Chemical and isotope compositions of rocks from altered ocean crust at DSDP/ODP Sites 417/418

Large-scale compositional domains at DSDP/ODP drill sites 417A, 417D and 418A were analyzed for O, Sr and Nd isotope ratios, and REE, U, K, Rb and Sr abundances, to constrain the bulk chemical composition of the oceanic crust that is recycled at subduction zones. The combination of the three sites gives the composition of the upper oceanic crust in this region over a distance of about 8 km. The d18O(SMOW) and 87Sr/86Sr(meas) of compositional domains 10-100 m in size correlate well, with a range of 7.7-19.2 and 0.70364-0.70744, and mean of 9.96 and 0.70475, respectively. The Rb inventory of the upper crust increases by about an order of magnitude, while Sr contents remain constant. U abundances increase moderately under oxidizing alteration conditions and nearly triple in the commonly reducing alteration environments of the upper oceanic crust. REEs are influenced by alteration only to a small extent, and recycled oceanic crust is similar to MORB with respect to 143Nd/144Nd. Even though the average composition of the upper oceanic crust is well defined, the large scale composition varies widely. Highly altered compositional domains may not have a large impact on the average composition of the oceanic crust, but they may preferentially contribute to fluids or partial melts derived from the crust by prograde metamorphic reactions.

Stable isotopes measured on Miocene benthic foraminifera from ODP sites 202-1237 and 184-1146

One of the most enigmatic features of Cenozoic long-term climate evolution is the long-lasting positive carbon-isotope excursion or "Monterey Excursion", which started during a period of global warmth after 16.9 Ma and ended at not, vert, similar 13.5 Ma, approximately 400 kyr after major expansion of the Antarctic ice-sheet. We present high-resolution (1-9 kyr) astronomically-tuned climate proxy records in two complete sedimentary successions from the northwestern and southeastern Pacific (ODP Sites 1146 and 1237), which shed new light on the middle Miocene carbon-isotope excursion and associated climatic transition over the interval 17.1-12.7 Ma. We recognize three distinct climate phases with different imprints of orbital variations into the climatic signals (1146 and 1237 d18O, d13C; 1237 XRF Fe, fraction > 63 µm): (1) climate optimum prior to 14.7 Ma characterized by minimum ice volume and prominent 100 and 400 kyr variability, (2) long-term cooling from 14.7 to 13.9 Ma, principally driven by obliquity and culminating with rapid cryosphere expansion and global cooling at the onset of the last and most pronounced d13C increase, (3) "Icehouse" mode after 13.9 Ma with distinct 100 kyr variability and improved ventilation of the deep Pacific. The "Monterey" carbon-isotope excursion (16.9-13.5 Ma) consists overall of nine 400 kyr cycles, which show high coherence with the long eccentricity period. Superposed on these low-frequency oscillations are high-frequency variations (100 kyr), which closely track the amplitude modulation of the short eccentricity period. In contrast to d13C, the d18O signal additionally shows significant power in the 41 kyr band, and the 1.2 Myr amplitude modulation of the obliquity cycle is clearly imprinted in the 1146 d18O signal. Our results suggest that eccentricity was a prime pacemaker of middle Miocene climate evolution through the modulation of long-term carbon budgets and that obliquity-paced changes in high-latitude seasonality favored the transition into the "Icehouse" climate.

Nd and Sr isotope record of ODP Sites 121-756 and 122-762 sediments

We have analyzed the Nd isotopic composition of both ancient seawater and detrital material from long sequences of carbonated oozes of the South Indian Ocean which are ODP Site 756 (Ninety East Ridge (-30°S), 1518 m water depth) and ODP Site 762 (Northwest Australian margin, 1360 m water depth). The measurements indicate that the epsilon-Nd changes in Indian seawater over the last 35 Ma result from changes in the oceanic circulation, large volcanic and continental weathering Nd inputs. This highlights the diverse nature of those controls and their interconnections in a small area of the ocean. These new records combined with those previously obtained at the equatorial ODP Sites 757 and 707 in the Indian Ocean (Gourlan et al., 2008, doi:10.1016/j.epsl.2007.11.054) established that the distribution of intermediate seawater epsilon-Nd was uniform over most of the Indian Ocean from 35 Ma to 10 Ma within a geographical area extending from 40°S to the equator and from -60°E to 120°E. However, the epsilon-Nd value of Indian Ocean seawater which kept an almost constant value (at about -7 to -8) from 35 to 15 Ma rose by 3 epsilon-Nd units from 15 to 10 Ma. This sharp increase has been caused by a radiogenic Nd enrichment of the water mass originating from the Pacific flowing through the Indonesian Passage. Using a two end-members model we calculated that the Nd transported to the Indian Ocean through the Indonesian Pathway was 1.7 times larger at 10 Ma than at 15 Ma. The Nd isotopic composition of ancient seawater and that of the sediment detrital component appear to be strongly correlated for some specific events. A first evidence occurs between 20 and 15 Ma with two positive spikes recorded in both epsilon-Nd signals that are clearly induced by a volcanic crisis of, most likely, the St. Paul hot-spot. A second evidence is the very large epsilon-Nd decrease recorded at ODP Sites 756 and 762 during the past 10 Ma which has never been previously observed. The synchronism between the epsilon-Nd decrease in seawater from 10 to 5 Ma and evidences of desertification in the western part of the nearly Australian continent suggests enhanced weathering inputs in this ocean from this continent as a result of climatic changes.

