(Table 2) Chemical composition of phosphates from the Namibian and Chilean shelves

This study on phosphorites of different compositions and ages from shelf sediments and seamounts of the Pacific Ocean by means of analytical electron microscopy showed that these phosphorites contain ultra-microscopic inclusions of authigenic minerals and, more rarely, of rare earth element (REE) minerals. In some of phosphorite samples of Pleistocene-Pliocene age from the Namibian shelf both kinds of minerals were found. Uranium minerals were represented by uraninite, coffinite, and ningioite; those of REE - by monazite, xenotime, and bastnesite, which points to their potential accumulation not only as isomorphous admixtures in calcium phosphate but also as independent mineral phases. Coexistence of the minerals noted in shelf phosphorites is caused by repeated changes in redox conditions during formation and then redeposition of phosphate concretions. Presence of uranium minerals in phosphorites from seamounts shows that during an initial step of formation of these phosphorites environment was rather suboxic or reductive than oxic.

An integrated biostratigraphy (conodonts and foraminifers) and chronostratigraphy (paleomagnetic reversals, magnetic susceptibility, elemental chemistry, carbon isotopes and geochronology) for the Permian-Triassic strata of Guandao section

The chronostratigraphy of Guandao section has served as the foundation for numerous studies of the end-Permian extinction and biotic recovery in south China. Guandao section is continuous from the Permian-Triassic boundary to the Upper Triassic.Conodonts enable broad delineation of stage and substage boundaries and calibration of foraminifer biostratigraphy as follows. Changhsingian- Griesbachian: first Hindeodus parvus, and first appearance of foraminifers Postcladella kalhori and Earlandia sp. Griesbachian-Dienerian: first Neospathodus dieneri, and last appearance of foraminifer P. grandis. Dienerian-Smithian: first Novispathodus waageni and late Dienerian first appearance of foraminifer Hoyenella ex gr. sinensis. Smithian-Spathian: first Nv? crassatus and last appearance of foraminifers Arenovidalina n. sp. and Glomospirella cf. vulgaris. Spathian-Aegean: first Chiosella timorensis and first appearance of foraminifer Meandrospira dinarica. Aegean-Bithynian: first Nicoraella germanica and first appearance of foraminifer Pilammina densa. Bithynian-Pelsonian: after last Neogondolella regalis, prior to first Paragondolella bulgarica and first appearance of foraminifer Aulotortus eotriasicus. Pelsonian-Illyrian: first Pg. excelsa and last appearance of foraminifers Meandrospira ? deformata and Pilamminella grandis. Illyrian-Fassanian: first Budurovignathus truempyi, and first appearance of foraminifers Abriolina mediterranea and Paleolituonella meridionalis. Fassanian-Longobardian: first Bv. mungoensis and last appearance of foraminifer A. mediterranea. Longobardian-Cordevolian: first Quadralella polygnathiformis and last appearance of foraminifers Turriglomina mesotriasica and Endotriadella wirzi. The section contains primary magnetic signature with frequent reversals occurring around the Permian-Triassic, Olenekian-Anisian, and Anisian-Ladinian boundaries. Predominantly normal polarity occurs in the lower Smithian, Bithynian, and Longobardian-Cordevolian. Predominantly reversed polarity occurs in the upper Griesbachian, Induan-Olenekian, Pelsonian and lower Illyrian. Reversals match well with the GPTS. Large amplitude carbon isotope excursions, attaining values as low as -2.9 per mil d13C and high as +5.7 per mil d13C, characterize the Lower Triassic and basal Anisian. Values stabilize around +2 per mil d13C through the Anisian to Carnian. Similar signatures have been reported globally. Magnetic susceptibility and synthetic gamma ray logs show large fluctuations in the Lower Triassic and an overall decline in magnitude of fluctuation through the Middle and Upper Triassic. The largest spikes in magnetic susceptibility and gamma ray, indicating greater terrestrial lithogenic flux, correspond to positive d13C excursions. Several volcanic ash horizons occur in the Lower Triassic and Olenekian-Anisian boundary. High resolution U-Pb analysis of zircons provide a robust age of 247.2 Ma for the Olenekian-Anisian boundary.

Geochemistry and mineralogy of sediments from the Atlantis II Fracture Zone

Thirteen sediment samples, including calcareous ooze, sandy clay, volcanic sand, gravel, and volcanic breccia, from Ocean Drilling Program (ODP) Sites 732B, 734B, 734G and Conrad Cruise 27-9, Station 17, were examined. Contents of major and trace elements were determined using XRF or ICP (on samples <0.5 g). Determinations of rare earth elements (REE) were performed using ICP-MS. Mineralogy was determined using XRD. On the basis of the samples studied, the sediments accumulating in the Atlantis II Fracture Zone are characterized by generally high MgO, Cr, and Ni contents compared with other deep-sea sediments. A variety of sources are reflected in the mineralogy and geochemistry of these sediments. Serpentine, brucite, magnetite, and high MgO, Cr, and Ni contents indicate derivation from ultramafic basement. The occurrence of albite, analcime, primary mafic minerals, and smectite/chlorite in some samples, coupled with high SiO2, Al2O3, TiO2, Fe2O3, V, and Y indicate contribution from basaltic basement. A third major sediment source is characterized as biogenic material and is reflected primarily in the presence of carbonate minerals, and high CaO, Sr, Pb, and Zn in certain samples. Kaolinite, illite, quartz, and some chlorite are most likely derived from continental areas or other parts of the ocean by long-distance sediment transport in surface or other ocean currents. Proportions of source materials in the sediments reflect the thickness of the sediment cover, slope of the seafloor, and the nature of and proximity to basement lithologies. REE values are low compared to other deep-sea sediments and indicate no evidence of hydrothermal activity in the Atlantis II Fracture Zone sediments. This is supported by major- and trace-element data.

