Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Geochemistry and oxygen and iron isotope ratios of mafic rocks

Recycling of oceanic crust into the deep mantle via subduction is a widely accepted mechanism for creating compositional heterogeneity in the upper mantle and for explaining the distinct geochemistry of mantle plumes. The oxygen isotope ratios (d18O) of some ocean island basalts (OIB) span values both above and below that of unmetasomatised upper mantle (5.5 ± 0.4 per mil) and provide support for this hypothesis, as it is widely assumed that most variations in d18O are produced by near-surface low-temperature processes. Here we show a significant linear relationship between d18O and stable iron isotope ratios (d57Fe) in a suite of pristine eclogite xenoliths. The d18O values of both bulk samples and garnets range from values within error of normal mantle to significantly lighter values. The observed range and correlation between d18O and d57Fe is unlikely to be inherited from oceanic crust, as d57Fe values determined for samples of hydrothermally altered oceanic crust do not differ significantly from the mantle value and show no correlation with d18O. It is proposed that the correlated d57Fe and d18O variations in this particular eclogite suite are predominantly related to isotopic fractionation by disequilibrium partial melting although modification by melt percolation processes cannot be ruled out. Fractionation of Fe and O isotopes by removal of partial melt enriched in isotopically heavy Fe and O is supported by negative correlations between bulk sample d57Fe and Cr content and bulk sample and garnet d18O and Sc contents, as Cr and Sc are elements that become enriched in garnet- and pyroxene-bearing melt residues. Melt extraction could take place either during subduction, where the eclogites represent the residues of melted oceanic lithosphere, or could take place during long-term residence within the lithospheric mantle, in which case the protoliths of the eclogites could be of either crustal or mantle origin. This modification of both d57Fe and d18O by melting processes and specifically the production of low-d18O signatures in mafic rocks implies that some of the isotopically light d18O values observed in OIB and eclogite xenoliths may not necessarily reflect near-surface processes or components.

Element and Sr isotope composition of interstitial waters in sediments of ODP Leg 129

Interstitial water samples from Leg 129, Sites 800, 801, and 802 in the Pigafetta and Mariana basins (central western Pacific), have been analyzed for major elements, B, Li, Mn, Sr, and 87Sr/86Sr. At all sites waters show enrichment in Ca and Sr and are depleted in Mg, K, Na, SO4, B, alkalinity, and 87Sr compared to seawater. These changes are related to alteration of basaltic material into secondary smectite and zeolite and recrystallization of biogenic carbonate. Water concentration depth profiles are characterized by breaks due to the presence of barriers to diffusion such as chert layers at Sites 800 and 801 and highly cemented volcanic ash at Site 802. In Site 800, below a chert layer, concentration depth profiles are vertical and reflect slight alteration of volcanic matter, either in situ or in the upper basaltic crust. Release of interlayer water from clay minerals is likely to induce observed Cl depletions. At Site 801, two units act as diffusion barrier and isolate the volcaniclastic sediments from ocean and basement. Diagenetic alteration of volcanic matter generates a chemical signature similar to that at Site 800. Just above the basaltic crust, interstitial waters are less evolved and reflect low alteration of the crust, probably because of the presence in the sediments of layers with low diffusivities. At Site 802, in Miocene tuffs, the chemical evolution generated by diagenetic alteration is extreme (Ca = 130 mmol, 87Sr/86Sr = 0.7042 at 83 meters below seafloor) and is accompanied by an increase of the Cl content (630 mmol) due to water uptake in secondary hydrous phases. Factors that enhance this evolution are a high sediment accumulation rate, high cementation preventing diffusive exchange and the reactive composition of the sediment (basaltic glass). The chemical variation is estimated to result in the alteration of more than 20% of the volcanic matter in a nearly closed system.

