(Table 1) Lead isotopic composition and concentration at DSDP Leg 82 Holes

The aim of DSDP Leg 82 was to decipher the temporal and spatial evolution of Azores Plume. The Pb-isotopic results of this leg are rather complex, and can be summarized as follows: 1. At a given site (561, 558), variations of Pb isotopic compositions are generally accompanied by major changes in trace-element ratios, indicating significant heterogeneity of the source region. There is a correlation between Pb isotopes and trace elements. 2. In contrast, if all the data (i.e., all studied sites) of Leg 82 are considered together, no correlation can be discerned between Pb isotopes and trace elements. Site 556, especially, shows abnormal behavior. 3. Leg 82 samples not only cover the entire range of Pb isotopic composition previously established for the Atlantic Ocean, but extend this field to more radiogenic values. 4. The data are compatible with the hot-spot model proposed by Schilling (1975), if one considers that the Azores Plume itself is isotopically heterogeneous, and that it has been progressively contaminated to various degrees by upper mantle material.

(Table 1) Sulfur content and sulfur-isotope ratios at DSDP Leg 82 Holes basalts

The sulfur contents of 21 basalt samples from four DSDP Leg 82 holes were determined and the isotopic compositions of sulfur were measured on 15 of them. Most of the basalts are altered and have sulfur contents of about 100 ppm. Isotopic ratios for sulfate and total sulfur range from +0.7 to +10.5 per mil, indicating almost complete leaching of the igneous sulfide in low-sulfur samples by alteration. Total sulfur content of some samples ranges between 960 and 1170 ppm, somewhat higher than expected for tholeiitic basalts. The isotope ratios of total sulfur in these samples are slightly shifted to values heavier than the generally assumed mantle ratio of zero, and this shift is thought to result from a secondary source of sulfur.

Chemical composition of basalts and basaltic glasses from the Sierra Leone Fracture Zone region

Major and trace element (including REE) geochemistry of basalts and chilled basaltic glasses from the MAR axial zone in the vicinity of the Sierra Leone FZ (5-7°10'N) has been studied. Associations of basalts of various compositions with particular ocean-floor geological structural features have been analyzed as well. Three basaltic varieties have been discriminated. Almost ubiquitous are high-Mg basalts (Variety 1) that are derivatives of N-MORB tholeiitic melts and that are produced in the axial zone of spreading. Variety 2 is alkaline basalts widespread on the southwestern flank of the MAR crest zone in the Sierra Leone region, likely generated through deep mantle melting under plume impact. Variety 3 is basalts derivative from T- and P-MORB-like tholeiitic melts and originating through addition of deeper mantle material to depleted upper mantle melts. Magma generation parameters, as calculated from chilled glass compositions, are different for depleted tholeiites (44-55 km, 1320-1370°C) and enriched tholeiites (45-78 km, 1330-1450°C). Mantle plume impact is shown to affect not only tholeiitic basalt compositions but also magma generation conditions in the axial spreading zone, resulting in higher Ti and Na concentrations in melts parental to rift-related basalts occurring near the plume. T- and P-MORBs are also developed near areas where mantle plumes are localized. High-Mg basalts are shown to come in several types with distinctive Ti and Na contents. Nearly every single MAR segment (bounded by sinistral strike slips and the Bogdanov Fracture Zone) is featured by its own basalt type suggesting that it has formed above an asthenospheric diapir with its unique magma generation conditions. These conditions are time variable. Likely causes of temporal and spatial instability of the mantle upwelling beneath this portion of the MAR are singular tectonic processes and plume activity. In sulfide-bearing rift morphostructures (so-called "Ore area'' and the Markov Basin), basalts make up highly evolved suites generated through olivine and plagioclase fractionation, which is suggestive of relatively long-lived magma chambers beneath the sulfide-bearing rift morphostructures. Functioning of these chambers is a combined effect of singular geodynamic regime and plume activity. In these chambers melts undergo deep differentiation leading to progressively increasing concentration of sulfide phase, eventually to be supplied to the hydrothermal plumbing system.