Geochemistry of the sheeted dike complex at Pito Deep

Alteration of sheeted dikes exposed along submarine escarpments at the Pito Deep Rift (NE edge of the Easter microplate) provides constraints on the crustal component of axial hydrothermal systems at fast spreading mid-ocean ridges. Samples from vertical transects through the upper crust constrain the temporal and spatial scales of hydrothermal fluid flow and fluid-rock reaction. The dikes are relatively fresh (average extent of alteration is 27%), with the extent of alteration ranging from 0 to >80%. Alteration is heterogeneous on scales of tens to hundreds of meters and displays few systematic spatial trends. Background alteration is amphibole-dominated, with chlorite-rich dikes sporadically distributed throughout the dike complex, indicating that peak temperatures ranged from <300°C to >450°C and did not vary systematically with depth. Dikes locally show substantial metal mobility, with Zn and Cu depletion and Mn enrichment. Amphibole and chlorite fill fractures throughout the dike complex, whereas quartz-filled fractures and faults are only locally present. Regional variability in alteration characteristics is found on a scale of <1-2 km, illustrating the diversity of fluid-rock interaction that can be expected in fast spreading crust. We propose that much of the alteration in sheeted dike complexes develops within broad, hot upwelling zones, as the inferred conditions of alteration cannot be achieved in downwelling zones, particularly in the shallow dikes. Migration of circulating cells along rides axes and local evolution of fluid compositions produce sections of the upper crust with a distinctive character of alteration, on a scale of <1-2 km and <5-20 ka.

Geochemistry of subducted volcaniclastic sediments from Mariana arc magmas

The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

Fe-Mn nodules and host sediments from the Gulf of Finland

Distributions of major and trace elements in ferromanganese nodules, which are buried or exposed on the sea floor and in host sediments, were studied in ten concretion/sediment pairs by various physical and chemical methods. It was established that, in addition to Fe and Mn, a limited number of major and trace elements (P, Ca, Sr, Ba, Mo, Co, Zn, Ni, As, Pb, Sb, Tl, U, W, Y, and Ga) is accumulated with variable degree of intensity (relative to sediments) in the nodules. The maximal content of Mn in the nodules is 100 times higher than in the host sediments, whereas for all other elements listed above these ratios vary from more than one to 10-20. Manganese and, to a lesser extent, Ba and Sr are concentrated in the buried concretions. Other elements are primarily concentrated in concretions exposed on the sea floor. The occurrence mode of the concretions and compositional data on interstitial water suggest that metals in the concretions derive from seawater and suspended particulates, in addition to sediments. Burial of concretions in the sediment pile is accompanied by alteration of their composition, accumulation of Mn (relative to Fe), and loss of several associated metals.

Oxygen isotope and Mg/Ca record of planktonic foraminifera of sediment core MD01-2390

Changes in the local freshwater budget over the last 22,000 years have been estimated from a sediment core located in the southern South China Sea (SCS) using a combined approach of Mg/Ca and oxygen isotopes on the planktonic foraminifera Globigerinoides ruber (white) sensu stricto (s.s.). Core MD01-2390 (06°28,12N, 113°24,56E; water depth 1591 m) is located near the glacial paleo-river mouths of the Baram, Rajang and North Sunda/Molengraaff Rivers that drained the exposed Sunda Shelf. The delta18Oseawater record reveals lower average values (-0.96±0.18 per mil) during the Last Glacial Maximum (LGM) when compared with modern values (-0.54±0.18 per mil). Low salinity during the LGM is interpreted to reflect a higher freshwater contribution due to a greater proximity of the core site to the mouths of the Baram, Rajang and North Sunda/Molengraaff Rivers at that time. A general deglacial increasing trend in salinity due to the progressive landward displacement of the coastline during deglacial shelf flooding is punctuated by several short-term shifts towards higher and lower salinity that are likely related to abrupt changes in the intensity of the East Asian summer monsoon. Thus, the deglacial delta18Oseawater changes reflect the combined effects of sea-level-induced environmental changes on the shelf (e.g. phases of retreat and breakdown of the shelf drainage systems) and East Asian monsoon climate change. Lower salinity than at present during the Early Holocene may be attributed to an increase in summer monsoonal precipitation that is corroborated by previous marine and terrestrial studies that report a Preboreal-Early Holocene monsoon optimum in the Asian monsoon region.

Chemical composition of Fe-Mn nodules and host bottom sediments along the submeridional profile across the Brazil Basin

Sedimentation and ore formation were studied in sediments from nine stations located along the 24°W profile in the Brazil Basin of the Atlantic Ocean. Bottom sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to bottom sediments from other basins of the Atlantic Ocean, the sediments in study are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to decrease of Ce anomaly and LREE/HREE ratio. In reduced sediments preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crusts and ferromanganese nodules. Judging from contents of iron, manganese, REE, and other trace elements, these formations are ascribed to sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. Extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).