Whole-rock oxygen and carbon isorope record across the Cretaceous/Tertiary boundary in ODP Hole 130-807C

Whole-rock d18O analyses of the Paleogene and Upper Cretaceous succession at Ocean Drilling Program Hole 807C suggest the presence of hiatuses between 876.95 and 894.47 mbsf and between 1138.82 and 1140.94 mbsf. The d13C data show a pronounced positive excursion between 1130 and 1180 mbsf that corresponds to the positive d13C values characteristic of the Paleocene. Despite the stratigraphic breaks in the section, the d18O data show a systematic increase between 1360 mbsf and the hiatus between 876.95 and 894.47 mbsf, which is consistent with previous suggestions of long-term climatic cooling through the Paleogene. The Cretaceous/Tertiary transition is apparently complete in this section and is of remarkable thickness. The expanded nature of this portion of the succession is probably the result of secondary depositional processes. High-resolution sampling across this boundary may reveal detailed structure of the d13C decline associated with the extinctions that mark the termination of the Cretaceous.

Magnetic observation of ODP Site 152-919 in the Irminger Basin, North Atlantic

Component natural remanent magnetizations derived from u-channel and 1-qcm discrete samples from ODP Site 919 (Irminger Basin) indicate the existence of four intervals of negative inclinations in the upper Brunhes Chronozone. According to the age model based on planktic oxygen isotope data, these "excursional" intervals occur in sediments deposited during the following time intervals: 32-34 ka, 39-41 ka, 180-188 ka and 205-225 ka. These time intervals correspond to polarity excursions detected elsewhere, known as Mono Lake, Laschamp, Iceland Basin and Pringle Falls. The isotope-based age model is supported by the normalized remanence (paleointensity) record that can be correlated to other calibrated paleointensity records for the 0-500 ka interval, such as that from ODP Site 983. For the intervals associated with the Mono Lake and Laschamp excursions, virtual geomagnetic poles (VGPs) reach equatorial latitudes and mid-southerly latitudes, respectively. For intervals associated with the Iceland Basin and Pringle Falls excursions, repeated excursions of VGPs to high southerly latitudes indicate rapid directional swings rather than a single short-lived polarity reversal. The directional instability associated with polarity excursions is not often recorded, probably due to smoothing of the sedimentary record by the process of detrital remanence (DRM) acquisition.

Age model and stable isotope record of DSDP holes 48-401 and 86-577

Early Paleogene warm climates may have been linked to different modes and sources of deepwater formation. Warm polar temperatures of the Paleocene and Eocene may have resulted from either increased atmospheric trace gases or increased heat transport through deep and intermediate waters. The possibility of increasing ocean heat transport through the production of warm saline deep waters (WSDW) in the Tethyan region has generated considerable interest. In addition, General Circulation Model results indicate that deepwater source regions may be highly sensitive to changing basin configurations. To decipher deepwater changes, we examined detailed benthic foraminiferal faunal and isotopic records of the late Paleocene through the early Eocene (~60 to 50 Ma) from two critical regions: the North Atlantic (Bay of Biscay Site 401) and the Pacific (Shatsky Rise Site 577). These records are compared with published data from the Southern Ocean (Maud Rise Site 690, Islas Orcadas Rise Site 702). During the late Paleocene, similar benthic foraminiferal delta18O values were recorded at all four sites. This indicates uniform deepwater temperatures, consistent with a single source of deep water. The highest delta13C values were recorded in the Southern Ocean and were 0.5 per mil more positive than those of the Pacific. We infer that the Southern Ocean was proximal to a source of nutrient-depleted deep water during the late Paleocene. Upper Paleocene Reflector Ab was cut on the western Bermuda Rise by cyclonically circulating bottom water, also suggesting a vigorous source of bottom water in the Southern Ocean. A dramatic negative excursion in both carbon and oxygen isotopes occurred in the latest Paleocene in the Southern Ocean. This is a short-term (<100 kyr), globally synchronous event which also is apparent in both the Atlantic and Pacific records as a carbon isotopic excursion of approximately 1 per mil. Faunal analyses from the North Atlantic and Pacific sites indicate that the largest benthic foraminiferal faunal turnover of the Cenozoic was synchronous with the isotopic excursion, lending support to the hypothesis that the extinctions were caused by a change in deepwater circulation. We speculate that the Southern Ocean deepwater source was reduced or eliminated at the time of the excursion. During the early Eocene, Southern Ocean delta13C values remained enriched relative to the North Atlantic and Pacific. However, the Southern Ocean was also enriched in delta18O relative to these basins. We interpret that these patterns indicate that although the Southern Ocean was proximal to a source of cool, nutrient-depleted water, the intermediate to upper deep water sites of the North Atlantic and Pacific were ventilated by a different source that probably originated in low latitudes, i.e., WSDW.

