Geochemistry and mineralogy of Eocene-Oligocene sediments of IODP Hole 302-M0002A

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~430 m composite depth). While the Neogene part of the record is characterized by grayish-yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene-Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene-Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

Chemical composition of bulk sediments from ODP Hole 199-1215A

Elemental concentrations were determined on 21 samples from Hole 1215A to evaluate the influence of hydrothermal sources on bulk sediment composition. Rare earth element (REE) concentrations were also determined on 10 of these samples. Concentration profiles and REE patterns are consistent with a strong hydrothermal influence on sediment composition at the base of Hole 1215A.

Trace metal content in Pliocene to Pleistocene sediments of ODP Leg 127 holes

Quaternary sedimentation within the Japan Sea was controlled by the configuration of peripheral sills, seasonal and long-term climatic variability, and the resultant fluctuations in sea level (Tamaki, 1988). Prior to drilling in the area, piston cores recovered from its basins contained Pleistocene sediments having distinctive color and fabric variation. Sedimentological and geochemical studies conducted on those facies indicated that the variability in fabric was the result of fluctuating marine and/or terrigenous influx to the deep-water basins of the Japan Sea (see, for example, Chough, 1984; Matoba, 1984). The sequences recovered during Leg 127 at Sites 794, 795, and 797 contain long, virtually undisturbed sequences (92.3, 123, and 119.9 mbsf [Hole 797B], respectively) of upper Miocene, upper Pliocene, and Pleistocene/Holocene sediments. The majority of these sequences consists of dark-colored (dark brown, green, and black) silty-clays, many of which are enriched in biogenic components (majority silicious, some carbonate) and/or organic matter, some containing pyrite and/or ash. These facies alternate with light-colored silty-clays, some containing ash and some showing signs of bioturbation (for example, Tamaki, Pisciotto, Allan, et al., 1990, p. 425-433). The dark-to-light sequences are present throughout the section, although they are especially dominant throughout the Pleistocene (for a more detailed lithology of Quaternary sequences recovered at Sites 794, 795, and 797, see Follmi et al. 1992 and Tada et al., 1992). This data report provides trace metal information on Pliocene-Pleistocene-Holocene samples at Sites 794,795, and 797. These data can be used (1) to provide information related to the depositional environments of the Japan Sea during the Quaternary period, (2) to permit comparisons between the dark organic-rich sediments recovered from this semi-enclosed basin and those reported for other silled basins (for example, the Mediterranean and Black seas), and (3) to permit comparisons between these sediments and contemporary equivalents found, for instance, beneath areas of high biogenic productivity. By providing such data, one should be able (1) to determine more precisely the processes governing the deposition of sediments with various levels of organic matter within enclosed basins, (2) to compare individual basin-wide processes, (3) to look for and compare the signatures present as a result of climatic fluctuation, and (4) to attempt to identify the presence and/or absence of cyclicity within such sequences.

Contents of rare earth and other chemical elements in Fe-Mn micronodules, nodules, and bottom sediments from the Clarion-Clipperton ore province in the Pacific Ocean

Processes governing the formation of rare earth element (REE) composition are under consideration for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different size fractions) within the Clarion-Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity size of micronodules has positive correlation with Mn content and Mn/Fe and P/Fe ratios and negative correlation with Fe, P, REE, and Ce anomaly. Behavior of REE in micronodules from sediments within bioproductive zones is related to increase of influence of diagenetic processes in sediments as a response to the growth of size of micronodules. Distinctions in chemical composition of micronodules and nodules are related to their interaction with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in labile fraction of sediments reworked during diagenesis. Sources of material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to sorption of phosphate-ion from bottom and pore waters. Sorption of phosphate-ion results in additional sorption of REE.

Composition of ferromanganese crusts from the Atlantic, Pacific and Indian Oceans

A collection of layered ferromanganese ores (27 samples) from the Atlantic and Pacific oceans was studied. Trace element and PGE contents were determined layer-by-layer (up to 10 microlayers) in 13 of these samples. The trace, rare earth, and platinum group element distributions, including their layer-to-layer variations, were compared in hydrogenic and hydrothermal crusts from different regions. It was found that the main PGE variations (by a factor of 10-50) are related to their layer-to-layer variations within a given ore field. The distributions of PGE and trace elements are strongly heterogeneous, which is related, first, to different contents of the elements in the layers of different age in ferromanganese crusts (FMC) and, second, to the observed regional heterogeneity and influence of hydrothermal fluids. Geochemical data indicate that CFC formation was mainly caused by the hydrochemical precipitation of material from seawater. This process was accompanied by diagenetic phenomena, water-rock interaction, and influence of volcanic and hydrothermal sources.