Osmium isotope composition of ODP Hole 121-758A

This study presents osmium (Os) isotope and elemental data for cleaned planktic foraminifera, authigenic Fe-Mn oxyhydroxides and pelagic carbonate host sediments from ODP site 758 in the southernmost reaches of the Bay of Bengal. The Os in the bulk sediments appears to be dominantly hydrogeneous (sourced by carbonate and Fe-Mn oxyhydroxide), but variations in this particular core are controlled by the presence of volcanic ash. Fe-Mn oxyhydroxide leachates (of the bulk sediments) from Holocene samples also yield an Os isotope composition close to that of seawater, but the record diverges from that of foraminifera at a depth corresponding to the oxic/post-oxic boundary, suggesting diagenetic mobilization of Os at depths below this. Holocene planktic foraminifera, cleaned using oxidative-reductive techniques, also give Os isotope compositions indistinguishable from modern seawater, but the record obtained for the past 150 kyr shows strong covaraitions of 187Os/188Os with both the local and global oxygen isotope record, with less radiogenic Os isotope compositions during glacial intervals. These results indicate that foraminifera provide a robust record of seawater Os isotope compositions, and comparison of the data obtained here with records from the other major oceans demonstrate global changes in 187Os/188Os over this time interval, while the covariation with oxygen isotopes suggest a process controlling the Os isotope composition that is in phase with global climate cycles. Global excursions to relatively unradiogenic 187Os/188Os during glacial intervals are consistent with decreased input of radiogenic continental material, reflecting cooler temperatures and reduced continental runoff. Modelling indicates that the shift to unradiogenic values during glacial intervals could be caused by an ~30% decrease in the global river flux, with an ~5% change in river composition. If the residence time of Os in the oceans is ~5 ka then the post-glacial recovery to present-day seawater values is consistent with a corresponding increase in the river flux of around 30%. However, if the residence time of Os is closer to 40 ka, as is suggested by the global river flux, then this demands either significant changes in both the riverine Os flux and composition of around 40% and 30%, respectively, that closely follow the oxygen isotope record, or else a short-lived post-glacial pulse of weathering some 75% greater than the steady-state flux. In either case, these results clearly indicate that climatic changes affect both the flux and composition of weathered material delivered to the oceans on glacial-interglacial timescales.

Stable and radiogenic isotope ratios in pore waters from ODP Leg 127 sites

Interstitial waters from four sites of the Japan Sea (794 to 797) have been analyzed for stable isotopes (delta D, delta11B, delta18O, and delta34S) and 87Sr/86Sr, besides major and minor ions. The isotopic composition is dominated by organic matter degradation, alteration of ash layers and volcaniclastic sands, silica transformation (opal A/CT), and basement alteration. Organic matter degradation and corresponding sulfate reduction leads to 32S depletion and is dependent upon sedimentation rate. The remaining sulfate reservoir is characterized by very "heavy" delta34S ratios, up to +93 ? (rel. CDT = Canyon Diabolo Troilite). "Barite fronts," which may develop in such sediments, should also be characterized by very "heavy" sulfur isotopes. The alteration of volcaniclastic material in the Quaternary sections influences the delta18O (-1.5 ? shift) and delta11B (desorption and later adsorption of "labile"11B). A pronounced positive delta11B anomaly at Site 795 represents the depth range of preferential 10B uptake by alteration products of the ash layers. At Site 796 delta D, delta11B, and 87Sr/86Sr are severely affected by alteration processes of volcaniclastic sands. The opal A/CT transformation may influence the oxygen isotopes and serves as a potential source for B, which is liberated at this interval at Site 795. This positive B anomaly is not reflected in the delta11B profile. Basement alteration processes dominate the sedimentary sequence below the opal A/CT transition, which serves as a chemical and physical boundary. The decreases in delta D and delta18O are probably related to a "paleo ocean water reservoir" situated in the permeable Layer II of the oceanic crust, as is indicated by the positive correlation between these two parameters. Besides Mg, alkalies and delta18O basement rocks also serve as a sink for 11 B (Site 795) and are the source for the Ca and Sr increases, as is documented by the less radiogenic 87Sr/86Sr ratio. 87Sr/86Sr ratios for the lowermost pore waters from Site 795 (0.70529) are comparable to those from volcaniclastic rocks from the "Green Tuff' region (0.704 to 0.706) and oil field brines from the Niigata Oil Field.

B-isotope and Mg/Ca ratios of planktonic foraminifera from ODP Hole 108-668B and esimates of salinity, alkalinity and pCO2 (Table 1)

Knowledge of past atmospheric pCO2 is important for evaluating the role of greenhouse gases in climate forcing. Ice core records show the tight correlation between climate change and pCO2, but records are limited to the past ~900 kyr. We present surface ocean pH and pCO2 data, reconstructed from boron isotopes in planktonic foraminifera over two full glacial cycles (0-140 and 300-420 kyr). The data co-vary strongly with the Vostok pCO2-record and demonstrate that the coupling between surface ocean chemistry and the atmosphere is recorded in marine archives, allowing for quantitative estimation of atmospheric pCO2 beyond the reach of ice cores.

Alkenone and boron based Oligocene pCO2 records

The Pliocene period is the most recent time when the Earth was globally significantly (~3°C) warmer than today. However, the existing pCO2 data for the Pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo-pCO2. Moreover, the temporal resolution of the published records does not allow a robust assessment of the role of declining pCO2 in the intensification of the Northern Hemisphere Glaciation (INHG) and a direct comparison to other proxy records are lacking. For the first time, we use a combination of foraminiferal (delta11B) and organic biomarker (alkenone-derived carbon isotopes) proxies to determine the concentration of atmospheric CO2 over the past 5 Ma. Both proxy records show that during the warm Pliocene pCO2 was between 330 and 400 ppm, i.e. similar to today. The decrease to values similar to pre-industrial times (275-285 ppm) occurred between 3.2 Ma and 2.8 Ma - coincident with the INHG and affirming the link between global climate, the cryosphere and pCO2.