Nd isotope composition of fossil fish teeth of ODP Hole 119-738B

We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ~0.23 epsilon-Nd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ~40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 epsilon-Nd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10X increase in sample throughput.

Stable carbon isotopic composition of biomarker lipids of DSDP Hole 31-302

The middle Paleocene through early Eocene long-term gradual warming was superimposed by several transient warming events, such as the Paleocene-Eocene Thermal Maximum (PETM) and Eocene Thermal Maximum 2 (ETM2). Both events show evidence for extreme global warming associated with a major injection of carbon into the ocean-atmosphere system, but the mechanisms of carbon injection and many aspects of the environmental response are still poorly understood. In this study, we analyzed the concentration and stable carbon isotopic (d13C) composition of several sulfur-bound biomarkers derived from marine photoautotrophs, deposited in the Arctic Ocean at ~85°N, during ETM2. The presence of sulfur-bound biomarkers across this event points toward high primary productivity and anoxic bottom water conditions. The previously reported presence of isorenieratene derivatives indicates euxinic conditions in the photic zone, likely caused by a combination of enhanced primary productivity and salinity stratification. The negative carbon isotope excursion measured at the onset of ETM2 for several biomarkers, ranges between 3 per mil and 4.5 per mil, much larger than the ~1.4 per mil recorded in marine carbonates elsewhere, suggesting substantial enhanced isotopic fractionation by the primary producers likely due to a significant rise in pCO2. In the absence of biogenic carbonates in the ETM2 section of our core we use coeval planktonic d13C from elsewhere to estimate surface water d13C in the Arctic Ocean and then apply the relation between isotopic fractionation and pCO2, originally calibrated for haptophyte alkenones, to three selected organic biomarkers (i.e., S-bound phytane, C35 hopane, and a C25 highly branched isoprenoid). This yields pCO2 values potentially in the range of four times preindustrial levels. However, these estimates are uncertain because of a lack of knowledge on the importance of pCO2 on photosynthetic isotopic fractionation.

Abundance of benthic foraminifera in late Paleocene to eraly Pliocene sediments of DSDP Hole 74-525A on the Walvis Ridge, South Atlantic (Table 1)

Benthic forammifers in the size-fraction greater than 0.073 mm were studied in 88 Paleocene to Pleistocene samples from Deep Sea Drilling Project Site 525 (Hole 525A, Walvis Ridge, eastern south Atlantic). Clustering of the samples on the basis of the 86 most abundant foramimfers (in total, 331 taxa were identified) allowed separating two major assemblage zones: the Paleocene to Eocene interval, and the Oligocene to Pleistocene interval. Each of these, in turn, were subdivided into three minor subzones as follows: lower upper Paleocene (approx. 62.4 to 57 8 Ma); upper upper Paleocene (56.6 to 56 2 Ma), lower and middle Eocene (55.3 to 46 8 Ma); upper Oligocene to middle Miocene (25.3 to 16 Ma), middle Miocene to Pliocene (15.7 to 4.2 Ma), and lower Pleistocene (0.4 to 0.02 Ma), with only minor differences with the previous zone. Some very abundant taxa span most of the column studies (Bolivina huneri, Cassidulina subglobosa, Eponides bradyi, E. weddellensis, Gavelinella micra, Oridorsalis umbonatus, etc.). Several of the faunal breaks recorded coincide with conspicuous minima in the specific diversity curve, thus suggesting that the corresponding turnovers signal the final stages of periods of faunal impoverishment. At least one major bottomwater temperature drop (as derived from delta18O data) is synchronous with a decrease in the forammiferal specific diversity. On the other hand, a specific diversity maximum in the middle Miocene might be associated with a delta13C increase at approx 16 to 12 Ma. Highest foraminiferal abundances (up to 600-800 individuals per gram of dry sediment) occurred in the late Paleocene and in the early Pleistocene, in coincidence with the lowest diversity figures calculated. The magnitude of the most important faunal turnover recorded, between the middle Eocene and the late Oligocene, is magnified in our data set by the large hiatus which separates the middle Eocene from the upper Oligocene sediments. Considerably smaller overturns occurred within the late Paleocene (in coincidence with changes in the specific diversity, absolute abundance of forammiferal tests, and delta13C), and in the middle Miocene (in coincidence with a specific diversity maximum and a delta13C excursion). New reformation on the morphology and the stratigraphic ranges of several species is furnished. For all the taxa recorded the number of occurrences, total number of individuals identified and first and last appearances are listed.

