Volcanic rocks from the submarine Vityaz Ridge: their age, chemical and isotopic compositions

Results of geological studies at the submarine Vityaz Ridge carried out during cruises 37 and 41 of R/V Akademik Lavrent'ev in 2005 and 2006 are reported. The studied area is located at an near-island trench of the slope in the central part of the Kuril Island arc. Morphologically it consists of two parts: an inner volcanic arc represented by the Great Kuril Range and an outer arc corresponding to the submarine Vityaz Ridge. Diverse rocks composing the basement and the sedimentary cover of the ridge were recovered by dredging. Based on K-Ar dating and geochemistry, volcanics were divided into Paleocene, Eocene, late Oligocene, and Pliocene-Pleistocene complexes. Each of the complexes reflects a tectonomagmatic stage in the ridge evolution. Geochemical and isotope data on the volcanics indicate contribution of ancient crustal material in the magma source and, correspondingly, formation of this structure on the continental basement. Two-stage model ages (TDM2) vary in a wide range from zero values in mafic rocks to 0.77 Ga in felsic varieties, pointing to presence of Precambrian protolith in the source of the felsic rocks of the Vityaz Ridge. The Pliocene-Pleistocene volcanics are classed with tholeiitic, calc-alkaline, and subalkaline series, which differ in alkali contents and REE fractionation. Values of (La/Sm)_n and (La/Yb)_n ratios vary from 0.74 and 0.84 in the tholeiitic varieties to 1.19 and 1.44 in the calc-alkaline and 2.32 and 3.73 in the subalkaline rocks. All three varieties occur within the same volcanic edifices and formed during differentiation of magmatic melts that were channeled along fault zones from the mantle source slightly enriched in crustal component.

Strontium isotope dating of ODP Leg 133 sediments

The strontium-isotope dating method, based on the strontium-isotope seawater curve, was used to date stratigraphic events recognized in carbonate sediments drilled during Leg 133 on the Queensland and Marion plateaus. The strontium isotope ages of these events are used to correlate paleoceanographic changes, delineated from oxygen isotope signals, and paleoenvironmental or facies changes recorded in the lithostratigraphy. Results indicate that a strong connection exists between prevailing paleoenvironmental conditions and the developmental style of a carbonate platform. Also, the strontium-isotope ages of discrete dolomite intervals within the sequences were determined, indicating that multiple dolomitization events took place and that a hydrodynamically driven process may be currently active within the modern carbonate platform.

Geochemistry of eolian dust from sediment core LL44-GPC-3

The large-diameter piston core LL44-GPC3 from the central North Pacific Ocean records continuous sedimentation of eolian dust since the Late Cretaceous. Two intervals resolved by Nd and Pb isotopic data relate to dust coming from America (prior to ~40 Ma) and dust coming from Asia (since ~40 Ma). The Intertropical Convergence Zone (ITCZ) separates these depositional regimes today and may have been at a paleolatitude of ~23°N prior to 40 Ma. Such a northerly location of the ITCZ is consistent with sluggish atmospheric circulation and warm climate for the Northern Hemisphere of the early to middle Eocene. Since ~40 Ma, correlations between Nd (~7.55 > epsilon-Nd(t) > ~10.81) and Pb (18.625 < 206/4Pb < 18.879; 15.624 < 207/4Pb < 15.666; 38.611 < 208/4Pb < 38.960; 0.8294 < 207/6Pb < 0.8389; 2.0539 < 208/6Pb < 2.0743) isotopes reflect the progressive drying of central Asia triggered by the westward retreat of the paleo-Tethys. Comparisons between the changes with time in the isotopically well-defined dust flux and Nd and Pb isotopic compositions of Pacific deep water allow one to draw two major conclusions: (1) dust-bound Nd became a resolvable contribution to Pacific seawater only after the one order of magnitude increase in dust flux starting at ~3.5 Ma. Therefore eolian Nd was unimportant for Pacific seawater Nd prior to 3.5 Ma. (2) The lack of a response of Pacific deep water Pb to this huge flux increase suggests that dust-bound Pb has never been important. Instead, mobile Pb associated with island arc volcanic exhalatives probably consists of a significant contribution to Pacific deep water Pb and possibly to seawater elsewhere far away from landmasses.

Boron isotope ratios of samples from ODP Leg 125 sites at a serpentine seamount, Mariana forearc

Serpentinite clasts and muds erupted from Conical Seamount, Mariana forearc, show substantial enrichment in boron (B) and 11B (delta11B up to +15?) relative to mantle values. These elevated B isotope signatures result from chemical exchange with B-rich pore fluids that are upwelling through the seamount. If the trends of decreasing delta11B with slab depth shown by cross-arc magmatic suites in the Izu and Kurile arcs of the western Pacific are extended to shallow depths (~25 km), they intersect the inferred delta11B of the slab-derived fluids (+13x) at Conical Seamount. Simple mixtures of a B-rich fluid with a high delta11B and B-poor mantle with a low delta11B are insufficient to explain the combined forearc and arc data sets. The B isotope systematics of subduction-related rocks thus indicate that the fluids evolved from downgoing slabs are more enriched in 11B than the slab materials from which they originate. Progressively lower delta11B in arc lavas erupted above deep slabs reflects both the progressive depletion of 11B from the slab and progressively greater inputs of mantle-derived B. This suggests that the slab releases 11B-enriched fluids from the shallowest levels to depths greater than 200 km.

