Geochemistry of pelagic and hemipelagic sediments of ODP Leg 126 sites

Chemical analyses were performed on major, minor, and rare-earth elements of pelagic and hemipelagic sediments of the forearc, arc, and backarc sites of the Izu-Bonin Arc, Ocean Drilling Program Leg 126. Analyses of the hemipelagic and pelagic sediments of this area indicate that the chemical composition of this arc is highly affected by the chemical composition of rocks of this arc as a source of sediments. The Oligocene sediments, which are characterized by high MgO contents, reflect the chemical composition of the Paleogene volcanic rocks of the immature arc. Moreover, the late Miocene to Quaternary sediments with low MgO contents are attributed to the composition of the present arc. We also suggest that the sedimentation rates and topography of the sedimentary basin affect the MnO and SiO2 contents of pelagic and hemipelagic sediments.

XRF iron (Fe) counts of ODP Hole 171-1050A and 171-1051A

Upper Paleocene to lower Eocene sediments drilled at Ocean Drilling Program (ODP) Site 1051 (Blake Nose, off Florida) display well-defined orbital cycles, a detailed magnetic stratigraphy, and a suite of planktonic foraminiferal datums. We derived a cyclostratigraphy by using spectral analysis of high-resolution records of elemental concentrations obtained by an X-ray fluorescence (XRF) Core Scanner. XRF counts of iron serve as a proxy for the relative amount of terrestrial material. Sliding-window spectral analysis, bandpass filtering, and direct counting of precession and obliquity cycles yield minimum durations for magnetic polarity chrons C22 to C26 (~49 to ~61 Ma), calculations of sediment accumulation rates, as well as constraints on the timing of biostratigraphic and climatological events in the vicinity of the Initial Eocene Thermal Maximum (IETM). Durations of polarity chrons as represented in sediments drilled at Site 1051 were estimated using a conservative assignment of 41 k.y. for obliquity cycles and 21 k.y. for precession cycles. Combined polarity chrons C26r and C26n span 3.61 m.y., and chron C25r spans 1.07 m.y. Polarity chron C24r is estimated as 2.877 m.y. The interpretation of polarity chron C24n is ambiguous, but its duration is probably <1.23 m.y. Polarity chron C23r spans 0.53 m.y., chron C23n is 0.74 m.y., and chron C22r is 0.9 m.y. Spectral analysis through this interval indicates that spectral peaks shift through time and are related to changes in sedimentation rate in Site 1051. The sedimentation rates dramatically increased ~200 k.y. after the IETM and remained high for most of chron C24r.

Major, trace and rare earth element concentrations of sediments from ODP Leg 207 sites

The Cretaceous and Paleogene sediments recovered during Ocean Drilling Program Leg 207 can be divided into three broad modes of deposition: synrift clastics (lithologic Unit V), organic matter-rich, laminated black shales (Unit IV), and open-marine chalk and calcareous claystones (Units III-I). The aim of this study is to provide a quantitative geochemical characterization of sediments representing these five lithologic units. For this work we used the residues (squeeze cakes) obtained from pore water sampling. Samples were analyzed for bulk parameters (total inorganic carbon, total organic carbon, and S) and by X-ray fluorescence for major (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P) and selected minor (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, U, V, Y, Zn, and Zr) elements. Inductively coupled plasma-mass spectrometry analyses for rare earth elements (REEs) were performed on acid digestions of the squeeze cake samples from Site 1258. The major element composition is governed by the mixture of a terrigenous detrital component of roughly average shale (AS) composition with biogenous carbonate and silica. The composition of the terrigenous detritus is close to AS in Units II-IV. For Unit I, a more weathered terrigenous source is suggested. Carbonate contents reach >60 wt% on average in chalks and calcareous claystones of Units II-IV. The SiO2 contribution in excess of the normal terrigenous-detrital background indicates the presence of biogenous silica, with highest amounts in Units II and III. The contents of coarse-grained material (quartz) are enhanced in Unit V, where Ti and Zr contents are also high. This indicates a high-energy depositional environment. REE patterns are generally similar to AS. A more pronounced negative Ce anomaly in Unit IV may indicate low-oxygen conditions in the water column. The Cretaceous black shales of Unit IV are clearly enriched in redox-sensitive and stable sulfide-forming elements (Mo, V, Zn, and As). High phosphate contents point toward enhanced nutrient supply and high bioproductivity. Ba/Al ratios are rather high throughout Unit IV despite the absence of sulfate in the pore water, indicating elevated primary production. Manganese contents are extremely low for most of the interval studied. Such an Mn depletion is only possible in an environment where Mn was mobilized and transported into an expanded oxygen minimum zone ("open system"). The sulfur contents show a complete sulfidation of the reactive iron of Unit IV and a significant excess of sulfur relative to that of iron, which indicates that part of the sulfur was incorporated into organic matter. We suppose extreme paleoenvironmental conditions during black shale deposition: high bioproductivity like in recent coastal upwelling settings together with severe oxygen depletion if not presence of hydrogen sulfide in the water column.

