Stable isotopes and element concentrations of samples from the Wadi Bih, United Arab Emirates

Ocean acidification triggered by Siberian Trap volcanism was a possible kill mechanism for the Permo-Triassic Boundary mass extinction, but direct evidence for an acidification event is lacking. We present a high-resolution seawater pH record across this interval, using boron isotope data combined with a quantitative modeling approach. In the latest Permian, increased ocean alkalinity primed the Earth system with a low level of atmospheric CO2 and a high ocean buffering capacity. The first phase of extinction was coincident with a slow injection of carbon into the atmosphere, and ocean pH remained stable. During the second extinction pulse, however, a rapid and large injection of carbon caused an abrupt acidification event that drove the preferential loss of heavily calcified marine biota.

Iron isotope and trace metal record of Cenomanian-Turonian sediments

he global carbon cycle during the mid-Cretaceous (~125-88 million years ago, Ma) experienced numerous major perturbations linked to increased organic carbon burial under widespread, possibly basin-scale oxygen deficiency and episodes of euxinia (anoxic and H2S-containing). The largest of these episodes, the Cenomanian-Turonian boundary event (ca. 93.5 Ma), or oceanic anoxic event (OAE) 2, was marked by pervasive deposition of organic-rich, laminated black shales in deep waters and in some cases across continental shelves. This deposition is recorded in a pronounced positive carbon isotope excursion seen ubiquitously in carbonates and organic matter. Enrichments of redox-sensitive, often bioessential trace metals, including Fe and Mo, indicate major shifts in their biogeochemical cycles under reducing conditions that may be linked to changes in primary production. Iron enrichments and bulk Fe isotope compositions track the sources and sinks of Fe in the proto-North Atlantic at seven localities marked by diverse depositional conditions. Included are an ancestral mid-ocean ridge and euxinic, intermittently euxinic, and oxic settings across varying paleodepths throughout the basin. These data yield evidence for a reactive Fe shuttle that likely delivered Fe from the shallow shelf to the deep ocean basin, as well as (1) hydrothermal sources enhanced by accelerated seafloor spreading or emplacement of large igneous province(s) and (2) local-scale Fe remobilization within the sediment column. This study, the first to explore Fe cycling and enrichment patterns on an ocean scale using iron isotope data, demonstrates the complex processes operating on this scale that can mask simple source-sink relationships. The data imply that the proto-North Atlantic received elevated Fe inputs from several sources (e.g., hydrothermal, shuttle and detrital inputs) and that the redox state of the basin was not exclusively euxinic, suggesting previously unknown heterogeneity in depositional conditions and biogeochemical cycling within those settings during OAE-2.

Chemical composition of ocean Fe-Mn ores

The monograph includes the study of chemical and mineral compositions of terrestrial and marine manganese ores, methods of their analysis, dependence of manganese crust geochemistry on tectonic position of their formation, problems of manganese genesis and sources of manganese in ocean ores in connection with geohistorical aspects of ocean formation and development. A hypothesis is offered that formation of giant manganese mineral basins on continental margins resulted from a large asteroid fall to the ocean.

Chemical and isotope compositions of rocks dredged from the Shatsky Rise

Magmatic rocks of the Shatsky Rise form two groups replacing one another in time. The earlier ferrotholeiites enriched in potassium compose large massifs. Trachybasalts form seamounts and neotectonic ridges. Composition of volcanites indicates that two sources of magmatism took part in their formation: a depleted source characteristic of basalts of mid-ocean ridges and a ''plume'' source participating in formation of oceanic plateaus.

