Geochemistry of the oldest Atlantic oceanic crust

Controversy has surrounded the issue of whether mantle plume activity was responsible for Pangaean continental rifting and massive flood volcanism (resulting in the Central Atlantic Magmatic Province or CAMP, emplaced around 200 Ma) preceding the opening of the central Atlantic Ocean in the Early Mesozoic. Our new Sr-Nd-Pb isotopic and trace element data for the oldest basalts sampled from central Atlantic oceanic crust by deep-sea drilling show that oceanic crust generated from about 160 to 120 Ma displays clear isotopic and chemical signals of plume contamination (e.g., 87Sr/86Sr(i) = 0.7032-0.7036, epsilonNd(t) =+6.2 to +8.2, incompatible element patterns with positive Nb anomalies), but these signals are muted or absent in crust generated between 120 and 80 Ma, which resembles young Atlantic normal mid-ocean ridge basalt. The plume-affected pre-120 Ma Atlantic crustal basalts are isotopically similar to lavas from the Ontong Java Plateau, and may represent one isotopic end-member for CAMP basalts. The strongest plume signature is displayed near the center of CAMP magmatism but the hotspots presently located nearest this location in the mantle reference frame do not appear to be older than latest Cretaceous and are isotopically distinct from the oldest Atlantic crust. The evidence for widespread plume contamination of the nascent Atlantic upper mantle, combined with a lack of evidence for a long-lived volcanic chain associated with this plume, leads us to propose that the enriched signature of early Atlantic crust and possibly the eruption of the CAMP were caused by a relatively short-lived, but large volume plume feature that was not rooted at a mantle boundary layer. Such a phenomenon has been predicted by recent numerical models of mantle circulation.

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.

Compound specific stable isotopes, BIT, pollen and spores of Miocene to Pliocene sediments of ODP Hole 175-1085A

Pollen and stable carbon (d13C) and hydrogen (dD) isotope ratios of terrestrial plant wax from the South Atlantic sediment core, ODP Site 1085, is used to reconstruct Miocene to Pliocene changes of vegetation and rainfall regime of western southern Africa. Our results reveal changes in the relative amount of precipitation and indicate a shift of the main moisture source from the Atlantic to the Indian Ocean during the onset of a major aridification 8 Ma ago. We emphasise the importance of declining precipitation during the expansion of C4 and CAM (mainly succulent) vegetation in South Africa. We suggest that the C4 plant expansion resulted from an increased equator-pole temperature gradient caused by the initiation of strong Atlantic Meridional Overturning Circulation following the shoaling of the Central American Seaway during the Late Miocene.

Th-U ages of a stalagmite from the Kleegruben Cave (Table 1)

A mass-spectrometric uranium-series dated stalagmite from the Central Alps of Austria provides unprecedented new insights into high-altitude climate change during the peak of isotope stage 3. The stalagmite formed continuously between 57 and 46 kyr before present. A series of 'Hendy tests' demonstrates that the outer parts of the sample show a progressive increase of both stable C and O isotope values. No such covariant increase was detected within the axial zone. This in conjunction with other observations suggests that the continuous stable oxygen isotope profile obtained from the axial zone of the stalagmite largely reflects the unaltered isotopic composition of the cave drip water. The delta18O record shows events of high delta18O values that correlate remarkably with Interstadials 15 (a and b), 14 and 12 identified in the Greenland ice cores. Interstadial 15b started rapidly at 55.6 kyr and lasted ~300 yr only, Interstadial 15a peaked 54.9 kyr ago and was even of shorter duration (~100 yr), and Interstadial 14 commenced 54.2 kyr ago and lasted ~3000 yr. This stalagmite thus represents one of the first terrestrial archives outside the high latitudes which record precisely dated Dansgaard-Oeschger (D/O) events during isotope stage 3. Provided that rapid D/O warmings occurred synchronously in Greenland and the European Alps, the new data provide an independent tool to improve the GRIP and GISP2 chronologies.