Sr/Ca ratios of Cenozoic benthic foraminifera

A Cenozoic multi-species record of benthic foraminiferal calcite Sr/Ca has been produced and is corrected for interspecific offsets (typically less than 0.3 mmol/mol) and for the linear relationship between decreasing benthic foraminiferal Sr/Ca and increasing water depth. The water depth correction, determined from Holocene, Late Glacial Maximum and Eocene paleowater-depth transects, is ~0.1 mmol/mol/km. The corrected Cenozoic benthic foraminiferal Sr/Ca record ranges from 1.2 to 2.0 mmol/mol, and has been interpreted in terms of long-term changes in seawater Sr/Ca, enabling issues related to higher-resolution variability in Sr/Ca to be ignored. We estimate that seawater Sr/Ca was ~1.5 times modern values in the late Cretaceous, but declined rapidly into the Paleogene. Following a minimum in the Eocene, seawater Sr/Ca increased gradually through to the present day with a minimum superimposed on this trend centered in the late Miocene. By assuming scenarios for changing seawater calcium concentration, and using published carbonate accumulation rate data combined with suitable values for Sr partition coefficients into carbonates, the seawater Sr/Ca record is used to estimate global average river Sr fluxes. These fluxes are used in conjunction with the seawater strontium isotope curve and estimates of hydrothermal activity/tectonic outgassing to calculate changes in global average river 87Sr/86Sr through the Cenozoic. The absolute magnitude of Sr fluxes and isotopic compositions calculated in this way are subject to relatively large uncertainties. Nevertheless, our results suggest that river Sr flux increased from 35 Ma to the present day (roughly two-fold) accompanied by an overall increase in 87Sr/86Sr (by ~0 to 0.001). Between 75 and 35 Ma, river 87Sr/86Sr also increased (by ~0.001 to 0.002) but was accompanied by a decrease (two- to three-fold) in river Sr flux.

Early Eocene benthic foraminifera of DSDP Hole 48-401

Within the last decade, several early Eocene hyperthermals have been detected globally. These transient warming events have mainly been characterized geochemically - using stable isotopes, carbonate content measurements or XRF core scanning - yet detailed micropaleontological records are sparse, limiting our understanding of the driving forces behind hyperthermals and of the contemporaneous paleoceanography. Here, detailed geochemical and quantitative benthic foraminiferal records are presented from lower Eocene pelagic sediments of Deep Sea Drilling Project Site 401 (Bay of Biscay, northeast Atlantic). In calcareous nannofossil zone NP11, several clay-enriched levels correspond to negative d13C and d18O bulk-rock excursions with amplitudes of up to ~0.75 per mil, suggesting that significant injections of 12C-enriched greenhouse gasses and small temperature rises took place. Coeval with several of these hyperthermal events, the benthic foraminiferal record reveals increased relative abundances of oligotrophic taxa (e.g. Nuttallides umbonifera) and a reduction in the abundance of buliminid species followed by an increase of opportunistic taxa (e.g. Globocassidulina subglobosa and Gyroidinoides spp.). These short-lived faunal perturbations are thought to be caused by reduced seasonality of productivity resulting in a decreased Corg flux to the seafloor. Moreover, the sedimentological record suggests that an enhanced influx of terrigenous material occurred during these events. Additionally, the most intense d13C decline (here called level d) gives rise to a small, yet pronounced long-term shift in the benthic foraminiferal composition at this site, possibly due to the reappraisal of upwelling and the intensification of bottom water currents. These observations imply that environmental changes during (smaller) hyperthermal events are also reflected in the composition of deep-sea benthic communities on both short (<100 kyr) and longer time scales. We conclude that the faunal patterns of the hyperthermals observed at Site 401 strongly resemble those observed in other deep-sea early Paleogene hyperthermal deposits, suggesting that similar processes have driven them.

