(Figure 2) Organic carbon content, stable isotope ratios, TEX86 index and sea surface temperature reconstruction for the early Aptian of ODP Hole 198-1207B

The Cretaceous has long been recognized as a time when greenhouse conditions were fueled by elevated atmospheric CO2 and accompanied by perturbations of the global carbon cycle described as oceanic anoxic events (OAEs). Yet, the magnitude and frequency of temperature change during this interval of warm and equable climate are poorly constrained. Here we present a high-resolution record of sea-surface temperatures (SSTs) reconstructed using the TEX86 paleothermometer for a sequence of early Aptian organic-rich sediments deposited during the first Cretaceous OAE (OAE1a) at Shatsky Rise in the tropical Pacific. SSTs range from ~30 to ~36 °C and include two prominent cooling episodes of ~4 °C. The cooler temperatures reflect significant temperature instability in the tropics likely triggered by changes in carbon cycling induced by enhanced burial of organic matter. SST instability recorded during the early Aptian in the Pacific is comparable to that reported for the late Albian-early Cenomanian in the Atlantic, suggesting that such climate perturbations may have recurred during the Cretaceous with concomitant consequences for biota and the marine environment.

(Table 1) Planktonic foraminifer abundance and stable isotope ratios of a sediment core near Baddeckenstedt, north Germany

A refined sample processing technique using glacial acetic acid has been applied to Upper Cenomanian and Lower Turonian limestones from Baddeckenstedt (Lower Saxony) enabeling the first quantitative analysis of planktonic foraminiferal populations through the Stage boundary succession in northwestern Germany. Measurements of carbonate contents, organic carbon and stable carbon and oxygen isotopes were also reported. These data allow a correlation to be made of the Baddeckenstedt section with those at Misburg (basinal facies, northwestern Germany) and Dover (Plenus Marls, southern England). Significant maxima of the organic carbon content at Baddeckenstedt correspond to prominent black shale couplets at Misburg. The planktonic foraminiferal generic groups show at Baddeckenstedt similar fluctuations as reported from Dover. Their correlation reveals details of a complex paleoceanographic regime in the NW-German Basin during the Cenomanian/Turonian Oceanic Anoxic Event.

Stable carbon and oxygen isotope record of foraminifera of IODP Site 303-1307

A major tipping point of Earth's history occurred during the mid-Pliocene: the onset of major Northern-Hemisphere Glaciation (NHG) and of pronounced, Quaternary-style cycles of glacial-to-interglacial climates, that contrast with more uniform climates over most of the preceding Cenozoic and continue until today (Zachos et al., 2001, doi:10.1126/science.1059412). The severe deterioration of climate occurred in three steps between 3.2 Ma (warm MIS K3) and 2.7 Ma (glacial MIS G6/4) (Lisiecki and Raymo, 2005, doi:10.1029/2004PA001071). Various models (sensu Driscoll and Haug, 1998, doi:10.1126/science.282.5388.436) and paleoceanographic records (intercalibrated using orbital age control) suggest clear linkages between the onset of NHG and the three steps in the final closure of the Central American Seaways (CAS), deduced from rising salinity differences between Caribbean and the East Pacific. Each closing event led to an enhanced North Atlantic meridional overturning circulation and this strengthened the poleward transport of salt and heat (warmings of +2-3°C) (Bartoli et al., 2005, doi:10.1016/j.epsl.2005.06.020). Also, the closing resulted in a slight rise in the poleward atmospheric moisture transport to northwestern Eurasia (Lunt et al., 2007, doi:10.1007/s00382-007-0265-6), which probably led to an enhanced precipitation and fluvial run-off, lower sea surface salinity (SSS), and an increased sea-ice cover in the Arctic Ocean, hence promoting albedo and the build-up of continental ice sheets. Most important, new evidence shows that the closing of the CAS led to greater steric height of the North Pacific and thus doubled the low-saline Arctic Throughflow from the Bering Strait to the East Greenland Current (EGC). Accordingly, Labrador Sea IODP Site 1307 displays an abrupt but irreversible EGC cooling of 6°C and freshening by ~2 psu from 3.25/3.16-3.00 Ma, right after the first but still reversible attempt of closing the CAS.

