(Table 1) Osmium concentrations and isotopic ratios for ODP Leg 125 peridotites

Mantle peridotites drilled from the Izu-Bonin-Mariana forearc have unradiogenic 187Os/188Os ratios (0.1193 to 0.1273), which give Proterozoic model ages of 820 to 1230 million years ago. If these peridotites are residues from magmatism during the initiation of subduction 40 to 48 million years ago, then the mantle that melted was much more depleted in incompatible elements than the source of mid-ocean ridge basalts (MORB). This result indicates that osmium isotopes record information about ancient melting events in the convecting upper mantle not recorded by incompatible lithophile isotope tracers. Subduction zones may be a graveyard for ancient depleted mantle material, and portions of the convecting upper mantle may be less radiogenic in osmium isotopes than previously recognized.

U-Pb, trace element, and Hf isotope analysis for Macquarie Island detrital zircon

Oceanic zircon trace element and Hf-isotope geochemistry offers a means to assess the magmatic evolution of a dying spreading ridge and provides an independent evaluation of the reliability of oceanic zircon as an indicator of mantle melting conditions. The Macquarie Island ophiolite in the Southern Ocean provides a unique testing ground for this approach due to its formation within a mid-ocean ridge that gradually changed into a transform plate boundary. Detrital zircon recovered from the island records this change through a progressive enrichment in incompatible trace elements. Oligocene age (33-27 Ma) paleo-detrital zircon in ophiolitic sandstones and breccias interbedded with pillow basalt have trace element compositions akin to a MORB crustal source, whereas Late Miocene age (8.5 Ma) modern-detrital zircon collected from gabbroic colluvium on the island have highly enriched compositions unlike typical oceanic zircon. This compositional disparity between age populations is not complimented by analytically equivalent eHf data that primarily ranges from 14 to 13 for sandstone and modern-detrital populations. A wider compositional range for the sandstone population reflects a multiple pluton source provenance and is augmented by a single cobble clast with eHf equivalent to the maximum observed composition in the sandstone (~17). Similar sandstone and colluvium Hf-isotope signatures indicate inheritance from a similar mantle reservoir that was enriched from the depleted MORB mantle average. The continuity in Hf-isotope signature relative to trace element enrichment in Macquarie Island zircon populations, suggests the latter formed by reduced partial melting linked to spreading-segment shortening and transform lengthening along the dying spreading ridge.

Geochemistry and minerals at DSDP Hole 76-534A

Leg 76 sampled 31.5 m of basaltic basement at Deep Sea Drilling Project Hole 534A in the Blake-Bahama Basin. The basalts represent a short section of mineralogically uniform, sparsely plagioclase-phyric pillow flows, composed mainly of plagioclase, augitic clinopyroxene, iron-titanium oxides with variable amounts of alteration products (smectite ± carbonate ± quartz). Their major element chemistry is typical of mid-ocean ridge tholeiites and has normative compositions of olivine tholeiites. Mg/(Mg + Fe**2+) ratios range from 0.58 to 0.60, which suggests that these basalts are evolved compared to primitive mantle melts.

Major and trace elements at DSDP Leg 74 Holes

Deep Sea Drilling Project Leg 74 drilled basement on the Walvis Ridge at Sites 525, 527, and 528. These sites are located on the crest and flanks of the segment of the Ridge about 68 to 70 m.y. old in the central province of the Ridge. Each site has a number of distinct subaqueous flows separated by sediment layers. Although variation in geochemistry among units and sites is related in part to alteration or crystal fractionation, some is caused by small-scale compositional variation in the mantle source of the basalts. Leg 74 basalts are similar to other basalts recovered from the Walvis Ridge and the Rio Grande Rise. They show distinct compositional differences to mid-ocean ridge basalts in general, to those recovered from the South Atlantic at this latitude, and to basalts presently erupting in Tristan da Cunha. The composition of the Walvis Ridge basalts does not suggest simple mixtures of present-day MORB and Tristan da Cunha melts. If the Walvis Ridge represents the trace of the Tristan da Cunha hot spot as the plates separated, then the composition of the mantle source has differed at different times in the past, which suggests mantle heterogeneity.