Neodymium isotope record of late Paleocene to eraly Eocene fish teeth

High-resolution, fish tooth Nd isotopic records for eight Deep Sea Drilling Project and Ocean Drilling Program sites were used to reconstruct the nature of late Paleocene-early Eocene deep-water circulation. The goal of this reconstruction was to test the hypothesis that a change in thermohaline circulation patterns caused the abrupt 4-5°C warming of deep and bottom waters at the Paleocene/Eocene boundary - the Paleocene-Eocene thermal maximum (PETM) event. The combined set of records indicates a deep-water mass common to the North and South Atlantic, Southern and Indian oceans characterized by mean epsilon-Nd values of ~-8.7, and different water masses found in the central Pacific Ocean (epsilon-Nd ~-4.3) and Caribbean Sea (epsilon-Nd ~1.2). The geographic pattern of Nd isotopic values before and during the PETM suggests a Southern Ocean deep-water formation site for deep and bottom waters in the Atlantic and Indian ocean basins. The Nd data do not contain evidence for a change in the composition of deep waters prior to the onset of the PETM. This finding is consistent with the pattern of warming established by recently published stable isotope records, suggesting that deep- and bottom-water warming during the PETM was gradual and the consequence of surface-water warming in regions of downwelling.

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.

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.

Geochemical analysis of nine sections from the Nama Group, Namibia

The first appearance of skeletal metazoans in the late Ediacaran (~550 million years ago; Ma) has been linked to the widespread development of oxygenated oceanic conditions, but a precise spatial and temporal reconstruction of their evolution has not been resolved. Here we consider the evolution of ocean chemistry from ~550 to ~541 Ma across shelf-to-basin transects in the Zaris and Witputs Sub-Basins of the Nama Group, Namibia. New carbon isotope data capture the final stages of the Shuram/Wonoka deep negative C-isotope excursion, and these are complemented with a reconstruction of water column redox dynamics utilising Fe-S-C systematics and the distribution of skeletal and soft-bodied metazoans. Combined, these inter-basinal datasets provide insight into the potential role of ocean redox chemistry during this pivotal interval of major biological innovation. The strongly negative d13C values in the lower parts of the sections reflect both a secular, global change in the C-isotopic composition of Ediacaran seawater, as well as the influence of 'local' basinal effects as shown by the most negative d13C values occurring in the transition from distal to proximal ramp settings. Critical, though, is that the transition to positive d13C values postdates the appearance of calcified metazoans, indicating that the onset of biomineralization did not occur under post-excursion conditions. Significantly, we find that anoxic and ferruginous deeper water column conditions were prevalent during and after the transition to positive d13C that marks the end of the Shuram/Wonoka excursion. Thus, if the C isotope trend reflects the transition to global-scale oxygenation in the aftermath of the oxidation of a large-scale, isotopically light organic carbon pool, it was not sufficient to fully oxygenate the deep ocean. Both sub-basins reveal highly dynamic redox structures, where shallow, inner ramp settings experienced transient oxygenation. Anoxic conditions were caused either by episodic upwelling of deeper anoxic waters or higher rates of productivity. These settings supported short-lived and monospecific skeletal metazoan communities. By contrast, microbial (thrombolite) reefs, found in deeper inner- and mid-ramp settings, supported more biodiverse communities with complex ecologies and large skeletal metazoans. These long-lived reef communities, as well as Ediacaran soft-bodied biotas, are found particularly within transgressive systems, where oxygenation was persistent. We suggest that a mid-ramp position enabled physical ventilation mechanisms for shallow water column oxygenation to operate during flooding and transgressive sea-level rise. Our data support a prominent role for oxygen, and for stable oxygenated conditions in particular, in controlling both the distribution and ecology of Ediacaran skeletal metazoan communities.

