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.

Geochemistry of Pliocene-Pleistocene volcanic rocks from the Izu Arc

The igneous geochemistry of lavas and breccias from the basement of Sites 790 and 791, and pumice clasts from the Pliocene-Pleistocene sedimentary section of Sites 788, 790, 791, and 793 were studied. Arc volcanism became silicic about 1.5 m.y. before the inception of rifting in the Sumisu Rift at 2 Ma, but eruption of these silicic magmas reflects changes in stress regime, especially during the last 130,000 yr, rather than crustal anatexis. Arc magmas have had a larger proportion of slab-derived components since the inception of rifting than before, but are otherwise similar. Rift basalts and rhyolites are derived from a different source than are arc andesites to rhyolites. The rift source has less slab-derived material and is an E-MORB-like source, in contrast to an N-MORB-type source overprinted with more slab-derived material beneath the arc. Rift magma types, in the form of rare pumice and lithic clasts, preceded the rift, and the earliest magmas that erupted in the rift already differed from those of the arc. The earliest large rift eruption produced an exotic explosion breccia ("mousse") despite eruption at >1800 mbsl. Although this rock type is attributed primarily to high magmatic water content, the clasts are more MORB-like in trace element and isotopic composition than are modern Mariana Trough basalts. After rifting began, arc volcanism continued to be predominantly silicic, with individual pumice deposits containing clasts that vary in composition by about 5 wt% SiO2, or about as much as in historical eruptions of submarine Izu Arc volcanoes. The overall variations in magma composition with time during the inception of arc rifting are broadly similar in the Sumisu Rift and Lau Basin, though newly tapped OIB-type mantle seems to be present earlier during basin formation in the Sumisu than Lau case.

Zircon U-Pb and Hf-O analysis of porphyries from the Duolong porphyry Cu-Au deposit in the Bangongco copper belt, central Tibet

The Duolong porphyry Cu-Au deposit (5.4 Mt at 0.72% Cu, 41 t at 0.23 g/t Au), which is related to the granodiorite porphyry and the quartz-diorite porphyry from the Bangongco copper belt in central Tibet, formed in a continental arc setting. Here, we present the zircon U-Pb ages, geochemical whole-rock, Sr-Nd whole-rock and zircon in-situ Hf-O isotopic data for the Duolong porphyries. Secondary ion mass spectrometry (SIMS) zircon U-Pb analyses for six samples yielded consistent ages of ~118 Ma, indicating a Cretaceous formation age. The Duolong porphyries (SiO2 of 58.81-68.81 wt.%, K2O of 2.90-5.17 wt.%) belong to the high-K calc-alkaline series. They show light rare earth element (LREE)-enriched distribution patterns with (La/Yb)N = 6.1-11.7, enrichment in large ion lithophile elements (e.g., Cs, Rb, and Ba) and depletion of high field strength elements (e.g., Nb), with negative Ti anomalies. All zircons from the Duolong porphyries share relatively similar Hf-O isotopic compositions (d18O=5.88-7.27 per mil; eHf(t)=3.6-7.3), indicating that they crystallized from a series of cogenetic melts with various degrees of fractional crystallization. This, along with the general absence of older inherited zircons, rules out significant crustal contamination during zircon growth. The zircons are mostly enriched in d18O relative to mantle values, indicating the involvement of an 18O-enriched crustal source in the generation of the Duolong porphyries. Together with the presence of syn-mineralization basaltic andesite, the mixing between silicic melts derived from the lower crust and evolved H2O-rich mafic melts derived from the metsomatizied mantle wedge, followed by subsequent fractional crystallization (FC) and minor crustal contamination in the shallow crust, could well explain the petrogenesis of the Duolong porphyries. Significantly, the hybrid melts possibly inherited the arc magma characteristics of abundant F, Cl, Cu, and Au elements and high oxidation state, which contributed to the formation of the Duolong porphyry Cu-Au deposit.

