(Table 2) Oxygen and carbon isotope composition of planktonic foraminiferal species from DSDP Holes 93-603B and 93-604, and one benthic species from Hole 93-604

Holes 603C and 604 of DSDP Leg 93 were drilled on the western Atlantic continental rise at water depths of 4633 m and 2364 m, respectively. In Hole 603C, a nearly continuous, undisturbed, and complete section of Pliocene and lower Pleistocene sediments was recovered by hydraulic piston coring; in Hole 604, a section of uppermost Miocene to Pleistocene sediments was incompletely recovered by rotary coring. In order to reconstruct the Pliocene and Pleistocene history of isotopic variations, 139 oxygen and carbon isotope values were determined for planktonic and monospecific benthic foraminifer samples from these holes. Large parts of the Pleistocene history could not, however, be documented because sample intervals were large and sediments at Site 604 were redeposited. Time correlation is based on magnetostratigraphic (Hole 603C) and micropaleontologic (Hole 603C, Site 604) interpretation. Stable isotope analyses were carried out on the planktonic foraminiferal species Globigerinoides ruber, G. obliquus, and Globorotalia inflata from Hole 603C (48 analyses) and from Site 604 (48 analyses); at Site 604, the benthic foraminifer Uvigerina peregrina (43 analyses) was also studied through the section. Age calibration for Hole 603C is based on the magnetostratigraphy of Canninga et al. (1987; doi:10.2973/dsdp.proc.93.130.1987), which uses the time scale of Lowrie and Alvarez (1981).

Stable carbon isotope ratios of alkane of IODP Hole 302-M0004A

The Palaeocene/Eocene thermal maximum represents a period of rapid, extreme global warming approx ~55 million years ago, superimposed on an already warm world (Zachos et al., 2003, doi:10.1126/science.1090110; Bowen et al., 2004, doi:10.1038/nature03115; Thomas et al., 2002, doi:10.1130/0091-7613(2002)030<1067:WTFFTF>2.0.CO;2). This warming is associated with a severe shoaling of the ocean calcite compensation depth **4 and a >2.5 per mil negative carbon isotope excursion in marine and soil carbonates (Zachos et al., 2003, doi:10.1126/science.1090110; Bowen et al., 2004, doi:10.1038/nature03115; Thomas et al., 2002, doi:10.1130/0091-7613(2002)030<1067:WTFFTF>2.0.CO;2; Zachos et al., doi:10.1126/science.1109004). Together these observations indicate a massive release of 13C-depleted carbon (Zachos et al., doi:10.1126/science.1109004) and greenhouse-gas-induced warming. Recently, sediments were recovered from the central Arctic Ocean (Backman et al., 2006, doi:10.2204/iodp.proc.302.2006), providing the first opportunity to evaluate the environmental response at the North Pole at this time. Here we present stable hydrogen and carbon isotope measurements of terrestrial-plant- and aquatic-derived n-alkanes that record changes in hydrology, including surface water salinity and precipitation, and the global carbon cycle. Hydrogen isotope records are interpreted as documenting decreased rainout during moisture transport from lower latitudes and increased moisture delivery to the Arctic at the onset of the Palaeocene/Eocene thermal maximum, consistent with predictions of poleward storm track migrations during global warming (Backman et al., 2006, doi:10.2204/iodp.proc.302.2006). The terrestrial-plant carbon isotope excursion (about ~4.5 to ~6 per mil) is substantially larger than those of marine carbonates. Previously, this offset was explained by the physiological response of plants to increases in surface humidity (Bowen et al., 2004, doi:10.1038/nature03115). But this mechanism is not an effective explanation in this wet Arctic setting, leading us to hypothesize that the true magnitude of the excursion - and associated carbon input - was greater than originally surmised. Greater carbon release and strong hydrological cycle feedbacks may help explain the maintenance of this unprecedented warmth.of this unprecedented warmth.

