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.

Concentration of the rare-earth elements in metalliferous sediments from DSDP Leg 92 holes

DSDP Leg 92 drilled at four sites along an east-west transect at 19°S on the western flank of the East Pacific Rise (EPR), in an area where sediments are essentially a mixture of hydrothermal and biogenic components, with only a minimal contribution of clastic material. Rare-earth element (REE) data on the metalliferous (non-carbonate) fraction of samples ranging in age from ~2 to ~27 Ma indicate the existence of two distinct groups of patterns corresponding to two broad age groups, one <=8 Ma, the other >=10 Ma. Within each group, REE patterns have characteristics which are near-uniform, despite large variations in total REE abundances. Sediments of the younger group are enriched in light REE (LREE) relative to deep bottom waters influenced by the hydrothermal plume extending west from the EPR at 19°S. Sediments of the older groups show further relative LREE enrichment and/or heavy REE (HREE) depletion. Surficial sediments deposited beneath the lysocline have high Sum REE concentrations resulting from slow accumulation rates, and patterns resembling older sediments due to early diagenetic effects. A correlation between the mass accumulation rates (MAR) of Sum REE and Fe + Mn suggests that ferromanganese particulate matter supplied by the hydrothermal plume scavenges REE; during this process the LREE are preferentially removed from plume seawater. The MAR of Fe + Mn shows a general decrease with age above basement, whereas Sum REE concentrations in the metalliferous component increase with age above basement. This supports the Ruhlin and Owen model wherein limited scavenging of REE, due to rapid burial of sediment near the palaeo-axis, leads to low concentrations (but high MAR-values) for the REE. Following deposition and burial of the hydrothermal component, further relative flattening of the REE pattern takes place, probably the result of diagenetic reactions over several million years. Phase partitioning data indicate that the proportion of REE residing in more poorly crystalline phases tends to increase with age (from ~45% to 90% of Sum REE). This suggests that as initial ferromanganese precipitates undergo diagenetic recrystallization, REE are transferred to the poorly crystalline phases, and/or are scavenged from pore waters by these phases. Because of the various modifications to REE patterns apparently produced both in the water column and post-depositional settings, the REE patterns of metalliferous sediments will not reflect fine-scale REE variations in associated oceanic water masses.

Elements and mineralogical compostions from different sediment cores off the southern China Sea

The mineralogy, major and trace elements, and neodymium and strontium isotopes of surface sediments in the South China Sea (SCS) are documented with the aim of investigating their applicability in provenance tracing. The results indicate that mineralogical compositions alone do not clearly identify the sources for the bulk sediments in the SCS. The Nd isotopic compositions of the SCS sediments show a clear zonal distribution. The most negative epsilon-Neodymium values were obtained for sediments from offshore South China (-13.0 to -10.7), while those from offshore Indochina are slightly more positive (-10.7 to -9.4). The Nd isotopic compositions of the sediments from offshore Borneo are even higher, with epsilon-Neodymium ranging from -8.8 to -7.0, and the sediments offshore from the southern Philippine Arc have the most positive epsilon-Neodymium values, from -3.7 to +5.3. This zonal distribution in epsilon-Neodymium is in good agreement with the Nd isotopic compositions of the sediments supplied by river systems that drain into the corresponding regions, indicating that Nd isotopic compositions are an adequate proxy for provenance tracing of SCS sediments. Sr isotopic compositions, in contrast, can only be used to identify the sediments from offshore South China and offshore from the southern Philippine Arc, as the 87Sr/86Sr ratios of sediments from other regions overlapped. Similar zonal distributions are also apparent in a La-Th-Sc discrimination diagram. Sediments fromthewestmargin of the SCS, such as those fromBeibuwan Bay, offshore fromHainan Island, offshore from Indochina, and from the Sunda Shelf plot in the same field, while those offshore from the northeastern SCS, offshore from Borneo, and offshore from the southern Philippine Arc plot in distinct fields. Thus, the La-Th-Sc discrimination diagram, coupledwith Nd isotopes, can be used to trace the provenance of SCS sediments. Using this method, we re-assessed the provenance changes of sediments at Ocean Drilling Program (ODP) Site 1148 since the late Oligocene. The results indicate that sediments deposited after 23.8 Ma (above 455 mcd: meters composite depth) were supplied mainly from the eastern South China Block, with a negligible contribution from the interior of the South China Block. Sediments deposited before 26 Ma (beneath 477 mcd) were supplied mainly from the North Palawan Continental Terrane, which may retain the geochemical characteristics of the materials covered on the late Mesozoic granitoids along the coastal South China. For that the North Palawan Continental Terrane is presently located within the southern Philippine Arc but was located close to ODP Site 1148 in the late Oligocene. The weathering products of volcanic material associated with the extension of the SCS ocean crust also contributed to these sediments. The rapid change in sediment source at 26-23.8 Ma probably resulted from a sudden cessation of sediment supply from the North Palawan Continental Terrane. Wesuggest that the North Palawan Continental Terrane drifted southwards alongwith the extension of the SCS ocean crust during that time, and when the basin was large enough, the supply of sediment from the south to ODP Site 1148 at the north slope may have ceased.

