP Holes 69-504B and 70-504B

Whole-rock basalt samples from the upper half of Deep Sea Drilling Project Hole 504B have oxygen-isotope compositions typical of mid-ocean-ridge basalts which have experienced a moderate degree of low-temperature alteration by sea water. By contrast, d18O values in the lower half of the hole correspond to basalts which have experienced almost no detectable oxygen-isotope alteration. These observations suggest that the overall water/rock ratio was lower in the lower half of the drilled crust. A correlation between d18O values and 87Sr/86Sr ratios suggests that the water/rock ratio, rather than temperature variation, was the main factor determining basalt d18O values. Hydrogen-isotope data appear to be consistent with a low water/rock ratio in the lower part of the crust.

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.

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.

Geochemistry and kinetic models od Cretaceous samples

The source rock potential of Cretaceous organic rich whole rock samples from deep sea drilling project (DSDP) wells offshore southwestern Africa was investigated using bulk and quantitative pyrolysis techniques. The sample material was taken from organic rich intervals of Aptian, Albian and Turonian aged core samples from DSDP site 364 offshore Angola, DSDP well 530A north of the Walvis Ridge offshore Namibia, and DSDP well 361 offshore South Africa. The analytical program included TOC, Rock-Eval, pyrolysis GC, bulk kinetics and micro-scale sealed vessel pyrolysis (MSSV) experiments. The results were used to determine differences in the source rock petroleum type organofacies, petroleum composition, gas/oil ratio (GOR) and pressure-volume-temperature (PVT) behavior of hydrocarbons generated from these black shales for petroleum system modeling purposes. The investigated Aptian and Albian organic rich shales proved to contain excellent quality marine kerogens. The highest source rock potential was identified in sapropelic shales in DSDP well 364, containing very homogeneous Type II and organic sulfur rich Type IIS kerogen. They generate P-N-A low wax oils and low GOR sulfur rich oils, whereas Type III kerogen rich silty sandstones of DSDP well 361 show a potential for gas/condensate generation. Bulk kinetic experiments on these samples indicate that the organic sulfur contents influence kerogen transformation rates, Type IIS kerogen being the least stable. South of the Walvis Ridge, the Turonian contains predominantly a Type III kerogen. North of the Walvis Ridge, the Turonian black shales contain Type II kerogen and have the potential to generate P-N-A low and high wax oils, the latter with a high GOR at high maturity. Our results provide the first compositional kinetic description of Cretaceous organic rich black shales, and demonstrate the excellent source rock potential, especially of the Aptian-aged source rock, that has been recognized in a number of the South Atlantic offshore basins.

Oxygen and hydrogen isotopes at DSDP Leg 65 Holes

In order to provide information on the degree of alteration of the very young basaltic basement drilled on Leg 65 in the mouth of the Gulf of California, we have measured the oxygen isotopic composition of whole rocks and mineral separates. Considerable data already exist for older ocean crust, in particular for the deep holes drilled in the Atlantic Ocean on Deep Sea Drilling Project (DSDP) Legs 37, 45, 46, and 51-53. These data indicate that in all of these holes, which include crust as young as 3.5 m.y. old, a significant amount of alteration has taken place as the result of low-temperature interaction between basalt and seawater (cf. Muehlenbachs, 1977, 1980; Hoernes et al., 1978; Friedrichsen and Hoernes, 1980). It is therefore of interest to determine whether Leg 65 crust, which is only 0.5 to 1.5 m.y. old, has experienced a similar degree of alteration.

Boron contents and boron, carbon, and oxygen isotope data for ODP Sites 160-970 and 160-971

Products of two mud volcanoes from the distal part of the Mediterranean Ridge accretionary complex have been investigated regarding their B, C, and O stable isotope signatures. The mud breccias have been divided into mud matrix, lithified clasts, biogenic deposits, and authigenic cements and crusts related to fluid flow and cementation. Isotope geochemistry is used to evaluate the depth of mobilization of each phase in the subduction zone. B contents and isotope ratios of the mud and mud clasts show a general trend of B enrichment and decreasing d11B values with increasing consolidation (i.e., depth). However, the majority of the clast and matrix samples relate to moderate depths of mobilization within the wedge (1-2 km below seafloor). The carbonate cements of most of these clasts as well as the authigenic crusts, however, provide evidence for a deep fluid influence, probably associated with the décollement at 5-6 km depth. This interpretation is supported by d13C ratios of the crust, which indicate precipitation of C from thermogenic methane, and by the d11B ratios of pore-water samples of mud-breccia drill cores. Clams (Vesicomya sp.) living adjacent to fluid vents have d11B and d18O values corresponding to brines known in the area, which acted as the parent solution for shell precipitation. Such brines are most likely Miocene pore waters trapped at deep levels within the backstop to the accretionary prism, probably prior to desiccation of the Mediterranean in the Messinian (6-5 Ma). Combining all results, deep fluid circulation and expulsion are identified as the main processes triggering mud liquefaction and extrusion, whereas brines contribute only locally. Given the high B contents, mud extrusion has to be considered a major backflux mechanism of B into the hydrosphere.

