Geochemical investigations of volcanic ash layers from ODP Leg 119

Geochemical investigations were carried out on 19 discrete ash layers and on 42 dispersed ash accumulations in Oligocene to Pleistocene sediments from Sites 736, 737, 745, and 746 of ODP Leg 119 (Kerguelen Plateau in the southern Indian Ocean). The chemical data obtained from more than 500 single-grain glass analyses allow the characterization of two dominant petrographic rock series. The first consists of transitional- to alkali-basalts, the second mainly of trachytes with subordinated alkali-rhyolites and rhyolites. Chemical correlation with possible source areas indicates that the tephra layers from the northern Kerguelen Plateau Sites 736 and 737 were probably erupted from the nearby Kerguelen Islands. The investigated ash layers clearly reflect the Oligocene to recent changes in the composition of the volcanic material recorded from the Kerguelen Islands. The dispersed ashes from Sites 745 and 746 in the Australian-Antarctic Basin display almost the same range in chemical compositions as those from the north. Heard Island and other sources may have contributed to their formation, in addition to the Kerguelen Islands. Dispersed ash of calc-alkaline composition is most probably derived from the South Sandwich island arc, indicating sea-ice rafting as an important mechanism of transport.

Chemical composition of rocks and minerals from the Karymsky volcanic center, Eastern Kamchatka

The powerful eruption in the Akademii Nauk caldera on January 2, 1996 marked a new activity phase of the Karymsky volcano and became a noticeable event in the history of modern volcanism in Kamchatka. The paper reports data obtained by studying more than 200 glassy melt inclusions in phenocrysts of olivine (Fo82-72), plagioclase (An92-73), and clinopyroxene (Mg# 83-70) in basalts of the 1996 eruption. The data were used to estimate composition of the parental melt and physicochemical parameters of the magma evolution. According to our data, the parental melt corresponded to low magnesium, high aluminum basalt (SiO2 = 50.2%, MgO = 5.6%, Al2O3 = 17%) of the mildly potassium type (K2O = 0.56%) and contained much dissolved volatile components (H2O = 2.8%, S = 0.17%, and Cl = 0.11%). Melt inclusions in the minerals are similar in chemical composition, a fact testifying that the minerals crystallized simultaneously with one another. Their crystallization started at pressure ~1.5 kbar, proceeded within a narrow temperature range of 1040+/-20°C, and continued until near-surface pressure ~100 bar was reached. Degree of crystallization of the parental melt during its eruption was close to 55%. Massive crystallization was triggered by H2O degassing under pressure <1 kbar. Magma degassing in an open system resulted in escape of 82% H2O, 93% S, and 24% Cl (of their initial contents in the parental melt) to the fluid phase. Release of volatile compounds to the atmosphere during the eruption that lasted for 18 h was estimated as 1.7x10**6 t H2O, 1.4x10**5 t S, and 1.5x10**4 t Cl. Concentrations of most incompatible trace elements in the melt inclusions are close to those in the rocks and to the expected fractional differentiation trend. Melt inclusions in plagioclase were found to be selectively enriched in Li. The Li-enriched plagioclase with melt inclusions thought to originate from cumulate layers in the feeding system beneath Karymsky volcano, in which plagioclase interacted with Li-rich melts/brines and was subsequently entrapped and entrained by the magma during the 1996 eruption.

(Table 2) Oxygen, carbon, and strontium isotopic composition of carbonate-brucite material from the Lost City hydrothermal field