Stable carbon and oxygen isotope ratios of Cibicidoides wuellerstorfi (Table 1)

Here we present the first species-specific study of boron isotopes in the epibenthic foraminifer species Cibicidoides wuellerstorfi. Coretop samples from a water depth profile from 1000 to 4500 m on the northern flank of the Walvis Ridge are 4.4 per mil lower than the values expected, based on calculations of the delta 11B(borate) of ambient seawater. Similar values for this foraminifer species are presented from ODP site 668B at the Sierra Leone Rise, in the equatorial Atlantic. The consistency between data of the same species suggests the offsets are primary, rather than diagenetic. Glacial C. wuellerstorfi from ODP 668B and Walvis Ridge have boron isotope compositions only slightly different to interglacial samples, that is no larger than +0.10 pH units, or +23 µmol/kg in [CO3[2-]] above the reconstructed glacial lysocline, and -0.07 pH units, or -14 µmol/kg in [CO3[2-]] below. We use these results to suggest that glacial deep water pH in the Atlantic was similar to interglacial pH. The new data resolve the inconsistency between the previously reported high bottom water pH and the lack of significant carbonate preservation of the glacial deep ocean.

Petrological and geochemical characteristics of DSDP Hole 37-334 gabbroic cumulates (Table 1)

The gabbronoritic cumulates drilled at DSDP Site 334 (Mid-Atlantic Ridge off the FAMOUS area) are neither crystallization products of the associated basalts, nor from any MORB composition documented along ocean ridges. Their parent melts are richer in SiO2 than MORB at a given MgO content, as attested by the crystallization sequence starting with an olivine+calcic and sub-calcic pyroxene assemblages. These melts are issued from a source highly depleted in incompatible elements, likely residual peridotite left after MORB extraction. To understand the role of water in the genesis of these lithologies whose occurrence in a mid-ocean ridge setting is rather puzzling, we performed a geochemical study on clinopyroxene separates following an analytical protocol able to remove the effects of water rock interactions post-dating their crystallization. Accordingly, the measured isotopic signatures can be used to trace magma sources. We find that Site 334 clinopyroxenes depart from the global mantle correlation: normal MORB values for the 143Nd/ 144Nd ratio (0.51307-0.51315) are associated to highly radiogenic 87Sr / 86Sr (0.7034-0.7067) ratios. This indicates that the parent melts of Site 334 cumulates are issued from a MORB source but that seawater contamination occurred at some stage of their genesis. The extent of contamination, traced by the Sr isotopic signature, is variable within all cumulates but more developed for gabbronorites sensus stricto, suggesting that seawater introduction was a continuous process during all the magmatic evolution of the system, from partial melting to fractional crystallization. Simple masse balance calculations are consistent with a contaminating agent having the characters of a highly hydrated (possibly water saturated) silica-rich melt depleted in almost all incompatible major, minor and trace elements relative to MORB. Mixing in various proportions of contaminated melts similar to the parent melts of Site 334 cumulates with MORB can account for part of the variability in the Sr isotopic signature of oceanic basalts, among other to the short wavelength isotopic "noise" superimposed on regional trends. We conclude that seawater introduction into residual peridotite at shallow depth beneath mid-ocean ridges can lead mantle rocks and their melts to follow complex P-T-fH2O paths that mimic petrogenetic contexts classically attributed to subduction zone environments, like the production of boninitic-andesitic magmas.