Age models and stable isotope ratios from the Mid-Miocene

Mid-Miocene pelagic sedimentary sections can be correlated using intermediate and high resolution oxygen and carbon isotopic records of benthic foraminifera. Precision of a few tens of thousands of years is readily achievable at sites with high sedimentation rates, for example, Deep Sea Drilling Project sites 289 and 574. The mid-Miocene carbon isotope records are characterized by an interval of high d13C values between 17 and 13.5 Ma (the Monterey Excursion of Vincent and Berger 1985) upon which are superimposed a series of periodic or quasi-periodic fluctuations in d13C values. These fluctuations have a period of approximately 440 kyr, suggestive of the 413 kyr cycle predicted by Milankovitch theory. Vincent and Berger proposed that the Monterey Excursion was the result of increased organic carbon burial in continental margins sediments. The increased d13C values (called 13C maxima) superimposed on the generally high mid-Miocene signal coincide with increases in d18O values suggesting that periods of cooling and/or ice buildup were associated with exceptionally rapid burial of organic carbon and lowered atmospheric CO2 levels. It is likely that during the Monterey Excursion the ocean/atmosphere system became progressively more sensitive to small changes in insolation, ultimately leading to major cooling of deep water and expansion of continental ice. We have assigned an absolute chronology, based on biostratigraphic and magneto-biostratigraphic datum levels, to the isotope stratigraphy and have used that chronology to correlate unconformities, seismic reflectors, carbonate minima, and dissolution intervals. Intervals of sediment containing 13C maxima are usually better preserved than the overlying and underlying sediments, indicating that the d13C values of TCO2 in deep water and the corrosiveness of seawater are inversely correlated. This again suggests that the 13C maxima were associated with rapid burial of organic carbon and reduced levels of atmospheric CO2. The absolute chronology we have assigned to the isotopic record indicates that the major mid-Miocene deepwater cooling/ice volume expansion took 2 m.y. and was not abrupt as had been reported previously. The cooling appears abrupt at many sites because the interval is characterized by a number of dissolution intervals. The cooling was not monotonic, and the 2 m.y. interval included an episode of especially rapid cooling as well as a brief return to warmer conditions before the final phase of the cooling period. The increase in d18O values of benthic foraminifera between 14.9 and 12.9 Ma was greatest at deeper water sites and at sites closest to Antarctica. The data suggest that the d18O value of seawater increased by no more than about 1.1 per mil during this interval and that the remainder of the change in benthic d18O values resulted from cooling in Antarctic regions of deepwater formation. Equatorial planktonic foraminifera from sites 237 and 289 exhibit a series of 0.4 per mil steplike increases in d13C values. Only one of these increases in planktonic d13C is correlated with any of the features in the mid-Miocene benthic carbon isotope record.

Organic matter C and N composition and N. pachyderma stable isotope ratios of ODP Hole 188-1166A sediments

We report the results of downhole stable isotopic (d13Corg [organic carbon] and d15N) and elemental measurements (total organic carbon [TOC], total nitrogen [TN], and carbon/nitrogen [C/N]) of sedimentary organic matter (SOM) along with stable isotopic measurements (d18O and d13C) of left-coiling Neogloboquadrina pachyderma planktonic foraminifers from Ocean Drilling Program Site 1166. TOC and TN measurements indicate a large change from organic-rich preglacial sediments with primary organic matter to organic-poor early glacial and glacial sediments, with mainly recycled organic matter. Results of the stable isotopic measurements of SOM show a range of values that are typical of both marine and terrestrial organic matter, probably reflecting a mixture of the two. However, C/N values are mostly high (>15), suggesting greater input and/or preservation of terrestrial organic matter. Foraminifers are only present in glacial/glaciomarine sediments of latest Pliocene to Pleistocene age at Site 1166 (lithostratigraphic Unit I). The majority of this unit has d13Corg and TOC values that are similar to those of glacial sediments recovered at Site 1167 (lithostratigraphic Unit II) on the slope and may have the same source(s). Although the low resolution of the N. pachyderma (s.) d18O and d13C data set precludes any specific paleoclimatic interpretation, downcore variations in foraminifer d18O and d13C values of 0.5 per mil to 1 per mil amplitude may indicate glacial-interglacial changes in ice volume/temperature in the Prydz Bay region.

