Geochemistry of DSDP Holes 60-453 and 60-454A

Pliocene and Pleistocene volcanic glass fragments from Mariana Trough sediments at Sites 453 (16 samples) and 454 (4 samples), located near the western edge of the trough and just west of the spreading axis, respectively, have been analyzed for major elements with an electron microprobe. They derive from volcanic activity on the present Mariana active arc. The glasses from Site 453 are all tholeiitic with a wide range of SiO2 contents. Those less than 2 m.y. old have slightly lower TiO2 and higher K2O contents than the older ones. The glasses from Site 454 are all Pleistocene and resemble the younger glasses at Site 453. Major element compositions of the older basaltic glasses at Site 453 are similar to those of the Mariana Trough basalts drilled on Leg 60. Both older and younger suites of glasses differ from the composition of rocks exposed on the active arc, which are assumed to be younger than any of the samples studied (i.e., about 200,000 y.). A third suite is represented by the arc rocks exposed on the volcanic islands. These have a smaller range of SiO2 contents and contain more A12O3 but less K2O, TiO2, and FeO1 (total Fe as FeO) than the sediment glasses studied. Further, a plot of FeO1 against MgO for the arc rocks does not follow the island arc tholeiite trend of the trough sediment glasses. Using the major element compositions of the arc rocks and sediment glasses, we can recognize three phases of volcanic activity, as indicated. The first evidence of the oldest phase of activity occurs 5 Ma, about 4.5 m.y. after the trough started to form. The second commenced about 2 Ma, and the last, including present-day activity, began within the last 200,000 y. Initially the rocks had major element affinities with the tholeiitic Mariana Trough seafloor, but this influence declined as the trough widened.

Geochemistry at DSDP Site 60-456

Basalts in two holes spaced 200 meters apart at DSDP Site 456 in the Mariana Trough both show a downward sequence of nonoxidative and oxidative zones of alteration, each 10 to 15 meters thick, overlying fresh basalts. Basalts in the nonoxidative zone have been extensively chloritized and have vein and vesicle fillings of quartz, opal, chlorite, calcite, and pyrite. Minor sulfides are chalcopyrite and digenite. Basalts in the oxidative zone have abundant smectites and iron hydroxides and are variably enriched in K, Rb, and Ba, unlike the nonoxidative basalts above them. We propose that the oxidative zone was a zone of mixing between high-temperature, reduced hydrothermal fluids moving horizontally beneath impermeable sediments at the top of the pillowed basement lavas and cold, oxygenated seawater in interpillow voids deeper in the basement. Recrystallized vitric tuffs immediately above the basalts containing authigenic quartz and wairakite, as well as occurrence of chlorite, epidote, and chalcopyrite in the basalts, suggest temperatures of alteration in excess of 200°C.

Geochemistry of minerals in medium-grained diabase from ODP Holes 137-504B and 140-504B

Samples recovered from Hole 504B during Leg 140 include a number of medium-grained, holocrystalline diabases that appear to represent the cores of thick dikes. The plagioclase and pyroxene in these samples occur in a variety of crystal morphologies. Plagioclase occurs as phenocrysts, microphenocrysts, elongate crystals, skeletal crystals, and branching radial clusters. Pyroxene occurs as phenocrysts, microphenocrysts, ophitic crystals, and poikilitic crystals. Plagioclase compositions became progressively poorer in anorthite and MgO and progressively richer in FeO as crystallization proceeded, while the average grain volume decreased and the aspect ratio of individual grains increased. Pyroxene compositions are largely independent of crystal morphology. The diabase dikes recovered from Hole 504B during Leg 140 appear to have crystallized in situ. Crystal compositions and morphologies are consistent with a rapid cooling rate and solidification times for individual dikes on the order of hours or days. The crystallization rate and nucleation rate of plagioclase lagged behind the cooling rate so that the degree of undercooling progressively increased as crystallization proceeded. Plagioclase crystal morphologies indicate much greater degrees of supersaturation than do pyroxene or olivine crystal morphologies. The 504B diabase magmas appear to have been emplaced with abundant preexisting pyroxene and olivine nuclei, but with few preexisting plagioclase nuclei. The suppression of plagioclase nucleation and crystallization relative to that of pyroxene and olivine could provide a mechanism by which the actual fractionation assemblage is more pyroxene-rich and plagioclase-poor than that predicted from thermodynamic models, or that observed in isothermal crystallization experiments.