Paleomagnetic and rock magnetic properties of IODP Expedition 318 cores

The Integrated Ocean Drilling Program Expedition 318 to the Wilkes Land margin of Antarctica recovered a sedimentary succession ranging in age from lower Eocene to the Holocene. Excellent stratigraphic control is key to understanding the timing of paleoceanographic events through critical climate intervals. Drill sites recovered the lower and middle Eocene, nearly the entire Oligocene, the Miocene from about 17 Ma, the entire Pliocene and much of the Pleistocene. The paleomagnetic properties are generally suitable for magnetostratigraphic interpretation, with well-behaved demagnetization diagrams, uniform distribution of declinations, and a clear separation into two inclination modes. Although the sequences were discontinuously recovered with many gaps due to coring, and there are hiatuses from sedimentary and tectonic processes, the magnetostratigraphic patterns are in general readily interpretable. Our interpretations are integrated with the diatom, radiolarian, calcareous nannofossils and dinoflagellate cyst (dinocyst) biostratigraphy. The magnetostratigraphy significantly improves the resolution of the chronostratigraphy, particularly in intervals with poor biostratigraphic control. However, Southern Ocean records with reliable magnetostratigraphies are notably scarce, and the data reported here provide an opportunity for improved calibration of the biostratigraphic records. In particular, we provide a rare magnetostratigraphic calibration for dinocyst biostratigraphy in the Paleogene and a substantially improved diatom calibration for the Pliocene. This paper presents the stratigraphic framework for future paleoceanographic proxy records which are being developed for the Wilkes Land margin cores. It further provides tight constraints on the duration of regional hiatuses inferred from seismic surveys of the region.

Occurrence of hiatuses PH and NH 1 through NH 7 in DSDP holes

Miocene paleoceanographic evolution exhibits major changes resulting from the opening and closing of passages, the subsequent changes in oceanic circulation, and development of major Antarctic glaciation. The consequences and timing of these events can be observed in variations in the distribution of deep-sea hiatuses, sedimentation patterns, and biogeographic distribution of planktic organisms. The opening of the Drake Passage in the latest Oligocene to early Miocene (25-20 Ma) resulted in the establishment of the deep circumpolar current, which led to thermal isolation of Antarctica and increased global cooling. This development was associated with a major turnover in planktic organisms, resulting in the evolution of Neogene assemblages and the eventual extinction of Paleogene assemblages. The erosive patterns of two widespread hiatuses (PH, 23.0-22.5 Ma; and NH 1, 20-18 Ma) indicate that a deep circumequatorial circulation existed at this time, characterized by a broad band of carbonate-ooze deposition. Siliceous sedimentation was restricted to the North Atlantic and a narrow band around Antarctica. A major reorganization in deep-sea sedimentation and hiatus distribution patterns occurred near the early/middle Miocene boundary, apparently resulting from changes in oceanic circulation. Beginning at this time, deep-sea erosion occurred throughout the Caribbean (hiatus NH 2, 16-15 Ma), suggesting disruption of the deep circumequatorial circulation and northward deflection of deep currents, and/or intensification of the Gulf Stream. Sediment distribution patterns changed dramatically with the sudden appearance of siliceous-ooze deposition in the marginal and east equatorial North Pacific by 16.0 to 15.5 Ma, coincident with the decline of siliceous sedimentation in the North Atlantic. This silica switch may have been caused by the introduction of Norwegian Overflow Water into the North Atlantic acting as a barrier to outcropping of silica-rich Antarctic Bottom Water. The main aspects of the present oceanic circulation system and sediment distribution pattern were established by 13.5 to 12.5 Ma (hiatus NH 3), coincident with the establishment of a major East Antarctic ice cap. Antarctic glaciation resulted in a broadening belt of siliceous-ooze deposition around Antarctica, increased siliceous sedimentation in the marginal and east equatorial North Pacific and Indian Oceans, and further northward restriction of siliceous sediments in the North Atlantic. Periodic cool climatic events were accompanied by lower eustatic sea levels and widespread deep-sea erosion at 12 to 11 Ma (NH 4), 10 to 9 Ma (NH 5), 7.5 to 6.2 Ma (NH 6), and 5.2 to 4.7 Ma (NH 7).