Chemistry and boron isotope ratios of Izu arc front volcanic rocks

The process of fluid release from the subducting slab beneath the Izu arc volcanic front (Izu VF) was examined by measuring B concentrations and B isotope ratios in the Neogene fallout tephra (ODP Site 782A). Both were measured by secondary ion mass spectrometry, in a subset of matrix glasses and glassy plagioclase-hosted melt inclusions selected from material previously analyzed for major and trace elements (glasses) and radiogenic isotopes (Sr, Nd, Pb; bulk tephra). These tephra glasses have high B abundances (~10-60 ppm) and heavy delta11B values (+4.5? to +12.0?), extending the previously reported range for Izu VF rocks (delta11B, +7.0? to +7.3?). The glasses show striking negative correlations of delta11B with large ion lithophile element (LILE)/Nb ratios. These correlations cannot be explained by mixing two separate slab fluids, originating from the subducting sediment and the subducting basaltic crust, respectively (model A). Two alternative models (models B and C) are proposed. Model B proposes that the inverse correlations are inherited from altered oceanic crust (AOC), which shows a systematic decrease of B and LILE with increasing depth (from basaltic layer 2A to layer 3), paralleled by an increase in delta11B (from ~ +1? to +10? to +24?). In this model, the contribution of sedimentary B is insignificant (<4% of B in the Izu VF rocks). Model C explains the correlation as a mixture of a low-delta11B (~ +1?) 'composite' slab fluid (a mixture of metasediment- and metabasalt-derived fluids) with a metasomatized mantle wedge containing elevated B (~1-2 ppm) and heavy delta11B (~ +14?). The mantle wedge was likely metasomatized by 11B-rich fluids beneath the outer forearc, and subsequently down dragged to arc front depths by the descending slab. Pb-B isotope systematics indicate that, at arc front depths, ~ 53% of the B in the Izu VF is derived from the wedge. This implies that the heavy delta11B values of Izu VF rocks are largely a result of fluid fractionation, and do not reflect variations in slab source provenance (i.e. subducting sediment vs. basaltic crust). Since the B content of the peridotite at the outer forearc (7-58 ppm B, mean 24 +/- 16 ppm) is much higher than beneath the arc front (~1-2 ppm B), the hydrated mantle wedge must have released a B-rich fluid on its downward path. This 'wedge flux' can explain (1) the across-arc decrease in B and delta11B (e.g. Izu, Kuriles), without requiring a progressive decrease in fluid flux from the subducting slab, and (2) the thermal structure of volcanic arcs, as reflected in the B and delta11B variations of volcanic arc rocks.

(Table 2) Radiocarbon contents of TOC and alkenone samples

Radiocarbon age relationships between co-occurring planktic foraminifera, alkenones, and total organic carbon in sediments from the continental margins of southern Chile, northwest Africa, and the South China Sea were compared with published results from the Namibian margin. Age relationships between the sediment components are site-specific and relatively constant over time. Similar to the Namibian slope, where alkenones have been reported to be 1000-4500 years older than co-occurring foraminifera, alkenones were significantly (~1000 years) older than co-occurring foraminifera in the Chilean margin sediments. In contrast, alkenones and foraminifera were of similar age (within 2 sigma error or better) in the NW African and South China Sea sediments. Total organic matter and alkenone ages were similar off Namibia (age difference TOC alkenones: 200-700 years), Chile (100-450 years), and NW Africa (360-770 years), suggesting minor contributions of preaged terrigenous material. In the South China Sea, total organic carbon is significantly (2000-3000 years) older owing to greater inputs of preaged terrigenous material. Age offsets between alkenones and planktic foraminifera are attributed to lateral advection of organic matter. Physical characteristics of the depositional setting, such as seafloor morphology, shelf width, and sediment composition, may control the age of co-occurring sediment components. In particular, offsets between alkenones and foraminifera appear to be greatest in deposition centers in morphologic depressions. Aging of organic matter is promoted by transport. Age offsets are correlated with organic richness, suggesting that formation of organic aggregates is a key process.

Total organic carbon content and redox-sensitiv trace metal concentrations of selected late Cenoman claystones from DSDP Hole 93-603B