Chemical and isotopic compositions of lavas from the Broken Ridge and Southern Kerguelen Plateau

Lavas from several major bathymetric highs in the eastern Indian Ocean that are likely to have formed as Early to Middle Cretaceous manifestations of the Kerguelen hotspot are predominantly tholeiitic; so too are glass shards from Eocene to Paleocene volcanic ash layers on Broken Ridge, which are believed to have come from eruptions on the Ninetyeast Ridge. The early dominance of tholeiitic compositions contrasts with the more recent intraplate, alkalic volcanism of the Kerguelen Archipelago. Isotopic and incompatible-element ratios of the plateau lavas are distinct from those of Indian mid-ocean ridge basalts; their Nd, Sr, 207Pb/204Pb and 2078b/204Pb isotopic ratios overlap with but cover a much wider range than measured for more recent oceanic products of the Kerguelen hotspot (including the Ninetyeast Ridge) or, indeed, oceanic lavas from any other hotspot in the world. Samples from the Naturaliste Plateau and ODP Site 738 on the southern tip of the Kerguelen Plateau are particularly noteworthy, with e-Nd(T) = -13 to -7, (87Sr/86Sr)T=0.7090 to 0.7130 and high 207Pb/204Pb relative to 206Pb/204Pb. In addition, the low-e-Nd(T) Naturaliste Plateau samples are elevated in SiO2 (>54 wt%). In contrast to "DUPAL" oceanic islands such as the Kerguelen Archipelago, Pitcairn and Tristan da Cunha, the plateau lavas with extreme isotopic characteristics also have relative depletions in Nb and Ta (e.g., Th/Ta, La Nb > primitive mantle values); the lowest e-Nd(T) and highest Th/Ta and La Nb values occur at sites located closest to rifted continental margins. Accepting a Kerguelen plume origin for the plateau lavas, these characteristics probably reflect the shallow-level incorporation of continental lithosphere in either the head of the early Kerguelen plume or in plume-derived magmas, and suggest that the influence of such material diminished after the period of plateau construction. Contamination of asthenosphere with the type of material affecting Naturaliste Plateau and Site 738 magmatism appears unlikely to be the cause of low-206Pb/204Pb Indian mid-ocean ridge basalts. Finally, because isotopic data for the plateaus do not cluster or form converging arrays in isotope-ratio plots, they provide no evidence for either a quickly evolving, positive ?Nd, relatively high-206Pb/204Pb plume composition, or a plume source dominated by mantle with e-Nd of -3 to ~0.

Petrology and geochemistry of the basement boninite series of ODP Site 125-786

The 720 m of igneous basement that was penetrated at Site 786 of Ocean Drilling Program Leg 125 consists of boninite-series volcanics. Bronzite andesites dominate the lithology and primitive magmas of high-Ca, intermediate-Ca, and low-Ca boninite are present in subordinate amounts. Sparsely phyric boninites typically contain olivine and orthopyroxene phenocrysts with Mg numbers [= Mg/(Mg + Fe) in moles] between 86% and 87%. Their high whole-rock Mg numbers, and the absence of zonation in the phenocrysts, imply equilibration at temperatures probably between 1200° and 1250°C, and 20° to 50°C below their liquidus. Equilibrium olivine and orthopyroxene have identical Mg numbers, and Mg/Fe partitioning between these minerals and the melt thus can be described with a single Kd. The invariably phenocryst-rich bronzite andesites contain Plagioclase that has spectacular zoning and mafic phases that can be as magnesian as those of the boninite parent. The most evolved melts are rhyolites with hypersthene, Plagioclase (An50), and magnetite. Eruption temperatures for the rhyolites are estimated at about 1000°C. Some magmas contain ferroactinolite in the groundmass, which is most likely a secondary, low-temperature phase. The locally large contrasts in degree of alteration are consistent with multiple episodes of magmatic activity. However, all igneous events produced boninite volcanics. Only the first, the edifice-building episode, gave rise to differentiated magmas. Differentiation of parental boninites took place by limited fractional crystallization, producing bronzite andesites. The erupted andesites, dacites and rhyolites are filter pressed extracts from these bronzite andesite magmas, which, as a result, have accumulated crystals. Subsequent younger igneous events produced high-Ca and intermediate-Ca boninites which intruded as dikes and sills throughout the basement sequence. The mineralogy of the dikes and sills reflects variable degrees of subliquidus cooling of the magma before emplacement.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Chemistry on manganese nodules from the Pacific Ocean

