Rhenium and platinum-group element concentrations and Os isotope data for Philippine Sea Plate basalts from DSDP Legs 31, 58, and 59

Platinum-group elements (PGE), rhenium and osmium isotope data are reported for basalts from Deep Sea Drilling Project cores in the Philippine Sea Plate (PSP). Lithophile trace element and isotopic characteristics indicate a range of source components including DMM, EMII and subduction-enriched mantle. MORB-like basalts possess smooth, inclined chondrite-normalised PGE patterns with high palladium-PGE/iridium-PGE ratios, consistent with previously published data for MORB, and with the inferred compatibility of PGE. In contrast, while basalts with EMII-type lithophile element chemistry possess high Pt/Ir ratios, many have much lower Pd/Ir and unusually high Ru/Ir of >10. Similarly, back-arc samples from the Shikoku and Parece-Vela basins have very high Ru/Ir ratios (>30) and Pd/Ir as low as 1.1. Such extreme Pd/Ir and Ru/Ir ratios have not been previously reported in mafic volcanic suites and cannot be easily explained by variable degrees of melting, fractional crystallisation or by a shallow-level process such as alteration or degassing. The data appear most consistent with sampling of at least two mantle components with distinct PGE compositions. Peridotites with the required PGE characteristics (i.e. low Pd, but relatively high Ru and Re) have not been documented in oceanic mantle, but have been found in sub-continental mantle lithosphere and are the result of considerable melt depletion and selective metasomatic enrichment (mainly Re). The long-term presence of subduction zones surrounding the Philippine Sea Plate makes this a prime location for metasomatic enrichment of mantle, either through fluid enrichment or infiltration by small melt fractions. The Re-Os isotope data are difficult to interpret with confidence due to low Os concentrations in most samples and the uncertainty in sample age. Data for Site 444A (Shikoku Basin) give an age of 17.7+/-1.3 Ma (MSWD = 14), consistent with the proposed age of basement at the site and thus provides the first robust radiometric age for these samples. The initial 187Os/188Os of 0.1298+/-0.0069 is consistent with global MORB, and precludes significant metasomatic enrichment of Os by radiogenic slab fluids. Re-Os data for Sites 446A (two suites, Daito Basin) and 450 (Parece-Vela Basin) indicate ages of 73, 68 and 43 Ma, which are respectively, 30, 17 and >12 Ma older than previously proposed ages. The alkalic and tholeiitic suites from Site 446A define regression lines with different 187Os/188Osinitial (0.170+/-0.033 and 0.112+/-0.024, respectively) which could perhaps be explained by preferential sampling of interstitial, metasomatic sulphides (with higher time-integrated Re/Os ratios) by smaller percentage alkalic melts. One sample, with lithophile elements indistinguishable from MORB, is Os-rich (146 pg/g) and has an initial 187Os/188Os of 0.1594, which is at the upper limit of the accepted OIB range. Given the Os-rich nature of this sample and the lack of evidence for subduction or recycled crust inputs, this osmium isotope ratio likely reflects heterogeneity in the DMM. The dataset as a whole is a striking indication of the possible PGE and Os isotope variability within a region of mantle that has experienced a complex tectonic history.

Chemical composition of basalts from coarse debris of the Kara Sea bottom sediments

Study of basaltic debris from the Kara Sea bottom has shown its similarity to traps of the Eastern Siberia in mineralogy, structures and chemical composition. In comparison with oceanic tholeiites, the source of traps and Kara Sea basin basaltic melts was enriched in REE and some other incompatible elements. K-Ar dating of two samples of supposed autochtonous location from the eastern part of the Kara Sea basin has shown 209 and 218 Ma - younger than traps (247-248 Ma). Origin of Siberian traps used to connect with action of the mantle plume (Iceland plume, according to geodinamic reconstruction). Our new age data may be interpreted as an evidence of the Siberian plate moving over the head of plume.

Isotopic composition of Manihiki and Ontong Java basalts

Pb, Nd, and Sr isotopic results for lavas of the Cretaceous Ontong Java and Manihiki oceanic plateaus fall well within the modern-day oceanic island or hot pot field. The data provide no evidence of old continental basements but indicate a major involvement of 'Kerguelen-type' or 'EM-I'-like mantle in the sources of both plateaus, which appear to have probably been formed, at least in part, by hotspots. However, the presently active hotspots that Pacific plate reconstructions suggest might have been possible plateau sources lack Kerguelen-type isotopic compositions. Either these hotspots did not participate in the formation of the two plateaus, or if they did, Kerguelen-type material must have been volumetrically much more important early in their existence. Two hypotheses for the origins of these plateaus which involve hotspot sources are consistent with the sparse available geochemical, geochronological and geophysical data. The first holds that the plateaus formed cataclysmically in association with surfacing plume heads; the second posits a relatively steady but robust hotspot at or near a ridge crest and requires a much longer period of formation. A near-ridge origin appears to be indicated by evidence that most of the Pacific plateaus were built largely on relatively young ocean crust. However, we suggest that a near-ridge origin is also compatible with the plume head concept in that plume heads appear very likely to become associated with spreading axes through their influence on rift propagation, which should be substantially greater than for ordinary hotspots. In either case, the lack of hotspot tracks (seamount chains) attached to the two plateaus would be a consequence of ridge migration or rift propagation in a near-ridge setting.

