Composition of matrix glasses and melt inclusions of fallout tephra from ODP Hole 125-782A

We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ~400-4000 ppm and F ~70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (~6600-8600 ppm) and F (~780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ~2 to ~10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (~3 to ~11 kbar, ~820° to ~1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94+/-0.25 wt%, F = 990+/-270 ppm and H2O = 25+/-7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (~77-129%). Conversely, H2O (~13-22% recycled at arc) and F (~4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (~37000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ~2.9-3.8 mln ton/yr and H2O ~70-100 mln ton/yr, respectively - comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ~0.3-0.4 mln ton/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (~9.5), slab melting will still produce components with low Cl/F ratios (~0.9), similar to those characteristic of the upper continental crust (Cl/F ~0.3-0.9).

Geochemistry of Lesser Antilles lavas

We present new U-series disequilibrium and radiogenic isotope data for 7 mafic lavas from the Lesser Antilles arc. These are combined with published data in an internally consistent model that quantitatively estimates the amount of sediment and fluid added to the source of the Lesser Antilles arc system. Some lavas form an array consistent with bulk sediment addition (0.2-2%) whereas others appear to require addition of 0.4-2% sediment melt, particularly in the south of the arc. Evidence for both bulk sediment and sediment melt addition can be found within both the northern and central sections of the arc suggesting a thermal structure whereby the upper portions of the subducted sediment pile lie close to their solidus beneath much of the arc. Addition of up to 5% fluid derived from altered oceanic crust to these sediment enriched mantle wedge source regions can simulate the majority of the lavas on a plot of 207Pb/204Pb versus Ce/Pb. By taking into account the range in calculated wedge compositions and allowing for some mobility of Th in the fluid, the same model can also account for much of the observed range of U-Th-Ra disequilibria, especially if the eclogitic residue contains trace amounts of rutile. The implication of this more complex model is that the time scales for fluid addition and differentiation could be significantly shorter than those estimated in some previous studies.

U-series ages from calcitic cold-water corals from the Amundsen Sea

Radiocarbon and uranium-thorium dating results are presented from a genus of calcitic Antarctic cold-water octocorals (family Coralliidae), which were collected from the Marie Byrd Seamounts in the Amundsen Sea (Pacific sector of the Southern Ocean) and which to date have not been investigated geochemically. The geochronological results are set in context with solution and laser ablation-based element/Ca ratios (Li, B, Mg, Mn, Sr, Ba, U, Th). Octocoral radiocarbon ages on living corals are in excellent agreement with modern ambient deep-water D14C, while multiple samples of individual fossil coral specimens yielded reproducible radiocarbon ages. Provided that local radiocarbon reservoir ages can be derived for a given time, fossil Amundsen Sea octocorals should be reliably dateable by means of radiocarbon. In contrast to the encouraging radiocarbon findings, the uranium-series data are more difficult to interpret. The uranium concentration of these calcitic octocorals is an order of magnitude lower than in the aragonitic hexacorals that are conventionally used for geochronological investigations. While modern and Late Holocene octocorals yield initial d234U in good agreement with modern seawater, our results reveal preferential inward diffusion of dissolved alpha-recoiled 234U and its impact on fossil coral d234U. Besides alpha-recoil related 234U diffusion, high-resolution sampling of two fossil octocorals further demonstrates that diagenetic uranium mobility has offset apparent coral U-series ages. Combined with the preferential alpha-recoil 234U diffusion, this process has prevented fossil octocorals from preserving a closed system U-series calendar age for longer than a few thousand years. Moreover, several corals investigated contain significant initial thorium, which cannot be adequately corrected for because of an apparently variable initial 232Th/230Th. Our results demonstrate that calcitic cold-water corals are unsuitable for reliable U-series dating. Mg/Ca ratios within single octocoral specimens are internally strikingly homogeneous, and appear promising in terms of their response to ambient temperature. Magnesium/lithium ratios are significantly higher than usually observed in other deep marine calcifiers and for many of our studied corals are remarkably close to seawater compositions. Although this family of octocorals is unsuitable for glacial deep-water D14C reconstructions, our findings highlight some important differences between hexacoral (aragonitic) and octocoral (calcitic) biomineralisation. Calcitic octocorals could still be useful for trace element and some isotopic studies, such as reconstruction of ambient deep water neodymium isotope composition or pH, via boron isotopic measurements.