Three manganese nodules from the Pacific Ocean have been analysed for 35 elements by using mainly spectrophotometric and spectrographic methods. Cu, Co, Ni, Zn, and Pb were found in amounts approaching 1 %, which far exceeds their average concentrations in igneous rocks. On the other hand, elements having readily hydrolysable ions, such as Ga, Sc, Zr, Y, La and Ti, are present only in amounts comparable with their concentrations in igneous rocks. Sb, Bit Be, and Cr were not detected. The hydrochloric acid-insoluble fraction of nodules is practically free of the heavy metals that are characteristic of the acid-soluble fraction; it consists principally of clay minerals, together with lesser amounts of quartz, apatite, biotite and sodium and potassium felspars.

Geochemistry and mineralogy of garnet grains from ODP Sample 183-1137A-33R-3,50-53

On Elan Bank, a southwestern promontory of the Kerguelen Plateau in the southern Indian Ocean, we cored an interval of conglomerate and minor sandstone within a thick section of Cretaceous flood basalts. Most of the detritus in these sedimentary rocks is volcanic with the exception of a small amount of conspicuous material of probable continental derivation. The anomalous clasts include several pebbles of gneiss (Nicolaysen et al., 2001, doi:10.1130/0091-7613(2001)029<0235:POPGBG>2.0.CO;2) and garnet sand grains. The presence of continental material on the plateau bears significantly on the interpretation of Indian Ocean basalts (Weis et al., 2001, doi:10.1130/0091-7613(2001)029<0147:OOCCII>2.0.CO;2). The purpose of the present study was to determine the composition of the garnets to provide additional constraints on the nature of the source area.

Geochemistry of Neogene volcanic ashs in ODP Leg 124 holes

Mineralogical and geochemical analyses were performed on 40 ash layers of Pleistocene to late Miocene age, recovered during Leg 124 in the Celebes and Sulu Seas (Sites 767, 768, and 769). They provide information on alteration processes related to burial diagenesis. The zonal distribution of secondary volcanic products emphasizes a major diagenetic change, characterized by the complete replacement of volcanic glass by an authigenic smectite-phillipsite assemblage, in tephra layers dated at 3.5-4 Ma. This diagenetic "event" occurs simultaneously in the two basins, and, on the basis of isotopic data, under low-temperature conditions. It is independent of distinct sedimentation rates and related to a relative quiescence of on-land volcanic activity. This period suggests a more uniform paleooceanographic situation having tectonic significance, and probably reflects a kinetic and environmental control of diagenetic reactions.

Description, geochemistry and mineral composition of ODP Site 193-1189 jasperoids, PACMANUS field

Bright red "jasperoids" were recovered at three positions during Leg 193 drilling below Roman Ruins (Site 1189) in the PACMANUS hydrothermal field. These do not represent fossil exhalative oxide deposits equivalent to those associated with sulfide chimneys at the Roman Ruins seafloor. Rather, they constitute an integral, relatively early stage involving oxidized fluids in the development of veins and breccias that characterize the mostly sulfidic stockwork zone intersected below Roman Ruins in Hole 1189B. They formed by growth of quartz in open spaces created by hydrofracturing, the characteristic feature being mostly euhedral cores dusted by tiny hematite flakes. In one occurrence there are also frondlike aggregates and possible earlier cavity linings of hematite, overgrown by quartz, that potentially formed by maturation of ferruginous gels first deposited in the openings. The trace element geochemistry of the jasperoids, apart from minor enrichment in uranium, provides no indication that they represent subsurface conduits for fluids that deposit Fe-Mn-Si at the seafloor, though this remains a possibility for some such deposits.