Cenozoic clay mineralogy of DSDP Sites 93-604 and 93-605

Examination of the clay mineralogy of Cenozoic sediment samples from Deep Sea Drilling Project Sites 604 and 605 on the upper continental rise off New Jersey indicates that sediment deposition of two different clay mineral facies has occurred. These sites are marked by Paleogene deposition of illite with subordinate kaolinite and smectite covarying in inverse proportion, and by Neogene deposition dominated by illite with subordinate kaolinite and chlorite. Leg 93 results agree with the clay mineral facies proposed by Hathaway (1972), which defined a "Northern facies" consisting of illite and chlorite, with feldspar and hornblende, from erosion of rocks north of Cape Hatteras, and a "Southern facies" composed of smectite, kaolinite, and mixed-layer illite-smectites. Neogene and Quaternary sediments at Sites 604 and 605 contain the "Northern facies," and Paleogene sediments contain the "Southern facies" minerals. Feldspar is exclusively found in Neogene-Quaternary sediments, as is the majority of the amphibole found in these samples. Widespread Paleogene volcanic source materials are suggested by the presence of smectite throughout the early Paleocenemiddle Eocene sediments recovered at Site 605. The clay mineral stratigraphy at Leg 93 sites is comparable to the record at nearby DSDP sites on the lower continental rise and abyssal plain of the northwestern Atlantic (DSDP Sites 388, 105, and 106), and also with the sediments recovered by drilling on the Mazagan Plateau off northwestern Morocco (DSDP Sites 544-547) in the eastern North Atlantic.

Siliceous microfossil assemblage and accumulation rate variations across the Middle Eocene Climatic Optimum at ODP Site 171-1051

The Middle Eocene Climatic Optimum (MECO; ~ 40 million years ago [Ma]) is one of the most prominent transient global warming events in the Paleogene. Although the event is well documented in geochemical and isotopic proxy records at many locations, the marine biotic response to the MECO remains poorly constrained. We present new high-resolution, quantitative records of siliceous microplankton assemblages from the MECO interval of Ocean Drilling Program (ODP) Site 1051 in the subtropical western North Atlantic Ocean, which are interpreted in the context of published foraminiferal and bulk carbonate stable isotope (d18O and d13C) records. High diatom, radiolarian and silicoflagellate accumulation rates between 40.5 and 40.0 Ma are interpreted to reflect an ~ 500 thousand year (kyr) interval of increased nutrient supply and resultant surface-water eutrophication that was associated with elevated sea-surface temperatures during the prolonged onset of the MECO. Relatively low pelagic siliceous phytoplankton sedimentation accompanied the peak MECO warming interval and the termination of the MECO during an ~ 70 kyr interval centered at ~ 40.0 Ma. Following the termination of the MECO, an ~ 200-kyr episode of increased siliceous plankton abundance indicates enhanced nutrient levels between ~ 39.9 and 39.7 Ma. Throughout the Site 1051 record, abundance and accumulation rate fluctuations in neritic diatom taxa are similar to the trends observed in pelagic taxa, implying either similar controls on diatom production in the neritic and pelagic zones of the western North Atlantic or fluctuations in sea level and/or shelf accommodation on the North American continental margin to the west of Site 1051. These results, combined with published records based on multiple proxies, indicate a geographically diverse pattern of surface ocean primary production changes across the MECO. Notably, however, increased biosiliceous accumulation is recorded at both ODP Sites 1051 and 748 (Southern Ocean) in response to MECO warming. This may suggest that increased biosiliceous sediment accumulation, if indeed a widespread phenomenon, resulted from higher continental silicate weathering rates and an increase in silicic acid supply to the oceans over several 100 kyr during the MECO.