Stable isotope composition of early Danian sediments from the Atlantic Ocean

A long-standing question in Paleogene climate concerns the frequency and mechanism of transient greenhouse gas-driven climate shifts (hyperthermals). The discovery of the greenhouse gas-driven Paleocene-Eocene Thermal Maximum (PETM; ~55 Ma) has spawned a search for analogous events in other parts of the Paleogene record. On the basis of high-resolution bulk sediment and foraminiferal stable isotope analyses performed on three lower Danian sections of the Atlantic Ocean, we report the discovery of a possible greenhouse gas-driven climatic event in the earliest Paleogene. This event - that we term the Dan-C2 event - is characterized by a conspicuous double negative excursion in delta13C and delta18O, associated with a double spike in increased clay content and decreased carbonate content. This suggests a double period of transient greenhouse gas-driven warming and dissolution of carbonates on the seafloor analogous to the PETMin the early Paleocene at ~65.2 Ma. However, the shape of the two negative carbon isotope excursions that make up the Dan-C2 event is different from the PETM carbon isotope profile. In the Dan-C2 event, these excursions are fairly symmetrical and each persisted for about ~40 ky and are separated by a short plateau that brings the combined duration to ~100 ky, suggesting a possible orbital control on the event. Because of the absence of a long recovery phase, we interpret the Dan-C2 event to have been associated with a redistribution of carbon that was already in the biosphere. The Dan-C2 event and other early Paleogene hyperthermals such as the short-lived early Eocene ELMO eventmay reflect amplification of a regular cycle in the size and productivity of the marine biosphere and the balance between burial of organic and carbonate carbon.

Stable isotopic record of late Pliocene and Pleistocene foraminifera of ODP Site 114-704

We studied the stable isotopic and carbonate stratigraphy of ODP Hole 704A to reconstruct the paleoceanographic evolution of the eastern subantarctic sector of the South Atlantic Ocean. Site 704 is well positioned with respect to latitude (46°52.8'S, 7°25.3'E) and bathymetry (2532 m) to monitor past migrations in the position of Polar Front Zone (PFZ) and changes in deep-water circulation during the late Pliocene-Pleistocene. Several important changes occurred in proxy paleoceanographic indicators across the Gauss/Matuyama boundary at 2.47 Ma: (1) accumulation rates of biogenic sedimentary components increased by an order of magnitude (Froelich et al., this volume); (2) planktonic d1 8O values increased by an average of 0.5 per mil; (3) the amplitude of the benthic d18O signal increased; (4) the accumulation rate of ice-rafted detritus increased several fold (Warnke and Allen, this volume); and (5) carbon isotopic ratios of benthic foraminifers decreased by 0.5 per mil, as did the d13C of the fine-fraction carbonate by 1.5 per mil (Mead et al., 1991, doi:10.2973/odp.proc.sr.114.152.1991), but no change occurred in planktonic foraminiferal d13C values. Most of these changes are consistent with more frequent expansions and contractions of the PFZ over Site 704 after 2.47 Ma, bringing cold, nutrient-rich waters to 47°S that stimulated both carbonate and siliceous productivity. The synchronous increase in d18O values and ice-rafted detritus accumulation in Hole 704A indicates that the 2.4 Ma paleoceanographic event included ice volume growth on both Antarctica and Northern Hemisphere continents. The decrease in benthic d13C values indicates that the ventilation rate of Southern Ocean deep water decreased and the nutrient content increased during glacial events after 2.5 Ma. At the Gauss/Matuyama boundary, benthic d13C values of the Southern Ocean shifted toward those of the Pacific end member, indicating a decrease in the relative mixing ratio of Northern Component Water and Circumpolar Deep Water. During the early Matuyama (~2.3 to 1.7 Ma), the PFZ generally occupied a southerly position with respect to Site 704 and carbonate productivity prevailed. Exceptions to these general conditions occurred during strong glacial events of the early Matuyama (e.g., isotopic stages 82, 78, 74, and 70), when the PFZ migrated to the north and opal sedimentation predominated at Site 704. At 1.7 Ma, the PFZ migrated toward the equator and occupied a more northerly position for a prolonged interval between ~1.7 and 1.5 Ma. Beginning at ~1.5-1.4 Ma, surface and bottom water parameters (d18O, d13C, %CaCO3, and %opal) in the subantarctic South Atlantic became highly correlated such that glacial events (d18O maxima) corresponded to d13C and carbonate minima and opal maxima. This pattern is typical of the correlation found during the latest Pleistocene in the Southern Ocean (Charles and Fairbanks, in press). This event coincided with increased suppression of Northern Component Water during glacial events after 1.5 Ma (Raymo et al., 1990, doi:10.1016/0012-821X(90)90051-X), which may have influenced the climatology of the Southern Hemisphere by altering the flux of heat and salt to the Southern Ocean).

