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).

Element and isotope compostion of basalts and sediments from the Japan Sea

Ocean Drilling Program Legs 127 and 128 in the Yamato Basin of the Japan Sea, a Miocene-age back-arc basin in the western Pacific Ocean, recovered incompatible-element-depleted and enriched tholeiitic dolerites and basalts from the basin floor, which provide evidence of a significant sedimentary component in their mantle source. Isotopically, the volcanic rocks cover a wide range of compositions (e.g., 87Sr/86Sr = 0.70369 - 0.70503, 206Pb/204Pb = 17.65 - 18.36) and define a mixing trend between a depleted mantle (DM) component and an enriched component with the composition of EM II. At Site 797, the combined isotope and trace element systematics support a model of two component mixing between depleted, MORB-like mantle and Pacific pelagic sediments. A best estimate of the composition of the sedimentary component has been determined by analyzing samples of differing lithology from DSDP Sites 579 and 581 in the western Pacific, east of the Japan arc. The sediments have large depletions in the high field strength elements and are relatively enriched in the large-ion-lithophile elements, including Pb. These characteristics are mirrored, with reduced amplitudes, in Japan Sea enriched tholeiites and northeast Japan arc lavas, which strengthens the link between source enrichment and subducted sediments. However, Site 579/581 sediments have higher LILE/REE and lower HFSE/REE than the enriched component inferred fiom mixing trends at Site 797. Sub-arc devolatilization of the sediments is a process that will lower LILE/REE and raise HFSE/REE in the residual sediment, and thus this residual sediment may serve as the enriched component in the back-arc basalt source. Samples from other potential sources of an enriched, EM II-like component beneath Japan, such as the subcontinental lithosphere or crust, have isotopic compositions which overlap those of the Japan Sea tholeiites and are not "enriched" enough to be the EM II end-member.

Mineral content, major oxides and trace elements concentrations in clay from different IODP Holes of 331-C0013, 331-C0017, East China sea shelf and different Taiwan rivers

The Okinawa Trough (OT) in the East Asian continental margin is characterized by thick terrigenous sediment and ubiquitous volcanic-hydrothermal activities. In this study, the clays collected during IODP Expedition 331 to the middle OT (Iheya North Knoll) were analyzed for mineralogical and geochemical compositions. By comparing with the clays from the East China Sea shelf and surrounding rivers, we examine different clay origins. The hydrothermal field in the mid-OT is dominated by Mg-rich chlorite, while the recharge zone has clay mineral assemblages similar to the shelf and rivers, showing high content of illite, subordinate chlorite and kaolinite and scarce smectite. Compared to the terrigenous clays, the hydrothermal clays in the OT have high concentrations of Mg, Mn and Zr but low Fe, Na, K, Ca, Ba, Sr, P, Sc and Ti, while the hydrothermal clays in the mid-ocean ridge are relatively enriched in Fe and V and depleted in Al, Mg, Zr, Sc and Ti. Different fractionation patterns of rare earth elements also register in the terrigenous and hydrothermal clays, diagnostic of variable clay origins. We infer that the OT hydrothermal clay was primarily formed by the chemical alteration of detrital sediments subject to the hydrothermal fluids. The remarkably different compositions of hydrothermal clays between the sediment-rich back arc basin like OT and the sediment-starved ocean ridge suggest different physical and chemical processes of hydrothermal fluids and fluid-rock/sediment reactions under various geologic settings.

Geochemistry of sands and sandstones in ODP Leg 126 sites

During Ocean Drilling Program Leg 126, six sites were cored in a young backarc rift basin and its flanks (rift onset 1.1-3.56 Ma) and in the forearc basin of the Izu-Bonin Arc. In the backarc area, strata are younger than about 4.5 Ma, whereas in the forearc, ages are about 0-31 Ma in sections punctuated by important Miocene unconformities. Bulk chemical analyses of volcaniclastic turbidite sands and sandstones, derived directly from the arc, were obtained from 271 atomic absorption analyses (major elements), 253 XRF analyses (trace elements) and 16 ICP-MS analyses (trace and rare-earth elements). Of the 271 samples, 78 come from the backarc area and the remainder from the forearc. The sands and sandstones reflect the igneous compositions of their sources. Most are formed of materials derived from subalkaline, low-K andesites, and dacites, although compositions range from basalt to rhyolite. Basic and acid andesites are predominant in Oligocene rocks; in contrast, Pliocene-Pleistocene sediments were derived from acid andesitic to rhyolitic sources. The oldest sandstones, estimated to have an age of about 31 Ma, were derived from an arc tholeiitic, not boninitic, source. The 26-31 Ma sandstones furthest to the north, at Sites 787 and 792, have higher relative concentrations of Ti, Zr, and Y than do those at southern Site 793. Data from younger samples indicate that, for more than 30 m.y., the average composition of volcaniclastic sediments and volcanism near Aoga Shima was more basic than to the south, near Sumisu Jima. Using the sandstones as igneous proxies, we conclude that magmas erupted along the arc have become more depleted in light-rare-earth elements (LREE) with time. There was a major change in rare-earth-element (REE) concentrations in the late Oligocene, from essentially flat patterns (normalized La/Yb about 1-1.5) to LREE-depleted patterns (normalized La/Yb about 0.5). At the same time, Zr/Y ratios decreased from about 2-4 to about 1.5-2.5. These changes may reflect a shift in provenance, or changes in the composition of the mantle wedge beneath the arc. In the backarc area, lithic clasts and glass shards of rift-facies basalt are present in sediments as old as 2.35-3.15 Ma. Two samples of mafic sand from the backarc basin have flat REE patterns (normalized La/Yb about 1.0), like some of the <1-Ma rift lavas and unlike pre-rift sand and sandstone samples. These possibly represent the local effects of sedimentary mixing of detritus from arc and backarc eruptions because no evidence from the arc itself exists to suggest a recent change in the REE content of magmas.

