Geochemical data from the USGS #1 Portland core, Canon City, Colorado

During the Cretaceous, widespread black shale deposition occurred during a series of Oceanic Anoxic Events (OAEs). Multiple processes are known to control the deposition of marine black shales, including changes in primary productivity, organic matter preservation, and dilution. OAEs offer an opportunity to evaluate the relative roles of these forcing factors. The youngest of these events-the Coniacian to Santonian OAE 3-resulted in a prolonged organic carbon burial event in shallow and restricted marine environments including the Western Interior Seaway. New high-resolution isotope, organic, and trace metal records from the latest Turonian to early Santonian Niobrara Formation are used to characterize the amount and composition of organic matter preserved, as well as the geochemical conditions under which it accumulated. Redox sensitive metals (Mo, Mn, and Re) indicate a gradual drawdown of oxygen leading into the abrupt onset of organic carbon-rich (up to 8%) deposition. High Hydrogen Indices (HI) and organic carbon to total nitrogen ratios (C:N) demonstrate that the elemental composition of preserved marine organic matter is distinct under different redox conditions. Local changes in d13C indicate that redox-controlled early diagenesis can also significantly alter d13Corg records. These results demonstrate that the development of anoxia is of primary importance in triggering the prolonged carbon burial in the Niobrara Formation. Sea level reconstructions, d18O results, and Mo/total organic carbon ratios suggest that stratification and enhanced bottom water restriction caused the drawdown of bottom water oxygen. Increased nutrients from benthic regeneration and/or continental runoff may have sustained primary productivity.

Biochemical, geochemical and sedimentological study of ODP Leg 112 samples

Organic-rich diatomaceous muds from Ocean Drilling Program Leg 112 (offshore Peru) are the subject of a comprehensive organic diagenetic study covering the burial interval, <1 to >100 m. The organic matter has been classified in terms of its elemental, biochemical, and geochemical compositions. About 60% of the organic carbon in sediments from <1 m can be attributed to hydrolyzable, biochemical constituents, while at 22 m this figure decreased to 20%. Pyrolysis-gas chromatography and gas chromatography-mass spectrometry chromatograms of these same sediments contain mainly hydrocarbons and nitrogenous compounds, with low amounts of other heteroatomic compounds, even though the total organic matter is rich in oxygen (about 35 atoms per 100 carbon atoms) and sulfur (1 to 5 atoms per 100 C atoms). Overall, the organic matter in these sediments, even at these shallow depths and young ages, has many of the geochemical features of far more deeply buried sediments, providing further strong evidence for the claim that "kerogen-formation" is a very early diagenetic process.

Strontium isotope ratios and concentrations in fossil fish teeth

We analyzed 87Sr/86Sr ratios in foraminifera, pore fluids, and fish teeth for samples ranging in age from Eocene to Pleistocene from four Ocean Drilling Program sites distributed around the globe: Site 1090 in the Cape Basin of the Southern Ocean, Site 757 on the Ninetyeast Ridge in the Indian Ocean, Site 807 on the Ontong-Java Plateau in the western equatorial Pacific, and Site 689 on the Maud Rise in the Southern Ocean. Sr isotopic ratios for dated foraminifera consistently plot on the global seawater Sr isotope curve. For Sites 1090, 757, and 807 Sr isotopic values of the pore fluids are generally less radiogenic than contemporaneous seawater values, as are values for fossil fish teeth. In contrast, pore fluid 87Sr/86Sr values at Site 689 are more radiogenic than contemporaneous seawater, and the corresponding fish teeth also record more radiogenic values. Thus, Sr isotopic values preserved in fossil fish teeth are consistently altered in the direction of the pore fluid values; furthermore, there is a correlation between the magnitude of the offset between the pore fluids and the seawater curve, and the associated offset between the fish teeth and the seawater curve. These data suggest that the hydroxyfluorapatite of the fossil fish teeth continues to recrystallize and exchange Sr with its surroundings during burial and diagenesis. Therefore, Sr chemostratigraphy can be used to determine rough ages for fossil fish teeth in these cores, but cannot be used to fine-tune age models. In contrast to the Sr isotopic system, our Nd concentration data, combined with published isotopic and rare earth element data, suggest that fish teeth acquire Nd during early diagenesis while they are still in direct contact with seawater. The concentrations of Nd acquired at this stage are extremely high relative to the concentrations in surrounding pore fluids. As a result, Nd isotopes are not altered during burial and later diagenesis. Therefore, fossil fish teeth from a variety of marine environments preserve a reliable and robust record of deep seawater Nd isotopic compositions from the time of deposition.