(Table 1) Stable isotope data of chemoherm carbonates at Hydrate Ridge on the Cascadia continental margin

Two active chemoherm build-ups growing freely up into the oceanic water column, the Pinnacle and the South East-Knoll Chemoherms, have been discovered at Hydrate Ridge on the Cascadia continental margin. These microbially-mediated carbonate formations rise above the seafloor by several tens of meters and display a pinnacle-shaped morphology with steep flanks. The recovered rocks are pure carbonates dominated by aragonite. Based on fabric and mineralogic composition different varieties of authigenic aragonite can be distinguished. Detailed visual and petrographic investigations unambiguously reveal the involvement of microbes during the formation of the carbonates. The fabric of the cryptocrystalline and fibrous aragonite can be described as thrombolitic. Fossilized microbial filaments in the microcrystalline aragonite indicate the intimate relationship between microbes and carbonates. The strongly 13C-depleted carbon isotope values of the samples (as low as -48.1 per mill PDB) are characteristic of methane as the major carbon source for the carbonate formation. The methane-rich fluids from which the carbonates are precipitated originate most probably from a gas reservoir below the bottom-simulating reflector (BSR) and rise through fault systems. The d18O values of the aragonitic chemoherm carbonates are substantially higher (as high as 5.0 per mill PDB) than the expected equilibrium value for an aragonite forming from ambient seawater (3.5 per mill PDB). As a first approximation this indicates formation from glacial ocean water but other factors are considered as well. A conceptual model is presented for the precipitation of these chemoherm carbonates based on in situ observations and the detailed petrographic investigation of the carbonates. This model explains the function of the consortium of archaea and sulfate-reducing bacteria that grows on the carbonates performing anaerobic oxidation of methane (AOM) and enabling the precipitation of the chemoherms above the seafloor surrounded by oxic seawater. Beggiatoa mats growing on the surface of the chemoherms oxidize the sulfide provided by sulfate-dependent anaerobic oxidation of methane within an oxic environment. The contact between Beggiatoa and the underlying microbial consortium represents the interface between the overlying oxic water column and an anoxic micro-environment where carbonate formation takes place.

Carbon and oxygen isotope data for carbonates and benthic foraminifers from ODP Hole 113-689B

At Ocean Drilling Program Site 689 (Maud Rise, Southern Ocean), d18O records of fine-fraction bulk carbonate and benthic foraminifers indicate that accelerated climate cooling took place following at least two closely spaced early late Eocene extraterrestrial impact events. A simultaneous surface-water productivity increase, as interpreted from d13C data, is explained by enhanced water-column mixing due to increased latitudinal temperature gradients. These isotope data appear to be in concert with organic-walled dinoflagellate-cyst records across the same microkrystite-bearing impact-ejecta layer in the mid-latitude Massignano section (central Italy). In particular, the strong abundance increase of Thalassiphora pelagica is interpreted to indicate cooling or increased productivity at Massignano. Because impact-induced cooling processes are active on time scales of a few years at most, the estimated 100 k.y. duration of the cooling event appears to be too long to be explained by impact scenarios alone. This implies that a feedback mechanism, such as a global albedo increase due to extended snow and ice cover, may have sustained impact-induced cooling for a longer time after the impacts.

Stable carbon and oxygen isotope ratios of bulk sediment from the Weddell Sea

Carbon isotope measurements were made on bulk sediments from the well preserved calcareous sequences recovered at ODP Sites 689 and 690 on the Maud Rise, Weddell Sea, Antarctica. The very positive delta13C values that characterize the late Paleocene and the rapid trend toward lighter values in the early Eocene established in other sites are clearly recorded here and may be of value for long-distance stratigraphic correlation. However, values in the late Eocene are significantly more positive than have been reported from other areas. The general pattern of the records from Sites 689 and 690 is sufficiently unlike those previously reported from lower latitudes that we suggest that carbon isotope data should be used only with considerable caution for correlating sequences from such high latitudes with lower latitude records.

