Geochemistry of interstitial gases in sedimentary deposits at DSDP Leg 64 Holes

We analyzed interstitial gases from holes at Sites 474, 477, 478, 479, and 481 in the Gulf of California, using gas chromatography and stable isotope mass spectrometry to evaluate their composition in terms of biogenic and thermogenic sources. The hydrocarbon gas (C1-C5) concentrations were comparable to the shipboard data, and no olefins could be detected. The ?13C data for the CH4 confirmed the effects of thermal stress on the sedimentary organic matter, because the values were typically biogenic near the surface and became more depleted in 12C versus depth in holes at Sites 474, 478, and 481. The CH4 at Site 477 was the heaviest, and in Hole 479 it did not show a dominant hightemperature component. The CO2 at depth in most holes was mostly thermogenic and derived from carbonates. The low concentrations of C2-C5 hydrocarbons in the headspace gas of canned sediments precluded a stable carbon-isotope analysis of their genetic origin.

Late Miocene development of the western Pacific warm pool: Planktonic foraminifer and oxygen isotopic evidence

The disappearance at ~10 Ma of the deep dwelling planktonic foraminifer Globoquadrina dehiscens from the western Pacific including the South China Sea was about 3 Myr earlier than its final extinction elsewhere. Accompanying this event at ~10 Ma was a series of faunal turnover characterized by increase in mixed layer, warm-water species and decrease to a minimum in deepwater species. Paleobiological and isotopic evidence indicates sea surface warming and a deepened local thermocline that we interpret as related to the development of an early western Pacific warm pool. The stepwise decline of G. dehiscens and other deep dwelling species from the NW and SW Pacific suggests more intensive warm water pileup than equatorial localities where surface bypass flow through the narrowing Indonesia seaway appears to remain efficient during the late Miocene. Planktonic delta18O values from the South China Sea consistently lighter than the tropical western Pacific during the Miocene also suggest, similar to today, more variable hydrologic conditions along the periphery than in the core of the warm pool. Stronger hydrologic variability affected mainly by monsoons and increased thermal gradient along the western margin of the late Miocene warm pool may have contributed to the decline of deep dwelling planktonic species including the early extinction of G. dehiscens from the South China Sea region. The late Miocene warm pool became influential and paleobiologically detectable from ~10 Ma, but the modern warm pool did not appear until about 4 Ma, in the middle Pliocene.

Age model and Plio-Pleistocene benthic stable oxygen isotope ratios of ODP Site 184-1143 in the Sourh China Sea

Based on benthic foraminiferal delta18O from ODP Site 1143, a 5-Myr astronomical timescale for the West Pacific Plio-Pleistocene was established using an automatic orbital tuning method. The tuned Brunhes/Matuyama paleomagnetic polarity reversal age agrees well with the previously published age of 0.78 Ma. The tuned ages for several planktonic foraminifer bio-events also agree well with published dates, and new ages for some other bio-events in the South China Sea were also estimated. The benthic delta18O from Site 1143 is highly coherent with the Earth's orbit (ETP) both at the obliquity and precession bands for the last 5 Myr, and at the eccentricity band for the last 2 Myr. In general, the 41-kyr cycle was dominant through the Plio-Pleistocene although the 23-kyr cycle was also very strong. The 100-kyr cycle became dominant only during the last 1 Myr. A comparison of the benthic delta18O between the Atlantic (ODP 659) and the East and West Pacific (846 and 1143) reveals that the Atlantic-Pacific benthic oxygen isotope difference ratio (Delta delta18OAtl-Pac) displays an increasing trend in three time intervals: 3.6-2.7 Ma, 2.7-2.1 Ma and 1.5-0.25 Ma. Each of the intervals begins with a rapid negative shift in Delta delta18OAtl-Pac, followed by a long period with an increasing trend, corresponding to the growth of the Northern Hemisphere ice sheet. This means that all three intervals of ice sheet growth in the Northern Hemisphere were accompanied at the beginning by a rapid relative warming of deep water in the Atlantic as compared to that of the Pacific, followed by its gradual relative cooling. This general trend, superimposed on the frequent fluctuations with glacial cycles, should yield insights into the processes leading to the boreal glaciation. Cross-spectral analyses of the Delta delta18OAtl-Pac with the Earth's orbit suggests that after the initiation of Northern Hemisphere glaciation at about 2.5 Ma, obliquity rather than precession had become the dominant force controlling the vertical structure or thermohaline circulation in the paleo-ocean.

