Stable isotope and Mg/Ca ratios of Paleogene benthic foraminifera in the western North Atlantic

Global cooling and the development of continental-scale Antarctic glaciation occurred in the late middle Eocene to early Oligocene (~38 to 28 million years ago), accompanied by deep-ocean reorganization attributed to gradual Antarctic Circumpolar Current (ACC) development. Our benthic foraminiferal stable isotope comparisons show that a large d13C offset developed between mid-depth (~600 meters) and deep (>1000 meters) western North Atlantic waters in the early Oligocene, indicating the development of intermediate-depth d13C and O2 minima closely linked in the modern ocean to northward incursion of Antarctic Intermediate Water. At the same time, the ocean's coldest waters became restricted to south of the ACC, probably forming a bottom-ocean layer, as in the modern ocean. We show that the modern four-layer ocean structure (surface, intermediate, deep, and bottom waters) developed during the early Oligocene as a consequence of the ACC.

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.

Siliceous phytoplankton in middle Eocene sediments of ODP Hole 207-1260A

The Middle Eocene diatom and silicoflagellate record of ODP Site 1260A (Demerara Rise) is studied quantitatively in order to throw light on the changes that siliceous phytoplankton communities experienced during a Middle Eocene warming event that occurred between 44.0 and 42.0 Ma. Both Pianka's overlap index, calculated per couple of successive samples, and cluster analysis, point to a number of significant turnover events highlighted by changes in the structure of floristic communities. The pre-warming flora, dominated by cosmopolitan species of the diatom genus Triceratium, is replaced during the warming interval by a new and more diverse assemblage, dominated by Paralia sulcata (an indicator of high productivity) and two endemic tropical species of the genus Hemiaulus. The critical warming interval is characterized by a steady increase in biogenic silica and a comparable increase in excess Ba, both reflecting an increase in productivity. In general, it appears that high productivity not only increased the flux of biogenic silica, but also sustained a higher diversity in the siliceous phytoplankton communities. The microflora preserved above the critical interval is once again of low diversity and dominated by various species of the diatom genus Hemiaulus. All assemblages in the studied material are characterized by the total absence of continental and benthic diatoms and the relative abundance of neritic forms, suggesting a transitional depositional environment between the neritic and the oceanic realms.

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.

Halogene concentrations and iodine isotopic composition in pore water on Hydrare Ridge, Cascadia continental margin

We report iodine and bromine concentrations in a total of 256 pore water samples collected from all nine sites of Ocean Drilling Program Leg 204, Hydrate Ridge. In a subset of these samples, we also determined iodine ages in the fluids using the cosmogenic isotope 129I (T1/2 = 15.7 Ma). The presence of this cosmogenic isotope, combined with the strong association of iodine with methane, allows the identification of the organic source material responsible for iodine and methane in gas hydrates. In all cores, iodine concentrations were found to increase strongly with depth from values close to that of seawater (0.0004 mM) to concentrations >0.5 mM. Several of the cores taken from the northwest flank of the southern summit show a pronounced maximum in iodine concentrations at depths between 100 and 150 meters below seafloor in the layer just above the bottom-simulating reflector. This maximum is especially visible at Site 1245, where concentrations reach values as high as 2.3 mM, but maxima are absent in the cores taken from the slope basin sites (Sites 1251 and 1252). Bromine concentrations follow similar trends, but enrichment factors for Br are only 4-8 times that of seawater (i.e., considerably lower than those for iodine). Iodine concentrations are sufficient to allow isotope determinations by accelerator mass spectrometry in individual pore water samples collected onboard (~5 mL). We report 129I/I ratios in a few samples from each core and a more complete profile for one flank site (Site 1245). All 129I/I ratios are below the marine input ratio (Ri = 1500x10**-15). The lowest values found at most sites are between 150 and 250x10**-15, which correspond to minimum ages between 40 and 55 Ma, respectively. These ages rule out derivation of most of the iodine (and, by association, of methane) from the sediments hosting the gas hydrates or from currently subducting sediments. The iodine maximum at Site 1245 is accompanied by an increase in 129I/I ratios, suggesting the presence of an additional source with an age younger than 10 Ma; there is indication that younger sources also contribute at other sites, but data coverage is not yet sufficient to allow a definitive identification of sources there. Likely sources for the older component are formations of early Eocene age close to the backstop in the overriding wedge, whereas the younger sources might be found in recent sediments underlying the current locations of the gas hydrates.