Early Eocene benthic carbon isotope data of ODP Site 208-1263

The early Eocene represents a time of major changes in the global carbon cycle and fluctuations in global temperatures on both short- and long-time scales. These perturbations of the ocean-atmosphere system have been linked to orbital forcing and changes in net organic carbon burial, but accurate age models are required to disentangle the various forcing mechanisms and assess causal relationships. Discrepancies between the employed astrochronological and radioisotopic dating techniques prevent the construction of a robust time frame between ~49 and ~54 Ma. Here we present an astronomically tuned age model for this critical time period based on a new high-resolution benthic d13C record of ODP Site 1263, SE Atlantic. First, we assess three possible tuning options to the stable long-eccentricity cycle (405-kyr), starting from Eocene Thermal Maximum 2 (ETM2, ~54 Ma). Next we compare our record to the existing bulk carbonate d13C record from the equatorial Atlantic (Demerara Rise, ODP Site 1258) to evaluate our three initial age models and compare them with alternative age models previously established for this site. Finally, we refine our preferred age model by expanding our tuning to the 100-kyr eccentricity cycle of the La2010d solution. This solution appears to accurately reflect the long- and short-term eccentricity-related patterns in our benthic d13C record of ODP Site 1263 back to at least 52 Ma and possibly to 54 Ma. Our time scale not only aims to provide a new detailed age model for this period, but it may also serve to enhance our understanding of the response of the climate system to orbital forcing during this super greenhouse period as well as trends in its background state.

Stable hydrogen and carbon isotope records and concentration data for four long chain n-alkanes from core GIK16160-3 derived from the Zambezi delta in the Mozambique Channel during the last 37,000 years

Hydrogen isotope values (dD) of sedimentary terrestrial leaf wax such as n-alkanes or n-acids have been used to map and understand past changes in rainfall amount in the tropics because dD of precipitation is commonly assumed as the first order controlling factor of leaf wax dD. Plant functional types and their photosynthetic pathways can also affect leaf wax dD but these biological effects are rarely taken into account in paleo studies relying on this rainfall proxy. To investigate how biological effects may influence dD values we here present a 37,000-year old record of dD and stable carbon isotopes (d13C) measured on four n-alkanes (n-C27, n-C29, n-C31, n-C33) from a marine sediment core collected off the Zambezi River mouth. Our paleo d13C records suggest that each individual n-alkanes had different C3/C4 proportional contributions. n-C29 was mostly derived from a C3 dicots (trees, shrubs and forbs) dominant vegetation throughout the entire record. In contrast, the longer chain n-C33 and n-C31 were mostly contributed by C4 grasses during the Glacial period but shifted to a mixture of C4 grasses and C3 dicots during the Holocene. Strong correlations between dD and d13C values of n-C33 (correlation coefficient R2 = 0.75, n = 58) and n-C31 (R2 = 0.48, n = 58) suggest that their dD values were strongly influenced by changes in the relative contributions of C3/C4 plant types in contrast to n-C29 (R2 = 0.07, n = 58). Within regions with variable C3/C4 input, we conclude that dD values of n-C29 are the most reliable and unbiased indicator for past changes in rainfall, and that dD and d13C values of n-C31 and n-C33 are sensitive to C3/C4 vegetation changes. Our results demonstrate that a robust interpretation of palaeohydrological data using n-alkane dD requires additional knowledge of regional vegetation changes from which nalkanes are synthesized, and that the combination of dD and d13C values of multiple n-alkanes can help to differentiate biological effects from those related to the hydrological cycle.

Carbon isotope record of 3 profiles from Campanian-Maastrichtian

Carbon-isotope stratigraphy has proven to be a powerful tool in the global correlation of Cretaceous successions. Here we present new, high-resolution carbon-isotope records for the Global Boundary Stratotype Section and Point (GSSP) of the Maastrichtian stage at Tercis les Bains (France), the Bottaccione and Contessa sections at Gubbio (Italy), and the coastal sections at Norfolk (UK) to provide a global d13C correlation between shelf-sea and oceanic sites. The new d13C records are correlated with d13C-stratigraphies of the boreal chalk sea (Trunch borehole, Norfolk, UK, Lägerdorf-Kronsmoor-Hemmoor section, northern Germany, Stevns-1 core, Denmark), the tropical Pacific (ODP-Hole 1210B, Shatsky Rise) and the South Atlantic and Southern Ocean (DSDP Hole 525A, ODP Hole 690C) by using an assembled Gubbio d13C record as a reference curve. The global correlation allows the identification of significant high-frequency d13C variations that occur superimposed on prominent Campanian-Maastrichtian events, namely the Late Campanian Event (LCE), the Campanian-Maastrichtian Boundary Event (CMBE), the mid-Maastrichtian Event (MME), and the Cretaceous-Paleogene transition (KPgE). The carbon-isotope events are correlated with the geomagnetic polarity scale recalculated using the astronomical 40Ar/39Ar calibration of the Fish Canyon sanidine. This technique allows the evaluation of the relative timing of base occurrences of stratigraphic index fossils such as ammonites, planktonic foraminifera and calcareous nannofossils. Furthermore, the Campanian-Maastrichtian boundary, as defined in the stratotype at Tercis, can be precisely positioned relative to carbon-isotope stratigraphy and the geomagnetic polarity timescale. The average value for the age of the Campanian-Maastrichtian boundary is 72.1 ± 0.1 Ma, estimated by three independent approaches that utilize the Fish Canyon sanidine calibration and Option 2 of the Maastrichtian astronomical timescale. The CMBE covers a time span of 2.5 Myr and reflects changes in the global carbon cycle probably related to tectonic processes than to glacioeustasy. The duration of the high-frequency d13C variations instead coincides with the frequency band of long eccentricity, indicative of orbital forcing of changes in climate and the global carbon cycle.