Age and strontium isotope composition for Cretaceous in DSDP Hole 74-525

Firm stratigraphic correlations are needed to evaluate the global significance of unconformity bounded units (sequences). We correlate the well-developed uppermost Campanian and Maestrichtian sequences of the New Jersey Coastal Plain to the geomagnetic polarity time scale (GPTS) by integrating Sr-isotopic stratigraphy and biostratigraphy. To do this, we developed a Maestrichtian (ca. 73-65 Ma) Sr-isotopic reference section at Deep Sea Drilling Project Hole 525A in the southeastern Atlantic Ocean. Maestrichtian strata can then be dated by measuring their 87Sr/86Sr composition, calibrating to the GPTS of S. C. Cande and D. V. Kent (1993, personal commun.), and using the equation Age (Ma) = 37326.894-52639.89 (87Sr/86Sr). Sr-stratigraphic resolution for the Maestrichtian is estimated as +-1.2 to +-2 m.y. At least two unconformity-bounded units comprise the uppermost Campanian to Maestrichtian strata in New Jersey. The lower one, the Marshalltown sequence, is assigned to calcareous nannofossil Zones CC20/21 (~NC19) and CC22b (~NC20). It ranges in age from ~74.1 to 69.9 Ma based on Sr-isotope age estimates. The overlying Navesink sequence is assigned to calcareous nannoplankton Zones CC25-26 (~NC21-23); it ranges in age from 69.3 to 65 Ma based on Sr-isotope age estimates. The upper part of this sequence, the Tinton Formation, has no calcareous planktonic control; Sr-isotopes provide an age estimate of 66 +- 1.2 Ma (latest Maestrichtian). Sequence boundaries at the base and the top of the Marshalltown sequence match boundaries elsewhere in the Atlantic Coastal Plain (Owens and Gohn, 1985) and the inferred global sea-level record of Haq et al. (1987); they support eustatic changes as the mechanism controlling depositional history of this sequence. However, the latest Maestrichtian record in New Jersey does not agree with Haq et al. (1987); we attribute this to correlation and time-scale differences near the Cretaceous/Paleogene boundary. High sedimentation rates in the latest Maestrichtian of New Jersey (Shrewsbury Member of the Red Bank Formation and the Tinton Formation) suggest tectonic uplift and/or rapid progradation during deposition of the highstand systems tract.

The early Eocene global warming events: Implications from ODP Leg 208 Walvis Ridge depth transect

Five sections drilled in multiple holes over a depth transect of more than 2200 m at the Walvis Ridge (SE Atlantic) during Ocean Drilling Program (ODP) Leg 208 resulted in the first complete early Paleogene deep-sea record. Here we present high-resolution stratigraphic records spanning a ~4.3 million yearlong interval of the late Paleocene to early Eocene. This interval includes the Paleocene-Eocene thermal maximum (PETM) as well as the Eocene thermal maximum (ETM) 2 event. A detailed chronology was developed with nondestructive X-ray fluorescence (XRF) core scanning records and shipboard color data. These records were used to refine the shipboard-derived spliced composite depth for each site and with a record from ODP Site 1051 were then used to establish a continuous time series over this interval. Extensive spectral analysis reveals that the early Paleogene sedimentary cyclicity is dominated by precession modulated by the short (100 kyr) and long (405 kyr) eccentricity cycles. Counting of precession-related cycles at multiple sites results in revised estimates for the duration of magnetochrons C24r and C25n. Direct comparison between the amplitude modulation of the precession component derived from XRF data and recent models of Earth's orbital eccentricity suggests that the onset of the PETM and ETM2 are related to a 100-kyr eccentricity maximum. Both events are approximately a quarter of a period offset from a maximum in the 405-kyr eccentricity cycle, with the major difference that the PETM is lagging and ETM2 is leading a 405-kyr eccentricity maximum. Absolute age estimates for the PETM, ETM2, and the magnetochron boundaries that are consistent with recalibrated radiometric ages and recent models of Earth's orbital eccentricity cannot be precisely determined at present because of too large uncertainties in these methods. Nevertheless, we provide two possible tuning options, which demonstrate the potential for the development of a cyclostratigraphic framework based on the stable 405-kyr eccentricity cycle for the entire Paleogene.