Geochemical and Nd isotopic investigations of sediments from the South China Sea

Secular variations in geochemistry and Nd isotopic data have been documented in sediment samples at ODP Site 1148 in the South China Sea. Major and trace elements show significant changes at ca. 29.5 Ma and 26-23 Ma, whereas epsilon-Nd values show a single change at ca. 26-23 Ma. Increases in Al/Ti, Al/K, Rb/Sr, and La/Lu ratios and a decrease in the Th/La ratio of the sediments beginning at 29.5 Ma are consistent with more intense chemical weathering in the source region. The abrupt change in Nd isotopes and geochemistry at ca. 26-23 Ma coincides with a major discontinuity in the sedimentology and physical properties of the sediments, implying a drastic change in sedimentary provenance and environment at the drill site. Comparison of the Nd isotopes of sediments from major rivers flowing into the South China Sea suggests that pre-27 Ma sediments were dominantly derived from a southwestern provenance (Indochina-Sunda Shelf and possibly northwestern Borneo), whereas post-23 Ma sediments were derived from a northern provenance (South China). This change in provenance from southwest to north was largely caused by ridge jumping during seafloor spreading of the South China Sea, associated with a southwestward expansion of the ocean basin crust and a global rise in sea level. Thus, the geochemical and Nd isotopic changes in the sediments at ODP Site 1148 are interpreted as a response to a major plate reorganization in SE Asia at ca. 25 Ma.

Major, trace element and XRF data for sediments and fish tooth samples, from a shallow marine setting with varying redox conditions (Site U1356, Wilkes Land Margin, E.Antarctica)

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources. This article is protected by copyright. All rights reserved.

Rare earth element contents in deposits and minerals of the ocean floor

Current understanding of rare earth element (REE) geochemistry in the ocean is given in the book. Chemical properties determining REE migration ability in natural processes, sources of REE in the ocean, behavior of REE in river-sea mixing zones, fractionation of dissolved and particulate REE in ocean waters under aerobic and anaerobic conditions, distribution of REE in terrigenous, authigenic, hydrothermal and biogenic sediment components (clay, bone detritus, barite, phillipsite, Fe- and Mn-oxyhydroxides, Fe-Ca hydroxophosphate, diatoms and foraminiferas) are under consideration.

Rare earth element contents and sources in phosphorites from Pacific seamounts

Distribution of rare earth elements (REE) was studied in phosphorites collected from seamounts at depths from about 400 to 3600 m. In general phosphorites are characterized by high REE con¬tent, by a strong negative Ce anomaly, by a slight positive Gd anomaly, and by slight enrichment in heavy REE, which is also characteristic of seawater, where, to certain extent, composition of REE depends on depth. Comparison of REE composition in phosphorites and in seawater from the Northwest Pacific by means of Q-mode factor analysis revealed that REE have been transported into the phosphorites from various water depths following submergence of the seamounts. This corresponds to paleotectonic reconstructions, but is only partially consistent with age determinations of phosphorites.

Major and trace element content of the 17 lithostratigraphic units recovered during DSDP Leg 49 (Table 1)

IPOD Leg 49 recovered basalts from 9 holes at 7 sites along 3 transects across the Mid-Atlantic Ridge: 63°N (Reykjanes), 45°N and 36°N (FAMOUS area). This has provided further information on the nature of mantle heterogeneity in the North Atlantic by enabling studies to be made of the variation of basalt composition with depth and with time near critical areas (Iceland and the Azores) where deep mantle plumes are thought to exist. Over 150 samples have been analysed for up to 40 major and trace elements and the results used to place constraints on the petrogenesis of the erupted basalts and hence on the geochemical nature of their source regions. It is apparent that few of the recovered basalts have the geochemical characteristics of typical "depleted" midocean ridge basalts (MORB). An unusually wide range of basalt compositions may be erupted at a single site: the range of rare earth patterns within the short section cored at Site 413, for instance, encompasses the total variation of REE patterns previously reported from the FAMOUS area. Nevertheless it is possible to account for most of the compositional variation at a single site by partial melting processes (including dynamic melting) and fractional crystallization. Partial melting mechanisms seem to be the dominant processes relating basalt compositions, particularly at 36°N and 45°N, suggesting that long-lived sub-axial magma chambers may not be a consistent feature of the slow-spreading Mid-Atlantic Ridge. Comparisons of basalts erupted at the same ridge segment for periods of the order of 35 m.y. (now lying along the same mantle flow line) do show some significant inter-site differences in Rb/Sr, Ce/Yb, 87Sr/86Sr, etc., which cannot be accounted for by fractionation mechanisms and which must reflect heterogeneities in the mantle source. However when hygromagmatophile (HYG) trace element levels and ratios are considered, it is the constancy or consistency of these HYG ratios which is the more remarkable, implying that the mantle source feeding a particular ridge segment was uniform with respect to these elements for periods of the order of 35 m.y. and probably since the opening of the Atlantic. Yet these HYG element ratios at 63°N are very different from those at 45°N and 36°N and significantly different from the values at 22°N and in "MORB". The observed variations are difficult to reconcile with current concepts of mantle plumes and binary mixing models. The mantle is certainly heterogeneous, but there is not simply an "enriched" and a "depleted" source, but rather a range of sources heterogeneous on different scales for different elements - to an extent and volume depending on previous depletion/enrichment events. HYG element ratios offer the best method of defining compositionally different mantle segments since they are little modified by the fractionation processes associated with basalt generation.