Geochemistry of ODP Hole 121-752A

The present study involves the analysis and interpretation of geochemical data from a suite of sediment samples recovered at ODP Hole 752A. The samples encompass the time period that includes the lithospheric extension and uplift of Broken Ridge, and they record deposition below and above the mid-Eocene angular unconformity that denotes this uplift. A Q-mode factor analysis of the geochemical data indicates that the sediments in this section are composed of a mixture of three geochemical end members that collectively account for 94.2% of the total variance in the data. An examination of interelement ratios for each of these end members suggests that they represent the following sedimentary components: (1) a biogenic component, (2) a volcanogenic component, and (3) a hydrothermal component. The flux of the biogenic component decreases almost thirtyfold across the Eocene unconformity. This drastic reduction in the deposition of biogenic materials corresponds to the almost complete disappearance of chert layers, diatoms, and siliceous microfossils and is coincident with the uplift of Broken Ridge. The volcanogenic component is similar in composition to Santonian ash recovered at Hole 755A on Broken Ridge and is the apparent source of the Fe-stained sediment that immediately overlies the angular unconformity. This finding suggests that significant amounts of Santonian ash were subaerially exposed, weathered, and redeposited and is consistent with data that suggest that the vertical uplift of Broken Ridge was both rapid and extensive. The greatest flux of hydrothermal materials is recorded in the sediments immediately below the angular unconformity. This implies that the uplift of Broken Ridge was preceded by a significant amount of rifting, during which faulting and fracturing of the lithosphere led to enhanced hydrothermal circulation. This time sequence of events is consistent with (but not necessarily diagnostic of) the passive model of lithospheric extension and uplift.

Element and isotope compostion of basalts and sediments from the Japan Sea

Ocean Drilling Program Legs 127 and 128 in the Yamato Basin of the Japan Sea, a Miocene-age back-arc basin in the western Pacific Ocean, recovered incompatible-element-depleted and enriched tholeiitic dolerites and basalts from the basin floor, which provide evidence of a significant sedimentary component in their mantle source. Isotopically, the volcanic rocks cover a wide range of compositions (e.g., 87Sr/86Sr = 0.70369 - 0.70503, 206Pb/204Pb = 17.65 - 18.36) and define a mixing trend between a depleted mantle (DM) component and an enriched component with the composition of EM II. At Site 797, the combined isotope and trace element systematics support a model of two component mixing between depleted, MORB-like mantle and Pacific pelagic sediments. A best estimate of the composition of the sedimentary component has been determined by analyzing samples of differing lithology from DSDP Sites 579 and 581 in the western Pacific, east of the Japan arc. The sediments have large depletions in the high field strength elements and are relatively enriched in the large-ion-lithophile elements, including Pb. These characteristics are mirrored, with reduced amplitudes, in Japan Sea enriched tholeiites and northeast Japan arc lavas, which strengthens the link between source enrichment and subducted sediments. However, Site 579/581 sediments have higher LILE/REE and lower HFSE/REE than the enriched component inferred fiom mixing trends at Site 797. Sub-arc devolatilization of the sediments is a process that will lower LILE/REE and raise HFSE/REE in the residual sediment, and thus this residual sediment may serve as the enriched component in the back-arc basalt source. Samples from other potential sources of an enriched, EM II-like component beneath Japan, such as the subcontinental lithosphere or crust, have isotopic compositions which overlap those of the Japan Sea tholeiites and are not "enriched" enough to be the EM II end-member.