Oxygen isotope concentrations of minerals from the upper kilometer of the ocean crust, DSDP Hole 504B

DSDP Hole 504B is the deepest basement hole in the oceanic crust, penetrating through a 571.5 m pillow section, a 209 m lithologic transition zone, and 295 m into a sheeted dike complex. An oxygen isotopic profile through the upper crust at Site 504 is similar to that in many ophiolite complexes, where the extrusive section is enriched in 18O relative to unaltered basalts, and the dike section is variably depleted and enriched. Basalts in the pillow section at Site 504 have delta 18O values generally ranging from +6.1 to +8.5? SMOW (mean= +7.0?), although minor zeolite-rich samples range up to 12.7?. Rocks depleted in 18O appear abruptly at 624 m sub-basement in the lithologic transition from 100% pillows to 100% dikes, coinciding with the appearance of greenschist facies minerals in the rocks. Whole-rock values range to as low as +3.6?, but the mean values for the lithologic transition zone and dike section are +5.8 and +5.4?, respectively. Oxygen and carbon isotopic data for secondary vein minerals combined with the whole rock data provide evidence for the former presence of two distinct circulation systems separated by a relatively sharp boundary at the top of the lithologic transition zone. The pillow section reacted with seawater at low temperatures (near 0°C up to a maximum of around 150°C) and relatively high water/rock mass ratios (10-100); water/rock ratios were greater and conditions were more oxidizing during submarine weathering of the uppermost 320 m than deeper in the pillow section. The transition zone and dikes were altered at much higher temperatures (up to about 350°C) and generally low water/rock mass ratios (~1), and hydrothermal fluids probably contained mantle-derived CO2. Mixing of axial hydrothermal fluids upwelling through the dike section with cooler seawater circulating in the overlying pillow section resulted in a steep temperature gradient (~2.5°C/m) across a 70 m interval at the top of the lithologic transition zone. Progressive reaction during axial hydrothermal metamorphism and later off-axis alteration led to the formation of albite- and Ca-zeolite-rich alteration halos around fractures. This enhanced the effects of cooling and 18O enrichment of fluids, resulting in local increases in delta 18O of rocks which had been previously depleted in 18O during prior axial metamorphism.

Magnetic properties and incompatible element geochemistry of some igneous rocks at DSDP Leg 64 Holes

I received five unoriented samples of igneous rocks from four Sites of Leg 64 of the Deep Sea Drilling Project (DSDP). I have measured several magnetic properties, alkalis (K, Rb, and Cs), alkaline-earth (Ba and Sr) element concentrations, and 87Sr/86Sr ratios of these samples. This study reports the results.

Organic geochemistry and sedimentology of lower to mid-Cretaceous at DSDP Leg 77 Holes

Analyses of 40 carbonate core samples - 27 from Site 535, 12 from Site 540, and 1 from Site 538A - have confirmed many of the findings of the Shipboard Scientific Party. The samples, all but one Early to mid-Cretaceous in age (Berriasian to Cenomanian), reflect sequences of cyclically anoxic and oxic depositional environments. They are moderately to very dark colored, dominantly planar-parallel, laminated lime mudstones. Most show the effects of intense mechanical compaction. Visual kerogen characteristics and conventional Rock-Eval parameters indicate that these deep basinal carbonates contain varying mixtures of thermally immature kerogen derived from both marine and terrigenous precursors. However, variations in kerogen chemistry are evident upon analysis of the pyrolysis mass spectral data in conjunction with the other geochemical analyses. Particularly diagnostic is the reduction index, Rl, a measure of H2S produced during pyrolysis. Total organic carbon, TOC, ranges from 0.6 to 6.6%, with an overall average of 2.4%. Average TOCs for these fine-grained mudstones are: late Eocene 2.5% (1 sample), Cenomanian 2.2% (6), Albian 2.0% (10), Aptian 1.3% (1), Barremian-Hauterivian 2.8% (11), late Valanginian 4.8% (3), Berriasian-early Valanginian 1.6% (7). Most of the carbonates have source-potential ratings of fair to very good of predominantly oil-prone to mixed kerogen, with only a few gas-prone samples. The ratings correlate well with the inferred depositional environments, i.e., whether oxic or anoxic. Several new organic-geochemical parameters, especially Rl, based on pyrolysis mass spectrometry of powdered whole-rock samples, support this view. Tar from fractures in laminated to bioturbated limestones of Unit IV (late Valanginian) at 535-58-4, 19-20 cm (530 m sub-bottom) appears to be mature, biodegraded, and of migrated rather than on site indigenous origin.