Stable isotope record of Cretaceous samples of DSDP Hole 71-511

Oxygen isotope data for upper Turonian planktonic foraminifera at Deep Sea Drilling Project Site 511 (Falkland Plateau, 60°S paleolatitude) exhibit an ~2 per mil excursion to values as low as -4.66 per mil (Vienna Peedee belemnite standard; PDB) coincident with the warmest tropical temperature estimates yet obtained for the open ocean. The lowest planktonic foraminifer d18O values suggest that the upper ocean was as warm as 30-32°C. This is an extraordinary temperature for 60°S latitude but is consistent with temperatures estimated from apparently coeval mollusc d18O from nearby James Ross Island (65°S paleolatitude). Glassy textural preservation, a well-defined depth distribution in Site 511 planktonics, low sediment burial temperature (~32°C), and lack of evidence of highly depleted pore waters argue against diagenesis (even solid state diffusion) as the cause of the very depleted planktonic values. The lack of change in benthic foraminifer d18O suggests brackish water capping as the mechanism for the low planktonic d18O values. However, mixing ratio calculations show that the amount of freshwater required to produce a 2 per mil shift in ambient water would drive a 7 psu decrease in salinity. The abundance and diversity of planktonic foraminifera and nannofossils, high planktonic:benthic ratios, and the appearance of keeled foraminifera argue against lower-than-normal marine salinities. Isotope calculations and climate models indicate that we cannot call upon more depleted freshwater d18O to explain this record. Without more late Turonian data, especially from outside the South Atlantic basin, we can currently only speculate on possible causes of this paradoxical record from the core of the Cretaceous greenhouse.

Lagrangian back-tracing results for Kohnen station; output of time dependent numerical experiment with a 3D nested Antarctic ice sheet model

A nested ice flow model was developed for eastern Dronning Maud Land to assist with the dating and interpretation of the EDML deep ice core. The model consists of a high-resolution higher-order ice dynamic flow model that was nested into a comprehensive 3-D thermomechanical model of the whole Antarctic ice sheet. As the drill site is on a flank position the calculations specifically take into account the effects of horizontal advection as deeper ice in the core originated from higher inland. First the regional velocity field and ice sheet geometry is obtained from a forward experiment over the last 8 glacial cycles. The result is subsequently employed in a Lagrangian backtracing algorithm to provide particle paths back to their time and place of deposition. The procedure directly yields the depth-age distribution, surface conditions at particle origin, and a suite of relevant parameters such as initial annual layer thickness. This paper discusses the method and the main results of the experiment, including the ice core chronology, the non-climatic corrections needed to extract the climatic part of the signal, and the thinning function. The focus is on the upper 89% of the ice core (appr. 170 kyears) as the dating below that is increasingly less robust owing to the unknown value of the geothermal heat flux. It is found that the temperature biases resulting from variations of surface elevation are up to half of the magnitude of the climatic changes themselves.