Macroturbidites of ODP Hole 103-641C

Barremian through uppermost Aptian strata from ODP Hole 641C, located upslope of a tilted fault block on the Galicia margin (northwest Spain), are syn-rift sediments deposited in the bathyal realm and are characterized by rapid sedimentation from turbidity currents and debris flows. Calcarenite and calcirudite turbidites contain shallow-water carbonate, terrigenous, and pelagic debris, in complete or partial Bouma sequences. These deposits contain abraded micritized bioclasts of reefal debris, including rudist fragments. The youngest turbidite containing shallow-water carbonate debris at Site 641 defines the boundary between syn-rift and post-rift sediments; this is also the boundary between Aptian and Albian sediments. Some Aptian turbidites are partially silicified, with pore-filling chalcedony and megaquartz. Adjacent layers of length-fast and -slow chalcedony are succeeded by megaquartz as the final pore-filling stage within carbonate reef debris. Temperatures of formation, calculated from the oxygen isotopic composition of the authigenic quartz, are relatively low for formation of quartz but are relatively warm for shallow burial depths. This quartz cement may be interpreted as a rift-associated precipitate from seawater-derived epithermal fluids that migrated along a fault associated with the tilted block and were injected into the porous turbidite beds. These warm fluids may have cooled rapidly and precipitated silica at the boundaries of the turbidite beds as a result of contact with cooler pore waters. The color pattern in the quartz cement, observed by cathodoluminescence and fluorescence techniques, and changes in the trace lement geochemistry mimic the textural change of the different quartz layers and indicates growth synchronism of the different quartz phases. Fluorescence petrography of neomorphosed low-Mg-calcite bioclasts in the silicified turbidites shows extensive zonation and details of replacive crystal growth in the bioclasts that are not observed by cathodoluminescence. Fluorescence microscopy also reveals a competitive growth history during neomorphism of the adjacent crystals in an altered carbonate bioclast. Barremian-Aptian background pelagic sediments from Hole 641C have characteristics similar to pelagic sediments from the Blake-Bahama Formation described by Jansa et al. (1979) from the western North Atlantic. Sediments at this site differ from the Blake-Bahama Formation type locality in that the Barremian-Aptian pelagic sediments have a higher percentage of dark calcareous claystone and some turbidites are silicified at Site 641. The stable isotopic composition of the pelagic marlstones from Site 641 is similar to those of other Berriasian-Aptian pelagic sediments from the Atlantic.

Pore-water chemistry of ODP Leg 115 samples

Analyses of the Sr2+ concentrations of interstitial fluids obtained from sediments squeezed during Leg 115 were used to estimate the rates and total amount of recrystallization of biogenic carbonates. The total amount of recrystallization calculated using this method varies from less than 1 % in sediments at Site 706 to more than 40% at Site 709 in sediments of 47 Ma. Five of the sites drilled during Leg 115 (Sites 707 through 711) were drilled in a depth transect within a restricted geographic area so that theoretically they received similar amounts of sediment input. Of these, the maximum rate of recrystallization occurred in the upper 50 m of Site 710 (3812 m). The amount of recrystallization decreased with increasing water depth at Sites 708 (4096 m) and 711 (4428 m), presumably as a result of the fact that most of the reactive calcium carbonate was dissolved before burial. We also observed significant alkalinity deficits at many of these sites, a condition which most likely resulted from the precipitation of calcium carbonate either in the sedimentary column, or during retrieval of the core. Precipitation of CaCO3 as a result of pressure changes during core retrieval was confirmed by the comparison of Ca2+ and alkalinity from water samples obtained using the in-situ sampler and squeezed from the sediments. At Sites 707 and 716, the shallowest sites, no calcium or alkalinity deficits were present. In spite of our estimations of as much as 45% recrystallization at Site 709, all the carbonate sites exhibited what would be previously considered conservative Ca2+/Mg2+ profiles, which varied from -1 to -0.5. By virtue of the position of these sites relative to known basaltic basement or through the actual penetration of basalt (i.e., Sites 706, 707 and 712), these sites are all known to be underlain by basalt. Our results suggest, therefore, that more positive Ca2 + /Mg2+ gradients cannot necessarily be used as indicators of the nature of basement material.