Osmium, and stable carbon and oxygen isotope record accross the PETM

In the latest Paleocene an abrupt shift to more negative d13C values has been documented at numerous marine and terrestrial sites (Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Cramer et al., 1999; Kaiho et al., 1996, doi:10.1029/96PA01021; Kennett and Stott, 1991, doi:10.1038/353225a0; Koch et al., 1992, doi:10.1038/358319a0; Stott et al., 1996; Thomas and Shackleton, 1996, doi:10.1144/GSL.SP.1996.101.01.20; Zachos et al., 1993). This carbon isotope event (CIE) is coincident with oxygen isotope data that indicate warming of surface waters at high latitudes of nearly 4°-6°C (Kennett and Stott, 1991, doi:10.1038/353225a0) and more moderate warming in the subtropics (Thomas et al., 1999, doi:10.1029/1999PA900031). Here we report 187Os/188Os isotope records from the North Atlantic and Indian Oceans which demonstrate a >10% increase in the 187Os/188Os ratio of seawater coincident with the late Paleocene CIE. This excursion to higher 187Os/188Os ratios is consistent with a global increase in weathering rates. The inference of increased chemical weathering during this interval of unusual warmth is significant because it provides empirical evidence supporting the operation of a feedback between chemical weathering rates and warm global climate, which acts to stabilize Earth's climate (Walker et al., 1981). Estimates of the duration of late Paleocene CIE (Bains et al., 1999, doi:10.1126/science.285.5428.724; Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Norris and Röhl, 1999, doi:10.1038/44545; Röhl et al., 2000, doi:10.1130/0091-7613(2000)28<927:NCFTLP>2.0.CO;2) in conjunction with the Os isotope data imply that intensified chemical weathering in response to warm, humid climates can occur on timescales of 104-105 years. This interpretation requires that the late Paleocene thermal maximum Os isotope excursion be produced mainly by increased Os flux to the ocean rather than a transient excursion to higher 187Os/188Os ratios in river runoff. Although we argue that the former is more likely than the latter, we cannot rule out significant changes in the 187Os/188Os ratio of rivers.

Pb isotope and geochemical record of Arctic sediments

Elemental and Pb isotope measurements were performed on leachates and residues from surface sediments and two <50 cm cores (MC04 and MC16) collected along a NE-SW transect through Fram Strait. Geochemical and isotopic properties of residues from surface sediments define three distinct spatial domains within the Strait: 1) the easternmost edge of the Strait; 2) the eastern part of the Strait off the Svalbard margins; and 3) the western part of the Strait, influenced by supplies from Svalbard, the Nordic seas with possible contributions from northwestern Siberian margins, and sea ice and water outflow from the Arctic, respectively. Core MC16, in the third domain beneath the outflowing Arctic waters, spans the Last Glacial Maximum present interval. Sediments from this core were leached to obtain detrital (residues) and exchangeable (leachates) fractions. Detrital supplies to core MC16 are believed to originate mainly from melting of the overlying sea ice and thus can be used to document changes in Arctic sedimentary sources. Detrital 206Pb/204Pb and 208Pb/206Pb ratios illustrate two mixing trends, Trends A and B, corresponding to the pre- and post-Younger Dryas (YD) intervals, respectively. These trends represent binary mixtures with a common end-member (Canadian margins) and either a Siberian (Trend A) or Greenland (Trend B) margin end-member. The YD is marked by an isotopic excursion toward the Canadian end-member, suggesting a very active Beaufort Gyre possibly triggered by massive drainage of the Laurentide ice sheet. Pb isotope compositions of leachates, thought to represent the signature of the overlying water masses, define a unique linear trend coincident with Trend A. This suggests that water masses acquired their signature through exchange with particulate fluxes along the Canadian and Siberian continental margins.

Stable oxygen isotope record and abundances of Globorotalia menardii in sediments from the tropical Atlantic Ocean

Eight box cores from the tropical Atlantic were studied in detail with regard to foraminiferal oxygen isotopes, radiocarbon, and Globorotalia menardii abundance. A standard Atlantic oxygen-isotope signal was reconstructed for the last 20,000 yr. It is quite similar to the west-equatorial Pacific signal published previously. Deglaciation is seen to occur in two steps which are separated by a pause. Onset of deglaciation is after 15,000 yr B.P. The pause is centered between 11,000 and 12,000 yr B.P., but may be correlative with the Younger Dryas (10,500 yr B.P.) if allowance is made for a scale shift due to mixing processes on the sea floor. Step 2 is centered near 10,000 yr B.P. and is followed by a brief excursion toward light oxygen values. This excursion (the M event) may correlate with the Gulf of Mexico meltwater spike.