The isotopic (dD, d18O, d13C, and 87Sr/86Sr) and geochemical characteristics of hydrothermal solutions from the Mid-Atlantic Ridge and the material of brucite-carbonate chimneys at the Lost City hydrothermal field at 30°N, MAR, were examined to assay the role of the major factors controlling the genesis of the fluid and hydrothermal chimneys of the Lost City field. The values of dD and d18O in fluid samples indicates that solutions at the Lost City field were produced during the serpentinization of basement ultramafic rocks at temperatures higher than 200°C and at relatively low fluid/rock ratios (<1). The active role of serpentinization processes in the genesis of the Lost City fluid also follows from the results of the electron-microscopic studying of the material of hydrothermal chimneys at this field. The isotopic (d18O, d13C, and 87Sr/86Sr) and geochemical (Sr/Ca and REE) signatures indicate that, before its submarine discharging at the Lost City field, the fluid filtered through already cold altered outer zones of the Atlantis Massif and cooled via conductive heat loss. During this stage, the fluid could partly dissolve previously deposited carbonates in veins cutting serpentinite at the upper levels of the Atlantis Massif and the carbonate cement of sedimentary breccias underlying the hydrothermal chimneys. Because of this, the age of modern hydrothermal activity at the Lost City field can be much younger than 25 ka.

Rock magnetic properties and titanomagnetite oxydation state of ODP Hole 109-648B (Table 1)

The titanomagnetite oxidation state of "zero age" ocean floor basalts was investigated. For this purpose the oxidation parameter, z, of Hole 648B basalts was determined by SEM observation of "shrinkage cracks" in individual titanomagnetite grains and by Curie temperature measurements. A mean z-value of 0.1 has been deduced for the Hole 648B basalts. Assuming a linear relationship between titanomagnetite low-temperature oxidation state and age of the oceanic basalt, an age of 0.7 m.y. is deduced for Hole 648B.

Carbon pools and fluxes measured during a field campaign conducted in 2010 on the Tibetan Plateau at Kema

The Tibetan highlands host the largest alpine grassland ecosystems worldwide, bearing soils that store substantial stocks of carbon (C) that are very sensitive to land use changes. This study focuses on the cycling of photoassimilated C within a Kobresia pygmaea pasture, the dominating ecosystems on the Tibetan highlands. We investigated short-term effects of grazing cessation and the role of the characteristic Kobresia root turf on C fluxes and belowground C turnover. By combining eddy-covariance measurements with 13CO2 pulse labeling we applied a powerful new approach to measure absolute fluxes of assimilates within and between various pools of the plant-soil-atmosphere system. The roots and soil each store roughly 50% of the overall C in the system (76 Mg C/ha), with only a minor contribution from shoots, which is also expressed in the root:shoot ratio of 90. During June and July the pasture acted as a weak C sink with a strong uptake of approximately 2 g C/m**2/ in the first half of July. The root turf was the main compartment for the turnover of photoassimilates, with a subset of highly dynamic roots (mean residence time 20 days), and plays a key role for the C cycling and C storage in this ecosystem. The short-term grazing cessation only affected aboveground biomass but not ecosystem scale C exchange or assimilate allocation into roots and soil.

Recalculated petrographic parameters and normalized microprobe analyses of volcanic glasses for DSDP Sites 63-467, 63-468 and 63-469

The southward passage of the Rivera triple junction and its effect on the North American plate are primary controls on the Miocene tectonic evolution of the outer borderland of California. Detrital modes of sand shed off the Patton Ridge and cored by the Deep Sea Drilling Project provide evidence of progressive tectonic erosion of the Patton accretionary prism and neartrench volcanism. Volcanic glass in the sediment is predominantly calcalkaline rhyolite and andesite, typical of subductionrelated volcanism, but also includes minor low-K2O tholeiitic basalt. We attribute these compositional features to interaction with a spreading ridge associated with a possible trench-ridge-trench triple junction along the Patton Escarpment from 18 to 16 Ma. This study suggests that evidence of ridge-trench interaction may be commonly preserved along submerged plate margins, in contrast to its more limited recognition and discussion in the literature based on exposed examples in Chile, Japan and Alaska.