Geochemistry of vein rocks of ODP Hole 118-735B

Rock samples from Hole 735B, Southwest Indian Ridge, were examined to determine the principal vein-related types of alteration that occurred, the nature of fluids that were present, and the temperatures and pressures of these fluids. Samples studied included veined metagabbro, veined mylonitic metagabbro, felsic trondhjemite, and late-stage leucocratic diopside-bearing veins. The methods used were standard petrographic analysis, mineral chemical analysis by electron microprobe, fluid inclusion petrography and analysis by heating/freezing techniques and laser Raman microspectroscopy, and oxygen isotopic analyses of mineral separates. Alteration in lithologic Units I and II (above the level of Core 118-735B-3OR; approximately 140 meters below the seafloor) is dominated by hydration by seawater-derived fluids at high temperature, up to about 700°C, and low water/rock ratio, during and immediately after pervasive ductile deformation. Below Core 118-735B-30R, pervasive deformation is less common, and brittle veining and brecciation are the major alteration styles. Leucocratic centimeter-scale veins, often containing diopside and plagioclase, were produced by interaction of hot (about 500°C) seawater-derived fluid and gabbro. The water/rock ratio was locally high at the veins and breccia zones, but the integrated water/rock ratio for the lower part of the hole is probably low. Accessory hydrous magmatic or deuteric phases formed from magmatic volatiles in some gabbro and in trondhjemite. Most subsequent alteration was affected by fluids that were seawater-derived, based on isotopic and chemical analyses of minerals and analyses of fluid inclusions. Many early-generation fluid inclusions, associated with high-temperature veining, contain appreciable methane as well as saline water. The source of methane is unclear, but it may have formed as seawater was reduced during low water/rock interaction with ultramafic upper mantle or ultramafic and mafic layer 3. Temperatures of alteration were calculated on the basis of coexisting mineral chemistry and isotopic values. Hydrothermal metamorphism commenced at about 720°C and continued to about 550°C. Leucocratic veining took place at about 500°C. Alteration within brecciated horizons was also at about 500° to less than 400°C, and the trondhjemite was altered at about 550° to below 490°C. Pressures calculated from a diopside-bearing vein, based on a combination of fluid inclusion and isotopic analysis, were 90 to 100 MPa. This pressure places the sample, from Core 118-735B-70R in Unit V, at about 2 km below the seafloor.

Major, trace and rare earth element concentration of ODP Site 210-1277 basalts, Newfoundland margin

Drilling of the distal Newfoundland margin at Ocean Drilling Program Site 1277 recovered part of the transition between exhumed sub-continental mantle lithosphere and normal mid-ocean-ridge basalt (N-MORB) volcanism perhaps related to the initiation of seafloor spreading, which may have occurred near the Aptian/Albian boundary, coincident with the final separation of subcontinental mantle lithosphere. Subcontinental mantle lithosphere was recovered near the crest of a basement high, the Mauzy Ridge. This ridge lies near magnetic Anomaly M1 and is inferred to be of Barremian age. The recovered section is dominated by serpentinized spinel harzburgite, with subordinate dunite and minor gabbroic intrusives, and it includes inferred high-temperature ductile shear zones. The serpentinite is capped by foliated gabbro cataclasite that is interpreted as the product of a major seafloor extensional detachment. The serpentinized harzburgite beneath is highly depleted subcontinental mantle lithosphere that was exhumed to create new seafloor within the ocean-continent transition zone. After inferred removal of overlying brittle crust, the detachment was eroded, producing multiple mass flows that were dominated by clasts of serpentinite and gabbro in a lithoclastic and calcareous matrix. Basaltic lavas were erupted spasmodically, mainly as sheet flows, with subordinate lava breccia, hyaloclastite, and possible pillow lava. The sedimentary-volcanic succession and the exhumed mantle lithosphere experienced later high-angle extensional fracturing and probably faulting. Extensional fissures opened incrementally and were filled with silt-sized carbonate, basalt-derived clastic sediment, and hyaloclastite, forming neptunian dykes and geopetal structures. Chemical analysis of representative basalts for major elements and trace elements were made using a high-precision, high-accuracy X-ray fluorescence method (utilizing increased count times) and by whole-rock inductively coupled plasma-mass spectrometry that yielded additional evidence for rare earth elements. The analyses indicate N-MORB to slightly enriched compositions. The MORB was produced by relatively high degree melting of a fertile mantle source that differed strongly from the cored serpentinized peridotites. The basalts exhibit a distinct negative Nb anomaly on MORB-normalized plots that can be explained by prior extraction of melt from upper mantle that had previously been affected by subduction, possibly during closure of the Iapetus or Rheic oceans. In the proposed interpretation, mantle lithosphere was exhumed to the seafloor and experienced mass wasting to form serpentinite-rich mass flows. The interbedded MORB records the beginning of a transition to "normal" seafloor spreading. This interpretation takes into account drilling results from the Iberia-Galicia margin and the Jurassic Alps-Apennines.

