Geochemistry of pelagic and hemipelagic sediments of ODP Leg 126 sites

Chemical analyses were performed on major, minor, and rare-earth elements of pelagic and hemipelagic sediments of the forearc, arc, and backarc sites of the Izu-Bonin Arc, Ocean Drilling Program Leg 126. Analyses of the hemipelagic and pelagic sediments of this area indicate that the chemical composition of this arc is highly affected by the chemical composition of rocks of this arc as a source of sediments. The Oligocene sediments, which are characterized by high MgO contents, reflect the chemical composition of the Paleogene volcanic rocks of the immature arc. Moreover, the late Miocene to Quaternary sediments with low MgO contents are attributed to the composition of the present arc. We also suggest that the sedimentation rates and topography of the sedimentary basin affect the MnO and SiO2 contents of pelagic and hemipelagic sediments.

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.

Geochemistry of serpentenites from DSDP Hole 84-566C

We studied a unique chrysotile-antigorite serpentinite, drilled on Deep Sea Drilling Project Leg 84 (Site 566) in the Guatemala forearc. Our in situ major and trace element data provide new constraints on possible reactions and associated trace element mobilisation during shallow serpentinite subduction. Chrysotile of the studied serpentinite, formed by the hydration of an upper mantle peridotite precursor, is partially replaced by antigorite (alone) which also occurs in 0.5 mm wide unoriented veins crosscutting the rock. Based on textural relationships and the P-T-X stability of the rock forming phases, the replacement of chrysotile by antigorite occurred at T < 300 °C, due to interaction between the chrysotile-serpentinite and an aqueous fluid. A comparison of the chemical compositions of reactant and product phases reveals that about 90% of the Cl, more than 80% of the B and about 50% of the Sr hosted originally by chrysotile was lost during fluid-assisted chrysotile-to-antigorite transformation and accompanying partial dehydration, and documents the much lower affinity of antigorite for trace element uptake than that of chrysotile. The fluid-assisted chrysotile-to-antigorite transformation and associated trace element loss documented here can occur in the shallow (< 30 km) region of subduction zones. This transformation decreases notably the Cl and B inventory of subducting serpentinites, which are regarded as one of the most important carriers of these elements into subduction zones. The evolution of serpentinites during initial subduction stages thus appears to be critical in the recycling of specific trace elements such as B or Cl from forearc to subarc depths.

Thallium isotope composition in pyrites

This paper presents the first study of Tl isotopes in early diagenetic pyrite. Measurements from two sections deposited during the Toarcian Ocean Anoxic Event (T-OAE, ~183 Ma) are compared with data from Late Neogene (<10 Ma) pyrite samples from ODP legs 165 and 167 that were deposited in relatively oxic marine environments. The Tl isotope compositions of Late Neogene pyrites are all significantly heavier than seawater, which most likely indicates that Tl in diagenetic pyrite is partially sourced from ferromanganese oxy-hydroxides that are known to display relatively heavy Tl isotope signatures. One of the T-OAE sections from Peniche in Portugal displays pyrite thallium isotope compositions indistinguishable from Late Neogene samples, whereas samples from Yorkshire in the UK are depleted in the heavy isotope of Tl. These lighter compositions are best explained by the lack of ferromanganese precipitation at the sediment-water interface due to the sulfidic (euxinic) conditions thought to be prevalent in the Cleveland Basin where the Yorkshire section was deposited. The heavier signatures in the Peniche samples appear to result from an oxic water column that enabled precipitation of ferromanganese oxy-hydroxides at the sediment-water interface. The Tl isotope profile from Yorkshire is also compared with previously published molybdenum isotope ratios determined on the same sedimentary succession. There is a suggestion of an anti-correlation between these two isotope systems, which is consistent with the expected isotope shifts that occur in seawater when marine oxic (ferromanganese minerals) fluxes fluctuate. The results outlined here represent the first evidence that Tl isotopes in early diagenetic pyrite have potential to reveal variations in past ocean oxygenation on a local scale and potentially also for global oceans. However, much more information about Tl isotopes in different marine environments, especially in anoxic/euxinic basins, is needed before Tl isotopes can be confidently utilized as a paleo-redox tracer.