(Table 1) Compressional-wave velocities and anisotropies and wet-bulk densities of calcareous rocks and some cherts at DSDP Holes 62-463 and 62-465A

Anisotropy in compressional-wave velocities in sedimentary rocks recovered by DSDP has been recognized by several investigators (Boyce, 1976; Tucholke et al., 1976; Carlson and Christensen, 1977). The anisotropy is also observed at elevated pressures in laboratory experiments, and thus probably persists at depth in some calcareous rocks (Schreiber et al., 1972; Christensen et al., 1973; Carlson and Christensen, 1979). Carlson and Christensen (1979) suggested that the observed velocity anisotropy was produced not by the alignment of cracks but by the alignment of c axes of calcite perpendicular to bedding during compaction, diagenesis, and recrystallization. On DSDP Leg 62, calcareous rocks were recovered from the western Mid-Pacific Mountains (sub-bottom depths of 452-823 m, Site 463) and southern Hess Rise (276-412 m, Site 465). Most of the calcareous rocks are horizontally laminated and color-banded, and ages are early Cenomanian to late Barremian (Site 463 and 465 reports, this volume). The purpose of this study is to confirm the velocity anisotropy in the calcareous rocks and to identify any relationship of anistropy to bulk density, mean velocity, and burial depth.

(Appendix) Bulk inorganic chemistry at DSDP Leg 77 Holes

Clay mineralogic and inorganic geochemical investigations of Cretaceous and Cenozoic sediments of the western Gulf of Mexico lead to the following main conclusions. (1) Transition of lowermost Cretaceous continental to marine sedimentation is marked by a clay evaporitic stage, north of the Campeche Escarpment. (2) Existence of combined mineralogic and geochemical stratigraphy allows us to propose correlations between Sites 535 and 540, especially for the Albian. (3) Predominance of detrital clay assemblages is indicative of hot and variably humid continental climate until the early late Cenozoic. (4) Tectonic destabilization of the margins of Gulf of Mexico occurred at different periods, especially until the middle Cretaceous, with a mixed erosion of rocks and soils and temporary oxidized conditions of deposition. (5) Successive developments of confined perimarine basins occurred from the earliest Cretaceous until the Miocene, chiefly in the Florida area. The sources of inorganic materials were chiefly situated on the east of the studied area until the late Tertiary and after that in the Mississippi River basin. (6) Occasionally, volcanic activity influenced the clay mineralogy and mainly the geochemistry, and possibly contributed to the rather strong magnesian character of the deposition until the late Paleogene. (7) The argillaceous diagenesis is weak; variability of the carbonate diagenesis is marked by the relation Sr = f(CaO) and chiefly depends on the depth of burial, the clay content, the porosity, and the geologic age.

