Cenozoic radiolarians from the Bahamas

Radiolarians from two sites north of Little Bahama Bank (Sites 627 and 628) are correlated with assemblages from sites on the southeastern U.S. coastal plain and continental shelf and from DSDP Sites 391 and 534 in the Blake-Bahama Basin. Results show that deposition of biogenic silica-rich sediments occurred in this region from the late Oligocene through middle Miocene, although the record is interrupted by unconformities. Radiolarians help constrain the age of a mass-transported deposit at Site 627 that appears to be coeval with the Great Abaco Member of the Blake Ridge Formation.

Susceptibility and time-dependent magnetization of basalts at DSDP Hole 76-534A

Basalts from Hole 534A are among the oldest recovered from the ocean bottom, dating from the opening of the Atlantic 155 Ma. Upon exposure to a 1-Oe field for one week, these basalts acquire a viscous remanent magnetization (VRM), which ranges from 4 to 223% of their natural remanent magnetization (NRM). A magnetic field of similar magnitude is observed in the paleomagnetic lab of the Glomar Challenger, and it is therefore doubtful if accurate measurements of magnetic moment in such rocks can be made on board unless the paleomagnetic area is magnetically shielded. No correlation is observed between the Konigsberger ratio (beta), which is usually less than 3, and the ability to acquire a VRM. The VRM shows both a log t dependence and a Richter aftereffect. Both of these, but especially the log t dependence, will cause the susceptibility measurements (made by applying a magnetic field for a very short time) to be minimum values. The susceptibility and derived Q should therefore be used cautiously for magnetic anomaly interpretation, because they can cause the importance of the induced magnetization to be underestimated.

Geochemistry at DSDP Site 76-533

Bulk X-ray mineralogy of 47 hemipelagic mud and clay samples from the Blake Outer Ridge has revealed that the sediments contain low magnesian calcite, calcian dolomite, ferroan dolomite, and magnesian siderite. Dolomite and siderite are authigenic and occur as rhombohedrons scattered through the sediments, whereas calcite is mostly biogenic. Pliocene dolomitic lenses are made up of interlocking polyhedral grains of ferroan dolomite. The contents of authigenic dolomite and siderite are 3 to 8% in carbonate sediments and 70 to 89% in dolomitic lenses. Dolomite occurs largely in the cores above 192 m sub-bottom depth, whereas siderite occurs in the cores below 87 m. The distribution and occurrence of dolomite and siderite have determined the diagenetic zonation of carbonates as Zone I (dolomitic zone, top-90 m), Zone II (transition zone, 90-180 m), and Zone III (sideritic zone, 180 m-bottom). Measurements of major and minor elements in the untreated total sediment samples and the insoluble residues after digestion in acid-reducing solution have revealed that the soluble fraction concentrates carbonates and ferromanganese associations (Ca, Mg, Sr, Fe, and Mn). Typical "hydrogenous elements" (Co, Cu, Ni, and V) are more concentrated in the insoluble residues rather than in the soluble fraction; the concentrations of these four elements are low and comparable to modern offshore mud, probably because the Site 533 sediments were deposited at a high rate of sedimentation. The contents of Fe2O3 and MnO are somewhat high for rapidly accumulated mud, particularly in the Pliocene sediments (8.09 and 0.26%, respectively, on a Carbonate-free basis). The high Fe and Mn contents are mainly due to the high contribution of the leacheable nonlithogenous fraction; leacheable Fe and Mn originate in the ferromanganese oxide accumulated on the seafloor. Only a small amount of ferric oxide was converted to iron sulfide in the surficial part of Zone I. Most ferromanganese oxide was reduced and precipitated as ferroan dolomite and magnesian siderite in Zones II and III under high alkalinity and high pH conditions in the organic-matter-rich sediments. Fe2+ and Mn2+ in the deeper sediments beneath Zone III possibly migrated upward and concentrated as siderite in Zone III, hence resulting in high contents of Fe and Mn in the Pliocene sediments. Analysis of carbonate zonation on the Blake Outer Ridge has revealed that the zonation is subparallel to the bedding plane rather than to the present seafloor. The sediments at Site 103 on the flank region of the Ridge are lacking Zone I and most of Zone II, probably the result of erosion of the most of the Pleistocene and Pliocene sediments by the enhanced bottom currents during the Pleistocene.