Biogenic sedimentation of DSDP Site 85-574

The equatorial Pacific is an important part of the global carbon cycle and has been affected by climate change through the Cenozoic (65 Ma to present). We present a Miocene (12-24 Ma) biogenic sediment record from Deep Sea Drilling Project (DSDP) Site 574 and show that a CaCO3 minimum at 17 Ma was caused by elevated CaCO3 dissolution. When Pacific Plate motion carried Site 574 under the equator at about 16.2 Ma, there is a minor increase in biogenic deposition associated with passing under the equatorial upwelling zone. The burial rates of the primary productivity proxies biogenic silica (bio-SiO2) and biogenic barium (bio-Ba) increase, but biogenic CaCO3 decreases. The carbonate minimum is at ~17 Ma coincident with the beginning of the Miocene climate optimum; the transient lasts from 18 to 15 Ma. Bio-SiO2 and bio-Ba are positively correlated and increase as the equator was approached. Corg is poorly preserved, and is strongly affected by changing carbonate burial. Terrestrial 232Th deposition, a proxy for aeolian dust, increases only after the Site 574 equator crossing. Since surface production of bio-SiO2, bio-Ba, and CaCO3 correlate in the modern equatorial Pacific, the decreased CaCO3 burial rate during the Site 574 equator crossing is driven by elevated CaCO3 dissolution, representing elevated ocean carbon storage and elevated atmospheric CO2. The length of the 17 Ma CaCO3 dissolution transient requires interaction with a 'slow' part of the carbon cycle, perhaps elevated mantle degassing associated with the early stages of Columbia River Basalt emplacement.

Petrology of high-MgO bronzite andesite resembling boninite at DSDP Hole 60-458

A high-MgO andesite which is texturally similar to boninite and a variolitic basalt collected from Site 458, about 100 km west of the Mariana Trench, have been studied through microprobe analyses and melting experiments at high water pressures. The boninite-type andesite is very similar in composition and texture to a boninite from Bonin Islands, except that the former is more calcic than the latter. The variolitic basalt contains magnesian pigeonite (Ca12Mg74Fe14) in cores of augite microphenocrysts. This pigeonite crystallized at temperatures above 1200°C. In the melting experiments of the boninite-type rock, clinopyroxene crystallizes as a liquidus phase at pressures at least above 8 kbar. No olivine crystallizes near the liquidus temperatures, indicating that the magma of this rock cannot be in equilibrium with the upper mantle periodotite (lherzolite) at depths at least greater than 25 km. The boninite-type rock is probably a product of fractional crystallization of a more primitive magma (e.g., olivine-bearing boninite magma) by separation of olivine and orthopyroxene. The magma of the variolitic basalt also cannot be in equilibrium with the upper mantle peridotite, and may be a product of fractional crystallization of a more primitive basaltic magma.

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.

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 Umantle-derived agent is thought to be the cause for the trend towards radiogenic Pb. This material had intermediate 87Sr/86Sr and may have originated from non-MORB off axis mantle. The main primary igneous isotopic variation of the gabbros is suggested to have been derived from the MORB-mantle and is defined mainly by leached samples from both ODP Leg 176 and Leg 118 and can be explained by two-component mixing of an end-member with composition like Central Indian Ridge basalts and an end-member with composition unlike any MORB. The latter is characterized by very unradiogenic Pb, in particular 207Pb/204Pb, and may have an origin with affinity to old depleted mantle (DM). The isotopic composition of the magmas parental to the FeTi-oxide rich rocks cannot be distinguished from the magmas parental to the primitive gabbros and an intimate relationship is indicated. The small-scale inhomogeneity indicated for the SWIR MORB-mantle at the Atlantis II Fracture Zone was probably inherited by the lower crustal rocks due to small-scale melting and monogenetic magma chambers at this slow spreading ridge.