Composition of pore water and diagenetic carbonates of ODP Site 123-765

Degradation of organic matter in slightly organic-rich (1 wt% organic carbon) Neogene calcareous turbidites of the Argo Basin at Site 765 by sulfate reduction results in pore-water phosphate, ammonium, manganese, and carbonate alkalinity maxima. Pore-water calcium and magnesium decrease in the uppermost 100 meters below seafloor (mbsf) in response to the precipitation of calcian dolomite with an average composition of Ca1.15Mg0.83Fe0.02(CO3)2. Clear, euhedral dolomite rhombs range from <1 to 40 µm in diameter and occur in trace to minor amounts (<1-2 wt%) in Pleistocene to Pliocene sediment (62-210 mbsf) The abundance of dolomite increases markedly (2-10 wt%) in Miocene sediment (210-440 mbsf). The dolomite is associated with diagenetic sepiolite and palygorskite, as well as redeposited biogenic low-Mg calcite and aragonitic benthic foraminifers. Currently, dolomite is precipitating at depth within the pore spaces of the sediment, largely as a result of aragonite dissolution. The rate of aragonite dissolution, calculated from the pore-water strontium profile, is sufficient to explain the amount of dolomite observed at Site 765. A foraminiferal aragonite precursor is further supported by the carbon and oxygen isotopic compositions of the dolomite, which are fairly close to the range of isotopic compositions observed for Miocene benthic foraminifers. Dolomite precipitation is promoted by the degradation of organic matter by sulfate-reducing bacteria because the lower pore-water sulfate concentration reduces the effect of sulfate inhibition on the dolomite reaction and because the higher carbonate alkalinity increases the degree of saturation of the pore waters with dolomite. Organic matter degradation also results in the precipitation of pyrite and trace amounts of apatite (francolite), and the release of iron and manganese to the pore water by reduction of Fe and Mn oxides. Spherical, silt-sized aggregates of microcrystalline calcian rhodochrosite occur in trace to minor amounts in Lower Cretaceous sediment from 740 to 900 mbsf at Site 765. A negative carbon isotopic composition suggests that the rhodochrosite formed early in the sulfate reduction zone, but a depleted oxygen isotopic composition suggests that the rhodochrosite may have recrystallized at deeper burial depths.

(Table 1) Sound velocity, wet-bulk density, and acoustic impedance of some indurated sediment from DSDP Leg 64 Holes

The Pliocene-Quaternary sediments that we drilled at eight sites in the Gulf of California consist of silty clays to clayey silts, diatomaceous oozes, and mixtures of both types. In this chapter I have summarized various measurements of their physical properties, relating this information to burial depth and effective overburden pressure. Rapid deposition and frequent intercalations of mud turbidites may cause underconsolidation in some cases; overconsolidation probably can be excluded. General lithification begins at depths between 200 and 300 meters sub-bottom, at porosities between 55 and 60% (for silty clays) and as high as 70% (for diatomaceous ooze). Diatom-rich sediments have low strength and very high porosities (70-90%) and can maintain this state to a depth of nearly 400 meters (where the overburden pressure = 1.4 MPa). The field compressibility curves of all sites are compared to data published earlier. Where sediments are affected by basaltic sills, these curves clearly show the effects of additional loading and thermal stress (diagenesis near the contacts). Strength measurements on well-preserved hydraulic piston cores yielded results similar to those obtained on selected samples from standard drilling. Volumetric shrinkage dropped to low values at 100 to 400 meters burial depth (0.3 to 2.0 MPa overburden pressure). Porosity after shrinkage depends on the composition of sediments.

Experimental assessment of sediment burial in eelgrass Zostera marina in Kiel Bight

Seagrass meadows, one of the world's most important and productive coastal habitats, are threatened by a range of anthropogenic actions. Burial of seagrass plants due to coastal activities is one important anthropogenic pressure leading to the decline of local populations. In our study, we assessed the response of eelgrass Zostera marina to sediment burial from physiological, morphological, and population parameters. In a full factorial field experiment, burial level (5-20cm) and burial duration (4-16 weeks) were manipulated. Negative effects were visible even at the lowest burial level (5 cm) and shortest duration (4 weeks), with increasing effects over time and burial level. Buried seagrasses showed higher shoot mortality, delayed growth and flowering and lower carbohydrate storage. The observed effects will likely have an impact on next year's survival of buried plants. Our results have implications for the management of this important coastal plant.