Stable oxygen and carbon isotope data for planktic and benthic foraminifera from southern Atlantic of DSDP Hole 74-525A and ODP Hole 113-690C

Published stable isotope records in marine carbonate are characterized by a positive d18O excursion associated with a negative d13C shift during the early Maastrichtian. However, the cause and even the precise timing of these excursions remain uncertain. We have generated high-resolution foraminiferal stable isotope and gray-scale records for the latest Campanian to early Maastrichtian (73-68 Ma) at two Ocean Drilling Program sites, 525 (Walvis Ridge) and 690 (Weddell Sea). We demonstrate that the negative d13C excursion is decoupled from the d18O increase with a lag of about 600 ka. Our d13C records (both planktic and benthic) show an amplitude for the negative excursion of 0.7 per mill that falls between about 72.1 and 70.7 Ma. Our planktic d18O records indicate an overall increase of 1.2 per mill from 73 to 68 Ma at Site 690, whereas at Site 525 they record a slightly smaller increase (1 per mill) that peaks around 70.1 Ma with decreasing values thereafter. Our benthic d18O data indicate an increase of 1.5 per mill at Site 525 and 0.7 per mill at Site 690 between about 71.4 and 69.9 Ma. Benthic d18O values show different baseline values at the two sites before and after the excursion, but the larger increase at Site 525 means that the values attained at the peak of the excursion are similar at the two sites. We interpret this observation in terms of water mass changes. The excursion is interpreted to reflect a cooling of bottom waters in response to the strengthening contribution of intermediate- to deep-water production in the high southern latitudes rather than increased ice volume. The associated carbon cycle perturbations that we observe are interpreted to reflect a weakening of surface water stratification and increased productivity, as supported by our gray value data.

Stable carbon isotope record of sediment core Ancora

The standard paradigm that the Paleocene/Eocene thermal maximum (PETM) represents a threshold event intrinsic to Earth's climate and connected in some way with long-term warming has influenced interpretations of the geochemical, climate, and biological perturbations that occurred at this event. As recent high-resolution data have demonstrated that the onset of the event was geologically instantaneous, attempts to account for the event solely through endogenous mechanisms have become increasingly strained. The rapid onset of the event indicates that it was triggered by a catastrophic event which we suggest was most likely a bolide impact. We discuss features of the PETM that require explanation and argue that mechanisms that have previously been proposed either cannot explain all of these features or would require some sort of high-energy trigger. A bolide impact could provide such a trigger and, in the event of a comet impact, could contribute directly to the shape of the carbon isotope curve. We introduce a carbon cycle model that would explain the PETM by global warming following a bolide impact, leading to the oxidation of terrestrial organic carbon stores built up during the late Paleocene. Our intention is to encourage other researchers to seriously consider an impact trigger for the PETM, especially in the absence of plausible alternative mechanisms.

Stable carbon isotope record of sediment core Bass_River_Site

A thick, apparently continuous section recording events of the latest Paleocene thermal maximum in a neritic setting was drilled at Bass River State Forest, New Jersey as part of ODP Leg 174AX [Miller, Sugarman, Browning et al., 1998]. Integrated nannofossil and magneto-stratigraphy provides a firm chronology supplemented by planktonic foraminiferal biostratigraphy. This chronologic study indicates that this neritic section rivals the best deep-sea sections in providing a complete record of late Paleocene climatic events. Carbon and oxygen isotopes measured on benthic foraminifera show a major (4.0% in carbon, 2.3% in oxygen) negative shift correlative with the global latest Paleocene carbon isotope excursion (CIE). A sharp increase in kaolinite content coincides with the isotope shift in the Bass River section, analogous to increases found in several other records. Carbon and oxygen isotopes remain low and kaolinite content remains high for the remainder of the depositional sequence above the CIE (32.5 ft, 9.9 m), which we estimate to represent 300-500 k.y. We interpret these data as indicative of an abrupt shift to a warmer and wetter climate along the North American mid-Atlantic coast, in concert with global events associated with the CIE.