Isotope composition of dolomite, calcite and pore-waters of ODP Leg 210 samples

Early diagenetic dolomite beds were sampled during the Ocean Drilling Programme (ODP) Leg 201 at four reoccupied ODP Leg 112 sites on the Peru continental margin (Sites 1227/684, 1228/680, 1229/681 and 1230/685) and analysed for petrography, mineralogy, d13C, d18O and 87Sr/86Sr values. The results are compared with the chemistry, and d13C and 87Sr/86Sr values of the associated porewater. Petrographic relationships indicate that dolomite forms as a primary precipitate in porous diatom ooze and siliciclastic sediment and is not replacing the small amounts of precursor carbonate. Dolomite precipitation often pre-dates the formation of framboidal pyrite. Most dolomite layers show 87Sr/86Sr-ratios similar to the composition of Quaternary seawater and do not indicate a contribution from the hypersaline brine, which is present at a greater burial depth. Also, the d13C values of the dolomite are not in equilibrium with the d13C values of the dissolved inorganic carbon in the associated modern porewater. Both petrography and 87Sr/86Sr ratios suggest a shallow depth of dolomite formation in the uppermost sediment (<30 m below the seafloor). A significant depletion in the dissolved Mg and Ca in the porewater constrains the present site of dolomite precipitation, which co-occurs with a sharp increase in alkalinity and microbial cell concentration at the sulphate-methane interface. It has been hypothesized that microbial 'hot-spots', such as the sulphate-methane interface, may act as focused sites of dolomite precipitation. Varying d13C values from -15 per mil to +15 per mil for the dolomite are consistent with precipitation at a dynamic sulphate-methane interface, where d13C of the dissolved inorganic carbon would likewise be variable. A dynamic deep biosphere with upward and downward migration of the sulphate-methane interface can be simulated using a simple numerical diffusion model for sulphate concentration in a sedimentary sequence with variable input of organic matter. Thus, the study of dolomite layers in ancient organic carbon-rich sedimentary sequences can provide a useful window into the palaeo-dynamics of the deep biosphere.

Composition and stable isotope record of bulk sediment and belemnite rostra from ODP Hole 122-761C

A sedimentary sequence documenting the early history of the proto-Indian Ocean was drilled at Site 761 on the Wombat Plateau, northwest Australia. Directly above the post-rift unconformity, two lithologic units were recovered which reflect deposition in incipient oceanic environments. The lower unit, composed of sandstone, contains abundant belemnites and a few lenses composed of low-diversity coccolith assemblages. The second unit, composed of chalk, contains abundant calcispheres, thoracospheres, low-diversity coccolith assemblages, and a few radiolarians. Belemnites and organisms that produced calcispheres and thoracospheres are thought to be opportunistic. Their abundance, and the absence of a normal marine fauna and flora, reflects an unstable early ocean environment. Stable oxygen and carbon isotopic data for the two units fall into almost separate fields. Heavy delta18O values for the belemnites indicate that they have not been affected by recrystallization. Instead, these isotopic values are thought to indicate either the deep, cool habitat of the belemnites or strong vital effects. A bulk chalk delta18O value from the belemnite sand is 3 to 4 parts per mil lighter than the belemnite delta18O values, possibly because it is largely composed of coccoliths which inhabited warmer surface waters. Light delta13C values for bulk calcisphere-bearing nannofossil chalk samples are thought to be a direct result of upwelling or of vital effects. Heavy delta18O values for the chalk unit are interpreted as resulting from upwelling of cool waters. Assemblage and isotopic data are consistent with this incipient ocean basin being highly productive, either as a result of upwelling or runoff of nutrient-rich waters from nearby land areas. However, it is not possible to rule out the control of vital effects on the isotopic signature of any of the fossil groups.

Cadmium/Calcium and stable isotope ratios of benthic foraminifera from the northeast Atlantic Ocean

The delta13C and Cd measurements from benthic foraminifera from Biogeochemical Ocean Flux Study (BOFS) northeast Atlantic Ocean sediment cores are presented. The delta13C values in glacial foraminifera are consistent with those from elsewhere in the North Atlantic Ocean. For intermediate water (1000 - 2000 m water depth), delta13C values were higher at the last glacial maximum than in present North Atlantic Deep Water (NADW), whereas for deep water (>2000 m) they were lower during the glacial maximum. The Cd concentrations of glacial northeast Atlantic intermediate water were lower than those of present NADW. However, deepwater Cd concentrations increased to values between NADW and present Pacific Deep Water (PDW). The delta13C and Cd data are consistent and show that the northeast Atlantic Ocean was strongly stratified with 13C enriched, low Cd intermediate water overlying 13C depleted, high Cd deep water. The glacial water column comprised two different water masses: deep water, similar in character to present Antarctic Bottom Water (AABW), and intermediate water, different in character from both AABW and NADW, and any present intermediate-depth North Atlantic water. The characteristics of glacial intermediate water were, however, similar to present near-surface waters in the North Atlantic, which suggests rapid ventilation of the glacial ocean to depths of up to 2000 m by cold, nutrient-depleted young surface waters.