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 Lesser Antilles forearc sediments

Oceanic sediments contain the products of erosion of continental crust, biologic activity and chemical precipitation. These processes create a large diversity of their chemical and isotopic compositions. Here we focus on the influence of the distance from a continental platform on the trace element and isotopic compositions of sediments deposited on the ocean floor and highlight the role of zircons in decoupling high-field strength elements and Hf isotopic compositions from other trace elements and Nd isotopic compositions. We report major and trace element concentrations as well as Sr and Hf isotopic data for 80 sediments from the Lesser Antilles forearc region. The trace-element characteristics and the Sr and Hf isotopic compositions are generally dominated by detrital material from the continental crust but are also variably influenced by chemical or biogenic carbonate and pure biogenic silica. Next to the South American continent, at DSDP Site 144 and on Barbados Island, sediments, coarse quartz arenites, exhibit marked Zr and Hf excesses that we attribute to the presence of zircon. In contrast, the sediments from DSDP Site 543, which were deposited farther away from the continental platform, consist of fine clay and they show strong deficiencies in Zr and Hf. The enrichment or depletion of Zr-Hf is coupled to large changes in Hf isotopic compositions (-30 < epsilon-Hf < +4) that vary independently from the Nd isotopes. We interpret this feature as a clear expression of the "zircon effect" suggested by Patchett and coauthors in 1984. Zircon-rich sediments deposited next to the South American continent have very low epsilon-Hf values inherited from old zircons. In contrast, in detrital clay-rich sediments deposited a few hundred kilometers farther north, the mineral fraction is devoid of zircon and they have drastically higher epsilon-Hf values inherited from finer, clay-rich continental material. In the two DSDP sites, average Hf isotopes are very unradiogenic relative to other oceanic sediments worldwide (epsilon-Hf = -14.4 and -7.4) and they define the low Hf end member of the sedimentary field in Hf-Nd space. Their compositions correspond to end members that, when mixed with mantle, are able to reproduce the pattern of volcanic rocks from the Lesser Antilles. More generally, we find a relationship between Nb/Zr ratios and the vertical deviation of Hf isotope ratios from the Nd-Hf terrestrial array and we suggest that this relationship can be used as a tool to distinguish sediment input from fractionation during melting during the formation of arc lavas.

Geochemistry of ODP Hole 135-841B

Two igneous rock units were recovered at Site 841. More than 200 m of island-arc rhyolites, rhyolitic tuffs, lapilli tuffs, and pumice breccias, divided into five units, compose the basement at the site. These rhyolitic volcanics are late middle Eocene or older and formed part of a subaerial rhyolitic volcano. These low-K rhyolites were produced by fractional crystallization of a more mafic arc-tholeiitic lava or by dehydration melting of lower crustal arc tholeiites. The Site 841 basement rocks are similar in composition to high-SiO2 lavas in the Eocene basement on 'Eua and crystallized from depleted island-arc-tholeiitic basalts like those exposed on 'Eua. No evidence is present in the rhyolites, or in the clasts enclosed within them, for boninite series magmas at Site 841. The Site 841 rhyolitic complex bears no resemblance to Cretaceous rhyolites from the Lord Howe Rise, which are enriched in K and incompatible elements. The volcanic rocks at Site 841 are part of a widely distributed Eocene volcanic episode that marked the earliest phases of subduction in the Tonga region; they are not part of an older crustal fragment. The second igneous sequence is a series of basaltic dikes and sills that intruded Miocene sediments. These basalts have trace element abundances and ratios identical to upper Miocene lavas from the Lau Ridge. The Site 841 basalts do not have any geochemical characteristics that suggest they were generated by unusual thermal conditions in the shallow sub-forearc mantle. They are most reasonably interpreted as intrusions fed by basement dikes propagated from the associated active arc. No evidence for local serpentinite exposures, like those that are common in the Mariana forearc, was found at Site 841. The results from Site 841 provide strong support for hypotheses of forearc evolution that have been advanced for the Izu-Bonin-Mariana system.