Chemical composition of bottom sediments at DSDP Sites 91-595 and 91-596 and ODP Sites 114-701 and 129-801

Subducted sediments play an important role in arc magmatism and crust-mantle recycling. Models of continental growth, continental composition, convergent margin magmatism and mantle heterogeneity all require a better understanding of the mass and chemical fluxes associated with subducting sediments. We have evaluated subducting sediments on a global basis in order to better define their chemical systematics and to determine both regional and global average compositions. We then use these compositions to assess the importance of sediments to arc volcanism and crust-mantle recycling, and to re-evaluate the chemical composition of the continental crust. The large variations in the chemical composition of marine sediments are for the most part linked to the main lithological constituents. The alkali elements (K, Rb and Cs) and high field strength elements (Ti, Nb, Hf, Zr) are closely linked to the detrital phase in marine sediments; Th is largely detrital but may be enriched in the hydrogenous Fe-Mn component of sediments; REE patterns are largely continental, but abundances are closely linked to fish debris phosphate; U is mostly detrital, but also dependent on the supply and burial rate of organic matter; Ba is linked to both biogenic barite and hydrothermal components; Sr is linked to carbonate phases. Thus, the important geochemical tracers follow the lithology of the sediments. Sediment lithologies are controlled in turn by a small number of factors: proximity of detrital sources (volcanic and continental); biological productivity and preservation of carbonate and opal; and sedimentation rate. Because of the link with lithology and the wealth of lithological data routinely collected for ODP and DSDP drill cores, bulk geochemical averages can be calculated to better than 30% for most elements from fewer than ten chemical analyses for a typical drill core (100-1000 m). Combining the geochemical systematics with convergence rate and other parameters permits calculation of regional compositional fluxes for subducting sediment. These regional fluxes can be compared to the compositions of arc volcanics to asses the importance of sediment subduction to arc volcanism. For the 70% of the trenches worldwide where estimates can be made, the regional fluxes also provide the basis for a global subducting sediment (GLOSS) composition and flux. GLOSS is dominated by terrigenous material (76 wt% terrigenous, 7 wt% calcium carbonate, 10 wt% opal, 7 wt% mineral-bound H2O+), and therefore similar to upper continental crust (UCC) in composition. Exceptions include enrichment in Ba, Mn and the middle and heavy REE, and depletions in detrital elements diluted by biogenic material (alkalis, Th, Zr, Hf). Sr and Pb are identical in GLOSS and UCC as a result of a balance between dilution and enrichment by marine phases. GLOSS and the systematics of marine sediments provide an independent approach to the composition of the upper continental crust for detrital elements. Significant discrepancies of up to a factor of two exist between the marine sediment data and current upper crustal estimates for Cs, Nb, Ta and Ti. Suggested revisions to UCC include Cs (7.3 ppm), Nb (13.7 ppm), Ta (0.96 ppm) and TiO2 (0.76 wt%). These revisions affect recent bulk continental crust estimates for La/Nb and U/Nb, and lead to an even greater contrast between the continents and mantle for these important trace element ratios. GLOSS and the regional sediment data also provide new insights into the mantle sources of oceanic basalts. The classical geochemical distinction between 'pelagic' and 'terrigenous' sediment sources is not valid and needs to be replaced by a more comprehensive understanding of the compositional variations in complete sedimentary columns. In addition, isotopic arguments based on surface sediments alone can lead to erroneous conclusions. Specifically, the Nd/Hf ratio of GLOSS relaxes considerably the severe constraints on the amount of sediment recycling into the mantle based on earlier estimates from surface sediment compositions.

Mineral and chemical compositions of authigenic carbonates from the northern Deryugin Basin, Sea of Okhotsk

Mineral and chemical compositions of authigenic carbonates are studied by several methods in a sediment core collected in the axial zone of the Deryugin riftogenic basin. Manganese carbonates (kutnahorite, rhodochrosite) associated with manganiferous calcite, manganiferous pyrite, and nontronite are firstly identified in the Sea of Okhotsk. Manganese carbonates in Holocene diatomaceous ooze were presumably formed due to diagenetic transformation of sedimentary manganese hydroxides, organic matter, and biogenic silica, while those found in the underlying turbidites precipitated owing to the intermittent influx of endogenic fluids migrating along sand interbeds.

