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.

Barium/Calcium and Cadmium/Calcium ratios of sediment core RC13-229

A new benthic foraminiferal Ba/Ca and Cd/Ca data set from core RC13-229 in the deep Cape Basin indicates only small variations in bottom water nutrient concentrations in Circumpolar Deep Water (CPDW) over the last 450 kyr. Variability in the Ba record is characterized by somewhat higher values during glacial periods, consistent with a reduction in the flux of Ba-depleted North Atlantic Deep Water to the Southern Ocean during glacial periods. The small changes in the Ba and Cd records contrast with the large and systematic increase in CPDW nutrients during glacial periods implied by the benthic delta13C record. This discrepancy, essentially an extension of the well-known Southern Ocean Cd-delta13C conflict, is evaluated by transforming RC13-229 paleochemical data into carbonate parameters using the modern oceanic relationships between delta13C, Cd, and SumCO2 and between Ba and alkalinity. Calculations using Cd/Ca to estimate past variations in CPDW SumCO2 and Ba/Ca to estimate past variations in CPDW alkalinity yield carbonate ion concentrations that exceed calcite saturation throughout the record length, with generally higher carbonate ion values associated with glacial intervals (opposite in sense to the RC13-229 %CaCO3 record). Substituting delta13C to estimate SumCO2 leads to extreme calcite undersaturation at this site during glacial periods, clearly inconsistent with the preservation of calcite throughout the length of RC13-229. Accepting the carbon isotope record as a direct measure of past variations in CPDW SumCO2 concentrations requires that both the Cd and Ba evidence for limited nutrient and alkalinity changes be disregarded.

Lavas from the Elbrus volcano, Greater Caucasus

Comprehensive geochronological and isotope-geochemical studies showed that the Late Quaternary Elbrus Volcano (Greater Caucasus) experienced long (approximately 200 ka) discrete evolution with protracted periods of igneous quiescence (approximately 50 ka) between large-scale eruptions. Volcanic activity of Elbrus is subdivided into three phases: Middle Neopleistocene (225-170 ka), Late Neopleistocene (110-70 ka), and Late Neopleistocene - Holocene (earlier than 35 ka). Petrogeochemical and isotope (Sr-Nd-Pb) signatures of Elbrus lavas point to their mantle-crustal origin. It was shown that hybrid parental magmas of the volcano formed due to mixing and/or contamination of deep-seated mantle melts by Paleozoic upper crustal material of the Greater Caucasus. Mantle reservoir that participated in genesis of Elbrus lavas as well as most other Neogene-Quaternary magmatic rocks of Caucasus was represented by the lower mantle "Caucasus" source. Primary melts generated by this source in composition corresponded to K-Na subalkali basalts with the following isotopic characteristics: 87Sr/86Sr = 0.7041+/-0.0001, e-Nd = +4.1+/-0.2, 147Sm/144Nd = 0.105-0.114, 206Pb/204Pb = 18.72, 207Pb/204Pb = 15.62, and 208Pb/204Pb = 38.78. Temporal evolution of isotope characteristics for lavas of the Elbrus Volcano is well described by a Sr-Nd mixing hyperbole between "Caucasus" source and estimated average composition of the Paleozoic upper crust of the Greater Caucasus. It was shown that, with time, proportions of mantle material in parental magmas of Elbrus gently increased: from ~60% at the Middle-Neopleistocene phase of activity to ~80% at the Late Neopleistocene - Holocene phase, which indicates an increase of activity of a deep-seated source at decreasing input of crustal melts or contamination with time. Unraveled evolution of the volcano with discrete eruption events, lacking signs of cessation of the Late Neopleistocene - Holocene phase, increasing contribution of the deep-seated mantle source in genesis of Elbrus lavas with time as deduced from isotope-geochemical data, as well as numerous geophysical and geological evidence indicate that Elbrus is a potentially active volcano and its eruptions may be resumed. Possible scenarios were proposed for evolution of the volcano, if its eruptive activity continued.

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.

Neodymium isotope record of ODP Site 177-1090

Age estimates for the opening of Drake Passage range from 49 to 17 million years ago (Ma), complicating interpretations of the relationship between ocean circulation and global cooling. Secular variations of neodymium isotope ratios at Agulhas Ridge (Southern Ocean, Atlantic sector) suggest an influx of shallow Pacific seawater approximately 41 Ma. The timing of this connection and the subsequent deepening of the passage coincide with increased biological productivity and abrupt climate reversals. Circulation/productivity linkages are proposed as a mechanism for declining atmospheric carbon dioxide. These results also indicate that Drake Passage opened before the Tasmanian Gateway, implying the late Eocene establishment of a complete circum-Antarctic pathway.

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.

Geochemistry of oceanic flood basalts from the Caribbean plate

The thick oceanic crust of the Caribbean plate appears to be the tectonized remnant of an eastern Pacific oceanic plateau that has been inserted between North and South America. The emplacement of the plateau into its present position has resulted in the obduction and exposure of its margins, providing an opportunity to study the age relations, internal structure and compositional features of the plateau. We present the results of 40Ar-39Ar radiometric dating, major-, trace-element, and isotopic compositions of basalts from some of the exposed sections as well as drill core basalt samples from Leg 15 of the Deep Sea Drilling Project. Five widely spaced, margin sections yielded ages ranging from 91 to 88 Ma. Less well-constrained radiometric ages from the drill cores, combined with the biostratigraphic age of surrounding sediments indicate a minimum crystallization age of ~90 Ma in the Venezuelan Basin. The synchroneity of ages across the region is consistent with a flood basalt origin for the bulk of the Caribbean plateau i.e., large volume, rapidly erupted, regionally extensive volcanism.. The ages and compositions are also consistent with plate reconstructions that place the Caribbean plateau in the vicinity of the Galápagos hotspot at its inception. The trace-element and isotopic compositions of the ~90 Ma rocks indicate a depleted mantle and an enriched, plume-like mantle were involved in melting to varying degrees across the plateau. Within the same region, a volumetrically secondary, but widespread magmatic event occurred at 76 Ma, as is evident in Curacao, western Colombia, Haiti, and at DSDP Site 152/ODP Site 1001 near the Hess Escarpment. Limited trace-element data indicate that this phase of magmatism was generally more depleted than the first. We speculate that magmatism may have resulted from upwelling of mantle, still hot from the 90 Ma event, during lithospheric extension attending gravitational collapse of the plateau, andror tectonic emplacement of the plateau between North and South America. Still younger volcanics are found in the Dominican Republic (69 Ma) and the Quepos Peninsula of Costa Rica (63 Ma). The latter occurrence conceivably formed over the Galápagos hotspot and subsequently accreted to the western edge of the plateau during subduction of the Farallon plate.

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.