Ar and U-Th-Pb age determinations for minerals from ODP Holes of ODP Legs 173 and 210

We report U-Pb and 39Ar-40Ar measurements on plutonic rocks recovered from the Ocean Drilling Program (ODP) Legs 173 and 210. Drilling revealed continental crust (Sites 1067 and 1069) and exhumed mantle (Sites 1070 and 1068) along the Iberia margin and exhumed mantle (Site 1277) on the conjugate Newfoundland margin. Our data record a complex igneous and thermal history related to the transition from rifting to seafloor spreading. The results show that the rift-to-drift transition is marked by a stuttering start of MORB-type magmatic activity. Subsequent to initial alkaline magmatism, localized mid-oceanic ridge basalts (MORB) magmatism was again replaced by basin-wide alkaline events, caused by a low degree of decompression melting due to tectonic delocalization of deformation. Such "off-axis" magmatism might be a common process in (ultra-) slow oceanic spreading systems, where "magmatic" and "tectonic" spreading varies in both space and time.

Geochemistry of Atlantis Massif serpentinites

The Lost City hydrothermal system at the southern Atlantis Massif (Mid-Atlantic Ridge, 30°N) provides a natural laboratory for studying serpentinization processes, the temporal evolution of ultramafic-hosted hydrothermal systems, and alteration conditions during formation and emplacement of an oceanic core complex. Here we present B, O, and Sr isotope data to investigate fluid/rock interaction and mass transfer during detachment faulting and exhumation of lithospheric sequences within the Atlantis Massif. Our data indicate that extensive serpentinization was a seawater-dominated process that occurred predominately at temperatures of 150-250 °C and at high integrated W/R ratios that led to a marked boron enrichment (34-91 ppm). Boron removal from seawater during serpentinization is positively correlated with changes in d11B (11-16 per mil) but shows no correlation with O-isotope composition. Modeling indicates that B concentrations and isotope values of the serpentinites are controlled by transient temperature-pH conditions. In contrast to prior studies, we conclude that low-temperature marine weathering processes are insignificant for boron geochemistry of the Atlantis Massif serpentinites. Talc- and amphibole-rich fault rocks formed within a zone of detachment faulting at temperatures of approximately 270-350 °C and at low W/R ratios. Talc formation in ultramafic domains in the massif was subsequent to an early stage of serpentinization and was controlled by the access of Si-rich fluids derived through seawater-gabbro interactions. Replacement of serpentine by talc resulted in boron loss and significant lowering of d11B values (9-10 per mil), which we model as the product of progressive extraction of boron. Our study provides new constraints on the boron geochemical cycle at oceanic spreading ridges and suggests that serpentinization associated with ultramafic-hosted hydrothermal systems may have important implications for the behavior of boron in subduction zone settings.

Chemical and isotope composition of poor fluid from gas-hydrate samples of ODP Site 146-892

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2-19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ~17 mbsf. Gas from a sample of this layer was composed of both CH4 and H2S. This sample is the first mixed-gas hydrate of CH4-H2S documented in ODP; it also contains ethane and minor amounts of CO2. Measured temperatures of the recovered core ranged from 2 to -1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH4-H2S hydrate during recovery without a pressure core sampler. During this dissociation, toxic levels of H2S (delta34S, +27.4?) were released. The delta13C values of the CH4 in the gas hydrate, -64.5 to -67.5? (PDB), together with deltaD values of -197 to -199? (SMOW) indicate a primarily microbial source for the CH4. The delta18O value of the hydrate H2O is +2.9? (SMOW), comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH4-H2S) and depth distribution (2-19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH4-H2S hydrate is primarily confined to the present day active sulfate reduction zone (2-19 mbsf), and that from here down to the BSR depth (19-68 mbsf) the gas hydrate inferred to exist is a >=99% CH4 hydrate, suggest that the mixing of CH4 and H2S is a geologically young process. Because the existence of a mixed CH4-H2S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.

Chemical and isotopic compositions of Archean magmatic and metasedimentary rocks and minerals from the Podolia domain, Ukrainian Shield

Zircons from the oldest magmatic and metasedimentary rocks in the Podolia domain of the Ukrainian shield were studied and dated by the U-Pb method on a NORDSIM secondary-ion mass spectrometer. Age of zircon cores in enderbite gneisses sampled in the Kazachii Yar and Odessa quarries on the opposite banks of the Yuzhnyi Bug River reaches 3790 Ma. Cores of terrigenous zircons in quartzites from the Odessa quarry as well as in garnet gneisses from the Zaval'e graphite quarry have age within 3650-3750 Ma. Zircon rims record two metamorphic events around 2750-2850 Ma and 1900-2000 Ma. Extremely low U content in zircons of the second age group indicates conditions of the granulite facies metamorphism in Paleoproterozoic within the Podolia domain. Measured data on orthorocks (enderbite-gneiss) and metasedimentary rocks unambiguously suggest existence of the ancient Paleoarchean crust in the Podolia (Dniester-Bug) domain of the Ukrainian shield. They contribute in our knowledge of scales of formation and geochemical features of the primordial crust.