Chemistry and boron isotope ratios of Izu arc front volcanic rocks

The process of fluid release from the subducting slab beneath the Izu arc volcanic front (Izu VF) was examined by measuring B concentrations and B isotope ratios in the Neogene fallout tephra (ODP Site 782A). Both were measured by secondary ion mass spectrometry, in a subset of matrix glasses and glassy plagioclase-hosted melt inclusions selected from material previously analyzed for major and trace elements (glasses) and radiogenic isotopes (Sr, Nd, Pb; bulk tephra). These tephra glasses have high B abundances (~10-60 ppm) and heavy delta11B values (+4.5? to +12.0?), extending the previously reported range for Izu VF rocks (delta11B, +7.0? to +7.3?). The glasses show striking negative correlations of delta11B with large ion lithophile element (LILE)/Nb ratios. These correlations cannot be explained by mixing two separate slab fluids, originating from the subducting sediment and the subducting basaltic crust, respectively (model A). Two alternative models (models B and C) are proposed. Model B proposes that the inverse correlations are inherited from altered oceanic crust (AOC), which shows a systematic decrease of B and LILE with increasing depth (from basaltic layer 2A to layer 3), paralleled by an increase in delta11B (from ~ +1? to +10? to +24?). In this model, the contribution of sedimentary B is insignificant (<4% of B in the Izu VF rocks). Model C explains the correlation as a mixture of a low-delta11B (~ +1?) 'composite' slab fluid (a mixture of metasediment- and metabasalt-derived fluids) with a metasomatized mantle wedge containing elevated B (~1-2 ppm) and heavy delta11B (~ +14?). The mantle wedge was likely metasomatized by 11B-rich fluids beneath the outer forearc, and subsequently down dragged to arc front depths by the descending slab. Pb-B isotope systematics indicate that, at arc front depths, ~ 53% of the B in the Izu VF is derived from the wedge. This implies that the heavy delta11B values of Izu VF rocks are largely a result of fluid fractionation, and do not reflect variations in slab source provenance (i.e. subducting sediment vs. basaltic crust). Since the B content of the peridotite at the outer forearc (7-58 ppm B, mean 24 +/- 16 ppm) is much higher than beneath the arc front (~1-2 ppm B), the hydrated mantle wedge must have released a B-rich fluid on its downward path. This 'wedge flux' can explain (1) the across-arc decrease in B and delta11B (e.g. Izu, Kuriles), without requiring a progressive decrease in fluid flux from the subducting slab, and (2) the thermal structure of volcanic arcs, as reflected in the B and delta11B variations of volcanic arc rocks.

Age and chemical composition of dredged igneous rocks from the Vityaz Ridge, Pacific slope of the Kuril Island Arc

Original results of igneous rock studies are presented. The rocks were dredged during a marine expedition (cruise 37 of R/V Akademik M.A. Lavrent'ev in August-September, 2005) in the region of the submarine Vityaz Ridge and the Kuril Arc outer slope. Several age complexes (Late Cretaceous, Eocene, Late Oligocene, Miocene, and Pliocene-Pleistocene) are recognizable on the Vityaz Ridge. These complexes are characterized by a number of common geochemical features since all of them represent formations of island arc calc-alkali series. At the same time, they also have individual features reflecting different geodynamic settings. The outer slope of the Kuril Arc demonstrates submarine volcanism. Pliocene-Pleistocene volcanic rocks dredged here are similar to volcanites of the Kuril-Kamchatka Arc frontal zone.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

Chemical composition and K-Ar age of rocks from the northern Sea of Japan

The Middle Paleozoic complex consists of terrigenous and volcanogenic materials metamorphized in greenschist facies. Clastic rocks have arkosic composition and are formed by alteration of basalts and metamorphic rocks. Metaeffusives were formed from basaltoid products of oceanic tholeiite magma indicating that underwater rise structures of the northern Sea of Japan were emplaced on the oceanic crust.