Mineralogy of Hawaiian Arch sediments

The mineralogy of both bulk- and clay-sized (<2 µm) fractions of sediments from Holes 842A and 842B of Ocean Drilling Program Leg 136 was determined by X-ray diffraction. The sediments consist of a combination of terrigenous (quartz, plagioclase, smectite, illite, kaolinite, and chlorite), volcaniclastic (augite, plagioclase, and volcanic glass), and diagenetic minerals (smectite, phillipsite, clinoptilolite, and opal-CT). Although biogenic silica (radiolarians and diatoms) is common in near-seafloor (<10 mbsf) sediments, biogenic calcite is rare. Variations with depth in abundances of the terrigenous minerals reflect temporal changes in the flux of eolian material to the site. Volcanogenic material derived from the Hawaiian Islands is present in lithologic Unit 1 (0-19.9 meters below seafloor) both as discrete layers and as finely disseminated silt- and clay-sized material. Volcanic glass is present only in the upper 10 m of the sediment column. In Unit 2 (19.9-35.7 mbsf), increased smectite and zeolite abundances with depth as well as indurated, zeolite-rich layers are thought to be the alteration products of volcanogenic material. The source of this older (late Oligocene to middle Miocene) volcanogenic detritus may be continental volcanism. Microfabrics imaged using back-scattered electron imaging reflect the effects of compaction and diagenesis on sediment porosity and matrix structure. As porosity decreases during burial, the matrix changes from an open, floc-like fabric, to an interlocking network of clay mineral domains, and finally to a dense intergrowth of clay minerals and zeolites. Despite the substantial changes in sediment microfabric and mineralogy, correlations between physical and acoustic properties and mineralogy are weak or absent. The sediment has maintained high porosity (>70%), and water content appears to dominate the sediment's physical character and acoustic response.

Geochemistry of tetrapyrrole, tetraterpenoid, and perylene pigments in sediments from the Gulf of California

Results and discussion cover pigment analyses of 36 sediment samples recovered by Deep Sea Drilling Project Leg 64, and six samples from the Leg 64 site-survey cruise in the Guaymas Basin (Scripps Institution of Oceanography, Leg 3). Pigments investigated were tetrapyrroles, tetraterpenoids, and the PAH compound perylene. Traces of mixed nickel and copper ETIO-porphyrins were ubiquitous in all sediment samples, except for the very surface (i.e., <2 m sub-bottom), and their presence is taken as an indication of minor influxes of previously oxidized allochthonous (terrestrial) organic matter. Phorbides and chlorins isolated from Site 479 sediment samples (i.e., the oxygen-minimum locale, northeast of the Guaymas Basin) well represent the reductive diagenesis ("Treibs Scheme"; see Baker and Palmer, 1978; Treibs, 1936) of chlorophyll derivatives. Three forms of pheophytin-a, plus a variety of phorbides, were found to give rise to freebase porphyrins, nickel phylloerythrin, and nickel porphyrins, with increasing depth of burial (increasing temperature). Sediments from Sites 481, 10G, and 18G yielded chlorophyll derivatives characteristic of early oxidative alterations. Included among these pigments are allomerized pheophytin-a, purpurin-18, and chlorin-p6. The high thermal gradient imposed upon the late Quaternary sediments of Site 477 greatly accelerated chlorophyll diagenesis in the adjacent overlying sediments, that is, the production of large quantities of free-base desoxophylloerythroetioporphyrin (DPEP) occurred in a section (477-7-5) presently only 49.8 meters sub-bottom. Present depth and age of these sediments are such that only chlorins and phorbides would be expected. Carotenoid (i.e., tetraterpenoids) concentrations were found to decrease rapidly with increasing sub-bottom depth. Less deeply buried sediments (e.g., 0-30 m) yielded mixtures of carotenes and oxygen-substituted carotenoids. Oxygencontaining (oxy-, oxo-, epoxy-) carotenoids were found to be lost preferentially with increased depth of burial. Early carotenoid diagenesis is suggested as involving interacting reductions and dehydrations whereby dehydro-, didehydro-, and retro-carotenes are generated. Destruction of carotenoids as pigments may involve oxidative cleavage of the isoprenoid chain through epoxy intermediates, akin to changes in the senescent cells of plants. Perylene was found to be a common component of the extractable organic matter from all sediments investigated. The generation of alkyl perylenes was found to parallel increases in the existing thermal regime at all sites. Igneous sills and sill complexes within the sediment profile of Site 481 altered (i.e., scrambled) the otherwise straightforward thermally induced alkylation of perylene. The degree of perylene alkylation is proposed as an indicator of geothermal stress for non-contemporaneous marine sediments.