Helium and neon isotopes in oceanic crust of ODP Hole 118-735B

In an attempt to determine the helium and neon isotopic composition of the lower oceanic crust, we report new noble gas measurements on 11 million year old gabbros from Ocean Drilling Program site 735B in the Indian Ocean. The nine whole rock samples analyzed came from 20 to 500 m depth below the seafloor. Helium contents vary from 3.3*10**-10 to 2.5*10**-7 ccSTP/g by crushing and from 5.4*10**-8 to 2.4*10**-7 ccSTP/g by melting. 3He/4He ratios vary between 2.2 and 8.6 Ra by crushing and between 2.9 and 8.2 by melting. The highest R/Ra ratios are similar to the mean mid-ocean ridge basalt (MORB) ratio of 8+/-1. The lower values are attributed to radiogenic helium from in situ alüha-particle production during uranium and thorium decay. Neon isotopic ratios are similar to atmospheric ratios, reflecting a significant seawater circulation in the upper 500 m of exposed crust at this site. MORB-like neon, with elevated 20Ne/22Ne and 21Ne/22Ne ratios, was found in some high temperature steps of heating experiments, but with very small anomalies compared to air. These first results from the lower oceanic crust indicate that subducted lower oceanic crust has an atmospheric 20Ne/22Ne ratio. Most of this neon must be removed during the subduction process, if the ocean crust is to be recirculated in the upper mantle, otherwise this atmospheric neon will overwhelm the upper mantle neon budget. Similarly, the high (U+Th)/3He ratio of these crustal gabbros will generate very radiogenic 4He/3He ratios on a 100 Ma time scale, so lower oceanic crust cannot be recycled into either MORB or oceanic island basalt without some form of processing.

Sedimentation rate calculations and isotopic analysis on sediment cores along the IODP Expedition 311 transect

The oceanographic and tectonic conditions of accretionary margins are well-suited for several potential processes governing methane generation, storage and release. To identify the relevant methane evolution pathways in the northern Cascadia accretionary margin, a four-site transect was drilled during Integrated Ocean Drilling Program Expedition 311. The d13C values of methane range from a minimum value of -82.2 per mil on an uplifted ridge of accreted sediment near the deformation front (Site U1326, 1829 mbsl, meters below sea level) to a maximum value of -39.5 per mil at the most landward location within an area of steep canyons near the shelf edge (Site U1329, 946 mbsl). An interpretation based solely on methane isotope values might conclude the 13C-enrichment of methane indicates a transition from microbially- to thermogenically-sourced methane. However, the co-existing CO2 exhibits a similar trend of 13C-enrichment along the transect with values ranging from -22.5 per mil to +25.7 per mil. The magnitude of the carbon isotope separation between methane and CO2 (Ec = 63.8 ± 5.8) is consistent with isotope fractionation during microbially mediated carbonate reduction. These results, in conjunction with a transect-wide gaseous hydrocarbon content composed of > 99.8% (by volume) methane and uniform dDCH4 values (-172 per mil ± 8) that are distinct from thermogenic methane at a seep located 60 km from the Expedition 311 transect, suggest microbial CO2 reduction is the predominant methane source at all investigated sites. The magnitude of the intra-site downhole 13C-enrichment of CO2 within the accreted ridge (Site U1326) and a slope basin nearest the deformation front (Site U1325, 2195 mbsl) is ~ 5 per mil. At the mid-slope site (Site U1327, 1304 mbsl) the downhole 13C-enrichment of the CO2 is ~ 25 per mil and increases to ~ 40 per mil at the near-shelf edge Site U1329. This isotope fractionation pattern is indicative of more extensive diagenetic alteration at sites with greater 13C-enrichment. The magnitude of the 13C-enrichment of CO2 correlates with decreasing sedimentation rates and a diminishing occurrence of stratigraphic gas hydrate. We suggest the decreasing sedimentation rates increase the exposure time of sedimentary organic matter to aerobic and anaerobic degradation, during burial, thereby reducing the availability of metabolizable organic matter available for methane production. This process is reflected in the occurrence and distribution of gas hydrate within the northern Cascadia margin accretionary prism. Our observations are relevant for evaluating methane production and the occurrence of stratigraphic gas hydrate within other convergent margins.

(Table S1) Cation compositions of titanomaghemite in DSDP Hole 89-462A basalts

Cretaceous lava flows overlie Jurassic to Early Cretaceous oceanic crust in the Nauru Basin of the western equatorial Pacific, but their exact age and origin is controversial. In one model, they are generically related to volcanism forming the Ontong Java Plateau. However, paleomagnetic data from basalts recovered by ocean drilling in the Nauru Basin have been interpreted as recording numerous geomagnetic reversals, suggesting the Nauru Basin basalts are older than the Early Aptian flows on the Ontong Java Plateau, and the correlative volcanism seen in the western equatorial and southwestern Pacific Ocean basin. Here, we examine the magnetic fidelity of the Nauru Basin basalts through rock magnetic and paleomagnetic approaches. We find the magnetic carriers in the lavas are unlike most basaltic units recovered by oceanic drilling in that they are magnetically soft. This quality makes the rocks especially prone to the acquisition of secondary magnetic components induced during drilling. We demonstrate that the reversed polarity intervals are illusory, and instead record subtle changes in magnetic hardness that result in partial and complete overprinting by the magnetic field associated with the drill string (e.g., the core barrel, drill pipe and bit). The recognition of these magnetic overprints, the identification of only normal polarity in the Nauru Basin basalts, and a critical consideration of the available radiometric and biostratigraphic age data lead us to conclude that coeval formation of the Nauru Basin basalts and Ontong Java Plateau in Aptian times remains a viable hypothesis.