Occurrence of interlayers in sediment cores collected in the East Indian Ocean

In the East Indian Ocean direct contribution of land volcanism to sedimentation appears as interlayers of tephra and tuffaceous sediments, pumice fragments, and dispersed volcanoclastic materials of silty grain size. Similarity of distribution of tephra, tuffaceous sediments, Ethmodiscus ooze, and turbidites in the Pleistocene section results from deposition of all these materials under controll of a single factor, namely synchronous redistribution owing to seismic activity on the ocean floor and on the Sunda Islands. Burial of layers of oxidized deposits and formation of iron-manganese nodules is at least partly related to global climate cooling and to circulation of ocean waters.

Alkenones and coccolithophorids in late Quaternary sediments from the Walvis Ridge

Sea surface temperatures (SSTs) derived from the alkenone UK'37) record of Quaternary sediments may be subject to bias if algae with different temperature sensitivities have contributed to the sedimentary alkenone record. The alkenone-derived SST records are usually based on a UK'37-temperature relationship which was measured in culture experiments using the coccolithophorid Emiliania huxleyi (F.G. Prahl, L.A. Muehlhausen and D.L. Zahnle, 1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochim. Cosmochim. Acta 52, 2303-2310). To assess possible effects of past species changes on the UK'37-temperature signal, we have analyzed long-chain alkenones and coccolithophorids in a late Quaternary sediment core from the Walvis Ridge and compared the results to SST estimates extracted from the d18O record of the planktonic foraminifer Globigerinoides ruber. Alkenones and isotopes were determined over the entire 400-kyr core record while the coccolithophorid study was confined to the last 200 kyr when the most pronounced changes in alkenone content occurred. Throughout oxygen-isotope stages 6 and 5, species of the genus Gephyrocapsa were the predominating coccolithophorids. E. huxleyi began to increase systematically in relative abundance since the stage 5/4 transition, became dominant over Gephyrocapsa spp. during stage 3 and reached the highest abundances in the Holocene. Carbon-normalized alkenone concentrations are inversely related to the relative abundances of E. huxleyi, and directly related to that of Gephyrocapsa spp., suggesting that species of this genus were the principal alkenone contributors to the sediments. Nevertheless, SST values obtained from the UK'37-temperature relationship for E. huxleyi compare favourably to the isotope-derived temperatures. The recently reported UK'37-temperature relationship for a single strain of Gephyrocapsa oceanica (J.K. Volkman. S.M. Barrett, S.I. Blackburn and E.L. Sikes, 1995. Alkenones in Gephyrocapsa oceanica: Implications for studies of paleoclimate. Geochim. Cosmochim. Acta 59, 513-520) produces unrealistically high SST values indicating that the temperature response of the examined strain is not typical for the genus Gephyrocapsa. This is supported by the C37:C38, alkenone ratios of the sediments which are comparable to average ratios reported for E. huxleyi, but significantly higher than for the G. oceanica strain. Most notably, the general accordance of the alkenone characteristics between sediments and E. huxleyi persists through stages 8 to 5 and even in times that predate the first appearance of this species (268 ka; H.R. Thierstein, K.R. Geitzenauer and B. Molfino, 1977. Global synchroneity of late Quaternary coccolith datum levels: Validation by oxygen isotopes. Geology 5, 400-404). Our results suggest that UK'37-temperature relationships based on E. huxleyi produce reasonable paleo-SST estimates even for late Quaternary periods when this species was scarce or absent because other alkenone-synthesizing algae, e.g. of the genus Gephyrocapsa.

Chronology and petrology of sediment cor DAPC2

Evidence from paleoclimatic archives suggests that Earth's climate experienced rapid temperature changes associated with pronounced interhemispheric asymmetry during the last glacial period. Explanations for these climate excursions have converged on nonlinear interactions between ice sheets and the ocean's thermohaline circulation, but the driving mechanism remains to be identified. Here we use multidecadal marine records of faunal, oxygen isotope, and sediment proxies from the northeast Atlantic proximal to the western margins of the last glacial British Ice Sheet (BIS) to document the coupling between ice sheet dynamics, ocean circulation, and insolation changes. The core data reveal successions of short-lived (80-100 years), high-amplitude ice-rafted debris (IRD) events that were initiated up to 2000 years before the deposition of detrital carbonate during Heinrich events (HE) 1 and 2. Progressive disintegration of the BIS 19-16 kyr before present (B.P.) occurred in response to abrupt ocean-climate warmings that impinged on the northeast Atlantic during the early deglaciation. Peak IRD deposition recurs at 180-220 year intervals plausibly involving repeated breakup of glacial tidewater margins and fringing marine ice shelves. The early deglaciation culminated in a major meltwater pulse at ~16.3 kyr B.P. followed by another discharge associated with HE1 some 300 years after. We conclude that temperature changes related to external forcing and marine heat transport caused a rapid response of the BIS and possibly other margins of the Eurasian Ice Sheet. Massive but short-lived meltwater surges influenced the Atlantic meridional overturning circulation thereby contributing to North Atlantic climate variability and bipolar climatic asymmetry.

