Lithology and geochemistry of ODP Leg 198 sites, Shatsky Rise

Samples of chert, porcellanite, and chalk/limestone from Cretaceous chert-bearing sections recovered during Leg 198 were studied to elucidate the nature and origin of chert color zonations with depth/age. Sedimentary structures, trace fossils, compactional features, sediment composition, texture, geochemistry, and diagenetic history were compared among lithologies. Trends in major and minor element composition were determined. Whereas geochemical analyses demonstrate systematic elemental differences among the different lithologies, there are less distinct patterns in composition for the colored cherts. The color of the chert appears to be related primarily to the amount of silica and secondarily to the proportion of other components. Red cherts are almost pure silica with only minor impurities. This may allow pigmentation from fine Fe oxides to dominate the color. These red cherts are from places where geophysical logs indicate that chert is the dominant rock type of the section. These red chert intervals cannot be unequivocally distinguished from surrounding chert-bearing lithologies in terms of sedimentary structures.

Composition of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus

Detailed data obtained on chemistry of sedimentary rocks from the Mountainous Crimea and the Northwestern Caucasus that were dated at the Cenomanian/Turonian boundary and formed during Oceanic Anoxic Event 2 make it possible to calculate dissolved oxygen concentration in bottom waters of the sedimentation basin. Enrichment factors of trace elements in black shales are revised and an explanation is suggested for genesis of the rocks with regard for unusual climatic changes.

Multi-proxy analyses of sediment cores from the Pakistan continental margin

Late Holocene laminated sediments from a core transect centred in the oxygen minimum zone (OMZ) impinging at the continental slope off Pakistan indicate stable oxygen minimum conditions for the past 7000 calendar years. High SW-monsoon-controlled biological productivity and enhanced organic matter preservation during this period is reflected in high contents of total organic carbon (TOC) and redox-sensitive elements (Ni, V), as well as by a low-diversity, high-abundance benthic foraminiferal Buliminacea association and high abundance of the planktonic species Globigerina bulloides indicative of upwelling conditions. Surface-water productivity was strongest during SW monsoon maxima. Stable OMZ conditions (reflected by laminated sediments) were found also during warm interstadial events (Preboreal, Bølling-Allerød, and Dansgaard-Oeschger events), as well as during peak glacial times (17-22.5 ka, all ages in calendar years). Sediment mass accumulation rates were at a maximum during the Preboreal and Younger Dryas periods due to strong riverine input and mobilisation of fine-grained sediment coinciding with rapid deglacial sea-level rise, whereas eolian input generally decreased from glacial to interglacial times. In contrast, the occurrence of bioturbated intervals from 7 to 10.5 ka (early Holocene), in the Younger Dryas (11.7-13 ka), from 15 to 17 ka (Heinrich event 1) and from 22.5 to 25 ka (Heinrich event 2) suggests completely different conditions of oxygen-rich bottom waters, extremely low mass and organic carbon accumulation rates, a high-diversity benthic fauna, all indicating lowered surface-water productivity. During these intervals the OMZ was very poorly developed or absent and a sharp fall of the aragonite compensation depth favoured the preservation of pteropods. The abundance of lithogenic proxies suggests aridity and wind transport by northwesterly or northeasterly winds during these periods coinciding with the North Atlantic Heinrich events and dust peaks in the Tibetan Loess records. The correlation of the monsoon-driven OMZ variability in the Arabian Sea with the rapid climatic fluctuations in the high northern latitudes suggests a close coupling between the climates of the high and low latitudes at a global scale.

(Table 1) Color, Fe-C-S chemistry and carbonate content from ODP Sites 172-1062 and 172-1063

Reflectance spectra collected during ODP Leg 172 were used in concert with solid phase iron chemistry, carbonate content, and organic carbon content measurements to evaluate the agents responsible for setting the color in sediments. Factor analysis has proved a valuable and rapid technique to detect the local and regional primary factors that influence sediment color. On the western North Atlantic drifts, sediment color is the result of primary mineralogy as well as diagenetic changes. Sediment lightness is controlled by the carbonate content while the hue is primarily due to the presence of hematite and Fe2+/Fe3+ changes in clay minerals. Hematite, most likely derived from the Permo-Carboniferous red beds of the Canadian Maritimes, is differentially preserved at various sites due to differences in reductive diagenesis and dilution by other sedimentary components. Various intensities for diagenesis result from changes in organic carbon content, sedimentation rates, and H2S production via anaerobic methane oxidation. Iron monosulfides occur extensively at all high sedimentation sites especially in glacial periods suggesting increased high terrigenous flux and/or increased reactive iron flux in glacials.

Geochemistry on Holocene sediments from the Mediterranean

The enhanced accumulation of organic matter in Eastern Mediterranean sapropels and their unusually low d15N values have been attributed to either enhanced nutrient availability which led to elevated primary production and carbon sequestration or to enhanced organic matter preservation under anoxic conditions. In order to evaluate these two hypothesis we have determined Ba/Al ratios, amino acid composition, N and organic C concentrations and d15N in sinking particles, surface sediments, eight spatially distributed core records of the youngest sapropel S1 (10-6 ka) and older sapropels (S5, S6) from two locations. These data suggest that (i) temporal and spatial variations in d15N of sedimentary N are driven by different degrees of diagenesis at different sites rather than by changes in N-sources or primary productivity and (ii) present day TOC export production would suffice to create a sapropel like S1 under conditions of deep-water anoxia. This implies that both enhanced TOC accumulation and d15N depletion in sapropels were due to the absence of oxygen in deep waters. Thus preservation plays a major role for the accumulation of organic-rich sediments casting doubt on the need of enhanced primary production for sapropel formation.