Calcium isotopic composition of planktonic foraminifera from ODP Site 154-925

An 18 million year record of the Ca isotopic composition (d44/42Ca) of planktonic foraminiferans from ODP site 925, in the Atlantic, on the Ceara Rise, provides the opportunity for critical analysis of Ca isotope-based reconstructions of the Ca cycle. ?44/42Ca in this record averages +0.37+/-0.05 (1 sigma SD) and ranges from +0.21? to +0.52?. The record is a good match to previously published Neogene Ca isotope records based on foraminiferans, but is not similar to the record based on bulk carbonates, which has values that are as much as 0.25? lower. Bulk carbonate and planktonic foraminiferans from core tops differ slightly in their d44/42Ca (i.e., by 0.06+/-0.06? (n = 5)), while the difference between bulk carbonate and foraminiferan values further back in time is markedly larger, leaving open the question of the cause of the difference. Modeling the global Ca cycle from downcore variations in d44/42Ca by assuming fixed values for the isotopic composition of weathering inputs (d44/42Ca_w) and for isotope fractionation associated with the production of carbonate sediments (D_sed) results in unrealistically large variations in the total mass of Ca2+ in the oceans over the Neogene. Alternatively, variations of +/-0.05? in the Ca isotope composition of weathering inputs or in the extent of fractionation of Ca isotopes during calcareous sediment formation could entirely account for variations in the Ca isotopic composition of marine carbonates. Ca isotope fractionation during continental weathering, such as has been recently observed, could easily result in variations in d44/42Ca_w of a few tenths of permil. Likewise a difference in the fractionation factors associated with aragonite versus calcite formation could drive shifts in D_sed of tenths of permil with shifts in the relative output of calcite and aragonite from the ocean. Until better constraints on variations in d44/42Ca_w and D_sed have been established, modeling the Ca2+ content of seawater from Ca isotope curves should be approached cautiously.

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.

Isotopic and chemical compositions of lower crust rocks and minerals from ODP Hole 176-735B

The composition of gabbroic rocks from the drill core of Hole 735B (ODP Leg 176) at the 11 Ma Atlantis II bank close to the slow spreading Southwest Indian Ridge (SWIR) has been analyzed for major and trace elements and Sr, Nd and Pb isotopic composition. The samples are thought to represent much of the mineralogical and geochemical variation in a vertical 1-km section (500-1500 m below the sea floor) of the lower ocean crust. Primitive troctolitic gabbros, olivine gabbros and gabbros that have Mg#=84-70, Ca#>61 and low Na# (Na/(Na+Al)) (8-17) are intruded by patches or veins of more evolved FeTi-oxide rich gabbroic and dioritic rocks with Mg# to 20, Ca# to 32, Na#=14-23, TiO2<7 wt.% and FeOtotal<18 wt.%. All rocks are acdcumulates, and incompatible element concentrations are low, e.g. Pb=0.1-0.7 ppm and U

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Carbonate system of surface sediments from the South Pacific

B/Ca ratios in Cibicides mundulus and Cibicides wuellerstorfi have been shown to correlate with the degree of calcite saturation in seawater (D[CO32-]). In the South Pacific, a region of high importance in the global carbon cycle, these species are not continuously present in down-core records. Small numbers of epibenthic foraminifera in samples present an additional challenge, which can be overcome by using laser ablation-inductively coupled-mass spectrometry (LA-ICP-MS). We present a laser ablation based core-top calibration for Cibicides cf. wuellerstorfi, a C. wuellerstorfi morphotype that is abundant in the South Pacific and extend the existing global core top calibration for C. mundulus and C. wuellerstorfi to this region. B/Ca in C. cf. wuellerstorfi are linearly correlated with D[CO32-] and possibly display a higher sensitivity to calcite saturation changes than C. wuellerstorfi. Trace element profiles through C. wuellerstorfi and C. mundulus reveal an intra-shell B/Ca variation of ±36% around the mean shell value. Mg/Ca and B/Ca display opposite trends along the shell. Both phenomena likely result from ontogenetic effects. Intra-shell variability equals intra-sample variability, mean sample B/Ca values can thus be reliably calculated from averaged spot results of single specimen. In the global B/Ca-D[CO32-] range, we observe an inverse relationship between water mass age and D[CO32-].