Chronology and annual proxy data of Lago Grande di Monticchio sediments

We present new annual sedimentological proxies and sub-annual element scanner data from the Lago Grande di Monticchio (MON) sediment record for the sequence 76-112 thousand years before present (ka). They are combined with the previously published decadal to centennial resolved pollen assemblage in order to provide a comprehensive reconstruction of six major abrupt stadial spells (MON 1-6) in the central Mediterranean during early phase of the last glaciation. These climatic oscillations are defined by intervals of thicker varves and high Ti-counts and coincide with episodes of forest depletion interpreted as Mediterranean stadial conditions (cold winter/dry summer). Our chronology, labelled as MON-2014, has been updated for the study interval by tephrochronology and repeated and more precise varve counts and is independent from ice-core and speleothem chronologies. The high-resolution Monticchio data then have been compared in detail with the Greenland ice-core d18O record (NorthGRIP) and the northern Alps speleothem d18Ocalcite data (NALPS). Based on visual inspection of major changes in the proxy data, MON 2-6 are suggested to correlate with Greenland stadials (GS) 25-20. MON 1 (Woillard event), the first and shortest cooling spell in the Mediterranean after a long phase of stable interglacial conditions, has no counterpart in the Greenland ice core, but coincides with the lowest isotope values at the end of the gradual decrease in d18Oice in NorthGRIP during the second half of the Greenland interstadial (GI) 25. MON 3 is the least pronounced cold spell and shows gradual transitions, whereas its NorthGRIP counterpart GS 24 is characterized by sharp changes in the isotope records. MON 2 and MON 4 are the longest most and pronounced oscillations in the MON sediments in good agreement with their counterparts identified in the ice and spelethem records. The length of MON 4 (correlating with GS 22) supports the duration of stadial proposed by the NALPS timescales and suggests ca 500 yr longer duration than calculated by the ice-core chronologies GICC05modelext and AICC2012. Absolute dating of the cold spells provided by the MON-2014 chronology shows good agreement among the MON-2014, the GICC05modelext and the NALPS timescales for the period between 112 and 100 ka. In contrast, the MON-2014 varve chronology dates the oscillations MON 4 to MON 6 (92-76 ka) ca. 3,500 years older than the most likely corresponding stadials GS 22 to GS 20 by the other chronologies.

Stable oxygen isotope record and lithogenic composition of ODP Hole 117-722B

The upper 38 m of Hole 722B sediments (Owen Ridge, northwest Arabian Sea) was sampled at 20 cm intervals and used to develop records of lithogenic percent, mass accumulation rate, and grain size spanning the past 1 m.y. Over this interval, the lithogenic component of Owen Ridge sediments can be used to infer variability in the strength of Arabian Sea summer monsoon winds (median grain size) and the aridity of surrounding dust source-areas (mass accumulation rate; MAR in g/cm**2/k.y). The lithogenic MAR has strong 100, 41, and 23 k.y. cyclicities and is forced primarily by changes in source-area aridity associated with glacial-interglacial cycles. The lithogenic grain size, on the other hand, exhibits higher frequency variability (23 k.y.) and is forced by the strength of summer monsoon winds which, in turn, are forced by the effective sensible heating of the Indian-Asian landmass and by the availability of latent heat from the Southern Hemisphere Indian Ocean. These forcing mechanisms combine to produce a wind-strength record which has no strong relationship to glacial-interglacial cycles. Discussion of the mechanisms responsible for production of primary Milankovitch cyclicities in lithogenic records from the Owen Ridge is presented elsewhere (Clemens and Prell, 1990, doi:10.1029/PA005i002p00109). Here we examine the 1 m.y. record from Hole 722B focusing on different aspects of the lithogenic components including an abrupt change in the monsoon wind-strength record at 500 k.y., core-to-core reproducibility, comparison with magnetic susceptibility, coherency with a wind-strength record from the Pacific Ocean, and combination frequencies in the wind-strength record. The Hole 722B lithogenic grain-size record shows an abrupt change at 500 k.y. possibly indicating decreased monsoon wind-strength over the interval from 500 k.y. to present. The grain-size decrease appears to be coincident with a loss of spectral power near the 41 k.y. periodicity. However, the grain-size decrease is not paralleled in the Globigerina bulloides upwelling record, an independent record of summer monsoon wind-strength (Prell, this volume). These observations leave us with competing hypotheses possibly involving: (1) a decrease in the sensitivity of monsoon windstrength to obliquity forcing, (2) decoupling of the grain size and G. bulloides records via a decoupling of the nutrient supply from wind-driven upwelling, and/or (3) a change in dust source-area or the patterns of dust transporting winds. Comparison of the lithogenic grain size and weight percent records from Hole 722B with those from a nearby core shows that the major and most minor events are well replicated. These close matches establish our confidence in the lithogenic extraction techniques and measurements. Further, reproducibility on a core-to-core scale indicates that the eolian depositional signal is regionally strong, coherent, and well preserved. The lithogenic weight percent and magnetic susceptibility are extremely well correlated in both the time and frequency domains. From this we infer that the magnetically susceptible component of Owen Ridge sediments is of terrestrial origin and transported to the Owen Ridge via summer monsoon winds. Because of the high correlation with the lithogenic percent record, the magnetic susceptibility record can be cast in terms of lithogenic MAR and used as a high resolution proxy for continental aridity. In addition to primary Milankovitch periodicities, the Hole 722B grain-size record exhibits periodicity at 52 k.y. and at 29 k.y. Both periodicities are also found in the grain-size record from piston core RC11-210 in the equatorial Pacific Ocean. Comparison of the two grain-size records shows significant coherence and zero phase relationships over both the 52 and 29 k.y. periodicities suggesting that the strengths of the Indian Ocean monsoon and the Pacific southeasterly trade winds share common forcing mechanisms. Two possible origins for the 52 and 29 k.y. periodicities in the Hole 722B wind-strength record are (1) direct Milankovitch forcing (54 and 29 k.y. components of obliquity) and (2) combination periodicities resulting from nonlinear interactions within the climate system. We find that the 52 and 29 k.y. periodicities show stronger coherency with crossproducts of eccentricity and obliquity (29 k.y.) and precession and obliquity (52 k.y.) than with direct obliquity forcing. Our working hypothesis attributes these periodicities to nonlinear interaction between external insolation forcing and internal climatic feedback mechanisms involving an interdependence of continental snow/ice-mass (albedo) and the hydrological cycle (latent heat availability).