Geochemisty at DSDP Hole 62-465A

Very significant enhancements of the element iridium have been observed in association with the Cretaceous/ Tertiary boundary in marine sediments laid down 65 m.y. ago and subsequently uplifted above the ocean's surface. If our hypothesis for the origin of the iridium and the cause of the Cretaceous/Tertiary life extinctions (the asteroid-impact theory) (Alvarez et al., 1980) is correct, the Ir anomaly should be associated with the Cretaceous/ Tertiary boundary region wherever it is intact. The present work was undertaken to search for the Ir anomaly in a deep-sea-drilling core, in order to check this aspect of the asteroid-impact theory.

Geochemistry and physics on sediment cores from the Peru Basin

We studied preservation/dissolution cycles and paleoproductivity in eight sediment cores from the Peru Basin south of the highly productive surface waters of the eastern equatorial Pacific. Stratigraphy is based on stable oxygen isotopes and on combined magnetostratigraphy and biostratigraphy. Sediment cores which span the last 8 m.y., were retrieved during cruise 79 with RV SONNE close to the carbonate compensation depth (CCD). In general, sediments show Pacific-type carbonate cycles. We interpret a pronounced carbonate peak between 6 and 7 Ma as the result of a western and northern extension of the highly productive Peru Current. Decreased carbonate contents from the late Miocene to the late Pliocene might be associated with a slow contraction of the latitudinal extent of the high-productivity belt north of the study areas. During the Pliocene, carbonate variations showed 400 kyr cycles indicating the growth and decay of ice sheets, which should have been associated with pulsations of the Antarctic ice cap. An abrupt collapse of the carbonate system occurred at 2.4 Ma. Higher frequency variations of the carbonate record indicate the major increase of the northern hemisphere glaciation. During the Quaternary, carbonate fluxes are high during glacials and low during interglacials. Large amplitude variations with long broad minima and maxima, associated with small migrations of the lysocline and the CCD (< 200 m), are indicative of the preservation/dissolution history in the Peru Basin. During the early Pleistocene, climatic forcing by the 41 kyr obliquity cycle is not observed in the carbonate record. During the last 800 kyr, variability in the carbonate record was dominated by the 100 kyr eccentricity cycle. Fluxes of biogenic material (calcium carbonate, organic carbon, opal, and barium) were greatest during glacials, which imply higher productivity and export production of the Peru Current during cold climatic periods. Dissolution was greatest during interglacials as inferred from the relatively poor preservation of planktonic foraminifera and from the low accumulation rate of carbonate. After the Mid-Brunhes Event (400 ka), we observe a plateaulike shift to enhanced dissolution and to intensified productivity.

Carbonate mineralogical and isotopic analyses of TV-guided grab samples and TV-guided box corer samples from the Shumagin area

Methane seepage leads to Mg-calcite and aragonite precipitation at a depth of 4,850 m on the Aleutian accretionary margin. Stromatolitic and oncoid growth structures imply encrustation of microorganisms (microbial mats) in the host sediment with a unique growth direction downward into the sediment, forming crust-shaped lithologies. Biomarker investigations of the residue after carbonate dissolution show strong enrichments in crocetane and archaeol, which contain extremely low d13C values. This indicates the presence of methane-consuming archaea, and d13C values of -42 to -51 per mill PDB indicate that methane is the carbon source for the carbonate crusts. Thus, it appears that stromatolitic encrustations of methanotrophic anaerobic archaea probably occurs in a consortium with sulphate-reducing bacteria and that carbonate precipitation proceeds downward into the sediment, where ascending cold fluids provide a methane source. Strontium and oxygen isotope analyses as well as 14C ages of the carbonates suggest that the fluids come from deep within the sediment and that carbonate precipitation began about 3,000 years ago.

Sedimentology on cores from the Peru Basin

We investigated surficial sediments for physico-chemical composition from numerous sites of seven study areas in the manganese nodule field of the northern Peru Basin as part of a deep-sea environmental study. Major results from this study are strong variability with respect to water depth, productivity in surface waters, locality, bottom water flow, and seafloor topography. Sediment sites are located mostly in 3900 to 4300 m water depth between the lysocline and the carbonate compensation depth (CCD). Large fluctuations in carbonate content (0% to 80%) determine sediment density and compressional-wave velocity, and, by dilution, contents of opal and non-biogenic material. Mass accumulation rates of biogenic components as well as geochemical proxies (barium and phosphorus) distinguish areas of higher productivity in the northwest near equatorial upwelling and in the northeast close to coastal upwelling, from areas of lower productivity in the west and south. Comparisons between the central Peru Basin area (Discol) and western Peru Basin area (Sediperu) reveals, for the Sediperu area, a shallower CCD, more carbonate but less opal, organic carbon, and non-biogenic material in sediments at the same water depth as well as larger down-core fluctuations of organic carbon and MnO2. Bottom water flow in the abyssal hill topography causes winnowing of material from summits of seamounts and ridges, where organic carbon preservation is poor, to basins where organic carbon preservation is better. Down-core measurements in box cores indicate a three-fold division in the upper 50 cm of the sediment column. An uppermost semi-liquid top layer is dark brown, 5-15 cm thick and contains most of the ferro-manganese nodules. A 5-15 cm thick transition zone of light sediment color has increasing shear strength, lowest opal contents and compressional-wave velocities, but highest carbonate contents and sediment densities. The lowermost layer contains stiffer light gray sediments.