Isotopic and chemical compositions of DSDP site 18-174 sediments

The Astoria submarine fan, located off the coast of Washington and Oregon, has grown throughout the Pleistocene from continental input delivered by the Columbia River drainage system. Enormous floods from the sudden release of glacial lake water occurred periodically during the Pleistocene, carrying vast amounts of sediment to the Pacific Ocean. DSDP site 174, located on the southern distal edge of the Astoria Fan, is composed of 879 m of terrigenous sediments. The section is divided into two major units separated by a distinct seismic discontinuity: an upper, turbidite fan unit (Unit I), and an underlying finer-grained unit (Unit II). Both units have overlapping ranges of Nd and Hf isotope compositions, with the majority of samples having e-Nd values of -7.1 to -15.2 and eHf values -6.2 to -20.0; the most notable exception is the uppermost sample in the section, which is identical to modern Columbia River sediment. Nd depleted mantle model ages for the site range from 2.0 to 1.2 Ga and are consistent with derivation from cratonic Proterozoic source regions, rather than Cenozoic and Mesozoic terranes proximal to the Washington-Oregon coast. The Astoria Fan sediments have significantly less radiogenic Nd (and Hf) isotopic compositions than present day Columbia River sediment (e-Nd=-3 to -4; [Goldstein, S.J., Jacobsen, S.B., 1987. Nd and Sr isotopic systematics of river water suspended material: implications for crustal evolution. Earth. Planet. Sci. Lett. 87, 249-265; doi:10.1016/0012-821X(88)90013-1]), and suggest that outburst flooding, tapping Proterozoic source regions, was the dominant sediment transport mechanism in the genesis and construction of the Astoria Fan. Pb isotopes form a highly linear 207Pb/204Pb - 206Pb/204Pb array, and indicate the sediments are a binary mixture of two disparate sources with isotopic compositions similar to Proterozoic Belt Supergroup metasediments and Columbia River Basalts. The combined major, trace and isotopic data argue that outburst flooding was responsible for depositing the majority (top 630 m) of the sediment in the Astoria Fan.

Age and isotopic and chemical compositions of volcanic rocks from the Japan and Okhotsk Seas

This paper reports results of petrographic and geochemical studies of Miocene-Pleistocene volcanic rocks that accompanied formation of deep-water basins of the Sea of Japan and Sea of Okhotsk. Geochemical types of these rocks, their geodynamic settings, and their derivation from different magmatic sources were determined. Marginal-sea basaltoids from the Sea of Japan are derivatives of fluid-enriched mantle (EMI), while volcanics from the Kuril basin were generated from mantle enriched in continental crust matter (EMU). In spite of different conditions of their genesis, they have some common geochemical features, in particular, their calc-alkaline signatures. These traces of influence of the sialic crust on magma generation confirm development of the basins of both these seas on the continental basement.

Radioisotopes and He accumulation in deep sea sediments of the Ontong Java Plateau

The accumulation of extraterrestrial 3He, a tracer for interplanetary dust particles (IDPs), in sediments from the Ontong Java Plateau (OJP; western equatorial Pacific Ocean) has been shown previously to exhibit a regular cyclicity during the late Pleistocene, with a period of ~100 ka. Those results have been interpreted to reflect periodic variability in the global accretion of IDPs that, in turn, has been linked to changes in the inclination of Earth's orbit with respect to the invariable plane of the solar system. Here we show that the accumulation in OJP sediments of authigenic 230Th, produced by radioactive decay of 234U in seawater, exhibits a 100-ka cyclicity similar in phase and amplitude to that evident in the 3He record. We interpret the similar patterns of 230Th and 3He accumulation to reflect a common origin within the ocean-climate system. Comparing spatial and temporal patterns of sediment accumulation against regional patterns of biological productivity and against the well-established pattern of CaCO3 dissolution in the deep Pacific Ocean leads to the further conclusion that a common 100-ka cycle in accumulation of biogenic, authigenic and extraterrestrial constituents in OJP sediments reflects the influence of climate-related changes in sediment focusing, rather than changes in the rate of production or supply of sedimentary constituents.