Geochemistry of fallout tephra from ODP Hole 125-782A

Very rare, halogen-rich andesite melt inclusions (HRA) in bytownitic plagioclase phenocrysts (An89-90) from tephra fallout of the Izu arc volcanic front (Izu VF) provide new insights into the processes of fluid release from slab trenchward to the volcanic front in a cool subduction zone. These HRA are markedly enriched in Cl, F and Li - by factors of up to 8 (Cl, F) and 1.5 (Li) - but indistinguishable with respect to the fluid-mobile large-ion lithophile elements (LILE; K, Sr, Rb, Cs, Ba, Pb, U), rare earths (REE) or high field strength elements (HFSE) from the low-K tholeiitic magmas of the Izu VF. We suggest that the chemical signature of the HRA reflects the presence of a fluid in the mantle source that originated from the serpentinized mantle peridotite above the metacrust. This "wedge serpentinite" presumably formed by fluid infiltration beneath the forearc and was subsequently down-dragged with the slab to arc front depths. The combined evidence from the Izu VF (?110 km above slab) and the outer forearc serpentinite seamounts (~25 to 30 km above slab) suggests that the slab flux of B and Cl is highest beneath the forearc, and decreases with increasing slab depths. In contrast, the slab flux of Li is minor beneath the forearc, but increases with depth. Fluorine may behave similarly to Li, whereas the fluid-mobile LILE appear to be largely retained in the slab trenchward from the Izu VF. Consequently, the chemical signatures of both Izu trench sediments and basaltic rocks appear preserved until arc front depths.

Geochemistry and isotopic ratios of samples obtained during R/V Akademik Nikolaj Strakhov cruise ANS24

New petrological and geochemical data were obtained for basalts recovered during cruise 24 of the R/V "Akademik Nikolay Strakhov" in 2006. These results significantly contributed to the understanding of the formation of tholeiitic magmatism at the northern end of the Knipovich Ridge of the Polar Atlantic. Dredging was performed for the first time both in the rift valley and on the flanks of the ridge. It showed that the conditions of magmatism have not changed since at least 10 Ma. The basalts correspond to slightly enriched tholeiites, whose primary melts were derived at the shallowest levels and were enriched in Na and depleted in Fe (Na-TOR type). The most enriched basalts are typical of the earlier stages of the opening and were found on the flanks of the ridge in its northernmost part. Variations in the ratios of Sr, Nd, and Pb isotopes and lithophile elements allowed us to conclude that the primary melts generated beneath the spreading zone of the Knipovich Ridge were modified by the addition of the enriched component that was present both in the Neogene and Quaternary basalts of Spitsbergen Island. Compared with the primitive mantle, the extruding magmas were characterized by positive Nb and Zr anomalies and a negative Th anomaly. The formation of primary melts involved melting of the metasomatized depleted mantle reservoir that appeared during the early stages of opening of the Norwegian-Greenland Basin and transformation of the paleo-Spitsbergen Fault into the Knipovich spreading ridge, which was accompanied by magmatism in western Spitsbergen during its separation from the northern part of Greenland.

Isotopic ratios, concentration of noble gases and mineral and bulk composition of extraterrestrial dust particles in Dome Fuji ice core, East Antarctica

Two silicate-rich dust layers were found in the Dome Fuji ice core in East Antarctica, at Marine Isotope Stages 12 and 13. Morphologies, textures, and chemical compositions of constituent particles reveal that they are high-temperature melting products and are of extraterrestrial origin. Because similar layers were found ~2000 km east of Dome Fuji, at EPICA (European Project for Ice Coring in Antarctica)-Dome C, particles must have rained down over a wide area 434 and 481 ka. The strewn fields occurred over an area of at least 3 × 10**6 km**2. Chemical compositions of constituent phases and oxygen isotopic composition of olivines suggest that the upper dust layer was produced by a high-temperature interaction between silicate-rich melt and water vapor due to an impact explosion or an aerial burst of a chondritic meteoroid on the inland East Antarctic ice sheet. An estimated total mass of the impactor, on the basis of particle flux and distribution area, is at least 3 × 10**9 kg. A possible parent material of the lower dust layer is a fragment of friable primitive asteroid or comet. A hypervelocity impact of asteroidal/cometary material on the upper atmosphere and an explosion might have produced aggregates of sub-µm to µm-sized spherules. Total mass of the parent material of the lower layer must exceed 1 × 10**9 kg. The two extraterrestrial horizons, each a few millimeters in thickness, represent regional or global meteoritic events not identified previously in the Southern Hemisphere.