Element concentrations of aluminosilicate components from ODP sites in the Pacific Ocean

We measured major and trace element concentrations in the operationally defined, chemically extracted, residual aluminosilicate component of sediment from Ocean Drilling Program Sites 1215 and 1256 in the central and eastern equatorial Pacific Ocean and found that this residual component contains volcanogenic and authigenic aluminosilicates in addition to inferred eolian material. While the residual component younger than 20 Ma from the central Pacific (ODP Site 1215) is similar compositionally to upper continental crust and suggests an increase in the delivery of Asian dust material since 20 Ma, the residual in sediment older than 20 Ma indicates significant amounts of volcanogenic and authigenic materials. Volcanogenic debris comprises as much as ~ 40% of the residual between 23-40 Ma, which coincides with the mid-Tertiary "ignimbrite flare-up" that occurred in much of western North America. The residual component extracted from the 50 Ma biogenic sediment reflects authigenic signatures (seawater-like negative cerium anomalies and elevated Fe/Si ratios). The previously interpreted increase in an andesitic detrital source in North Pacific locations may instead be authigenic material, presenting significant challenges for many paleoclimate proxies. Additionally, in the eastern Pacific (ODP Site 1256), the residual component contains ~70% of volcanogenic material, most likely originating from Central America, and also includes refractory barite. The ability to separately identify eolian, volcanogenic, and authigenic materials in the aluminosilicate component of pelagic sediment allows resolution, respectively, of the climatic, geologic, and chemical processes contributing to the paleoceanographic archive in this critical oceanic region.

Geochemistry of hydrate gas and water at DSDP Hole 84-570

Molecular and isotopic measurements of gas and water obtained from a gas hydrate at Site 570, DSDP Leg 84, are reported. The hydrate appeared to be Structure I and was composed of a solid framework of water molecules enclosing methane and small amounts of ethane and carbon dioxide. Carbon isotopic values for the hydrate-bound methane, ethane, and carbon dioxide were -41 to about -44, -27, and -2.9 per mil, respectively. The d13C-C1 values are consistent with void gas values that were determined to have a biogenic source. A significant thermogenic source was discounted because of high C1/C2 ratios and because the d13C-CO2 values in these sections were also anomalously heavy (or more positive) isotopically, suggesting that the methane was formed biogenically by reduction of heavy CO2 . The isotopically heavy hydrate d13C-C2 is also similar to void gas isotopic compositions and is either a result of low-temperature diagenesis producing heavy C2 in these immature sediment sections or upward migration of deeper thermogenic gas. The salinity of the hydrate water was 2.6 per mil with dDH2O and d18OH2O values of +1 and +2.2 per mil, respectively.

Chemical composition of ODP Leg 138 sediments

A major oceanographic event preserved in the Cocos plate sedimentary column survived subduction and is recorded in the changing composition of Nicaraguan magmas. A uranium increase in these magmas since the latest Miocene (after 7 Ma) resulted from the 'carbonate crash' at 10 Ma and the ensuing high organic carbon burial in the sediments. The response of the arc to this paleoceanographic event requires near steady-state sediment recycling at this margin since 20 Ma. This relative stability in sediment subduction invites one of the first attempts to balance sedimentary input and arc output across a subduction zone. Calculations based on Th indicate that as much as 75% of the sedimentary column was subducted beneath the arc. The Nicaraguan margin is one of the few places to observe such strong links between the oceans and the solid earth.

(Table 2, Page 106-107) Composition of the HCl-soluble fraction in Barents Sea iron-manganese deposits

Ferromanganese concretions from ten stations in the Barents Sea have been analysed for 24 elements. The deposits occur as discoidal and flat concretions and as coatings, in the latter case on lithified or detrital material or as extensive pavements on the Svalbard shelf. The concretions are compositionally similar to Baltic concretions but differ considerably from deep-ocean nodules, particularly in Cu, Ni and Co contents. Statistical analyses reveal distinct correlations between Mn, Na, Ba, Ni and Cu; the Mn-rich coatings showed enrichment of Mo, Zn and possibly Co in a Mn-phase. The iron phase holds high concretions of P and As. Two iron-rich concretions with high contents of P, Ca, Sr, Y, Yb and La were found east and northeast of Spitsbergen Banken, probably indicating upwelling of nutrient-rich, cold polar water along the Svalbard shelf.