The magnesium isotope composition of diagenetic dolomites from ODP Hole 112-685A and 201-1230A of the Peru Margin

The magnesium isotope composition of diagenetic dolomites and their adjacent pore fluids were studied in a 250 m thick sedimentary section drilled into the Peru Margin during Ocean Drilling Program (ODP) Leg 201 (Site 1230) and Leg 112 (Site 685). Previous studies revealed the presence of two types of dolomite: type I dolomite forms at ~ 6 m below seafloor (mbsf) due to an increase in alkalinity associated with anaerobic methane oxidation, and type II dolomite forms at focused sites below ~ 230 mbsf due to episodic inflow of deep-sourced fluids into an intense methanogenesis zone. The pore fluid delta 26Mg composition becomes progressively enriched in 26Mg with depth from values similar to seawater (i.e. -0.8 per mil, relative to DSM3 Mg reference material) in the top few meters below seafloor (mbsf) to 0.8 ± 0.2 per mil within the sediments located below 100 mbsf. Type I dolomites have a delta 26Mg of -3.5 per mil, and exhibit apparent dolomite-pore fluid fractionation factors of about -2.6 per mil consistent with previous studies of dolomite precipitation from seawater. In contrast, type II dolomites have delta 26Mg values ranging from -2.5 to -3.0 per mil and are up to -3.6 per mil lighter than the modern pore fluid Mg isotope composition. The enrichment of pore fluids in 26Mg and depletion in total Mg concentration below ~ 200 mbsf is likely the result of Mg isotope fractionation during dolomite formation, The 26Mg enrichment of pore fluids in the upper ~ 200 mbsf of the sediment sequence can be attributed to desorption of Mg from clay mineral surfaces. The obtained results indicate that Mg isotopes recorded in the diagenetic carbonate record can distinguish near surface versus deep formed dolomite demonstrating their usefulness as a paleo-diagenetic proxy.

Neodymium isotope composition of planktonic foraminifera from ODP Hole 121-758A

This study presents neodymium isotope and elemental data for cleaned planktonic foraminifera from ODP site 758 in the southernmost reaches of the Bay of Bengal in the north-east Indian Ocean. Cleaning experiments using oxidative-reductive techniques suggest that diagenetic Fe-Mn oxyhydroxide coatings can be effectively removed, and that the measured Nd isotope composition reflects the composition of seawater from which the foraminiferal calcium carbonate was precipitated. Modern core-top Pulleniatina obliquiloculata and Globorotalia menardii give epsilon-Nd values of 310.12 +/- 0.16 and 310.28 +/- 0.16, respectively, indistinguishable from recent direct measurements of surface seawater in this area. A high-resolution Nd isotope record obtained from G. menardii for the past 150 kyr shows systematic variations (Delta epsilon-Nd = 3) on glacial-interglacial timescales. The timing of those variations shows a remarkable correspondence with the global oxygen isotope record, which suggests a process controlling the Nd isotope composition that responds in phase with global climate cycles. Palaeoclimate reconstruction indicates that during the last glacial maximum changes in monsoon circulation resulted in a reduction in rainfall over the Indian subcontinent, and a decrease in the flux of river water delivered to the Bay of Bengal. Thus, changes in the riverine input of Nd, a change in either flux or composition, most likely caused the isotope variations, although changes in dust source or local ocean circulation may have also played a role. These results clearly establish a link between climate change and variations in radiogenic isotopes in the oceans, and illustrate the potential of Nd isotopes in foraminifera for highresolution palaeoceanographic reconstruction.