Dinoflagellate abundance and events of ODP Site 189-1172 sediments

Palynomorphs were studied in samples from Ocean Drilling Program (ODP) Leg 189, Holes 1172A and 1172D (East Tasman Plateau; 2620 m water depth). Besides organic walled dinoflagellate cysts (dinocysts), broad categories of other palynomorphs were quantified in terms of relative abundance. In this contribution, we provide an overview of the dinocyst distribution from the Maastrichtian to lowermost Oligocene and Quaternary intervals and illustrate main trends in palynomorph distribution. The uppermost Cretaceous-lowermost Oligocene succession of Site 1172 has a confident biomagnetostratigraphy, enabling us to tie early Paleogene Southern Hemisphere dinocyst events to the geomagnetic polarity timescale for the first time. Dinocyst species from the Maastrichtian to earliest Oligocene at Site 1172 are largely endemic ("Transantarctic Flora") or bipolar; cosmopolitan taxa are present in the background as well. The Maastrichtian-early late Eocene dinocyst assemblages are indicative of shallow-marine to restricted marine, pro-deltaic conditions, closely tied to a massive siliciclastic sequence. By middle late Eocene times (~35.5 Ma), the siliciclastic sequence gave way to a thin glauconitic unit, considered to reflect the deepening of the Tasmanian Gateway. This transition coincides with the most prominent change in dinocyst associations of the Paleogene. The turnover is inferred to reflect a change from marginal marine to more offshore conditions, with increased winnowing and oxidation. Overlying pelagic carbonate ooze of middle early Oligocene and younger age is virtually barren of organic microfossils, although Quaternary assemblages have been recovered. This aspect is taken to reflect average low sedimentation rates and well-oxygenated water masses during most of the Oligocene and Neogene. The few palynologically productive samples from the Oligocene-Quaternary interval have a stronger cosmopolitan to subtropical signature, with warm-water species being common to abundant.

Paleocene-Eocene calcareous nannofossils of onshore wells from the Coastal Plain of New Jersey and Maryland, USA

Paleogene calcareous nannofossils from split spoon cores recovered from five wells along the Coastal Plain of New Jersey and Maryland have been analyzed in order to provide onshore information complementary to that derived from the offshore DSDP Site 605 (upper continental rise off New Jersey). Hiatuses are more numerous and of greater extent in the onshore sections, but the major ones correlate well with those noted in the offshore section. At one site at least (Leggett Well), sedimentation may well have been continuous across the Cretaceous/Tertiary boundary, as it is believed to have been at DSDP Site 605. These various correlations are discussed elsewhere in a companion paper (Olsson and Wise, this volume). Important differences in nannofossil assemblages are noted between the onshore (shelf paleoenvironment) and offshore (slope-rise paleoenvironment) sections. Lithostromation simplex, not present offshore, is consistently present onshore and seems to be confined to the Eocene shelf sediments of this region. The same relationship holds for the zonal marker, Rhabdosphaera gladius Locker. The Rhomboaster-Tribrachiatus plexus is more diverse and better preserved in the onshore sections, where the lowermost Eocene Zone CP9 is well represented. Differential preservation is postulated to account for two morphotypes of Tribrachiatus bramlettei (Brönnimann and Stradner). Type A is represented at DSDP Site 605 by individuals with short, stubby arms, but these forms are not present in the equivalent onshore sections. There they are replaced by the Type B morphotypes, which exhibit a similar basic construction but possess much longer, more delicate arms.