(Table 1) Position and astronomical ages of sedimentary cycles in the eastern Mediterranean Sea

An astronomically calibrated timescale has recently been established [Hilgen, 1991, doi:10.1016/0012-821X(91)90082-S; doi:10.1016/0012-821X(91)90206-W] for the Pliocene and earliest Pleistocene based on the correlation of dominantly precession controlled sedimentary cycles (sapropels and carbonate cycles) in Mediterranean marine sequences to the precession time series of the astronomical solution of Berger and Loutre [1991, doi:10.1016/0277-3791(91)90033-Q ] (hereinafter referred to as Ber90). Here we evaluate the accuracy of this timescale by (1) comparing the sedimentary cycle patterns with 65°N summer insolation time series of different astronomical solutions and (2) a cross-spectral comparison between the obliquity-related components in the 65°N summer insolation curves and high-resolution paleoclimatic records derived from the same sections used to construct the timescale. Our results show that the carbonate cycles older than 3.5 m.y. should be calibrated to one precession cycle older than previously proposed. Application of the astronomical solution of Laskar [1990, doi:10.1016/0019-1035(90)90084-M], (hereinafter referred to as La90) with present-day values for the dynamical ellipticity of the Earth and tidal dissipation by the Sun and Moon results in the best fit with the geological record, indicating that this solution is the most accurate from a geological point of view. Application of Ber90, or La90 solutions with dynamical ellipticity values smaller or larger than the present-day value, results in a less obvious fit with the geological record. This implies that the change in the planetary shape of the Earth associated with ice loading and unloading near the poles during the last 5.3 million years was too small to drive the precession into resonance with the perturbation term, s6-g6+g5, of Jupiter and Saturn. Our new timescale results in a slight but significant modification of all ages of the sedimentary cycles, bioevents, reversal boundaries, chronostratigraphic boundaries, and glacial cycles. Moreover, a comparison of this timescale with the astronomical timescales of ODP site 846 [Shackleton et al., 1995, doi:10.2973/odp.proc.sr.138.106.1995; doi:10.2973/odp.proc.sr.138.117.1995] and ODP site 659 [Tiedemann et al., 1994, doi:10.1029/94PA00208] indicates that all obliquity-related glacial cycles prior to ~4.7 Ma in ODP sites 659 and 846 should be correlated with one obliquity cycle older than previously proposed.

Geochemical provenance analysis of fine-grained sediment of sediment core AND1-1

Bulk chemical fine-grained sediment compositions from southern Victoria Land glacimarine sediments provide significant constraints on the reconstruction of sediment provenance models in the McMurdo Sound during Late Cenozoic time. High-resolution (~ 1 ka) geochemical data were obtained with a non-destructive AVAATECH XRF Core Scanner (XRF-CS) on the 1285 m long ANDRILL McMurdo Ice Shelf Project (MIS) sediment core AND-1B. This data set is complemented by high-precision chemical analyses (XRF and ICP-OES) on discrete samples. Statistical analyses reveal three geochemical facies which are interpreted to represent the following sources for the sediments recovered in the AND-1B core: 1) local McMurdo Volcanic Group (MVG) rocks, 2) Transantarctic Mountain rocks west of Ross Island (W TAM), and 3) Transantarctic Mountain rocks from more southerly areas (S TAM). Data indicate in combination with other sediment facies analyses (McKay et al., 2009, doi:10.1130/B26540.1) and provenance scenarios (Talarico and Sandroni, 2009, doi:10.1016/j.gloplacha.2009.04.007) that diamictites at the drill site are largely dominated by local sources (MVG) and are interpreted to indicate cold polar conditions with dry-based ice. MVG is interpreted to indicate cold polar condition with dry-based ice. A mixture of MVG and W TAM is interpreted to represent polar conditions and the S TAM facies is interpreted to represent open-marine conditions. Down-core variations in geochemical facies in the AND-1B core are interpreted to represent five major paleoclimate phases over the past 14 Ma. Cold polar conditions with major MVG influence occur below 1045 mbsf and above 120 mbsf. A section of warmer climate conditions with extensive peaks of S TAM influence characterizes the rest of the core, which is interrupted by a section from 525 to 855 mbsf of alternating influences of MVG and W TAM.

Lead isotopic ratios of Barremian-Aptian marine sediments

We present initial isotopic ratios of lead for Early Cretaceous (Barremian-Aptian) sections from Shatsky Rise (Pacific) and Gorgo a Cerbara (Italy). Our Pb isotopic data track an interval representing Oceanic Anoxic Event (OAE)-1a, which is characterized by quasi-global deposition of organic carbon-rich black shale. Pb isotopic compositions of sediments from Shatsky Rise decrease at the end of Barremian time, from radiogenic continental values to unradiogenic values, and subsequently remained less radiogenic until the end of early Aptian time. We explain the isotopic shift by a significant increase in supply rate of unradiogenic Pb, most likely due to massive volcanism. In contrast, the Pb isotopic compositions from the Italian section, which was situated at the western end of Tethys, are mostly identical to those of upper continental crust, showing no significant change in supply rate of unradiogenic Pb. The discrepancy between two sites is attributed to quiescent deep-submarine eruptions of Pacific large igneous provinces (LIPs) such as the Ontong Java Plateau (OJP), which severely limited dispersion of Pb-carrying particles out of the Pacific Ocean. Published Os isotopic data from the Italian section indicate two episodes of massive eruptions of OJP or contemporaneous Manihiki and Hikurangi plateaus starting from earliest Aptian time, slightly later than that indicated by the sedimentary Pb isotopic record from Shatsky Rise. Differences in isotopic variations between Pb and Os likely reflect differences in their chemical behaviors in the oceans, i.e., Pb isotopic compositions would have varied in response to local or regional changes in sediment provenances, whereas large-scale changes in Os inputs are required to explain variations in seawater Os isotopic compositions. Our Pb isotopic data, together with the published Os isotopic record, provide new evidence for the eruptive history of OJP together with contemporaneous Pacific plateaus and its environmental consequences, starting from end-Barremian time and extending through early Aptian time.