Chemical and germanium isotopic compositions of sediments and sedimentary rocks from ODP Sites 129-801 and 185-1149

A new technique for the precise and accurate determination of Ge stable isotope compositions has been developed and applied to silicate rocks and biogenic opal. The analyses were performed using a continuous flow hydride generation system coupled to a MC-ICP-MS. Samples have been purified through anion- and cation-exchange resins to separate Ge from matrix elements and eliminate potential isobaric interferences. Variations of 74Ge/70Ge ratios are expressed as d74Ge values relative to our internal standard and the long-term external reproducibility of the data is better than 0.2? for sample size as low as 15 ng of Ge. Data are presented for igneous and sedimentary rocks, and the overall variation is 2.4? in d74Ge, representing 12 times the uncertainty of the measurements and demonstrating that the terrestrial isotopic composition of Ge is not unique. Co-variations of 74Ge/70Ge, 73Ge/70Ge and 72Ge/70Ge ratios follow a mass-dependent behaviour and imply natural isotopic fractionation of Ge by physicochemical processes. The range of d74Ge in igneous rocks is only 0.25? without systematic differences among continental crust, oceanic crust or mantle material. On this basis, a Bulk Silicate Earth reservoir with a d74Ge of 1.3+/-0.2? can be defined. In contrast, modern biogenic opal such as marine sponges and authigenic glauconite displayed higher d74Ge values between 2.0? and 3.0?. This suggests that biogenic opal may be significantly enriched in light isotopes with respect to seawater and places a lower bound on the d74Ge of the seawater to +3.0?.This suggests that seawater is isotopically heavy relative to Bulk Silicate Earth and that biogenic opal may be significantly fractionated with respect to seawater. Deep-sea sediments are within the range of the Bulk Silicate Earth while Mesozoic deep-sea cherts (opal and quartz) have d74Ge values ranging from 0.7? to 2.0?. The variable values of the cherts cannot be explained by binary mixing between a biogenic component and a detrital component and are suggestive of enrichment in the light isotope of diagenetic quartz. Further work is now required to determine Ge isotope fractionation by siliceous organisms and to investigate the effect of diagenetic processes during chert lithification.

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.

Sr, C and O isotope ratios of Neogene sediments from DSDP Hole 38-341, Voring Plateau

The Neogene sediments from DSDP site 341 on the Voring Plateau, Norwegian Sea, contain a thin glauconitic pellet-bearing subunit, which separates underlying pelagic clays from overlying glacial-marine sediments. Oxygen isotope measurements of benthic foraminifera show a delta18O shift of + 1? during deposition of this subunit, probably a combined effect of a drop in bottom water temperature and a rise in seawater delta18O. The chronology of this sedimentological and O isotope transition is, however, poorly constrained by fossil evidence. Rb-Sr dating of glauconitic pellets indicates that the lower part of the glauconitic subunit was deposited 11.6 +/- 0.2 Ma ago. Further geochronological evidence, derived from the Sr and C isotopic compositions of foraminifera compared with known seawater-time variations, indicates that the lower pelagic clays are early to middle Miocene, deposited at a mean rate of ~15 m/Ma. The glauconitic subunit contains part of the middle Miocene and probably all of the late Miocene in a condensed sequence with a very low mean depositional rate (~0.2 m/Ma). The overlying glacial marine sediments are probably Pliocene, with a high mean rate of deposition, ~45 m/Ma. This is the first application of C, O and Sr isotopic stratigraphy combined with Rb-Sr dating of glauconitic minerals, and it illustrates the applications of this integrated approach in geochronology.