Chemical composition of volcanic glass of some tephra layers in Northeastern Pacific Ocean

Five widespread upper Cenozoic tephra layers that are found within continental sediments of the western United States have been correlated with tephra layers in marine sediments in the Humboldt and Ventura basins of coastal California by similarities in major-and trace-element abundances; four of these layers have also been identified in deep-ocean sediments at DSDP sites 34, 36, 173, and 470 in the northeastern Pacific Ocean. These layers, erupted from vents in the Yellowstone National Park area of Wyoming and Idaho (Y), the Cascade Range of the Pacific Northwest (C), and the Long Valley area, California (L), are the Huckleberry Ridge ash bed (2.0 Ma, Y), Rio Dell ash bed (ca. 1.5 Ma, C), Bishop ash bed (0.74 Ma, L), Lava Creek B ash bed (0.62 Ma, Y), and Loleta ash bed (ca. 0.4 Ma, C). The isochronous nature of these beds allows direct comparison of chronologic and climatic data in a variety of depositional environments. For example, the widespread Bishop ash bed is correlated from proximal localities near Bishop in east-central California, where it is interbedded with volcanic and glacial deposits, to lacustrine beds near Tecopa, southeastern California, to deformed on-shore marine strata near Ventura, southwestern California, to deep-ocean sediments at site 470 in the eastern Pacific Ocean west of northern Mexico. The correlations allow us to compare isotopic ages determined for the tephra layers with ages of continental and marine biostratigraphic zones determined by magnetostratigraphy and other numerical age control and also provide iterative checks for available age control. Relative age variations of as much as 0.5 m.y. exist between marine biostratigraphic datums [for example, highest occurrence level of Discoaster brouweri and Calcidiscus tropicus (= C. macintyrei)], as determined from sedimentation rate curves derived from other age control available at each of several sites. These discrepancies may be due to several factors, among which are (1) diachronism of the lowest and highest occurrence levels of marine faunal and floral species with latitude because of ecologic thresholds, (2) upward reworking of older forms in hemipelagic sections adjacent to the tectonically active coast of the western United States and other similar analytical problems in identification of biostratigraphic and magnetostratigraphic datums, (3) dissolution of microfossils or selective diagenesis of some taxa, (4) lack of precision in isotopic age calibration of these datums, (5) errors in isotopic ages of tephra beds, and (6) large variations in sedimentation rates or hiatuses in stratigraphic sections that result in age errors of interpolated datums. Correlation of tephra layers between on-land marine and deep-ocean deposits indicates that some biostratigraphic datums (diatom and calcareous nannofossil) may be truly time transgressive because at some sites, they are found above and, at other sites, below the same tephra layers.

Chemical and boron isotopic compositions of volcanics from ODP Sites 135-834 to 135-840

The influence of fluid flux on petrogenesis in the Tonga-Kermadec Arc was investigated using ion microprobe measurements of B/Be and boron isotope ratios (11B/10B) to document the source and relative volumes of the fluids released from the subducting oceanic plate. We analyzed young lavas from eight different islands along the Tonga-Kermadec Arc, as well as glass shards in volcanic sediments from Ocean Drilling Program (ODP) Site 840, which record the variations in the chemistry of Tonga magmatism since 7 Ma. B/Be is variable (5.8-122), in young Tonga-Kermadec Arc lavas. In contrast, glass shards from around 3 to 4 Ma old volcanic sediments at Site 840 have the highest B/Be values yet reported for arc lavas (18-607). These values are too high to be related simply to a sediment influence on petrogenesis. Together with very high d11B values (-11.6 to +37.5) for the same shards and lavas these data indicate that most of the B is derived from fluid escaped from the subducting altered Pacific oceanic crust, rather than from sediment. High d11B values also reflect large degrees of isotopic fractionation in this cold fast subduction zone. Lower d11B values noted in the Kermadec Arc (17 to -4.4) are related to the influence of sediment eroded from New Zealand and slower convergence. High fluid flux (B/Be) is synchronous in Tonga and the Marianas at 3 to 4 Ma and may be related to acceleration of the Pacific Plate just prior to this time. The timing of maximum B/Be at 3 to 4 Ma correlates with maximum light rare earth (LREE) and high field strength element depletion. This suggests maximum degrees of partial melting at this time. Although thinning of the arc lithosphere during rifting to form the Lau Basin is expected to influence the arc geochemistry, variable aqueous fluid flux from the subducting plate alone appears capable of explaining boron and other trace element systematics in the Tonga-Kermadec Arc with no indication of slab melting.