Mineral composition and experimental results from XRD analyses of sediments from ODP Leg 190 sites

X-ray diffraction analyses of the clay-sized fraction of sediments from the Nankai Trough and Shikoku Basin (Sites 1173, 1174, and 1177 of the Ocean Drilling Program) reveal spatial and temporal trends in clay minerals and diagenesis. More detrital smectite was transported into the Shikoku Basin during the early-middle Miocene than what we observe today, and smectite input decreased progressively through the late Miocene and Pliocene. Volcanic ash has been altered to dioctahedral smectite in the upper Shikoku Basin facies at Site 1173; the ash alteration front shifts upsection to the outer trench-wedge facies at Site 1174. At greater depths (lower Shikoku Basin facies), smectite alters to illite/smectite mixed-layer clay, but reaction progress is incomplete. Using ambient geothermal conditions, a kinetic model overpredicts the amount of illite in illite/smectite clays by 15%-20% at Site 1174. Numerical simulations come closer to observations if the concentration of potassium in pore water is reduced or the time of burial is shortened. Model results match X-ray diffraction results fairly well at Site 1173. The geothermal gradient at Site 1177 is substantially lower than at Sites 1173 and 1174; consequently, volcanic ash alters to smectite in lower Shikoku Basin deposits but smectite-illite diagenesis has not started. The absolute abundance of smectite in mudstones from Site 1177 is sufficient (30-60 wt%) to influence the strata's shear strength and hydrogeology as they subduct along the Ashizuri Transect.

Facies and diagenesis of organic matter in sediments at DSDP Leg 87

A series of upper Pliocene to Pleistocene sediment samples from DSDP Sites 582 and 583 (Nankai Trough, active margin off Japan) were investigated by organic geochemical methods including organic carbon determination, Rock- Eval pyrolysis, gas chromatography of extractable hydrocarbons, and kerogen microscopy. The organic carbon content is fairly uniform and moderately low (0.35 to 0.77%) at both sites, although accompanied by high sedimentation rates. The low organic matter concentrations are the result of the combined effect of several factors: low bioproductivity, oxic depositional environment, and dilution with lithogenic material. Organic petrography revealed a mixture of three maceral types: (1) fresh, green fluorescent alginites of aquatic origin probably transported by turbidites from the shelf edge, (2) gelified huminites and paniculate liptinites derived from the erosion of unconsolidated peat, and (3) highly reflecting inertinites derived from continental erosion. By a combination of organic petrography and Rock-Eval pyrolysis results, the organic matter is characterized as mainly type III kerogen with a slight tendency to a mixed type II-III. During Rock-Eval pyrolysis, a mineral matrix effect on the generated hydrocarbons was observed. The organic matter in all sediments has a low level of maturity (below 0.45% Rm) and has not yet reached the onset of thermal hydrocarbon generation according to several geochemical maturation parameters. This low maturity is in contrast to anomalously high extract yields at both sites and large hydrocarbon proportions in the extracts at Site 583. This contrast may be due to early generation of polar compounds and perhaps redistribution of hydrocarbons caused by subduction tectonics. Carbon isotope data of the interstitial hydrocarbon gases indicate their origin from bacterial degradation of organic matter, although only very few bacterially degraded maceral components were detected.