Stable oxygen isotope record and relative abundances of planktonic foraminifera of ODP Hole 117-728A

High resolution stratigraphy based on oxygen isotope ratios of the planktonic foraminifers Neogloboquadrina dutertrei (d'Orbigny), Globigeriniodes ruber (d'Orbigny), and Globigerina bulloides (d'Orbigny), magnetic susceptibility, and calcium carbonate content covers the sedimentary record of ODP Hole 728A drilled on the Oman Margin from approximately 10 k.y. to 525 k.y., comprising isotopic stages 1-13. Below stage 13 isotopic stage boundaries cannot be defined with certainty in our data. Sediment accumulation rates were calculated from the isotopic record of N. dutertrei by matching it with the age model SPECMAP curve. During the glacial periods sediment accumulation rates were higher than during the interglacial periods, reflecting increased input from the shelf during low-stands of sea level and increased eolian input. Periodograms for the past 524 k.y. on oxygen isotope records of N. dutertrei, G. ruber, and G. bulloides, on calcium carbonate content, magnetic susceptibility, and on a foraminiferal fragmentation record show powers matching the Milankovitch periodicities. High powers are concentrated around 103 k.y. In the spectra of oxygen isotope ratios of N. dutertrei, magnetic susceptibility, and foraminiferal fragmentation these are significant at the 80% confidence level with respect to a first order autoregressive model. Power concentrations near 43 k.y., matching obliquity, are present but subdued in all spectra. Power concentrations near 23 k.y., matching precession, are significant in the spectra of the oxygen isotope record of N. dutertrei, magnetic susceptibility, and calcium carbonate content record. Fragmentation of planktonic foraminifers increased during the interglacial periods. This is attributed to dissolution of the tests in an expanded oxygen minimum zone (OMZ), where undersaturation of calcium carbonate is caused by enhanced production in the euphotic zone, which would suggest stronger monsoonal induced upwelling during interglacial periods. Extension of the OMZ could also be increased by outflow of low oxygen marginal basin bottom water.