Appendix A. Whole-rock major, trace and rare earth element analyses of the Ulubey volcanics, Appendix B. Analytical standards and detection limits for analyses

Collisional and post-collisional volcanic rocks in the Ulubey (Ordu) area at the western edge of the Eastern Pontide Tertiary Volcanic Province (EPTVP) in NE Turkey are divided into four suites; Middle Eocene (49.4-44.6 Ma) aged Andesite-Trachyandesite (AT), Trachyandesite-Trachydacite-Rhyolite (TTR), Trachydacite-Dacite (TD) suites, and Middle Miocene (15.1 Ma) aged Trachybasalt (TB) suite. Local stratigraphy in the Ulubey area starts with shallow marine environment sediments of the Paleocene-Eocene time and then continues extensively with sub-aerial andesitic to rhyolitic and rare basaltic volcanism during Eocene and Miocene time, respectively. Petrographically, the volcanic rocks are composed primarily of andesites/trachyandesites, with minor trachydacites/rhyolites, basalts/trachybasalts and pyroclastics, and show porphyric, hyalo-microlitic porphyric and rarely glomeroporphyric, intersertal, intergranular, fluidal and sieve textures. The Ulubey (Ordu) volcanic rocks indicate magma evolution from tholeiitic-alkaline to calc-alkaline with medium-K contents. Primitive mantle normalized trace element and chondrite normalized rare earth element (REE) patterns show that the volcanic rocks have moderate light rare earth element (LREE)/heavy rare earth element (HREE) ratios relative to E-Type MORB and depletion in Nb, Ta and Ti. High Th/Yb ratios indicate parental magma(s) derived from an enriched source formed by mixing of slab and asthenospheric melts previously modified by fluids and sediments from a subduction zone. All of the volcanic rocks share similar incompatible element ratios (e.g., La/Sm, Zr/Nb, La/Nb) and chondrite-normalized REE patterns, indicating that the basic to acidic rocks originated from the same source. The volcanic rocks were produced by the slab dehydration-induced melting of an existing metasomatized mantle source, and the fluids from the slab dehydration introduced significant large ion lithophile element (LILE) and LREE to the source, masking its inherent HFSE-enriched characteristics. The initial 87Sr/86Sr (0.7044-0.7050) and eNd (-0.3 to +3.4) ratios of the volcanics suggest that they originated from an enriched lithospheric mantle source with low Sm/Nd ratios. Integration of the geochemical, petrological and isotopical with regional and local geological data suggest that the Tertiary volcanic rocks from the Ulubey (Ordu) area were derived from an enriched mantle, which had been previously metasomatized by fluids derived from subducted slab during Eocene to Miocene in collisional and post-collisional extension-related geodynamic setting following Late Mesozoic continental collision between the Eurasian plate and the Tauride-Anatolide platform.

Major ion concentrations and chlorine isotope composition of water-soluble chloride and structurally bound chloride in DSDP/ODP serpentinized ultramafic rocks

Eight DSDP/ODP cores were analyzed for major ion concentrations and d37Cl values of water-soluble chloride (d37Clwsc) and structurally bound chloride (d37Clsbc) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition. The average total Cl content of all 86 samples is 0.26±0.16 wt.% (0.19±0.10 wt.% as water-soluble Cl (Xwsc) and 0.09±0.09 wt.% as structurally bound Cl (Xsbc)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl**- site and the water-soluble Cl**- site varies from -1.08? to +1.16?, averaging to +0.21?. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk d37Cl values (+0.05? to +0.36?); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk d37Cl values (-1.26? and -0.54?). The cores with negative d37Cl values also have variable Cl**-/SO4**2- ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ~1? with depth for both the water-soluble and structurally bound Cl fractions. Non-zero bulk d37Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive d37Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of 37Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low d37Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative d37Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.

Paleoceanography of sediment cores SO202-27-6 during MIS 3

The modern subarctic Pacific is characterized by a steep salinity-driven surface water stratification, which hampers the supply of saline and nutrient-rich deeper waters into the euphotic zone, limiting productivity. However, the strength of the halocline might have varied in the past. Here, we present diatom oxygen (d18Odiat) and silicon (d30Sidiat) stable isotope data from the open subarctic North-East (NE) Pacific (SO202-27-6; Gulf of Alaska), in combination with other proxy data (Neogloboquadrina pachydermasin d18O, biogenic opal, Ca and Fe intensities, IRD), to evaluate changes in surface water hydrography and productivity during Marine Isotope Stage (MIS) 3, characterized by millennial-scale temperature changes (Dansgaard-Oeschger (D-O) cycles) documented in Greenland ice cores.