Geochemistry of the lower sheeted dike complex of ODP Holes 137-504B and 140-504B

Sixty-three samples representing 379 m of sheeted dikes from Deep Sea Drilling Project/Ocean Drilling Program Site 504B have been analyzed for major and selected trace elements by X-ray fluorescence. The samples range from microcrystalline aphyric basalts to moderately phyric (2%-10% phenocrysts) diabase that are typically multiply saturated with plagioclase, olivine, and clinopyroxene, in order of relative abundance. All analyzed samples are classified as Group D compositions with moderate to slightly elevated compatible elements (MgÆ-value = 0.65% ± 0.03%; Al2O3 = 15.5% ± 0.8%; CaO = 13.0% ± 0.3%; Ni = 114 ± 29 ppm), and unusually depleted levels of moderate to highly incompatible elements (Nb < 1 ppm; Zr = 44 ± 7 ppm; Rb < 0.5 ppm; Ba ~ 1 ppm; P2O5 = 0.07% ± 0.02%). These compositions are consistent with a multistage melting of a normal ocean ridge basaltic mantle source followed by extensive fractionation of olivine, plagioclase, and clinopyroxene. Leg 140 aphyric to sparsely phyric (0%-2% phenocrysts) basalts and diabases are compositionally indistinguishable from similarly phyric samples at higher levels in the hole. An examination of the entire crustal section, from the overlying volcanics through the sheeted dikes observed in Leg 140, reveals no significant trends indicating the enrichment or depletion of Costa Rica Rift Zone source magmas over time. Similarly, significant trends toward increased or decreased differentiation cannot be identified, although compositional patterns reflecting variable amounts of phenocryst addition are apparent at various depths. Below ? 1700 mbsf to the bottom of the Leg 140 section, there is a broadly systematic pattern of Zn depletion with depth, the result of high-temperature hydrothermal leaching. This zone of depletion is thought to be a significant source of Zn for the hydrothermal fluids depositing metal sulfides at ridge-crest hydrothermal vents and the sulfide-mineralization zone, located in the transition between pillow lavas and sheeted dikes. Localized zones of intense alteration (60%-95% recrystallization) are present on a centimeter to meter scale in many lithologic units. Within these zones, normally immobile elements Ti, Zr, Y, and rare-earth elements are strongly depleted compared with "fresher" samples centimeters away. The extent of compositional variability of these elements tends to obscure primary igneous trends if the highly altered samples are not identified or removed. At levels up to 40% (or possibly 60%) recrystallization, Ti, Zr, and Y retain their primary signatures. Although the mechanisms are unclear, it is possible that these intense alteration zones are a source of Y and rare-earth elements for the typically rare-earth-element-enriched hydrothermal vent fluids of mid-ocean ridges.

Geochemistry and radionuclide content of sediment and water samples obtained from the Ob and Irtysh river, Russia

This paper reports the results of the investigations of 2006-2007 on the distribution and migration forms of artificial radionuclides and chemical elements in the Ob-Irtysh water system. Three regions were studied. One of them is a local segment of the Ob River upstream from the confluence with the Irtysh River; its investigation allowed us to estimate the general radioecological state of the aquatic environment affected by the activity of the Tomsk 7 plant. The second region is a local segment of the Irtysh River upstream from its confluence with the Ob River, where the influence of emissions from the NPO Mayak could be estimated. The third region is the water area of the Ob River after its confluence with the Irtysh River. It characterizes the real level of radioactive and chemical contamination of the middle reaches of the Ob River. In order to explain horizontal variations in the distribution of radionuclides in the upper layer of bottom sediments collected at various sites, the results of sorption-kinetic experiments with radioactive tracers in the precipitate-solution system were used. The investigation of the migration forms of trace elements and radionuclides occurring in river water was based on the method of tangential-flow membrane filtration. Chemical element contents were determined in 400-ml water samples. A set of Millipore polysulfone membranes with pore sizes of 8, 1.2, 0.45, 0.1, and 0.025 µm was employed. Taking into account the ultralow specific concentrations of radionuclides in the water, they were analyzed in 300-500 litre samples using Millipore polysulfone membranes with pore sizes of 0.45 µm and 15 kDa. This allowed us to estimate the percentages of cesium-137 and plutonium-239, 240 in the suspended particulate fraction, colloids, and dissolved species.