(Table 1) Compressional and shear wave velocities and elastic constants of DSDP Hole 83-504B basalts

Compressional and shear wave velocities at confining pressures to 6 kb, densities, and porosities were measured for 32 samples obtained from 836 to 1350 m below seafloor (BSF) in Hole 504B, the section drilled on Leg 83 of the Deep Sea Drilling Project. These data in combination with similar measurements on 28 basalt samples from the section from 274.5 to 836 m, drilled on Legs 69 and 70, provide a comprehensive set of physical property data for over 1000 m of oceanic crust. The velocities, densities, and porosities measured in the laboratory exhibit greater variability in the upper portion of the hole. In general, compressional and shear wave velocities and densities increase with depth, reaching average values at 1 kbar of Vp = 6.45 km/s, Ks = 3.45 km/s and p = 2.94 g/cm3 within the sheeted dike section. Porosities decrease with depth to values generally less than 1% near the bottom of the hole

Silicate mineralogy of basalts at DSDP Leg 54 Holes

Basalts drilled from the East Pacific Rise, OCP Ridge, and Siqueiros fracture zone during Leg 54 are texturally diverse. Dolerites are equigranular at Sites 422 and 428 and porphyritic, with phenocrysts of plagioclase (An69.73) and Ca-rich clinopyroxene (Ca42Mg48Fe10) at Site 427. The East Pacific Rise lavas and some of those from the OCP Ridge are fine-grained and porphyritic. The majority of the large crystals are clustered skeletal glomerocrysts of plagioclase An64-77), together with olivine (Fo80-87), Ca-rich clinopyroxene, or both. Euhedral phenocrysts of plagioclase, together with olivine, Carich clinopyroxene, and Cr-Al spinel in some cases, occur in most of the fine-grained lavas. These phenocrysts are small (maximum dimension <1 mm in all but one sample), sparse (combined modal amount <1% in all samples), and distinctive from the megacrysts which characterize many ocean-floor lavas. In two East Pacific Rise lavas, zoned plagioclase (An83 cores) is the sole phenocryst phase. In other porphyritic lavas from all the main East Pacific Rise and OCP Ridge units drilled during Leg 54, the plagioclase phenocrysts contain cores of bytownite (An79-87) surrounded by more-sodic feldspar (An67-77). Core/rim relationships vary from continuous normal zoning, through discontinuous zoning, to extensive resorption of the calcic cores in some samples. The compositions of the plagioclase calcic cores are systematically related to those of the glomerophyric plagioclase and olivine in the lavas containing them. Furthermore, only one compositional population of calcic cores occurs in each rock. The possible causes of these relationships are far from clear. Magma mixing, although superficially applicable, is inconsistent with important aspects of the phenocryst mineralogy of these particular lavas. A more satisfactory model to explain both phenocryst zoning and rapid glomerocryst growth immediately before extrusion may be constructed by postulating influx of water into the upwelling magmas within Layer 3 of the oceanic crust beneath the East Pacific Rise, and subsequent loss of part of this water during effervescence within feeder dykes between Layer 3 and the ocean floor. It is shown that this model is fully consistent with published data on water and carbon dioxide contents and ratios in the pillow-margin glasses, vesicles, and phenocryst inclusions of ocean-floor basalts. The evidence for the precipitation of plagioclase- dominated crystalline assemblages from these magmas in the upper part of Layer 3 is concordant with recent geophysically based modeling of the structure of the East Pacific Rise. Calcium-rich clinopyroxenes in dolerites from the OCP Ridge and Siqueiros fracture zone show radial, oscillatory, and sector-zoning. In Sample 428A-5-2 (Piece 5a), the compositional trends resulting from this zoning closely resemble those of the pyroxenes in some lunar lavas. The controls on crystallization of interstitial pigeonite - epitaxial upon augite - in this rock are discussed. Both sector-zoning of the augite and nucleation of pigeonite within microvolumes of magma with a low Ca(Mg + Fe) ratio appear to be important factors.

Element analyses and isotope composition of basalts from the West Valley segment, Juan de Fuca Ridge, northeast Pacific