Geochemistry and degree of organic carbon preservation in non-bioturbated, shaly sediments

Based on 13 published porewater H2S and sulphate profiles the amount of H2S escaping from non-bioturbated shales varies between some few % to 45% of the amount of bacterially generated H2S. This finding permits calculation of the original organic carbon (TOCor) content of immature nonbioturbated shales using TOC and sulphur content data. In two immature non-bioturbated sequences from Hungary (Toarcian and Oligocene) the first-order correlation between HI and TOC/TOCor was found to be stronger than that between HI and TOC, indicating that sulphate reduction was the leading process both in decrease in TOC content and degradation of kerogen source potential.

Stable carbon and oxygen isotope ratios of Late Miocene and Early Pliocene foraminifera from the Southwest Pacific

The Late Miocene-Early Pliocene paleoclimatic history has been evaluated for a deep drilled sediment sequence at Deep Sea Drilling Project Site 281 and a shallow water marine sediment sequence at Blind River, New Zealand, both of which lay within the Subantarctic water mass during the Late Miocene. A major, faunally determined, cooling event within the latest Miocene at Site 281 and Blind River coincides with oxygen isotopic changes in benthonic foraminiferal composition at DSDP Site 284 considered by Shackleton and Kennett (1975) to indicate a significant increase in Antarctic ice sheet volume. However, at Site 281 benthonic foraminiferal oxygen isotopic changes do not record such a large increase in Antarctic ice volume. It is possible that the critical interval is within an unsampled section (no recovery) in the latest Miocene. Two benthonic oxygen isotopic events in the Late Miocene (0.5 ? and 1 ? in the light direction) may be useful as time-stratigraphic markers. A permanent, negative, carbon isotopic shift at both Site 281 and Blind River allows precise correlations to be made between the two sections and to other sites in the Pacific region. Close interval sampling below the carbon shift at Site 281 revealed dramatic fluctuations in surface-water temperatures prior to a latest Miocene interval of refrigeration (Kapitean) and a strong pulse of dissolution between 6.6 and 6.2 +/- 0.1 m.y. which may be related to a fundamental geochemical change in the oceans at the time of the carbon shift (6.3-6.2 m.y.). No similar close interval sampling at Blind River was possible because of a lack of outcrop over the critical interval. Paleoclimatic histories from the two sections are very similar. Surface water temperatures and Antarctic ice-cap volume appear to have been relatively stable during the late Middle-early Late Miocene (early-late Tongaporutuan). By 6.4 m.y. cooler conditions prevailed at Site 281. Between 6.3 and 6.2 -+ 0.1 m.y. the carbon isotopic shift occurred followed, within 100,000 yr, by a distinct shallowing of water depths at Blind River. The earliest Pliocene (Opoitian) is marked by increasing surface-water temperatures.

Geochemistry of the Kimmeridge Clay Formation, Dorset Coast

The Kimmeridge Clay Formation (KCF) and its equivalents worldwide represent one of the most prolonged periods of organic carbon accumulation of the Mesozoic. In this study, we use the molybdenum (Mo) stable isotope system in conjunction with a range of trace metal paleoredox proxies to assess how seawater redox varied both locally and globally during the deposition of the KCF. Facies with lower organic carbon contents (TOC 1-7 wt %) were deposited under mildly reducing (suboxic) conditions, while organic-rich facies (TOC >7 wt %) accumulated under more strongly reducing (anoxic or euxinic) local conditions. Trace metal abundances are closely linked to TOC content, suggesting that the intensity of reducing conditions varied repeatedly during the deposition of the KCF and may have been related to orbitally controlled climate changes. Long-term variations in d98/95Mo are associated with the formation of organic-rich intervals and are related to third-order fluctuations in relative sea level. Differences in the mean d98/95Mo composition of the organic-rich intervals suggest that the global distribution of reducing conditions was more extensive during the deposition of the Pectinatites wheatleyensis and lower Pectinatites hudlestoni zones than during the deposition of the upper Pectinatites hudlestoni and Pectinatites pectinatus zones. The global extent of reducing conditions during the Kimmerigidan was greater than today but was less widespread than during the Toarcian (Early Jurassic) oceanic anoxic event. This study also demonstrates that the Mo isotope system in Jurassic seawater responded to changes in redox conditions in a manner consistent with its behavior in present-day sedimentary environments.