Oxygen and sulfur isotopes of peridotite and gabbro from the Mid-Atlantic Ridge

Whole rock sulfur and oxygen isotope compositions of altered peridotites and gabbros from near the 15°20'N Fracture Zone on the Mid-Atlantic Ridge were analyzed to investigate hydrothermal alteration processes and test for a subsurface biosphere in oceanic basement. Three processes are identified. (1) High-temperature hydrothermal alteration (~250-350°C) at Sites 1268 and 1271 is characterized by 18O depletion (2.6-4.4 per mil), elevated sulfide-S, and high delta34S (up to ~2 wt% and 4.4-10.8 per mil). Fluids were derived from high-temperature (>350°C) reaction of seawater with gabbro at depth. These cores contain gabbroic rocks, suggesting that associated heat may influence serpentinization. (2) Low-temperature (<150°C) serpentinization at Sites 1272 and 1274 is characterized by elevated delta18O (up to 8.1 per mil), high sulfide-S (up to ~3000 ppm), and negative delta34S (to -32.1 per mil) that reflect microbial reduction of seawater sulfate. These holes penetrate faults at depth, suggesting links between faulting and temperatures of serpentinization. (3) Late low-temperature oxidation of sulfide minerals caused loss of sulfur from rocks close to the seafloor. Sulfate at all sites contains a component of oxidized sulfide minerals. Low delta34S of sulfate may result from kinetic isotope fractionation during oxidation or may indicate readily oxidized low-delta34S sulfide derived from microbial sulfate reduction. Results show that peridotite alteration may be commonly affected by fluids +/- heat derived from mafic intrusions and that microbial sulfate reduction is widespread in mantle exposed at the seafloor.

Element stratigraphy across the Cretaceous-Tertiary boundary in ODP Hole 119-738C

Neutron activation analyses of iridium and other chemical elements were performed across a 1-m-thick, partly nonbioturbated, clay-rich interval at the Cretaceous/Tertiary boundary in ODP Hole 738C. The results show that the boundary interval holds one of the highest Ir enrichments (320 ng Ir/cm2) of all known Cretaceous/Tertiary boundary layers. Iridium concentrations are highest (18 ppb Ir, whole-rock samples) a few centimeters above the base of the clayrich interval and gradually tail off upsection. Compared with background levels the most Ir-rich interval also shows strongly enhanced concentrations of Cr (215 ppm) and slightly elevated Co concentrations (13 ppm). The Ir-rich interval shows low As (< 15 ppm) and Sb (<0.8 ppm) concentrations, a fact that is congruent with absence of abundant authigenic sulfides in the sediment. Irregularly distributed Fe enrichments and a greenish gray color of the Fe-rich intervals may indicate the presence of glauconitic clay minerals and suboxic, slightly reducing conditions during deposition. Rare earth element (REE) abundance patterns change considerably across the Cretaceous/Tertiary boundary interval, reflecting either a change in Cretaceous/Tertiary boundary seawater REE composition or the occurrence of different REE fractionation processes due to changing depositional environment. Element-vs.-element ratios of Hf, Ta, Th, U, Cs, and Sc are similar between the most Ir-rich layers of the boundary section and other levels with lower Ir concentrations. This may imply that the clay fraction of the Ir-rich layers of the Cretaceous/Tertiary boundary interval is made up predominantly of locally derived material. Calculated calcite-free abundances of Hf, Ta, Th, U, Cs, and Sc, on the other hand, are reconcilable with an extraneous origin of the bulk of the clay in the most Ir-rich layers. The Ir in the Cretaceous/Tertiary boundary clay-rich zone in Hole 738C is most likely derived from an earth-impacting asteroid; however, the origin of the clay-rich zone remains enigmatic.

Geochemical compositions of minerals from chilled dike margins of ODP Hole 140-504B

Mineral and whole-rock geochemical data are presented for chilled dike margins from the lower sheeted dike complex of Deep Sea Drilling Project/Ocean Drilling Program (DSDP/ODP) Hole 504B. Compositions of phenocrystic plagioclase (An80-89); olivine (Fo82-86); clinopyroxene (Wo52En40Fs8, with Cr2O3 up to 1.2%); and rare chromian spinel (Cr# 43) are consistent with those from the lavas and the upper dike complex recovered previously (DSDP Legs 69, 70, 83, and ODP Leg 111). Major and trace element compositions fall in group D of Autio and Rhodes (1983) and have high CaO/Na2O, and low TiO2, K2O, and (La/Sm)N values consistent with previous analyses from this site.