A deep-sea coral record of the North Atlantic

Our record of Younger Dryas intermediate-depth seawater D14C from North Atlantic deep-sea corals supports a link between abrupt climate change and intermediate ocean variability. Our data show that northern source intermediate water (~1700 m) was partially replaced by 14C-depleted southern source water at the onset of the event, consistent with a reduction in the rate of North Atlantic Deep Water formation. This transition requires the existence of large, mobile gradients of D14C in the ocean during the Younger Dryas. The D14C water column profile from Keigwin (2004) provides direct evidence for the presence of one such gradient at the beginning of the Younger Dryas (~12.9 ka), with a 100 per mil offset between shallow (<~2400 m) and deep water. Our early Younger Dryas data are consistent with this profile and also show a D14C inversion, with 35 per mil more enriched water at ~2400 m than at ~1700 m. This feature is probably the result of mixing between relatively well 14C ventilated northern source water and more poorly 14C ventilated southern source intermediate water, which is slightly shallower. Over the rest of the Younger Dryas our intermediate water/deepwater coral D14C data gradually increase, while the atmosphere D14C drops. For a very brief interval at ~12.0 ka and at the end of the Younger Dryas (11.5 ka), intermediate water D14C (~1200 m) approached atmospheric D14C. These enriched D14C results suggest an enhanced initial D14C content of the water and demonstrate the presence of large lateral D14C gradients in the intermediate/deep ocean in addition to the sharp vertical shift at ~2500 m. The transient D14C enrichment at ~12.0 ka occurred in the middle of the Younger Dryas and demonstrates that there is at least one time when the intermediate/deep ocean underwent dramatic change but with much smaller effects in other paleoclimatic records.

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.

Neodymium isotope record of ODP Site 177-1090

Age estimates for the opening of Drake Passage range from 49 to 17 million years ago (Ma), complicating interpretations of the relationship between ocean circulation and global cooling. Secular variations of neodymium isotope ratios at Agulhas Ridge (Southern Ocean, Atlantic sector) suggest an influx of shallow Pacific seawater approximately 41 Ma. The timing of this connection and the subsequent deepening of the passage coincide with increased biological productivity and abrupt climate reversals. Circulation/productivity linkages are proposed as a mechanism for declining atmospheric carbon dioxide. These results also indicate that Drake Passage opened before the Tasmanian Gateway, implying the late Eocene establishment of a complete circum-Antarctic pathway.

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.

Geochemistry of oceanic crust beneath Costa Rica

Resolving flow geometry in the mantle wedge is central to understanding the thermal and chemical structure of subduction zones, subducting plate dehydration, and melting that leads to arc volcanism, which can threaten large populations and alter climate through gas and particle emission. Here we show that isotope geochemistry and seismic velocity anisotropy provide strong evidence for trench-parallel flow in the mantle wedge beneath Costa Rica and Nicaragua. This finding contradicts classical models, which predict trench-normal flow owing to the overlying wedge mantle being dragged downwards by the subducting plate. The isotopic signature of central Costa Rican volcanic rocks is not consistent with its derivation from the mantle wedge (Feigenson et al., 2004, doi:10.1029/2003GC000621; Herrstom et al., 1995, doi:10.1130/0091-7613(1995)023<0617:VILCAW>2.3.CO;2; Abratis and Woerner, 2001) or eroded fore-arc complexes (Goss and Kay, 2006, doi:10.1029/2005GC001163) but instead from seamounts of the Galapagos hotspot track on the subducting Cocos plate. This isotopic signature decreases continuously from central Costa Rica to northwestern Nicaragua. As the age of the isotopic signature beneath Costa Rica can be constrained and its transport distance is known, minimum northwestward flow rates can be estimated (~63-190 mm/yr) and are comparable to the magnitude of subducting Cocos plate motion (approx85 mm/yr). Trench-parallel flow needs to be taken into account in models evaluating thermal and chemical structure and melt generation in subduction zones.