Geochemistry at DSDP Leg 75 Holes

Samples of sediments and rocks collected at DSDP Sites 530 and 532 were analyzed for 44 major, minor, and trace elements for the following purposes: (1) to document the downhole variability in geochemistry within and between lithologic units; (2) to document trace-element enrichment, if any, in Cretaceous organic-carbon-rich black shales at Site 530; (3) to document trace-element enrichment, if any, in Neogene organic-carbon-rich sediments at Site 532; (4) to document trace-element enrichment, if any, in red claystone above basalt basement at Site 530 that might be attributed to hydrothermal activity or weathering of basalt. Results of the geochemical analyses showed that there are no significant enrichments of elements in the organic-carbon-rich sediments at Site 532, but a number of elements, notably Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn, are enriched in the Cretaceous black shales. These elements have different concentration gradients within the black-shale section, however, which suggests that there was differential mobility of trace elements during diagenesis of interbedded more-oxidized and less-oxidized sediments. There is little or no enrichment of elements from hydrothermal activity in the red claystone immediately overlying basalt basement at Site 530, but slight enrichments of several elements in the lowest meter of sediment may be related to subsea weathering of basalt

Geochemistry of felsic rocks and minerals of ODP Hole 135-841B

A felsic volcanic series (605-825 mbsf) overlain by upper Eocene shallow-water sediments (500-605 mbsf) and basalticandesitic sills that intruded into sediments of Holocene to Miocene age (0-500 mbsf) was drilled in the forearc region of the Lau Basin at a water depth of 4810 m. The volcanic sequence at Site 841 includes altered and mineralized calc-alkaline rhyolites and dacites, dacitic tuffs, lapilli tuffs, flow breccias, and welded tuffs. These rocks formed subaerially or in a very shallow-water environment suffering a subsidence of >5000 m since Eocene times. Calculations of gains and losses of the major components during alteration show most pronounced changes in the uppermost 70 m of the volcanic sequence. Here, Al, Fe, Mg, and K are enriched, whereas Si and Na are strongly depleted. Illite, vermiculite, chlorite, and hematite predominate in this part of the hole. Throughout the section, quartz, plagioclase, kaolinite, and calcite are present. Sulfide mineralization (up to 10 vol%) consisting mainly of disseminated pyrite (with minor pyrrhotite inclusions) and marcasite together with minor amounts of chalcopyrite is pervasive throughout. Locally, a few sulfide-bearing quartz-carbonate veins as well as Ti-amphibole replacement by rutile and then by pyrite were observed. Strong variations in the As content of sulfides (from 0 to 0.69 wt%) from the same depth interval and local enrichments of Co, Ni, and Cu in pyrite are interpreted to result from fluctuations in fluid composition. Calculations of oxygen and sulfur fugacities indicate that fO2 and fS2 were high at the top and lower at the bottom of the sequence. Sulfur isotope determinations on separated pyrite grains from two samples give d34S values of +6.4ë and +8.4ë, which are close to those reported from Kuroko and Okinawa Trough massive sulfide deposits and calc-alkaline volcanic rocks of the Japanese Ryukyu Island Arc. Calculated chlorite formation temperatures of 265°-290°C at the top of the sequence are consistent with minimum formation temperatures of fluid inclusions in secondary quartz, revealing a narrow range of 270°-297°C. Chlorite formation temperatures are constant downhole and do not exceed 300°C. The presence of marcasite and 4C-type pyrrhotite indicates a formation temperature of <= 250°C. At a later stage, illite was formed at the top of the volcanic series at temperatures well below 200°C.

Mineralogy and isotopic composition of sulfur in ODP Hole 118-735B gabbros

Sulfide mineralogy, sulfur contents, and sulfur isotopic compositions were determined for samples from the 500-m gabbroic section of Ocean Drilling Program Hole 735B in the southwest Indian Ocean. Igneous sulfides (pyrrhotite, chalcopyrite, pentlandite, and troilite) formed by accumulation of immiscible sulfide droplets and crystallization from intercumulus liquids. Primary sulfur contents average around 600 ppm, with a mean sulfide d34S value near 0 per mil, similar to the isotopic composition of sulfur in mid-ocean ridge basalt glass. Rocks from a 48-m interval of oxide gabbros have much higher sulfur contents (1090-2530 ppm S) due to the increased solubility of sulfur in Fe-rich melts. Rocks that were locally affected by early dynamothermal metamorphism (e.g., the upper 40 m of the core) have lost sulfur, averaging only 90 ppm S. Samples from the upper 200 m of the core, which underwent subsequent hydrothermal alteration, also lost sulfur and contain an average of 300 ppm S. Monosulfide minerals in some of the latter have elevated d34S values (up to +6.9 per mil), suggesting local incorporation of seawater-derived sulfur. Secondary sulfides (pyrrhotite, chalcopyrite, pentlandite, troilite, and pyrite) are ubiquitous in trace amounts throughout the core, particularly in altered olivine and in green amphibole. Pyrite also locally replaces igneous pyrrhotite. Rocks containing secondary pyrite associated with late low-temperature smectitic alteration have low d34S values for pyrite sulfur (to - 16.6 per mil). These low values are attributed to isotopic fractionation produced during partial oxidation of igneous sulfides by cold seawater. The rocks contain small amounts of soluble sulfate (6% of total S), which is composed of variable proportions of seawater sulfate and oxidized igneous sulfur. The ultimate effect of secondary processes on layer 3 gabbros is a loss of sulfur to hydrothermal fluids, with little or no net change in d34S.