Geochemistry of Lesser Antilles forearc sediments

Oceanic sediments contain the products of erosion of continental crust, biologic activity and chemical precipitation. These processes create a large diversity of their chemical and isotopic compositions. Here we focus on the influence of the distance from a continental platform on the trace element and isotopic compositions of sediments deposited on the ocean floor and highlight the role of zircons in decoupling high-field strength elements and Hf isotopic compositions from other trace elements and Nd isotopic compositions. We report major and trace element concentrations as well as Sr and Hf isotopic data for 80 sediments from the Lesser Antilles forearc region. The trace-element characteristics and the Sr and Hf isotopic compositions are generally dominated by detrital material from the continental crust but are also variably influenced by chemical or biogenic carbonate and pure biogenic silica. Next to the South American continent, at DSDP Site 144 and on Barbados Island, sediments, coarse quartz arenites, exhibit marked Zr and Hf excesses that we attribute to the presence of zircon. In contrast, the sediments from DSDP Site 543, which were deposited farther away from the continental platform, consist of fine clay and they show strong deficiencies in Zr and Hf. The enrichment or depletion of Zr-Hf is coupled to large changes in Hf isotopic compositions (-30 < epsilon-Hf < +4) that vary independently from the Nd isotopes. We interpret this feature as a clear expression of the "zircon effect" suggested by Patchett and coauthors in 1984. Zircon-rich sediments deposited next to the South American continent have very low epsilon-Hf values inherited from old zircons. In contrast, in detrital clay-rich sediments deposited a few hundred kilometers farther north, the mineral fraction is devoid of zircon and they have drastically higher epsilon-Hf values inherited from finer, clay-rich continental material. In the two DSDP sites, average Hf isotopes are very unradiogenic relative to other oceanic sediments worldwide (epsilon-Hf = -14.4 and -7.4) and they define the low Hf end member of the sedimentary field in Hf-Nd space. Their compositions correspond to end members that, when mixed with mantle, are able to reproduce the pattern of volcanic rocks from the Lesser Antilles. More generally, we find a relationship between Nb/Zr ratios and the vertical deviation of Hf isotope ratios from the Nd-Hf terrestrial array and we suggest that this relationship can be used as a tool to distinguish sediment input from fractionation during melting during the formation of arc lavas.

Geochemistry of Central American Volcanic Arc basement samples

The Central American Volcanic Arc (CAVA) has been the subject of intensive research over the past few years, leading to a variety of distinct models for the origin of CAVA lavas with various source components. We present a new model for the NW Central American Volcanic Arc based on a comprehensive new geochemical data set (major and trace element and Sr-Nd-Pb-Hf-O isotope ratios) of mafic volcanic front (VF), behind the volcanic front (BVF) and back-arc (BA) lava and tephra samples from NW Nicaragua, Honduras, El Salvador and Guatemala. Additionally we present data on subducting Cocos Plate sediments (from DSDP Leg 67 Sites 495 and 499) and igneous oceanic crust (from DSDP Leg 67 Site 495), and Guatemalan (Chortis Block) granitic and metamorphic continental basement. We observe systematic variations in trace element and isotopic compositions both along and across the arc. The data require at least three different endmembers for the volcanism in NW Central America. (1) The NW Nicaragua VF lavas require an endmember with very high Ba/(La, Th) and U/Th, relatively radiogenic Sr, Nd and Hf but unradiogenic Pb and low d18O, reflecting a largely serpentinite-derived fluid/hydrous melt flux from the subducting slab into a depleted N-MORB type of mantle wedge. (2) The Guatemala VF and BVF mafic lavas require an enriched endmember with low Ba/(La, Th), U/Th, high d18O and radiogenic Sr and Pb but unradiogenic Nd and Hf isotope ratios. Correlations of Hf with both Nd and Pb isotopic compositions are not consistent with this endmember being subducted sediments. Granitic samples from the Chiquimula Plutonic Complex in Guatemala have the appropriate isotopic composition to serve as this endmember, but the large amounts of assimilation required to explain the isotope data are not consistent with the basaltic compositions of the volcanic rocks. In addition, mixing regressions on Nd vs. Hf and the Sr and O isotope plots do not go through the data. Therefore, we propose that this endmember could represent pyroxenites in the lithosphere (mantle and possibly lower crust), derived from parental magmas for the plutonic rocks. (3) The Honduras and Caribbean BA lavas define an isotopically depleted endmember (with unradiogenic Sr but radiogenic Nd, Hf and Pb isotope ratios), having OIB-like major and trace element compositions (e.g. low Ba/(La, Th) and U/Th, high La/Yb). This endmember is possibly derived from melting of young, recycled oceanic crust in the asthenosphere upwelling in the back-arc. Mixing between these three endmember types of magmas can explain the observed systematic geochemical variations along and across the NW Central American Arc.