Component composition and benthic foraminifera in sediments of ODP Leg 112

Indicators of surface-water productivity and bottom-water oxygenation have been studied for the age interval from the latest Pleistocene to the Holocene at three holes (679D, 680B, and 68IB) located in the center and at the edges of an upwelling cell at approximately 11°S on the Peruvian continental margin. Upwelling activity was maximal at this latitude during d18O Stages 1 (lower part), 3, the upper part of 5, the lower part of 6, and 7, as documented by high diatom abundance. During these time intervals, the bottom water was poorly oxygenated, as documented by low diversity benthic foraminiferal assemblages that are dominated by B. seminuda s.l. Both surface- and bottom-water-circulation patterns appear to have changed rapidly over short time intervals. Due to changes in surface circulation, the intensity of upwelling decreased, thereby decreasing the concentration of nutrients, and reducing the supply of organic matter to the bottom. Radiolarians became more abundant in the surface waters, and the bottom-water environment was less depleted in oxygen, allowing for the establishment of more diverse benthic foraminiferal assemblages. Surface-water productivity was probably minimal during the early part of d18O Stages 5 and 9, as indicated by the increased abundance of planktonic foraminifers and pteropods and their subsequent preservation.

Stable oxygen isotope record and benthic foraminiferal abundances in Cretaceous sediments of Demerara Rise

During the mid-Cretaceous period, the global subsurface oceans were relatively warm, but the origins of the high temperatures are debated. One hypothesis suggests that high sea levels and the continental configuration allowed high-salinity waters in low-latitude epicontinental shelf seas to sink and form deep-water masses (Brass et al., 1982, doi:10.1038/296620a0; Arthur and Natland, 1979; Chamberlin, 1906). In another scenario, surface waters in high-latitude regions, the modern area of deep-water formation, were warmed through greenhouse forcing (Bice and Marotzke, 2001, doi:10.1029/2000JC000561), which then propagated through deep-water circulation. Here, we use oxygen isotopes and Mg/Ca ratios from benthic foraminifera to reconstruct intermediate-water conditions in the tropical proto-Atlantic Ocean from 97 to 92 Myr ago. According to our reconstruction, intermediate-water temperatures ranged between 20 and 25 °C, the warmest ever documented for depths of 500-1,000 m. Our record also reveals intervals of high-salinity conditions, which we suggest reflect an influx of saline water derived from epicontinental seas around the tropical proto-North Atlantic Ocean. Although derived from only one site, our data indicate the existence of warm, saline intermediate waters in this silled basin. This combination of warm saline intermediate waters and restricted palaeogeography probably acted as preconditioning factors for the prolonged period of anoxia and black-shale formation in the equatorial proto-North Atlantic Ocean during the Cretaceous period.

Age model for the time between 3.45 and 2.45 Ma of ODP Site 189-1172

Calcareous nannoplankton assemblages and benthic d18O isotopes of Pliocene deep-sea sediments of ODP site 1172 (East of Tasmania) have been studied to improve our knowledge of the Southern Ocean paleoceanography. Our study site is located just north of the Subtropical Front (STF), an ideal setting to monitor migrations of the STF during our study period, between 3.45 and 2.45 Ma. The assemblage identified at ODP site 1172 has been interpreted as characteristic for the transitional zone water mass, located south of the STF, based on: (i) the low abundances (< 1%) of subtropical taxa, (ii) relatively high percentages of Coccolithus pelagicus, a subpolar type species, (iii) abundances from 2-10% of Calcidiscus leptoporus, a species that frequently inhabits the zone south of the STF and (iv) the high abundances of small Noelaerhabdaceae which at present dominates the zone south of the STF. Across our interval the calcareous nannoplankton manifests glacial-interglacial variability. We have identified cold events, characterized by high abundances of C. pelagicus which coincide with glacial periods, except during G7. After 3.1 Ma cold events are more frequent, in concordance with global cooling trends. Around 2.75 Ma, the interglacial stage G7 is characterized by anomalous low temperatures which most likely are linked to definite closure of the Central American Seaway (CAS), an event that is believed to have had global consequences. A gradual increase of very small Reticulofenestra across our section marks a significant trend in the small Noelaerhabdaceae species group and has been linked to a general enhanced mixing of the water column in agreement with previous studies. It is suggested that a rapid decline of small Gephyrocapsa after isotopic stage G7 might be related to the cooling observed in our study site after the closure of the CAS.