Major elements oxides and mineralogy of primary minerals in ODP Hole 195-1201D basalts

The basement cored at Site 1201 (west Philippine Basin) during Ocean Drilling Program Leg 195 consists of a 91-m-thick sequence of basalts, mostly pillow lavas and perhaps one sheet lava flow, with a few intercalations of hyaloclastite and interpillow sedimentary material. Hydrothermal alteration pervasively affected the basalt sequence, giving rise to a variety of secondary minerals such as K-Fe-Mg-clay minerals, oxyhydroxides and clay minerals mixtures, natrolite group zeolites, analcite, alkali feldspar, and carbonate. The primary minerals of pillow and sheet basalts that survived the intense hydrothermal alteration were investigated by electron microprobe with the aim of characterizing their chemical composition and variability. The primary minerals are mostly plagioclase, ranging in composition from bytownite through labradorite to andesine, chromian-magnesian-diopside, and spinels, both Ti magnetite (partially maghemitized) and chromian spinel. Overall, the chemical features of the primary minerals of Site 1201 basalts correspond to the primitive character of the bulk rocks, suggesting that the parent magma of these basalts was a mafic tholeiitic magma that most likely only suffered limited fractional crystallization and crystallized at high temperatures (slightly below 1200°C) and under increasing fO2 conditions. The major element composition of clinopyroxene suggests a backarc affinity of the mantle source of Site 1201 basement.

Composition of matrix glasses and melt inclusions of fallout tephra from ODP Hole 125-782A

We studied the systematics of Cl, F and H2O in Izu arc front volcanic rocks using basaltic through rhyolitic glass shards and melt inclusions (Izu glasses) from Oligocene to Quaternary distal fallout tephra. These glasses are low-K basalts to rhyolites that are equivalent to the Quaternary lavas of the Izu arc front (Izu VF). Most of the Izu glasses have Cl ~400-4000 ppm and F ~70-400 ppm (normal-group glasses). Rare andesitic melt inclusions (halogen-rich andesites; HRA) have very high abundances of Cl (~6600-8600 ppm) and F (~780-910 ppm), but their contents of incompatible large ion lithophile elements (LILE) are similar to the normal-group glasses. The preeruptive H2O of basalt to andesite melt inclusions in plagioclase is estimated to range from ~2 to ~10 wt% H2O. The Izu magmas should be undersaturated in H2O and the halogens at their preferred levels of crystallization in the middle to lower crust (~3 to ~11 kbar, ~820° to ~1200°C). A substantial portion of the original H2O is lost due to degassing during the final ascent to surface. By contrast, halogen loss is minor, except for loss of Cl from siliceous dacitic and rhyolitic compositions. The behavior of Cl, F and H2O in undegassed melts resembles the fluid mobile LILE (e.g.; K, Rb, Cs, Ba, U, Pb, Li). Most of the Cl (>99%), H2O (>95%) and F (>53%) in the Izu VF melts appear to originate from the subducting slab. At arc front depths, the slab fluid contains Cl = 0.94+/-0.25 wt%, F = 990+/-270 ppm and H2O = 25+/-7 wt%. If the subducting sediment and the altered basaltic crust were the only slab sources, then the subducted Cl appears to be almost entirely recycled at the Izu arc (~77-129%). Conversely, H2O (~13-22% recycled at arc) and F (~4-6% recycled) must be either lost during shallow subduction or retained in the slab to greater depths. If a seawater-impregnated serpentinite layer below the basaltic crust were an additional source of Cl and H2O, the calculated percentage of Cl and H2O recycled at arc would be lower. Extrapolating the Izu data to the total length of global arcs (~37000 km), the global arc outflux of fluid-recycled Cl and H2O at subduction zones amounts to Cl ~2.9-3.8 mln ton/yr and H2O ~70-100 mln ton/yr, respectively - comparable to previous estimates. Further, we obtain a first estimate of global arc outflux of fluid-recycled F of ~0.3-0.4 mln ton/yr. Despite the inherent uncertainties, our results support models suggesting that the slab becomes strongly depleted in Cl and H2O in subduction zones. In contrast, much of the subducted F appears to be returned to the deep mantle, implying efficient fractionation of Cl and H2O from F during the subduction process. However, if slab devolatilization produces slab fluids with high Cl/F (~9.5), slab melting will still produce components with low Cl/F ratios (~0.9), similar to those characteristic of the upper continental crust (Cl/F ~0.3-0.9).