Chemical composition of rhyolites of ODP Site 103-639

Holes 639E and 639F were drilled along the western slope of a tilted fault block in an attempt to recover complete syn- and pre-rift stratigraphic sections and continental basement. Both holes ended in an apparent talus pile or conglomerate that includes cobbles of altered rhyolitic rock. Three small pieces of rhyolite (comprising about 20 cm of sample) were recovered from the bottoms of Holes 639E and 639F in the core catchers of the deepest cores. This note presents geochemical data from these rhyolitic rocks. Also recovered were quartz sandstones, graywackes, metasandstones, and quartz breccias. This assemblage of continentally derived 'basement' material was overlain by mudstones, limestones, and crystalline dolomites (see 'Site 639' chapter; Shipboard Scientific Party, 1987, doi:10.2973/odp.proc.ir.103.110.1987).

Chemical composition of celadonite-glauconite minerals and cristobalite from altered oceanic basalts of DSDP Hole 49-407

Features of associations of newly formed minerals in Oligocene basalts from the Reykjanes Ridge (DSDP Hole 407), which consist in wide development of celadonite-glauconite group minerals, as well as saponite, cristobalite and specific Fe-Si formations is shown. Detailed mineralogical and geochemical characteristics of these newly formed minerals are reported. It is firstly shown that at underwater alteration of basalts not only celadonite can be generated, but also glauconite. Dependence of secondary mineral composition from petrochemical features of original basalts and from their permeability is revealed. It is concluded that complexes of secondary minerals formed during alteration of basalts with similar petrochemical characteristics in the ocean and on the continent are different.

Chemistry and fluid inclusions of the sheeted dike comples of ODP Holes 137-504B and 140-504B

Fluid inclusions in variably altered diabase recovered from Ocean Drilling Program Legs 137 and 140 at Hole 504B, Costa Rica Rift, exhibit fluid salinities up to 3.7 times that of seawater values (11.7 wt% NaCl equivalent) and exhibit uncorrected homogenization temperatures of 125°C to 202°C. The liquid-dominated inclusions commonly are entrapped in zones of secondary plagioclase and may be primary in origin. Fluid salinities are similar to compositions of fluids venting on the seafloor (0.4-7.0 wt% NaCl) and overlap with those measured in metabasalt samples recovered from near the Kane Fracture Zone on the Mid-Atlantic Ridge and from the Troodos ophiolite, Cyprus. The salinity variations may reflect hydration reactions involving formation of secondary mineral assemblages under rock-dominated conditions, which modify the ionic strength of hydrothermal fluids by consuming or liberating water and chloride ion. Rare CO2-CH4-bearing inclusions, subjacent to zones where talc after olivine becomes an important secondary mineral phase (1700 mbsf), may have formed due to local interaction of seawater and olivine at low water to rock ratios. Corrected average fluid inclusion homogenization temperatures exhibit a gradient from 159°C at a depth of 1370 mbsf to 183°C at a depth of 1992 mbsf and are in apparent equilibrium with the present conductive downhole temperatures. These data indicate that fluid inclusions may be used to estimate downhole temperatures if logging data are unavailable. The compositional and thermal evolution of the diabase-hosted fluids may reflect late-stage, off-axis circulation and conductive heating of compositionally modified seawater in the sheeted dike complex at Hole 504B.

Geochemistry and Fe/(Ti + Ti), x, Curie temperature, and oxidation parameter z at DSDP Hole 597C

Electron microprobe and thermomagnetic analyses of selected basalt samples from Hole 597C were performed. The main purpose of this work was to investigate and estimate the degree of oxidation of the samples using the ratios of Fe to Ti and the Curie temperatures obtained from thermomagnetic curves. The results show that the magnetic properties of samples from Hole 597C change at a sub-bottom depth of 100 m, and that low-temperature and high-temperature oxidation processes prevailed above and below 100 m, respectively.

Geochemistry, minerals and b-parameter at DSDP Leg 70 Holes

Clay minerals recovered from the Galapagos hydrothermal mounds (Holes 506C, 507D, and 509B) are mainly iron-rich nontronite-like minerals enriched in potassium. Nontronites from Hole 509B show a distinct tendency to become micaceous toward the lower beds of clay sediments. Mn-crusts consist mainly of todorokite or a mixture of todorokite and nontronite. Minerals of clay and Mnrich sediments in the mounds originated from hydrothermal solutions of uncertain origin. Pelagic oozes from hydrothermal mounds and from areas between mounds (Hole 506D) consist mainly of calcite. In the carbonate beds on or near the hydrothermal mounds an admixture of smectite is often found.