Paleoceanography of sediment cores SO202-27-6 and MD01-2416

The glacial-to-Holocene evolution of subarctic Pacific surface water stratification and silicic acid (Si) dynamics is investigated based on new combined diatom oxygen (d18Odiat) and silicon (d30Sidiat) isotope records, along with new biogenic opal, subsurface foraminiferal d18O, alkenone-based sea surface temperature, sea ice, diatom, and core logging data from the NE Pacific. Our results suggest that d18Odiat values are primarily influenced by changes in freshwater discharge from the Cordilleran Ice Sheet (CIS), while corresponding d30Sidiat are primarily influenced by changes in Si supply to surface waters. Our data indicate enhanced glacial to mid Heinrich Stadial 1 (HS1) NE Pacific surface water stratification, generally limiting the Si supply to surface waters. However, we suggest that an increase in Si supply during early HS1, when surface waters were still stratified, is linked to increased North Pacific Intermediate Water formation. The coincidence between fresh surface waters during HS1 and enhanced ice-rafted debris sedimentation in the North Atlantic indicates a close link between CIS and Laurentide Ice Sheet dynamics and a dominant atmospheric control on CIS deglaciation. The Bølling/Allerød (B/A) is characterized by destratification in the subarctic Pacific and an increased supply of saline, Si-rich waters to surface waters. This change toward increased convection occurred prior to the Bølling warming and is likely triggered by a switch to sea ice-free conditions during late HS1. Our results furthermore indicate a decreased efficiency of the biological pump during late HS1 and the B/A (possibly also the Younger Dryas), suggesting that the subarctic Pacific has then been a source region of atmospheric CO2.

Nd-Sr isotopic composition of foraminifera and bulk sediments

We present new isotopic data for sedimentary planktonic foraminifera, as well as for potential water column and sedimentary sources of neodymium (Nd), which confirm that the isotopic composition of the foraminifera is the same as surface seawater and very different from deep water and sedimentary Nd. The faithfulness with which sedimentary foraminifera record the isotopic signature of surface seawater Nd is difficult to explain given their variable and high Nd/Ca ratios, ratios that are often sedimentary foraminifera, ratios that are often much higher than is plausible for direct incorporation within the calcite structure. We present further data that demonstrate a similarly large range in Nd/Ca ratios in plankton tow foraminifera, a range that may be controlled by redox conditions in the water column. Cleaning experiments reveal, in common with earlier work, that large amounts of Nd are released by cleaning with both hydrazine and diethylene triamine penta-acetic acid, but that the Nd released at each step is of surface origin. While further detailed studies are required to verify the exact location of the surface isotopic signature and the key controls on foraminiferal Nd isotope systematics, these new data place the use of planktonic foraminifera as recorders of surface water Nd isotope ratios, and thus of variations in the past supply of Nd to the oceans from the continents via weathering and erosion, on a reasonably sure footing.

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.

Late Miocene to Pleistocene paleoceanographic records from the Feni and Gardar Drifts: Pliocene reduction in abyssal flow

Magnetic fabric analyses from two North Atlantic drift deposits provide proxies for determining relative variations in the strength of abyssal flow over the last 10 my. The data show a cessation of current-controlled sedimentation at the shallower Feni Drift (2417 m) at the time of onset of Northern Hemisphere glaciation (2.6 Ma). Drift formation ended nearly 2 my earlier (4.2 Ma) at the deeper Gardar Drift (3220 m), implying stepwise reduction in deep-water flow. Relatively light delta18O values at the deeper Gardar Drift indicate a warmer, thus also more salty, water mass site prior to 6 Ma. We interpret this as representing Mediterranean Sea water, which flowed north at depths greater than that of the Feni Drift Site. The supply of Mediterranean Water to the North Atlantic was shut off as the Gibraltar Straits closed, causing the Messinian salinity crisis, and never returned to that position in the water column after the Mediterranean opened again.

