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.

Benthic foraminiferal assemblages and epifaunal isotope record of the Agulhas Plateau

Benthic foraminiferal assemblages and the carbon isotope composition of the epifaunal benthic foraminifera Epistominella exigua and Fontbotia wuellerstorfi have been investigated along core MD02-2589 located at the southern Agulhas Plateau (41°26.03'S, 25°15.30'E, 2660 m water depth). This study aims to evaluate changes in the benthic paleoenvironment and its influence on benthic d13C with a notable focus on E. exigua, a species associated with phytodetritus deposits and poorly studied in isotope paleoceanographic reconstructions. The benthic foraminiferal assemblages (>63 µm) show large fluctuations in species composition suggesting significant changes in the pattern of ocean surface productivity conceivably related to migrations of the Subtropical Convergence (STC) and Subantarctic Front (SAF). Low to moderate seasonality and relatively higher food supply to the seafloor are indicated during glacial marine isotope stages (MIS) 6, 4, and 2 and during MIS 3, probably associated with the northward migration of the SAF and confluence with the more stationary STC above the southern flank of the Agulhas Plateau. The lowest organic carbon supply to the seafloor is indicated from late MIS 5b to MIS 4 as a consequence of increased influence of the Agulhas Front (AF) and/or weakening of the influence of the STC over the region. Episodic delivery of fresh organic matter, similar to modern conditions at the core location, is indicated during MIS 5c-MIS 5e and at Termination I. Comparison of this paleoenvironmental information with the paired d13C records of E. exigua and F. wuellerstorfi suggests that organic carbon offsets d13C of E. exigua from ambient bottom water d13CDIC, while its d13C amplitude, on glacial-interglacial timescales, does not seem affected by changes of organic carbon supply to the seafloor. This suggests that this species calcifies preferentially during the short time span of the year when productivity peaks and phytodetritus is delivered to the seafloor. Therefore E. exigua, while offset from d13CDIC, potentially more faithfully records the amplitude of ambient bottom water d13CDIC changes than F. wuellerstorfi, notably in settings such as the Southern Ocean that experienced substantial changes through time in the organic carbon supply to the seafloor.

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.

The record of stable isotope composition of surface and thermocline planktic foraminifera from sediment core 64PE-174P13 for the last 460,000 years

The upper branch of the Atlantic Meridional Overturning Circulation predominantly enters the Atlantic Ocean through the southeast, where the subtropical gyre is exposed to the influence of the Agulhas leakage (AL). To understand how the transfer of Indian Ocean waters via the AL affected the upper water column of this region, we have generated new proxy records of planktic foraminifera from a core on the central Walvis Ridge, on the eastern flank of the South Atlantic Gyre (SAG). We analyzed the isotopic composition of subsurface dweller Globigerinoides ruber sensu lato, and thermocline Globorotalia truncatulinoides sinistral, spanning the last five Pleistocene glacial-interglacial (G-IG) cycles. The former displays a response to obliquity, suggesting connection with high latitude forcing, and a warming tendency during each glacial termination, in response to the interhemispheric seesaw. The d18O difference between the two species, interpreted as a proxy for upper ocean stratification, reveals a remarkably regular sawtooth pattern, bound to G-IG cyclicity. It rises from interglacials until glacial terminations, with fast subsequent decrease, appearing to promptly respond to deglacial peaks of AL. Stratification, however, bears a different structure during the last cycle, being minimal at Last Glacial Maximum, and peaking at Termination I. We suggest this to be the result of the intensified glacial wind field over the SAG and/or of the invasion of the South Atlantic thermocline by Glacial North Atlantic Intermediate Waters. The d13C time series of the two species have similar G-IG pattern, whereas their difference is higher during interglacials. We propose that this may be the result of the alternation of intermediate water masses in different circulation modes, and of a regionally more efficient biological pump at times of high pCO2.

(Table 2) Oxygen isotope composition of authigenic and detrital phosphates from ODL Leg 201 sites

Many (bio)geochemical processes that bring about changes in sediment chemistry normally begin at the sediment-water interface, continue at depth within the sediment column and may persist throughout the lifetime of sediments. Because of the differential reactivity of sedimentary phosphate phases in response to diagenesis, dissolution/precipitation and biological cycling, the oxygen isotope ratios of phosphate (d18OP) can carry a distinct signature of these processes, as well as inform on the origin of specific P phases. Here, we present results of sequential sediment extraction (SEDEX) analyses combined with d18OP measurements, aimed at characterizing authigenic and detrital phosphate phases in continental margin sediments from three sites (Sites 1227, 1228 and 1229) along the Peru Margin collected during ODP Leg 201. Our results show that the amount of P in different reservoirs varies significantly in the upper 50 m of the sediment column, but with a consistent pattern, for example, detrital P is highest in siliciclastic-rich layers. The d18OP values of authigenic phosphate vary between 20.2 per mil and 24.8 per mil and can be classified into at least two major groups: authigenic phosphate precipitated at/near the sediment-water interface in equilibrium with paleo-water oxygen isotope ratios (d18Ow) and temperature, and phosphate derived from hydrolysis of organic matter (Porg) with subsequent incomplete to complete re-equlibration and precipitated deeper in the sediments column. The d18OP values of detrital phosphate, which vary from 7.7-15.4 per mil, suggest two possible terrigenous sources and their mixtures in different proportions: phosphate from igneous/metamorphic rocks and phosphate precipitated in source regions in equilibrium with d18Ow of meteoric water. More importantly, original isotopic compositions of at least one phase of authigenic phosphates and all detrital phosphates are not altered by diagenesis and other biogeochemical changes within the sediment column. These findings help to understand the origin and provenance of P phases and paleoenvironmental conditions at/near the sediment-water interface, and to infer post-depositional activities within the sediment column.

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.

Thallium concentrations and isotope composition of MORB glasses and altered oceani crust from DSDP/ODP Hole 504B and DSDP Hole 52-417D

Hydrothermal fluids expelled from the seafloor at high and low temperatures play pivotal roles in controlling seawater chemistry. However, the magnitude of the high temperature water flux of mid-ocean ridge axes remains widely disputed and the volume of low temperature vent fluids at ridge flanks is virtually unconstrained. Here, we determine both high and low temperature hydrothermal fluid fluxes using the chemical and isotopic mass balance of the element thallium (Tl) in the ocean crust. Thallium is a unique tracer of ocean floor hydrothermal exchange because of its contrasting behavior during seafloor alteration at low and high temperatures and the distinctive isotopic signatures of fresh and altered MORB and seawater. The calculated high temperature hydrothermal water flux is (0.17-2.93)*10**13 kg/yr with a best estimate of 0.72*10**13 kg/yr. This result suggests that only about 5 to 80% of the heat available at mid-ocean ridge axes from the crystallization and cooling of the freshly formed ocean crust, is released by high temperature black smoker fluids.The residual thermal energy ismost likely lost via conduction and/or through the circulation of intermediate temperature hydrothermal fluids that do not alter the chemical budgets of Tl in the ocean crust. The Tl-based calculations indicate that the low temperature hydrothermal water flux at ridge flanks is (0.2-5.4)*10**17 kg/yr. This implies that the fluids have an average temperature anomaly of only about 0.1 to 3.6 °C relative to ambient seawater. If these low temperatures are correct then both Sr and Mg are expected to be relatively unreactive in ridge-flank hydrothermal systems and this may explain why the extent of basalt alteration that is observed for altered ocean crust appears insufficient to balance the oceanic budgets of 87Sr/86Sr and Mg.

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.