The 50 km-long West Valley segment of the northern Juan de Fuca Ridge is a young, extension-dominated spreading centre, with volcanic activity concentrated in its southern half. A suite of basalts dredged from the West Valley floor, the adjacent Heck Seamount chain, and a small near-axis cone here named Southwest Seamount, includes a spectrum of geochemical compositions ranging from highly depleted normal (N-) MORB to enriched (E-) MORB. Heck Seamount lavas have chondrite-normalized La/Sm en -0.3, 87Sr/86Sr = 0.70235 - 0.70242, and 206Pb/204Pb = 18.22 - 18.44, requiring a source which is highly depleted in trace elements both at the time of melt generation and over geologic time. The E-MORB from Southwest Seamount have La/Sm en -1.8, 87Sr/86Sr = 0.70245 - 0.70260, and 206Pb/204Pb = 18.73 - 19.15, indicating a more enriched source. Basalts from the West Valley floor have chemical compositions intermediate between these two end-members. As a group, West Valley basalts from a two-component mixing array in element-element and element-isotope plots which is best explained by magma mixing. Evidence for crustal-level magma mixing in some basalts includes mineral-melt chemical and isotopic disequilibrium, but mixing of melts at depth (within the mantle) may also occur. The mantle beneath the northern Juan de Fuca Ridge is modelled as a plum-pudding, with "plums" of enriched, amphibole-bearing peridotite floating in a depleted matrix (DM). Low degrees of melting preferentially melt the "plums", initially removing only the amphibole component and producing alkaline to transitional E-MORB. Higher degrees of melting tap both the "plums" and the depleted matrix to yield N-MORB. The subtly different isotopic compositions of the E-MORBs compared to the N-MORBs require that any enriched component in the upper mantle was derived from a depleted source. If the enriched component crystallized from fluids with a DM source, the "plums" could evolve to their more evolved isotopic composition after a period of 1.5-2.0 Ga. Alternatively, the enriched component could have formed recently from fluids with a lessdepleted source than DM, such as subducted oceanic crust. A third possibility is that enriched material might be dispersed as "plums" throughout the upper mantle, transported from depth by mantle plumes.

Geochemistry of altered phases, basalts and sediments of ODP Site 136-843

40Ar-39Ar incremental heating experiments on a relatively unaltered basalt from Site 843 yield a crystallization age of 110 ± 2 Ma for the central Pacific Ocean igneous basement near Hawaii. Previous estimates of the age of the basement inferred by indirect methods and from radiometric dates of the South Hawaiian Seamounts are too young by 20-30 m.y. Phyllosilicate alteration minerals from veins in the Site 843 basalts define a Rb/Sr isochron with an age of 94.5 ± 0.5 Ma. The isochron records the last equilibration of the phyllosilicate minerals with a hydrothermal fluid at about 16 m.y. after the formation of the igneous basement. The last event recorded by calcite veins is the sealing of the crust by a sufficient thickness of sediment to impede the free circulation of seawater into the crust. The chemistry of the alteration minerals indicates the rare earth elements in the hydrothermal solutions were derived from alteration of the basalts and, furthermore, were transported in solution as metal species and carbonate complexes. Calcite with approximately seawater 87Sr/86Sr, but Sr contents too low to precipitate directly from seawater, is suggested to have formed at a late stage in the alteration history of the crust by the reaction of seawater with calcite precipitated earlier from basalt-dominated hydrothermal fluids.

Geochemistry of oceanic crust of the North Atlantic

87Sr/a6Sr ratios, Sr, K, Rb and Cs contents and the petrology of basalts and secondary phases recovered from deep basement drilling at DSDP Sites 332B, 417A, 417D and 418A show that the oceanic crust alters in four distinct stages characterized by formation of palagonite, smectite and calcite (Stages I, II and III, respectively). Stage IV represents the final compaction of the crust, including a dehydration of the crust without major chemical changes. Isotopic age determinations by Hart and Staudigel (1978, doi:10.1029/GL005i012p01009) and Richardson et al. (doi:10.1029/JB085iB12p07195), show that, at least for Atlantic-type crustal regimes, Stage I and II last for a maximum of 3 m.y., and Stage III lasts beyond Stage I and II, but is probably completed in significantly less than 10 m.y. Stage IV is long-lived and may still be active at 100 m.y. Stages I and II, the phase of halmyrolysis, include geochemically significant interactions between seawater and basalt for the upper 500 m of layer II and involve volumes of seawater containing a large basaltic component. Stage III solutions show evidence of less seawater-basalt interaction, at least to depths of 500 m; calcites deposited from these solutions have Sr isotopic ratios close to seawater values; but also have very low Sr/Ca ratios indicating a large basalt Ca component in the solutions. Smectite formation is the result of the interaction of seawater and basalt. The initial 87Sr/a6Sr ratios of smectites represent the Sr isotopic composition of the solution when the smectite is being formed. Thereafter, alkalies may be continuously added to interlayer positions in the smectite in order of decreasing hydration energy (Cs is more enriched than Rb, Rb more than K). The later-formed carbonates have very low alkali concentrations, and 87Sr/86Sr ratios identical to contemporaneous seawater. Therefore, since the alkali concentrations in a whole rock sample are affected by different alteration processes, the alkali concentrations alone are not reliable indicators of the degree of alteration.

C and H geochemistry of altered oceanic crus of ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with dD values from -64per mil to -25per mil. All samples are enriched in water relative to fresh basalts. The dD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO2, extracted by step-heating technique, ranges between 564 and 2823 ppm with d13C values from -14.9per mil to -26.6per mil. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with d13C = -4.5per mil and (2) an organic compound with d13C = -26.6per mil. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO2 yield after H3PO4 attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO2 degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO2 is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when "fresh" oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO2, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ? -4.7per mil, similar to the d13C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 * 10**12 molC/yr.