Chemistry of bulk-rocks and minerals of ODP Hole 120-748C

Five hundred meters of a unique Upper Cretaceous Cr-rich glauconitic sequence (Unit III) that overlies a 3-m-thick alkali-basalt flow with underlying epiclastic volcanogenic sediments was drilled at ODP Leg 120 Site 748. The Cr-rich glauconitic sequence is lithostratigraphically and biostratigraphically divided into three subunits (IIIA, IIIB, IIIC) that can also be recognized by the Cr concentration of the bulk sediment, which is low (<200 ppm) in Subunits IIIC and IIIA and high (400-800 ppm) in Subunit IIIB. The Cr enrichment is caused by Cr-spinel, which is the only significant heavy mineral component beside Fe-Ti ores. Other Cr-bearing components are glauconite pellets and possibly some other clay minerals. The glauconitic sequence of Subunit IIIB was formed by reworking of glauconite and volcanogenic components that were transported restricted distances and redeposited downslope by mass-transportation processes. The site of formation was a nearshore, shallow inner shelf environment, and final deposition may have been on the outer part of a narrow shelf, at the slope toward the restricted, probably synsedimentary, faulted Raggatt Basin. The volcanic edifices uncovered on land were tholeiitic basalts (T-MORB), alkali-basaltic (OIB) and (?)silicic volcanic complexes, and ultramafic rocks. The latter were the ultimate source for the Cr-spinel contribution. Terrestrial aqueous solutions carried Fe, K, Cr, Si, and probably Al into the marine environment, where, depending on the redox conditions of microenvironments in the sediment, green (Fe- and K-rich) or brown (Al-rich) glauconite pellets formed. The Upper Cretaceous glauconitic sequence at Site 748 on the Southern Kerguelen Plateau constitutes the transition in space and time from terrestrial to marine, from magmatically active subaerial to magmatically passive submarine conditions, and from a tranquil platform to active rifting conditions.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Composition of minerals at DSDP Leg 67 Holes

During the Leg 67 drilling of the Middle America Trench (Guatemala transect), basalts were reached in Hole 495, 22 km seaward from the Trench axis, in Holes 500 and 500B at the foot of the continental slope, and at four other holes not sampled for this study. Only olivine-plagioclase phyric basalts are present in Hole 495, whereas in Holes 500 and 500B these rocks are associated with plagioclase phyric high-alumina basalts. As illustrated by the content of TiO2, Al2O3, and the K2O/K2O + Na2O ratio, some of the Middle America Trench basalts do not differ essentially from oceanic tholeiites, but others have a composition transitional to island-arc tholeiitic basalts. It is suggested that basalts transitional from oceanic to island-arc tholeiites are typical manifestations of magmatism in zones of convergence of the oceanic and continental or island-arc crust.

Minerals of bulk samples and clay fraction at DSDP Leg 80 Holes

At the request of the Leg 80 scientific party, selected samples of Cretaceous age were processed by X-ray diffraction at the mineralogy laboratories at the Ecole des Mines (Albian to Late Cretaceous samples) and at the Institut de Géologie at Dijon (Barremian samples). The results were used in developing the lithostratigraphy and sedimentology discussed in this volume by Rat et al. 1985 (doi:10.2973/dsdp.proc.80.140.1985) in their study of Barremian-Albian paleoenvironment, by Graciansky and Gillot in their study of Albian and Cenomanian limestones, and by Graciansky and Bourbon in their paleoenvironmental reconstructions for the Late Cretaceous chalks.

Composition of bottom sediments, rocks, and ores from the Tropical Atlantic

Geological features of some areas of the Tropical Atlantic (stratigraphy, tectonic structure, lithology, distribution of ore components in bottom sediments, petrography of bedrocks, etc.) are under consideration in the book. Regularities of concentration of trace elements in iron-manganese nodules, features of these nodules in bottom sediments, distribution of phosphorite nodules and other phosphorites have been studied. Much attention is paid to rocks of the ocean crust. A wide range of mineralization represented by magnetite, chromite, chalcopyrite, pyrite, pentlandite, and other minerals has been found.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.