Geochemistry of microtektites from Victoria Land Transantarctic Mountains

We extended the petrographic and geochemical dataset for the recently discovered Transantarctic Mountain microtektites in order to check our previous claim that they are related to the Australasian strewn field. Based on color and composition, the 465 microtektites so far identified include two groups of transparent glass spheres less than ca. 800 µm in diameter: the most abundant pale-yellow, or normal, microtektites, and the rare pale-green, or high-Mg, microtektites. The major element composition of normal microtektites determined through electron microprobe analysis is characterized by high contents of silica (SiO2 = 71.5 ± 3.6 (1 sigma) wt%) and alumina (Al2O3 = 15.5 ± 2.2 (1 sigma) wt%), low total alkali element contents (0.50-1.85 wt%), and MgO abundances <6 wt%. The high-Mg microtektites have a distinctly higher MgO content >10 wt%. Transantarctic Mountain microtektites contain rare silica-rich (up to 93 wt% SiO2) glassy inclusions similar to those found in two Australasian microtektites analyzed here for comparison. These inclusions are interpreted as partially digested, lechatelierite-like inclusions typically found in tektites and microtektites. The major and trace element (by laser ablation - inductively coupled plasma - mass spectrometry) abundance pattern of the Transantarctic Mountain microtektites matches the average upper continental crust composition for most elements. Major deviations include a strong to moderate depletion in volatile elements including Pb, Zn, Na, K, Rb, Sr and Cs, as a likely result of severe volatile loss during the high temperature melting and vaporization of crustal target rocks. The normal and high-Mg Transantarctic Mountain microtektites have compositions similar to the most volatile-poor normal and high-Mg Australasian microtektites reported in the literature. Their very low H2O and B contents (by secondary ion mass spectrometry) of 85 ± 58 (1 sigma) ?g/g and 0.53 ± 0.21 ?g/g, respectively, evidence the extreme volatile loss characteristically observed in tektites. The Sr and Nd isotopic compositions of multigrain samples of Transantarctic Mountain microtektites are 87Sr/86Sr ~ 0.71629 and 143Nd/144Nd ~ 0.51209, and fall into the Australasian tektite compositional field. The Nd model age calculated with respect to the chondritic uniform reservoir (CHUR) is TNdCHUR ~ 1.1 Ga, indicating a Meso-Proterozoic crustal source rock, as was derived for Australasian tektites as well. Coupled with the Quaternary age from the literature, the extended dataset presented in this work strengthens our previous conclusion that Transantarctic Mountain microtektites represent a major southward extension of the Australasian tektite/microtektite strewn field. Furthermore, the significant depletion in volatile elements (i.e., Pb, B, Na, K, Zn, Rb, Sr and Cs) of both normal and high-Mg Transantarctic Mountain microtektites relative to the Australasian ones provide us with further confirmation of a possible relationship between high temperature-time regimes in the microtektite-forming process and ejection distance.

Chemistry of very young basalts from ODP Hole 106-648B

Basalts in Hole 648B, located in the rift valley of the Mid-Atlantic Ridge at 23°N in crust estimated to be less than 100,000 years old, are mainly fresh, but small amounts of secondary phases are found on fracture surfaces and in alteration halos within the rocks. The halos are defined by dark bands 1-4 mm thick that have developed parallel to fracture surfaces or pillow margins and which in some cases have migrated some centimeters into the rock. The dark bands are the principal locus of secondary phases. The secondary phases are olive-green and yellow protoceladonites, of composition and structure intermediate between celadonite and iron-rich saponite, red (Mn-poor) to opaque (Mn-rich) iron oxyhydroxides, mixtures of protoceladonite and iron oxyhydroxide, and rare manganese oxides. These phases occur mainly as linings or fillings of open spaces in the basalt within the dark bands. Sulfides and intersertal glass are the only primary phases that can be seen to have been altered. Where dark bands have migrated into the rock, the rock behind the advancing band is almost devoid of secondary phases, implying redissolution. The potassium and magnesium in the secondary phases could have been supplied from ambient seawater. The aluminum in the protoceladonites must have been derived from local reaction of intergranular glass. The source of iron and silica could have been intergranular glass or low temperature mineralizing solutions of the type responsible for the formation of deposits of manganese oxides and iron oxyhydroxides and silicates on the seafloor.