Age determination and stable carbon isotope ratios of Neogloboquadrina pachyderma of IODP Hole 302-M0004C

The Integrated Ocean Drilling Program (IODP) Arctic Coring Expedition (ACEX) Hole 4C from the Lomonosov Ridge in the central Arctic Ocean recovered a continuous 18 m record of Quaternary foraminifera yielding evidence for seasonally ice-free interglacials during the Matuyama, progressive development of large glacials during the mid-Pleistocene transition (MPT) ~1.2-0.9 Ma, and the onset of high-amplitude 100-ka orbital cycles ~500 ka. Foraminiferal preservation in sediments from the Arctic is influenced by primary (sea ice, organic input, and other environmental conditions) and secondary factors (syndepositional, long-term pore water dissolution). Taking these into account, the ACEX 4C record shows distinct maxima in agglutinated foraminiferal abundance corresponding to several interglacials and deglacials between marine isotope stages (MIS) 13-37, and although less precise dating is available for older sediments, these trends appear to continue through the Matuyama. The MPT is characterized by nearly barren intervals during major glacials (MIS 12, 16, and 22-24) and faunal turnover (MIS 12-24). Abundant calcareous planktonic (mainly Neogloboquadrina pachyderma sin.) and benthic foraminifers occur mainly in interglacial intervals during the Brunhes and very rarely in the Matuyama. A distinct faunal transition from calcareous to agglutinated foraminifers 200-300 ka in ACEX 4C is comparable to that found in Arctic sediments from the Lomonosov, Alpha, and Northwind ridges and the Morris Jesup Rise. Down-core disappearance of calcareous taxa is probably related to either reduced sea ice cover prior to the last few 100-ka cycles, pore water dissolution, or both.

Stable carbon isotope record and geochemistry of late Miocene-early Pliocene sediments from DSDP Site 90-590 in the Tasman Sea

Biogenic components of sediment accumulated at high rates beneath frontal zones of the Indian and Pacific oceans during the late Miocene and early Pliocene. The delta13C of bulk and foraminiferal carbonate also decreased during this time interval. Although the two observations may be causally linked, and signify a major perturbation in global biogeochemical cycling, no site beneath a frontal zone has independent records of export production and delta13C on multiple carbonate phases across the critical interval of interest. Deep Sea Drilling Project (DSDP) site 590 lies beneath the Tasman Front (TF), an eddy-generating jetstream in the southwest Pacific Ocean. To complement previous delta13C records of planktic and benthic foraminifera at this location, late Neogene records of CaCO3 mass accumulation rate (MAR), Ca/Ti, Ba/Ti, Al/Ti, and of bulk carbonate and foraminiferal delta13C were constructed at site 590. The delta13C records include bulk sediment, bulk sediment fractions (<63 µm and 5-25 µm), and the planktic foraminifera Globigerina bulloides, Globigerinoides sacculifer (with and without sac), and Orbulina universa. Using current time scales, CaCO3 MARs, Ca/Ti, Al/Ti and Ba/Ti ratios are two to three times higher in upper Miocene and lower Pliocene sediment relative to overlying and underlying units. A significant decrease also occurs in all delta13C records. All evidence indicates that enhanced export production - the 'biogenic bloom' - extended to the southwest Pacific Ocean between ca. 9 and 3.8 Ma, and this phenomenon is coupled with changes in delta13C - the 'Chron C3AR carbon shift'. However, CaCO3 MARs peak ca. 5 Ma whereas elemental ratios are highest ca. 6.5 Ma; foraminiferal delta13C starts to decrease ca. 8 Ma whereas bulk carbonate delta13C begins to drop ca. 5.6 Ma. Temporal discrepancies between the records can be explained by changes in the upwelling regime at the TF, perhaps signifying a link between changes in ocean-atmosphere circulation change and widespread primary productivity.