Organic geochemical characteristics at DSDP Holes 76-534A and 44-391C

Pyrolysis assay, bitumen analysis, and elemental analysis of kerogen were used to characterize the organic matter of selected core samples from Hole 534A (Leg 76) and Hole 391C (Leg 44) on the Blake-Bahama Plateau. The organic matter throughout the stratigraphic section appears to be principally of a terrestrial origin. The data from several isolated horizons in the Hatteras and Blake-Bahama Formations imply the presence of significant quantities of autochthonous marine organic matter. However, these horizons appear so limited that they cannot be considered potential liquid hydrocarbon source rocks. All the analyzed samples are immature and have not evolved sufficiently to enter into the main stage of hydrocarbon generation. The temporal and spatial restrictions of strata rich in marine organic matter suggest that they do not represent major expansions and contractions of anoxic bottom-water masses, but represent limited occurrences of anoxic conditions.

Geochemistry and isotopes at DSDP Site 76-533

Concentrations and d34S and d13C values were determined on SO4, HCO3, CO2, and CH4 in interstitial water and gas samples from the uppermost 400 m of sediment on the Blake Outer Ridge. These measurements provide the basis for detailed interpretation of diagenetic processes associated with anaerobic respiration of electrons generated by organic- matter decomposition. The sediments are anaerobic at very shallow depths (<1 m) below the seafloor. Sulfate reduction is confined to the uppermost 15 m of sediment and results in a significant outflux of oxidized carbon from the sediments. At the base of the sulfate reduction zone, upward-diffusing CH4 is being oxidized, apparently in conjunction with SO4 reduction. CH4 generation by CO2 reduction is the most important metabolic process below the 15-m depth. CO2 removal is more rapid than CO2 input over the depth interval from 15 to 100 m, and results in a slight decrease in HCO3 concentration accompanied by a 40 per mil positive shift in d13C. The differences among coexisting CH4, CO2, and HCO3 are consistent with kinetic fractionation between CH4 and dissolved CO2, and equilibrium fractionation between CO2 and HCO3. At depths greater than 100 m, the rate of input of CO2 (d13C = -25 per mil) exceeds by 2 times the rate of removal of CO2 by conversion to CH4 (d13C of -60 to -65 per mil). This results in an increase of dissolved HCO3 concentration while maintaining d13C of HCO3 relatively constant at +10 per mil. Non-steady-state deposition has resulted in significantly higher organic carbon contents and unusually high (70 meq/l) pore-water alkalinities below 150 m. These high alkalinities are believed to be related more to spontaneous decarboxylation reactions than to biological processes. The general decrease in HCO3 concentration with constant d13C over the depth interval of 200 to 400 m probably reflects increased precipitation of authigenic carbonate. Input-output carbon isotope-mass balance calculations, and carbonate system equilibria in conjunction with observed CO2-CH4 ratios in the gas phase, independently suggest that CH4 concentrations on the order of 100 mmol/kg are present in the pore waters of Blake Outer Ridge sediments. This quantity of CH4 is believed to be insufficient to saturate pore waters and stabilize the CH4*6H2O gas hydrate. Results of these calculations are in conflict with the physical recovery of gas hydrate from 238 m, and with the indirect evidence (seismic reflectors, sediment frothing, slightly decreasing salinity and chlorinity with depth, and pressure core barrel observations) of gas-hydrate occurrence in these sediments. Resolution of this apparent conflict would be possible if CH4 generation were restricted to relatively thin (1-10 m) depth intervals, and did not occur uniformly at all depths throughout the sediment column, or if another methanogenic process (e.g., acetate fermentation) were a major contributor of gas.