Age and chemical composition of volcaniclastic rocks from the Sea of Japan

Petrographic and geochemical studies showed that Oligocene - Early Miocene volcaniclastic rocks from the southern part of the Sea of Japan are ascribed to high-potassium aluminous rocks of sub-alkaline volcanic series from active continental margins. A comparative analysis revealed spatiotemporal relation of Oligocene - Early Miocene subaerial volcanism of the Sea of Japan with Late Cretaceous and Eocene - Early Miocene ignimbrite volcanism of the East Eurasian margin. This allows to refer the volcaniclastic rocks of the Sea of Japan to the stage of ignimbrite volcanism that occurred during relative quiescence against general extension in the continental margin setting.

Investigation of manganese nodules from the Malvinas (Falkland) Plateau

Manganese nodules occurring within marine sediments of presumably Upper Miocene-Lower Pliocene age from cores obtained by the Argentine oceanographic vessel ARA Islas Orcadas in 1977 on the Malvinas (Falkland) Plateau and neighbouring Scotia Sea were studied with the aim of comparing them with other fossil nodules found on the mainland of Argentina that were also ascribed to the marine environment. After optical mineralogical, chemical, X-ray and trace element analysis, the studied "nodules" proved to be actually wacke clasts cemented by manganese oxides with a high Fe/Mn ratio corresponding to a continental environment. The studied "nodules" thus differ from the Argentine mainland nodules and are supposed to have been transported from continental environments and then deposited in the marine realms. The wacke clasts became then nuclei for the deposition of the marine manganese oxides of the coatings. The proportion of trace elements, which is high, suggests the growth of the nodules in the marine environment.

Liquidus temperatures in calcium ferrite slags in equilibrium with molten copper

Experimental laboratory methods have been developed that enable phase-equilibria studies to be carried out on slags in the system Ca-Cu-Fe-O in equilibrium with metallic copper. These techniques involve equilibration at temperature, rapid quenching, and chemical analysis of the phases using electron-probe X-ray microanalysis (EPNIA). Equilibration experiments have been carried out in the temperature range of 1150 degreesC to 1250 degreesC (1423 to 1523 K) and in the composition range of 4 to 80 wt pct "Cu2O," 0 to 25 wt pct CaO, and 20 to 75 wt pct "Fe2O3" in equilibrium with metallic copper. Liquidus and solidus data are reported for the primary-phase fields of spinel (magnetite) and dicalcium ferrite. The resulting data have been used to construct liquidus isotherms of the CaO-"Cu2O"-"Fe2O3" system at metallic copper saturation.

Phase equilibria in the ZnO-rich area of the Fe-Zn-O system in air

The phase equilibria in the Fe-Zn-O system in the range 900-1580degreesC in air have been experimentally studied using equilibration and quenching techniques. The compositions of the phases at equilibrium were determined using electron probe X-ray microanalysis (EPMA). The ferrous and ferric bulk iron concentrations were measured with a wet chemical analysis using the ammonium metavanadate technique. X-ray powder diffraction analysis (XRD) was used to characterise the phases. Iron oxide dissolved in zincite was found to be present principally in the ferric form. The XRD analysis and the composition measurements both indicate that zincite is the only phase stable in the ZnO-rich area in the range of conditions investigated. The solubility of the iron oxide in zincite rapidly increases at temperatures above 1200degreesC; the morphology of the zincite crystals also sharply changes between 1200 and 1300degreesC from rounded to plate-like crystals. The plate-like zincite forms a refractory network-the type of microstructure beneficial to the Imperial Smelting Process (ISP) sinter performance. The software program FactSage with a thermodynamically optimised database was used to predict phase equilibria in the Fe-Zn-O system.