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.

Sedimentological and geochemical characteristics of upper Cretaceous and lower Tertiary sediments of ODP Hole 108-661A

Based on sedimentological and geochemical data, the Upper Cretaceous and Tertiary sequence at Ocean Drilling Program Site 661 was subdivided into four intervals: Interval I (Campanian age) is characterized by sediments deposited below the calcite compensation depth (CCD) inside a high-productivity area and well-oxygenated bottom waters, indicated by the absence of carbonate, the major occurrence of zeolites and opal-CT, and intense bioturbation. Very fine-grained siliciclastic sediments and the lack of any erosional features suggest a low-energy environment. The terrigenous fraction was probably supplied by winds from the nontropical areas in South Africa. Interval II (Maestrichtian age) is characterized by high-amplitude variations in the carbonate content indicative of a deposition above the CCD, superimposed by (climate-controlled) short-term fluctuations of the CCD. The absence of both zeolites and opal-CT imply a position of Site 661 outside high-productivity areas. The first occurrence of higher amounts of kaolinite (especially during the middle Maestrichtian) suggests the onset of a terrigenous sediment supply from tropical areas. Interval III (between uppermost Cretaceous to early Tertiary) is characterized by the absence of carbonate and zeolites, interpreted as deposition below the CCD and outside an oceanic high-productivity belt. The kaolinite-over-illite dominance suggests a terrigenous sediment supply from tropical areas. Interval IV (between early Tertiary and Miocene age) is characterized by the occurrence of black manganeserich layers, major nodules/pebbles, and erosional surfaces, indicating phases of extremely reduced sediment accumulation and bottom-current activities. In the lower part of this interval (?Eocene age), higher amounts of zeolites occur, which suggest a higher oceanic productivity caused by equatorial upwelling. The source area of the terrigenous sediment fraction at Site 661 was the tropical region of northwest Africa, as suggested by the kaolinite-over-illite dominance.

Terrigenous proxy record from ODP Site 202-1237 and sediment core RRV9702a-69PC

ODP Site 1237 and sediment core RRV9702a-69PC were investigated for siliciclastic grain-size distributions and changes in geochemical composition to reconstruct southeast trade-wind variability during the past 5 Ma. Because both, working and archive halves of all ODP Site 1237 cores were completely depleted between 3.3 and 8.1 meters composite depths, (mcd), the corresponding sections of pre-site survey core RRV9702A-69PC were sampled and investigated to fill the gap.

Chemistry of biogenic sediments from the equatorial Pacific

To increase our understanding of the mechanisms that control the distribution of Al and Ti within marine sediment, we performed sequential extractions targeting the chemical signatures of the loosely bound, exchangeable, carbonate, oxide, organic, opal, and residual fraction of sediment from a carbonate-dominated regime (equatorial Pacific) and from a mixed opal-terrigenous regime (West Antarctic Peninsula). We observe a systematic partitioning of Al and Ti between sediment phases that is related to bulk Al/Ti. We show that, where we can quantify an Al(excess) component, the dissolved Al is preferentially affiliated with the oxide fraction, resulting in Al/Ti molar ratios of 500-3000. This is interpreted as the result of surface complexation in the water column of dissolved Al onto oxyhydroxides. We also observe a previously undetected Ti(excess) with as much as 80% of the total Ti in the organic fraction, which is most likely a function of metal-organic colloidal removal from the water column. In samples where the excess metals are obscured by the detrital load, the Al and Ti are almost exclusively found in the residual phase. This argues for the paired removal of Al (preferentially by the oxide component) and Ti (preferentially by the organic component) from the water column by settling particulate matter. This research builds upon earlier work that shows changes in the bulk ratio of Al to Ti in carbonate sediment from the central-equatorial Pacific that coincide with changes in the sedimentary bulk accumulation rate (BAR). The ratios that are observed are as much as three times higher than typical shale values, and were interpreted as the result of scavenging of dissolved Al onto particles settling in the water column. Because this non-terrigenous Al(excess) accounts for up to 50% of the total sedimentary Al inventory and correlates best with BAR, the bulk Al/Ti may be a sensitive tracer of particle flux and, therefore, export production. Because we show that the excess metals are the result of scavenging processes, the bulk Al/Ti may be considered a sensitive proxy for this region.