Planktic foraminiferal abundance and stable oxygen isotope ratios of sediment cores from the Southern California Borderlands

A variety of evidence suggests that average sea surface temperatures (SSTs) during the last glacial maximum in the California Borderlands region were significantly colder than during the Holocene. Planktonic foraminiferal delta18O evidence and average SST estimates derived by the modern analog technique indicate that temperatures were 6°-10°C cooler during the last glacial relative to the present. The glacial plankton assemblage is dominated by the planktonic foraminifer Neogloboquadrina pachyderma (sinistral coiling) and the coccolith Coccolithus pelagicus, both of which are currently restricted to subpolar regions of the North Pacific. The glacial-interglacial average SST change determined in this study is considerably larger than the 2°C change estimated by Climate: Long-Range Investigation, Mapping, and Prediction (CLIMAP) [1981]. We propose that a strengthened California Current flow was associated with the advance of subpolar surface waters into the Borderlands region during the last glacial.

Geochemistry and radiolarian distribution of sediment core MD96-2073

A combination of changes in the species composition of the radiolarian populations, and in the sediment chemical composition (content and mass accumulation rates of carbonate, organic carbon, and selected major and trace elements, with special attention paid to Ba) is used to reconstruct the variations in upwelling activity over the last 250 kyr in the Socotra gyre area (Somali-Socotra upwelling system, NW Indian Ocean). In the Socotra gyre (Core MD 962073 at 10°N), the variations in upwelling intensity are reconstructed by the upwelling radiolarian index (URI) while the thermocline/surface radiolarian index (TSRI) testifies to productivity variations during non-upwelling intervals. Despite an origin related both to marine and terrigenous inputs, the geochemical records of organic carbon, silica, and trace elements (Ba, P, Cu, and Zn) normalized to Al are controlled by the variations in surface paleoproductivity. The data indicate a continuous increase in upwelling intensity during the last 250 kyr with a maximum activity within the MIS 3, while high productivity periods in between the upwelling seasons occurred both during glacial and interglacial intervals. A comparison of our data with published observations from another gyre of the Somalian upwelling area located at 5°N in the Somali gyre area shows differences regarding periods of upwelling activity and their geochemical imprint. Three hypotheses are proposed to explain these differences: (1) changes in the planktonic community, resulting in more silica-rich deposits in the Socotra gyre, and more carbonate-rich deposits in the Somali gyre, that are controlled by differences in the source water of the upwelling; (2) a more important terrigenous input in the southern gyre; and (3) a different location of the sites relative to the geographic distribution of the upwelling gyres and hydrologic fronts.

Quaternary isotope stratigraphy of DSDP Hole 90-593 from the Challenegr Plateau, South Tasman Sea

A moderate-resolution isotope stratigraphy (with an average of one sample per 17,500 yr.) derived from the benthic foraminifer Uvigerina (or Cibicides), the planktonic foraminifer Globigerina bulloides, and calcareous nannofossil concentrates is presented for the entire Quaternary (and latest Pliocene) section of mid-upper bathyal calcareous oozes from DSDP Site 593, western Challenger Plateau, south Tasman Sea. Superimposed on a trend of gradually increasing average delta18O values through the Pleistocene, reflecting the progressive buildup of polar ice sheets, is a record of highfrequency but generally low amplitude (0.5-1?) isotope fluctuations in the early Quaternary (1.9-1.0 m.y.), followed by a greatly increased intensity (1.5-2.0 ?) of glacial-interglacial fluctuations during the late Quaternary (< 1.0 m.y.). The standard late Quaternary isotope stages 1 to 24 are mainly resolvable. Significant excursions in both delta18O and delta13C values at various times during the Quaternary are suggested to be due to periodic, fundamental changes in ocean circulation properties over the plateau. For example, intensified upwelling of Antarctic Intermediate Waters during several glacial periods is indicated by the convergence of benthic and planktonic foraminiferal delta18O data, and productivity variations may account for certain delta13C spikes in the record. With increasingly higher resolution analysis this core will provide a useful Quaternary isotope reference section for southern temperate waters in the southwest Pacific, centered on New Zealand.