The Cenomanian/Turonian (C/T) intervals at DSDP Sites 105 and 603B from the northern part of the proto-North Atlantic show high amplitude, short-term cyclic variations in total organic carbon (TOC) content. The more pronounced changes in TOC are also reflected by changes in lithology from green claystones (TOC<1%) to black claystones (TOC>1%). Although their depositional history was different, the individual TOC cycles at Sites 105 and 603B can be correlated using stable carbon isotope stratigraphy. Sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled. The coinciding variations in HI, OI, delta13Corg and the abundance of marine relative to terrestrial biomarkers, as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones, indicate that these cyclic variations reflect changes in the contribution of marine organic matter (OM). The cooccurrence of lamination, enrichment of redox-sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto-North Atlantic Ocean water column was periodically euxinic from the bottom to at least the base of the photic zone (<150 m) during the deposition of the black claystones. In contrast, the green claystones are bioturbated, are enriched in Mn, do not show enrichments in redox-sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times, indicating more oxic water conditions. At the same time, there is evidence (e.g., abundance of biogenic silica and significant 13C-enrichment for OC of phytoplanktic origin) for enhanced primary productivity during the deposition of the black claystones. We propose that increased primary productivity periodically overwhelmed the oxic OM remineralisation potential of the bottom waters resulting in the deposition of OM-rich black claystones. Because the amount of oxygen used for OM remineralisation exceeded the amount supplied by diffusion and deep-water circulation, the northern proto-North Atlantic became euxinic during these periods. Both Sites 105 and 603B show trends of continually increasing TOC contents and HI values of the black claystones up section, which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine OM during oceanic anoxic event 2 (OAE2).

Sedimentologic and magnetic data of sediment cores on the western slope of the Mid-Atlantic Ridge

The relative paleointensity (RPI) method assumes that the intensity of post depositional remanent magnetization (PDRM) depends exclusively on the magnetic field strength and the concentration of the magnetic carriers. Sedimentary remanence is regarded as an equilibrium state between aligning geomagnetic and randomizing interparticle forces. Just how strong these mechanical and electrostatic forces are, depends on many petrophysical factors related to mineralogy, particle size and shape of the matrix constituents. We therefore test the hypothesis that variations in sediment lithology modulate RPI records. For 90 selected Late Quaternary sediment samples from the subtropical and subantarctic South Atlantic Ocean a combined paleomagnetic and sedimentological dataset was established. Misleading alterations of the magnetic mineral fraction were detected by a routine Fe/kappa test (Funk, J., von Dobeneck, T., Reitz, A., 2004. Integrated rock magnetic and geochemical quantification of redoxomorphic iron mineral diagenesis in Late Quaternary sediments from the Equatorial Atlantic. In: Wefer, G., Mulitza, S., Ratmeyer, V. (Eds.), The South Atlantic in the Late Quaternary: reconstruction of material budgets and current systems. Springer-Verlag, Berlin/Heidelberg/New York/Tokyo, pp. 239-262). Samples with any indication of suboxic magnetite dissolution were excluded from the dataset. The parameters under study include carbonate, opal and terrigenous content, grain size distribution and clay mineral composition. Their bi- and multivariate correlations with the RPI signal were statistically investigated using standard techniques and criteria. While several of the parameters did not yield significant results, clay grain size and chlorite correlate weakly and opal, illite and kaolinite correlate moderately to the NRM/ARM signal used here as a RPI measure. The most influential single sedimentological factor is the kaolinite/illite ratio with a Pearson's coefficient of 0.51 and 99.9% significance. A three-member regression model suggests that matrix effects can make up over 50% of the observed RPI dynamics.

Thallium concentrations and isotope composition of MORB glasses and altered oceani crust from DSDP/ODP Hole 504B and DSDP Hole 52-417D

Hydrothermal fluids expelled from the seafloor at high and low temperatures play pivotal roles in controlling seawater chemistry. However, the magnitude of the high temperature water flux of mid-ocean ridge axes remains widely disputed and the volume of low temperature vent fluids at ridge flanks is virtually unconstrained. Here, we determine both high and low temperature hydrothermal fluid fluxes using the chemical and isotopic mass balance of the element thallium (Tl) in the ocean crust. Thallium is a unique tracer of ocean floor hydrothermal exchange because of its contrasting behavior during seafloor alteration at low and high temperatures and the distinctive isotopic signatures of fresh and altered MORB and seawater. The calculated high temperature hydrothermal water flux is (0.17-2.93)*10**13 kg/yr with a best estimate of 0.72*10**13 kg/yr. This result suggests that only about 5 to 80% of the heat available at mid-ocean ridge axes from the crystallization and cooling of the freshly formed ocean crust, is released by high temperature black smoker fluids.The residual thermal energy ismost likely lost via conduction and/or through the circulation of intermediate temperature hydrothermal fluids that do not alter the chemical budgets of Tl in the ocean crust. The Tl-based calculations indicate that the low temperature hydrothermal water flux at ridge flanks is (0.2-5.4)*10**17 kg/yr. This implies that the fluids have an average temperature anomaly of only about 0.1 to 3.6 °C relative to ambient seawater. If these low temperatures are correct then both Sr and Mg are expected to be relatively unreactive in ridge-flank hydrothermal systems and this may explain why the extent of basalt alteration that is observed for altered ocean crust appears insufficient to balance the oceanic budgets of 87Sr/86Sr and Mg.