Elements and mineralogical compostions from different sediment cores off the southern China Sea

The mineralogy, major and trace elements, and neodymium and strontium isotopes of surface sediments in the South China Sea (SCS) are documented with the aim of investigating their applicability in provenance tracing. The results indicate that mineralogical compositions alone do not clearly identify the sources for the bulk sediments in the SCS. The Nd isotopic compositions of the SCS sediments show a clear zonal distribution. The most negative epsilon-Neodymium values were obtained for sediments from offshore South China (-13.0 to -10.7), while those from offshore Indochina are slightly more positive (-10.7 to -9.4). The Nd isotopic compositions of the sediments from offshore Borneo are even higher, with epsilon-Neodymium ranging from -8.8 to -7.0, and the sediments offshore from the southern Philippine Arc have the most positive epsilon-Neodymium values, from -3.7 to +5.3. This zonal distribution in epsilon-Neodymium is in good agreement with the Nd isotopic compositions of the sediments supplied by river systems that drain into the corresponding regions, indicating that Nd isotopic compositions are an adequate proxy for provenance tracing of SCS sediments. Sr isotopic compositions, in contrast, can only be used to identify the sediments from offshore South China and offshore from the southern Philippine Arc, as the 87Sr/86Sr ratios of sediments from other regions overlapped. Similar zonal distributions are also apparent in a La-Th-Sc discrimination diagram. Sediments fromthewestmargin of the SCS, such as those fromBeibuwan Bay, offshore fromHainan Island, offshore from Indochina, and from the Sunda Shelf plot in the same field, while those offshore from the northeastern SCS, offshore from Borneo, and offshore from the southern Philippine Arc plot in distinct fields. Thus, the La-Th-Sc discrimination diagram, coupledwith Nd isotopes, can be used to trace the provenance of SCS sediments. Using this method, we re-assessed the provenance changes of sediments at Ocean Drilling Program (ODP) Site 1148 since the late Oligocene. The results indicate that sediments deposited after 23.8 Ma (above 455 mcd: meters composite depth) were supplied mainly from the eastern South China Block, with a negligible contribution from the interior of the South China Block. Sediments deposited before 26 Ma (beneath 477 mcd) were supplied mainly from the North Palawan Continental Terrane, which may retain the geochemical characteristics of the materials covered on the late Mesozoic granitoids along the coastal South China. For that the North Palawan Continental Terrane is presently located within the southern Philippine Arc but was located close to ODP Site 1148 in the late Oligocene. The weathering products of volcanic material associated with the extension of the SCS ocean crust also contributed to these sediments. The rapid change in sediment source at 26-23.8 Ma probably resulted from a sudden cessation of sediment supply from the North Palawan Continental Terrane. Wesuggest that the North Palawan Continental Terrane drifted southwards alongwith the extension of the SCS ocean crust during that time, and when the basin was large enough, the supply of sediment from the south to ODP Site 1148 at the north slope may have ceased.