Os isotope ratios of Late Eocene sediments from the tropical Pacific

High resolution records (ca. 100 kyr) of Os isotope composition (187Os/188Os) in bulk sediments from two tropical Pacific sites (ODP Sites 1218 and 1219) capture the complete Late Eocene 187Os/188Os excursion and confirm that the Late Eocene 187Os/ 188Os minimum, earlier reported by Ravizza and Peucker-Ehrenbrink (2003, doi:10.1016/S0012-821X(03)00137-7), is a global feature. Using the astronomically tuned age models available for these sites, it is suggested that the Late Eocene 187Os/188Os minimum can be placed at 34.5 +/- 0.1 Ma in the marine records. In addition, two other distinct features of the 187Os/188Os excursion that are correlatable among sections are proposed as chemostratigraphic markers which can serve as age control points with a precision of ca. +/-0.1 Myr. We propose a speculative hypothesis that higher cosmic dust flux in the Late Eocene may have contributed to global cooling and Early Oligocene glaciation (Oi-1) by supplying bio-essential trace elements to the oceans and thereby resulting in higher ocean productivity, enhanced burial of organic carbon and draw down of atmospheric CO2. To determine if the hypothesis that enhanced cosmic dust flux in the Late Eocene was a cause for the 187Os/188Os excursion can be tested by using the paired bulk sediment and leachate Os isotope composition; 187Os/188Os were also measured in sediment leachates. Results of analyses of leachates are inconsistent between the south Atlantic and the Pacific sites, and therefore do not yield a robust test of this hypothesis. Comparison of 187Os/188Os records with high resolution benthic foraminiferal delta18O records across the Eocene-Oligocene transition suggests that 187Os flux to the oceans decreased during cooling and ice growth leading to the Oi-1 glaciation, whereas subsequent decay of ice-sheets and deglacial weathering drove seawater 187Os/188Os to higher values. Although the precise timing and magnitude of these changes in weathering fluxes and their effects on the marine 187Os/188Os records are obscured by recovery from the Late Eocene 187Os/188Os excursion, evidence of the global influence of glaciation on supply of Os to the ocean is robust as it has now been documented in both Pacific and Atlantic records.

40Ar-39Ar dating and isotopic composition of groundmass and felspar samples from core AND-2A

The AND-2A drillcore (Antarctic Drilling Program-ANDRILL) was successfully completed in late 2007 on the Antarctic continental margin (Southern McMurdo Sound, Ross Sea) with the aim of tracking ice proximal to shallow marine environmental fluctuations and to document the 20-Ma evolution of the Erebus Volcanic Province. Lava clasts and tephra layers from the AND-2A drillcore were investigated from a petrographic and stratigraphic point of view and analyzed by the 40Ar-39Ar laser technique in order to constrain the age model of the core and to gain information on the style and nature of sediment deposition in the Victoria Land Basin since Early Miocene. Ten out of 17 samples yielded statistically robust 40Ar-39Ar ages, indicating that the AND-2A drillcore recovered <230 m of Middle Miocene (~128-358 m below sea floor, ~11.5-16.0 Ma) and >780 m of Early Miocene (~358-1093 m below sea floor, ~16.0-20.1 Ma). Results also highlight a nearly continuous stratigraphic record from at least 358 m below sea floor down hole, characterized by a mean sedimentation rate of ~19 cm/ka, possible oscillations of no more than a few hundreds of ka and a break within ~17.5-18.1 Ma. Comparison with available data from volcanic deposits on land, suggests that volcanic rocks within the AND-2A core were supplied from the south, possibly with source areas closer to the drill site for the upper core levels, and from 358 m below sea floor down hole, with the 'proto-Mount Morning' as the main source.

Geochemistry and isotopic composition of volcanic rocks of ODP Hole 128-794D

The Yamato Basin basement in the Sea of Japan was drilled below the sediment pile during Legs 127 and 128. Two superposed volcanic complexes are distinguished. The upper complex consists of continental tholeiite sills dated around 20-18 Ma and attributed to the rifting stage of the backarc basin. The lower complex consists of backarc basin basalts probably intruded below the upper complex during the spreading stage. Trace-element compositions and Sr and Nd isotopic signatures may be explained by mixing of at least two end members with a very small addition of crustal and subducted sediment component. Thus, upwelling of mantle diapir occurred during the rifting stage. Contribution of the depleted mantle increased in the spreading stage. The Neogene magmatic history of the Japan Sea is reviewed in the light of the ODP new data.