Age determination and sedimentation rates of the subpolar northeast Atlantic

In order to monitor the evolution of the British-Irish Ice Sheet (BIIS) and its influence in surface ocean structure during marine isotopic stages (MIS) 2 and 3, we have analyzed the sediments recovered in core MD04-2829CQ (Rosemary Bank, north Rockall Trough, northeast Atlantic) dated between ~41 and ~18 ka B.P. Ice-rafted debris flux and composition, 40Ar/39Ar ages of individual hornblende grains, multispecies planktonic stable isotope records, planktonic foraminifera assemblage data and faunal-based sea surface temperatures (SSTs) demonstrate a close interaction between BIIS dynamics and surface ocean structure and water properties in this region. The core location lies beneath the North Atlantic Current (NAC) and is ideal for monitoring the shifts in the position of its associated oceanic fronts, as recorded by faunal changes. These data reveal a succession of BIIS-sourced iceberg calving events related to low SST, usually synchronous with dramatic changes in the composition of the planktonic foraminifera assemblage and with variations in the stable isotope records of the taxa Neogloboquadrina pachyderma (sinistral coiling) and Globigerina bulloides. The pacing of the calving events, from typically Dansgaard-Oeschger millennial timescales during late MIS 3 to multicentennial cyclicity from ~28 ka B.P., represents the build-up of the BIIS and its growing instability toward Heinrich Event (HE) 2 and the Last Glacial Maximum. Our data confirm the strong coupling between BIIS instabilities and the temperature and salinity of surface waters in the adjacent northeast Atlantic and demonstrate the BIIS's ability to modify the NAC on its flow toward the Nordic Seas. In contrast, subsurface water masses were less affected except during the Greenland stadials that contain HEs, when most intense water column reorganizations occurred simultaneously with the deposition of cream-colored carbonate sourced from the Laurentide Ice Sheet.

Depth ranges of calcareous nannofossil datums from ODP Holes 113-689B and 113-690B

Magnetostratigraphic studies of Paleogene sediments piston-cored on Maud Rise, Weddell Sea (ODP Sites 689 and 690), are a cornerstone of Southern Ocean Paleogene and Neogene chronostratigraphy. However, parts of previous magnetostratigraphic interpretations have been called into question, and recent reinvestigation of the upper Paleocene-middle Eocene portion of Site 690 suggested that the records might be contaminated by spurious magnetizations, which raises doubts about the reliability of these important records. We undertook a high-resolution magnetostratigraphic study of Eocene-Oligocene u-channel samples from ODP Holes 689B, 689D, 690B, and 690C in order to address these concerns. A pervasive overprint appears to be present below the middle Eocene, which compromises magnetobiostratigraphic interpretations for the upper Cretaceous and lower Paleogene. Nevertheless, our new results provide a robust record of geomagnetic field behavior from 38.5 to 25 Ma and confirm the reliability of these sediments for calibration of biostratigraphic datum events during a crucial phase of earth history when major Antarctic ice sheets developed. Also, comparison of magnetozone thicknesses in multiple holes at the same site indicates that ~1.2-1.8 m of the stratigraphic record is missing at each core break, which corresponds to time breaks of 120-360 k.y. Lack of a continuous record within a single hole renders useless spectral analyses for investigating long geomagnetic and paleoclimatic time series. This observation reinforces the need for coring of multiple offset holes to obtain continuous paleoceanographic records. Sedimentary hiatuses have been identified only at the deeper of the two investigated sites (Site 690), which could mark a local response to the onset of the Antarctic Circumpolar Current.