d18O, lithologies, mineralogy and determination of temperature and depth of formation of DSDP Site 69-504 siliceous rocks

Seven opal-CT-rich and five quartz-rich porcellanites and cherts from Site 504 have a range in oxygen-isotope values of 24.4 and 29.4 per mil. In opal-CT rocks, d18O becomes larger with sub-bottom depth and with age. Quartz-rich rocks do not show these trends. Boron, in general, increases with decreasing d18O for porcellanites and cherts considered together, supporting the conclusion that boron is incorporated within the quartz crystal structure during precipitation of the SiO2. Silicification of the chalks at Site 504 began 1 m.y. ago - that is, 5 m.y. after sedimentation commenced on the oceanic crust. Temperatures of chert formation determined from oxygen-isotope compositions reflect diagenetic temperatures rather than bottom-water temperatures, and are comparable to temperatures of formation determined by down-hole measurements. Opal-A in the chalks began conversion to opal-CT when a temperature of 50°C was reached in the sediment column. Conversion of opal-CT to quartz started at 55 °C. Silicification occurred over a stratigraphic thickness of about 10 meters when the temperature at the top of the 10 meters reached about 50°C. It took about 250,000 years to complete the silica transformation within each 10-meter interval of sediment at Site 504. Quartz formed over a stratigraphic range of at least 30 meters, at temperatures of about 54 to 60°C. The time and temperatures of silicification of Site 504 rocks are more like those at continental margins than those in deep-sea, open-ocean deposits.

Texture, geochemistry, isotope composition, petrography and epoch at DSDP Site 93-603

Abundant Fe-Mn carbonate concretions (mainly siderite, manganosiderite, and rhodochrosite) were found in the hemipelagic claystones of Site 603 on the eastern North American continental rise. They occur as nodules, micronodules, or carbonate-replaced burrow fills and layers at a subbottom depth of between ~ 120 (Pliocene) and 1160 m (Albian-Cenomanian). In general, the Fe-Mn carbonate concretions form from CO3- produced by the microbiological degradation of organic matter in the presence of abundant Fe + or Mn + and very low S- concentrations. However, there is also some evidence for diagenetic replacement of preexisting calcite by siderite. The carbon isotope composition of diagenetic Fe-Mn carbonate nodules is determined by CO2 reduction during methanogenesis. Carbonate nodules in Cretaceous sediments at sub-bottom depths of 1085 and 1160 m have distinctly lower d13C values (- 12.2 and - 12.9 per mil) than Neogene siderites, associated with abundant biogenic methane in the pore space (-8.9 to 1.7 per mil between 330 and 780 m depth). Since no isotopic zonation could be detected within individual nodules, we assume that the isotopic composition reflects more or less geochemical conditions at the present burial depth of the carbonate nodules. Carbonates did not precipitate within the zone of sulfate reduction (approximately 0.01 to 10 m), where all of the pyrite was formed. The oxygen isotope composition indicates precipitation from seawater-derived interstitial waters. The d18O values decrease with increasing burial depth from + 5.1 to - 1.2 per mil, suggesting successively higher temperatures during carbonate formation.

Geochemistry, SiO2 minerals and isotopes at DSDP Hole 72-516F

Cherts recovered during DSDP Leg 72 from Rio Grande Rise sediments (Site 516) consist of both cristobalite and quartz, and contain ghosts of foraminifers and (more rare) radiolarians. Porcelanite made of disordered cristobalite is found in most old enclosing sediments. Local dissolution of siliceous microfossils during diagenesis is the most likely source of the silica required for the chert formation. As sediment age increases, the proportion of biogenic silica decreases and authigenic silica increases.

Authigenic carbonate of ODP SIte 104-643

Different generations of complex authigenic carbonates formed in siliceous muds (lithologic Unit IV) and hemipelagic clays (lithologic Unit V) of ODP Site 643, Leg 104 Norwegian Sea. The dominant phase in Unit IV is an early diagenetic Mn, Fe-calcite with a strong negative d13C ( -14 to -16 per mil) signature, and slightly negative d180 values. The strong negative d13C results from extensive incorporation of 12C-enriched CO2 derived from bacterial degradation of marine organic matter into early Mn, Fe - calcite cements. Concomitant framboidal pyrite precipitation and abundant SEM microtextures showing excellent preservation of delicate structures of fragile diatom valves by outpourings with early Mn-calcites strongly support their shallow burial formation before the onset of compaction. Later generations of authigenic mineralizations in lithologic Unit IV include minor amounts of a second generation of calcite with platy crystals, possibly precipitated along with opal-A dissolution, and finally opal-CT crystallization in deeper seated environments overgrowing earlier precipitates with films and lepispheres. The last mineralization is collophane (fluor apatite) forming amorphous aggregates and tiny hexagonal crystals. Authigenic mineral assemblages in lithologic Unit V consist of rhodochrosites, transitional rhodochrosite/manganosiderites, and apatite. A negative d13C ( -7.1 to -15.6 per mil) and a fluctuating d18O signal indicates that the micritic to sparitic rhodochrosites, transitional rhodochrosites/manganosiderites were formed at various burial depths. CO2 resulted from organic matter degradation in the lowermost sulfate reduction zone and from biogenic methane generation in the lowermost sediments, resulting in variable and negative d13C signals. The change in carbonate mineralogy reflects major compositional differences compared to sediments in Unit IV. Most prominent is an increase in altered ash as a primary sediment component and a sudden decrease of siliceous microfossils. Upward diffusion of cations, lowered salinities in pore waters, and elevated temperatures provide diagenetic environments favoring increased remobilization processes.