Os isotope ratios of sediments from the Eocene-Oligocene boundary

Osmium (Os) isotope analyses of bulk sediments from the South Atlantic, Equatorial Pacific, and the Italian Apennines yield a well-dated and coherent pattern of 187Os/188Os variation from the late Eocene to the early Oligocene. The resulting composite record demonstrates the global character of two prominent features of the low-resolution LL44-GPC3 Os isotope record (Pegram and Turekian, 1999, doi:10.1016/S0016-7037(99)00308-7). These are: (1) a pronounced minimum in 187Os/188Os (0.22-0.27) in the late Eocene, between 34 and 34.5 Ma, and (2) a subsequent rapid increase in 187Os/188Os, to approximately 0.6 by 32 Ma. An ultramafic weathering event and an increased influx of extraterrestrial particles to the Earth are discussed as alternative explanations for the late Eocene 187Os/188Os minimum. Comparison of the 187Os/188Os to benthic foraminiferal oxygen isotope records demonstrates that the nearly three-fold increase in 187Os/188Os from the late Eocene minimum coincides with the growth and decay of the first large ice sheet of the Oligocene (Oi1 (Miller et al., 1991, doi:10.1029/90JB02015)). The fine structure of the Os isotope record indicates that enhanced release of radiogenic Os, unrelated to the recovery from late Eocene minimum, lagged the initiation of the Oi1 event by roughly 0.5 Myr. This record, in conjunction with weathering studies in modern glacial soils (Blum, in: W.F. Ruddiman (Ed.), Tectonic Uplift and Climate Change, Plenum Press, New York, 1997, pp. 259-288; Peucker-Ehrenbrink and Blum, 1998, doi:10.1016/S0016-7037(98)00227-0), suggests that exposure of freshly eroded material during deglaciation following Oi1 enhanced chemical weathering rates, and may have contributed to ice sheet stabilization by drawing down atmospheric carbon dioxide. The improved temporal resolution and age control of the refined Eocene-Oligocene Os isotope record also makes it possible to illustrate the late Eocene Os isotope excursion as a tool for global correlation of marine sediments.

Pb-, Sr-, and Nd-isotopic composition of basaltic rocks from the Lau Basin

New Pb, Sr, and Nd isotope data are presented for 64 samples from the six backarc sites drilled during Leg 135. Systematic changes in Pb and Sr compositions illustrate significant isotopic variations between and within sites as well as provide two key pieces of information. First, a recent influx of asthenosphere with Indian Ocean mantle affinities has occurred and has successfully displaced older "Pacific" asthenosphere from the mantle underlying the backarc region. Second, clear evidence exists for mixing between these two asthenospheric end-members and at least one "arc-like" component. The latter was not the same as most material currently erupting in the Tofua Arc, but it must have had a more radiogenic Pb-isotope signature, perhaps similar to rocks analyzed from the islands of Tafahi, and Niuatoputapu. A comparison between the isotopic variations and the tectonic setting of the drill sites reveals consistent and important information regarding the mantle dynamics beneath the evolving backarc basin. We propose a model in which the source of upwelling magmas changes from Pacific to Indian Ocean asthenosphere with the propagation of seafloor spreading, a model with important implications for the rate of mantle influx into this region. Although the chemistries of backarc magmas have been profoundly influenced by this process, an additional consequence is the advection of Indian Ocean asthenosphere into the sub-arc mantle source. The isotopic compositions of arc rocks from the vicinity have been reevaluated on the basis of the proposed mantle advection model. We suggest that the slab-derived flux of trace elements into the arc wedge has remained relatively uniform with time (i.e., ~40 Ma), so that the change in arc chemistry results from mantle source substitution, rather than from differences in the composition of the downgoing plate.

Geochemistry of ODP Site 145-882

Measurements of benthic foraminiferal cadmium:calcium (Cd/Ca) have indicated that the glacial-interglacial change in deep North Pacific phosphate (PO4) concentration was minimal, which has been taken by some workers as a sign that the biological pump did not store more carbon in the deep glacial ocean. Here we present sedimentary redox-sensitive trace metal records from Ocean Drilling Program (ODP) Site 882 (NW subarctic Pacific, water depth 3244 m) to make inferences about changes in deep North Pacific oxygenation - and thus respired carbon storage - over the past 150,000 yr. These observations are complemented with biogenic barium and opal measurements as indicators for past organic carbon export to separate the influences of deep-water oxygen concentration and sedimentary organic carbon respiration on the redox state of the sediment. Our results suggest that the deep subarctic Pacific water mass was depleted in oxygen during glacial maxima, though it was not anoxic. We reconcile our results with the existing benthic foraminiferal Cd/Ca by invoking a decrease in the fraction of the deep ocean nutrient inventory that was preformed, rather than remineralized. This change would have corresponded to an increase in the deep Pacific storage of respired carbon, which would have lowered atmospheric carbon dioxide (CO2) by sequestering CO2 away from the atmosphere and by increasing ocean alkalinity through a transient dissolution event in the deep sea. The magnitude of change in preformed nutrients suggested by the North Pacific data would have accounted for a majority of the observed decrease in glacial atmospheric pCO2.