Oxygen isotope concentrations of minerals from the upper kilometer of the ocean crust, DSDP Hole 504B

DSDP Hole 504B is the deepest basement hole in the oceanic crust, penetrating through a 571.5 m pillow section, a 209 m lithologic transition zone, and 295 m into a sheeted dike complex. An oxygen isotopic profile through the upper crust at Site 504 is similar to that in many ophiolite complexes, where the extrusive section is enriched in 18O relative to unaltered basalts, and the dike section is variably depleted and enriched. Basalts in the pillow section at Site 504 have delta 18O values generally ranging from +6.1 to +8.5? SMOW (mean= +7.0?), although minor zeolite-rich samples range up to 12.7?. Rocks depleted in 18O appear abruptly at 624 m sub-basement in the lithologic transition from 100% pillows to 100% dikes, coinciding with the appearance of greenschist facies minerals in the rocks. Whole-rock values range to as low as +3.6?, but the mean values for the lithologic transition zone and dike section are +5.8 and +5.4?, respectively. Oxygen and carbon isotopic data for secondary vein minerals combined with the whole rock data provide evidence for the former presence of two distinct circulation systems separated by a relatively sharp boundary at the top of the lithologic transition zone. The pillow section reacted with seawater at low temperatures (near 0°C up to a maximum of around 150°C) and relatively high water/rock mass ratios (10-100); water/rock ratios were greater and conditions were more oxidizing during submarine weathering of the uppermost 320 m than deeper in the pillow section. The transition zone and dikes were altered at much higher temperatures (up to about 350°C) and generally low water/rock mass ratios (~1), and hydrothermal fluids probably contained mantle-derived CO2. Mixing of axial hydrothermal fluids upwelling through the dike section with cooler seawater circulating in the overlying pillow section resulted in a steep temperature gradient (~2.5°C/m) across a 70 m interval at the top of the lithologic transition zone. Progressive reaction during axial hydrothermal metamorphism and later off-axis alteration led to the formation of albite- and Ca-zeolite-rich alteration halos around fractures. This enhanced the effects of cooling and 18O enrichment of fluids, resulting in local increases in delta 18O of rocks which had been previously depleted in 18O during prior axial metamorphism.

Ages of rocks and minerals from the Okhotsk-Chukotka volcanic belt

Current geochronological data on the Okhotsk-Chukotka volcanic belt (OCVB) and relevant problems are discussed. The belt evolution is suggested to be modeled based on 40Ar/39Ar and U-Pb dates more useful in several aspects than common K-Ar or Rb-Sr dates and methods of paleobotanical correlation. Based on new40Ar/39Ar and U-Pb dates obtained for volcanic rocks in the OCVB northern part, the younger (Coniacian) age is established for lower stratigraphic units in the Central Chukotka segment of the belt, and eastward migration of volcanic activity is shown for terminal stages of this structure evolution.

Concentrations of rare earth elements in pore waters of IODP Holes 323-U1345A and 323-U1345B

We studied the diagenetic behavior of rare earth elements (REEs) in a highly productive passive margin setting of the Bering Sea Slope. Site U1345 was drilled during the Integrated Ocean Drilling Program Expedition 323 at a water depth of 1008 m currently in the center of an oxygen minimum zone. Pore water concentrations of fourteen REEs were determined down to ~ 140 meters below the seafloor (mbsf). The REE concentrations were higher in the pore water than the deep seawater, indicating that there was significant liberation from the sediments during diagenesis. There was a major peak at ~ 10 mbsf that was more pronounced for the heavy REE (HREE); this peak occurred below the sulfate-methane transition zone (6.3 mbsf) and coincided with high concentrations of dissolved iron and manganese. At ~ 2 mbsf, there was a minor peak in REE and Mn contents. Below ~ 40 mbsf, the REE concentration profiles remained constant. The Ce anomaly was insignificant and relatively constant (PAAS-normalized Ce/Ce = 1.1 ± 0.2) throughout the depth profile, showing that the Ce depleted in seawater was restored in the pore water. HREE-enrichment was observed over the entire 140 m except for the upper ~ 1 m, where a middle REE (MREE)-bulge was apparent. REE release in shallow depths (2-4 mbsf) is attributed to the release of light REEs (LREEs) and MREEs during the organoclastic reduction of Mn oxides in anoxic sediments. The high HREE concentrations observed at ~ 10 mbsf can be attributed to the reduction of Fe and Mn minerals tied to anaerobic oxidation of methane or, less significantly, to ferromagnesian silicate mineral weathering. The upward diffusion flux across the sediment-water interface was between 3 (for Tm) and 290 (for Ce) pmol/m**2/y.