Lavas from the Elbrus volcano, Greater Caucasus

Comprehensive geochronological and isotope-geochemical studies showed that the Late Quaternary Elbrus Volcano (Greater Caucasus) experienced long (approximately 200 ka) discrete evolution with protracted periods of igneous quiescence (approximately 50 ka) between large-scale eruptions. Volcanic activity of Elbrus is subdivided into three phases: Middle Neopleistocene (225-170 ka), Late Neopleistocene (110-70 ka), and Late Neopleistocene - Holocene (earlier than 35 ka). Petrogeochemical and isotope (Sr-Nd-Pb) signatures of Elbrus lavas point to their mantle-crustal origin. It was shown that hybrid parental magmas of the volcano formed due to mixing and/or contamination of deep-seated mantle melts by Paleozoic upper crustal material of the Greater Caucasus. Mantle reservoir that participated in genesis of Elbrus lavas as well as most other Neogene-Quaternary magmatic rocks of Caucasus was represented by the lower mantle "Caucasus" source. Primary melts generated by this source in composition corresponded to K-Na subalkali basalts with the following isotopic characteristics: 87Sr/86Sr = 0.7041+/-0.0001, e-Nd = +4.1+/-0.2, 147Sm/144Nd = 0.105-0.114, 206Pb/204Pb = 18.72, 207Pb/204Pb = 15.62, and 208Pb/204Pb = 38.78. Temporal evolution of isotope characteristics for lavas of the Elbrus Volcano is well described by a Sr-Nd mixing hyperbole between "Caucasus" source and estimated average composition of the Paleozoic upper crust of the Greater Caucasus. It was shown that, with time, proportions of mantle material in parental magmas of Elbrus gently increased: from ~60% at the Middle-Neopleistocene phase of activity to ~80% at the Late Neopleistocene - Holocene phase, which indicates an increase of activity of a deep-seated source at decreasing input of crustal melts or contamination with time. Unraveled evolution of the volcano with discrete eruption events, lacking signs of cessation of the Late Neopleistocene - Holocene phase, increasing contribution of the deep-seated mantle source in genesis of Elbrus lavas with time as deduced from isotope-geochemical data, as well as numerous geophysical and geological evidence indicate that Elbrus is a potentially active volcano and its eruptions may be resumed. Possible scenarios were proposed for evolution of the volcano, if its eruptive activity continued.

Mineral content, major oxides and trace elements concentrations in clay from different IODP Holes of 331-C0013, 331-C0017, East China sea shelf and different Taiwan rivers

The Okinawa Trough (OT) in the East Asian continental margin is characterized by thick terrigenous sediment and ubiquitous volcanic-hydrothermal activities. In this study, the clays collected during IODP Expedition 331 to the middle OT (Iheya North Knoll) were analyzed for mineralogical and geochemical compositions. By comparing with the clays from the East China Sea shelf and surrounding rivers, we examine different clay origins. The hydrothermal field in the mid-OT is dominated by Mg-rich chlorite, while the recharge zone has clay mineral assemblages similar to the shelf and rivers, showing high content of illite, subordinate chlorite and kaolinite and scarce smectite. Compared to the terrigenous clays, the hydrothermal clays in the OT have high concentrations of Mg, Mn and Zr but low Fe, Na, K, Ca, Ba, Sr, P, Sc and Ti, while the hydrothermal clays in the mid-ocean ridge are relatively enriched in Fe and V and depleted in Al, Mg, Zr, Sc and Ti. Different fractionation patterns of rare earth elements also register in the terrigenous and hydrothermal clays, diagnostic of variable clay origins. We infer that the OT hydrothermal clay was primarily formed by the chemical alteration of detrital sediments subject to the hydrothermal fluids. The remarkably different compositions of hydrothermal clays between the sediment-rich back arc basin like OT and the sediment-starved ocean ridge suggest different physical and chemical processes of hydrothermal fluids and fluid-rock/sediment reactions under various geologic settings.

Nd isotope composition of fossil fish teeth of ODP Hole 119-738B

We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ~0.23 epsilon-Nd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ~40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 epsilon-Nd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10X increase in sample throughput.