Geochemistry of subducted volcaniclastic sediments from Mariana arc magmas

The phase relations of natural volcaniclastic sediments from the west Pacific Ocean were investigated experimentally at conditions of 3-6 GPa and 800-900 °C with 10 wt.% added H2O (in addition to ~ 10 wt.% structurally-bound H2O) to induce hydrous melting. Volcaniclastic sediments are shown to produce a sub-solidus assemblage of garnet, clinopyroxene, biotite, quartz/coesite and the accessory phases rutile ± Fe-Ti oxide ± apatite ± monazite ± zircon. Hydrous melt appears at temperatures exceeding 800-850 °C, irrespective of pressure. The melt-producing reaction consumes clinopyroxene, biotite and quartz/coesite and produces orthopyroxene. These phase relations differ from those of pelagic clays and K-bearing mid ocean ridge basalts (e.g. altered oceanic crust) that contain phengite, rather than biotite, as a sub-solidus phase. Despite their relatively high melt productivity, the wet solidus for volcaniclastic sediments is found to be higher (825-850 °C) than other marine sediments (700-750 °C) at 3 GPa. This trend is reversed at high-pressure conditions (6 GPa) where the biotite melting reaction occurs at lower temperatures (800-850 °C) than the phengite melting reaction (900-1000 °C). Trace element data was obtained from the 3 GPa run products, showing that partial melts are depleted in heavy rare earth elements (REE) and high field strength elements (HFSE), due to the presence of residual garnet and rutile, and are enriched in large ion lithophile elements (LILE), except for Sr and Ba. This is in contrast to previous experimental studies on pelagic sediments at sub-arc depths, where Sr and Ba are among the most enriched trace elements in glasses. This behavior can be partly attributed to the presence of residual apatite, which also host some light REE in our supra-solidus residues. Our new experimental results account for a wide range of trace element and U-series geochemical features of the sedimentary component of the Mariana arc magmas, including imparting a substantial Nb anomaly to melts from an anomaly-free protolith.

Geochemistry of basalts of the Indian Ocean

Indian Ocean crust formed at Sites 765 and 766 is geochemically comparable to that presently forming in the Red Sea. In both cases, we interpret the crust as reflecting high degrees of mantle melting that are associated with an enhanced thermal gradient below recently rifted continental lithosphere. Asthenospheric melts formed in this environment are rich in CaO and FeO, poor in Na2O and Al2O3, and characterized by depleted rare earth element (REE) profiles ([La/Sm]n approximately 0.5-0.6). Both the Red Sea basalts and the basalts at Sites 765 and 766 are distinct from those erupted at the present Mid-Indian Ocean Ridge. The isotope characteristics of the Site 765 basalts define a geochemical signature similar to that of the present-day Mid-Indian Ocean Ridge basalts (MIORB). The Indian Ocean mantle domain is distinct from that of the Atlantic and Pacific oceans, and this distinction has persisted since Jurassic time, when the Site 765 oceanic crust was formed.

Strontium and rubidium isotopes in serpentinites from ODP Site 195-1200

Subduction of the Pacific plate beneath the Mariana forearc releases fluids to the overlying mantle wedge that ascend, producing serpentinite "mud" that discharges on the ocean floor. As part of Leg 195 of the Ocean Drilling Program cores were obtained from drill-holes into the mud volcanoes. We report the isotopic composition of Sr in water squeezed from intervals of the cores, in the serpentinite mud, in leaches of the serpentinite mud, and in entrained small harzburgitic clasts. Except in the upper few meters below the seawater-mud interface, where pore water approaches seawater Sr concentration and isotopic ratio, Sr concentration and isotopic composition remain constant at 3-6 µmol/kg and ~0.7054. Because the elemental chemistry of the pore water is unlike seawater, this isotopic composition reflects fluids derived from the subducted slab, probably modified by reaction with mantle material during ascent. Higher Sr isotopic ratios, up to 0.7087, - but not with higher Sr concentrations in pore water - occur superimposed on an advection profile at 13-16 mbsf surrounding a thin layer of foraminiferal sand. Since the upward seepage velocity of slab fluids in the mud volcano vents is a few cm/yr, exchange of Sr between these carbonates and the rising fluids must have occurred within a maximum of a few hundred years, essentially instantaneously given the millions, or tens of millions, of years the mud volcanoes have been in existence. In contrast, the strontium isotopic compositions of leached serpentinite mud, and of small harzburgite clasts entrained in the mud, are always significantly greater than that of the pore water. In small harzburgite clasts the ratio reaches 0.7088, almost as high as the seawater value of 0.7092 and much higher than the value of typical mantle-derived strontium of ~0.704. The serpentinite muds and harzburgite clasts clearly equilibrated with seawater Sr when they were initially deposited at the surface of the seamount, but following burial they have not fully equilibrated with strontium in the pore water now discharging through the vents. These variations in the strontium isotopic composition of solids and pore waters are more consistent with episodic expulsion of fluids in the subduction zone than steady state flow. Whereas strontium in carbonates equilibrates isotopically within a few hundred years, strontium in buried harzburgite clasts does not equilibrate in the same time, assuming steady state rates of upward fluid flow. By inference, the harzburgite clasts and associated serpentinite mud must have been near the seafloor, unburied, for a yet undetermined but much longer period of time to have equilibrated from ~0.704 to 0.709 prior to subsequent burial. It may be possible to characterize at least the periodicity of fluid release in the mud volcano setting by investigating the zonation of strontium isotopic composition of hartzburgite clasts throughout the 60-meter deep composite cores.

(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.