Uranium in marine basalts

The uranium content of glass from chilled margins of oceanic tholeiitic basalt flows is generally <0.1 ppm, even for old samples with highly altered crystalline interiors. Such low values represent the original whole rock concentrations, although subsequent to eruption low-temperature weathering has added uranium, and other elements, to the crystalline portions of these basalts. Consideration of the K/U ratios of altered samples suggests that basalt weathering may provide the major oceanic sink for these two elements.

Radiocarbon ages and 230Th data of five sediment cores from the Björn and Gardar Drift, North Atlantic

In locations of rapid sediment accumulation receiving substantial amounts of laterally transported material the timescales of transport and accurate quantification of the transported material are at the focus of intense research. Here we present radiocarbon data obtained on co-occurring planktic foraminifera, marine haptophyte biomarkers (alkenones) and total organic carbon (TOC) coupled with excess Thorium-230 (230Thxs) measurements on four sediment cores retrieved in 1649-2879 m water depth from two such high accumulation drift deposits in the Northeast Atlantic, Björn and Gardar Drifts. While 230Thxs inventories imply strong sediment focussing, no age offsets are observed between planktic foraminifera and alkenones, suggesting that redistribution of sediments is rapid and occurs soon after formation of marine organic matter, or that transported material contains negligible amounts of alkenones. An isotopic mass balance calculation based on radiocarbon concentrations of co-occurring sediment components leads us to estimate that transported sediment components contain up to 12% of fossil organic matter that is free of or very poor in alkenones, but nevertheless appears to consist of a mixture of fresh and eroded fossil material. Considering all available constraints to characterize transported material, our results show that although focussing factors calculated from bulk sediment 230Thxs inventories may allow useful approximations of bulk redeposition, they do not provide a unique estimate of the amount of each laterally transported sediment component. Furthermore, our findings provide evidence that the occurrence of lateral sediment redistribution alone does not always hinder the use of multiple proxies but that individual sediment fractions are affected to variable extents by sediment focussing.

Chlorine stable isotopic composition of basement fluids from ODP Leg 168 sites

This paper presents chlorine stable isotope compositions (delta37Cl) of sediment pore waters collected by squeezing sediment cores from the sediment-basement interface along an East-West transect through the eastern flank of the Juan de Fuca Ridge (ODP Leg 168). These "near basement fluids" (NBF) are generally thought to be representative of low-temperature fluids circulating in the off-axis basaltic crust. The delta37Cl value of the fluid directly sampled from a flow at the base of Site 1026 (WSTP1026) is also reported. NBF display delta37Cl values between -2.09? and -0.12? relative to the Standard Mean Ocean Chloride (SMOC defined as 0?) and small variations in chlorinity (~4%). These data contrast with the homogeneity of delta37Cl values associated with highly variable chlorinities observed in high-temperature on-axis fluids [Bonifacie et al., 2005, doi:10.1016/j.chemgeo.2005.06.008]. The NBF delta37Cl values show a general decreasing trend with distance from the ridge-axis except for two fluids. When plotted against delta18O values, the delta37Cl of the NBF show two different trends. This paper discusses the possible contributions on NBF delta37Cl values of fluid-mixing, water-rock interactions and transport processes (diffusion, ion membrane filtration) that can occur in the igneous basement. However, as none of these processes can fully explain the observed delta37Cl variations, the potential effect of the sediment cover is also investigated. At site 1026, the interstitial pore fluid displays a delta37Cl signature significantly lower than that of the fluid discharge sample (-1.90? and -0.28?, respectively). This difference, demonstrated here cannot be an artifact of the sampling method, rather indicates the influence of the sediment cover on NBF delta37Cl values. The potential contributions of physical processes associated with transport/compaction (e.g., diffusion, ion membrane filtration, adsorption, ion exchange) on NBF delta37Cl values are qualitatively discussed here but require additional studies for further insights. However, this study indicates that "near basement fluids" (NBF) are not, at least for Cl isotopic compositions, necessarily as representative of fluids circulating in the basaltic crust as initially thought. These results add new constraints on Cl geodynamics and show that Cl-isotopes fractionate during low-temperature circulation of fluids in off-axis and off-margin flow contexts, but not to the extent observed for active margins. Fluids circulating at low-temperature in the magmatic and/or the sedimentary part of the oceanic crust might have played a major role on the delta37Cl evolution of seawater over geologic time.