Stable isotope record of Globorotalia inflata

We sampled the upper water column for living planktic foraminifera along the SW-African continental margin. The species Globorotalia inflata strongly dominates the foraminiferal assemblages with an overall relative abundance of 70-90%. The shell delta18O and delta13C values of G. inflata were measured and compared to the predicted oxygen isotope equilibrium values (delta18O(eq)) and to the carbon isotope composition of the total dissolved inorganic carbon (delta13C(DIC)) of seawater. The delta18O of G. inflata reflects the general gradient observed in the predicted delta18O(eq) profile, while the delta13C of G. inflata shows almost no variation with depth and the reflection of the delta13C(DIC) in the foraminiferal shell seems to be covered by other effects. We found that offsets between delta18O(shell) and predicted delta18O(eq) in the surface mixed layer do not correlate to changes in seawater [CO3[2-]]. To calculate an isotopic mass balance of depth integrated growth, we used the oxygen isotope composition of G. inflata to estimate the fraction of the total shell mass that is grown within each plankton tow depth interval of the upper 500 m of the water column. This approach allows us to calculate the DELTA delta13C(interval added-DIC); i.e. the isotopic composition of calcite that was grown within a given depth interval. Our results consistently show that the DELTA delta13C(IA-DIC) correlates negatively with in situ measured [CO3[2-]] of the ambient water. Using this approach, we found DELTA delta13C(IA-DIC)/[CO3[2-]] slopes for G. inflata in the large size fraction (250-355 µm) of -0.013 per mil to 0.015 per mil (µmol/kg)**-1 and of -0.013 per mil to 0.017 per mil (µmol/kg)**-1 for the smaller specimens (150-250 µm). These slopes are in the range of those found for other non-symbiotic species, such as Globigerina bulloides, from laboratory culture experiments. Since the DELTA delta13C(IA-DIC)/[CO3[2-]] slopes from our field data are nearly identical to the slopes established from laboratory culture experiments we assume that the influence of other effects, such as temperature, are negligibly small. If we correct the delta13C values of G. inflata for a carbonate ion effect, the delta13C(shell) and delta13C(DIC) are correlated with an average offset of 2.11.

Carbon sources in the North Sea evaluated by means of carbon isotope tracers

A multitracer approach is applied to assess the impact of boundary fluxes (e.g., benthic input from sedi- ments or lateral inputs from the coastline) on the acid-base buffering capacity, and overall biogeochemistry, of the North Sea. Analyses of both basin-wide observations in the North Sea and transects through tidal basins at the North-Frisian coastline, reveal that surface distributions of the d13C signature of dissolved inorganic carbon (DIC) are predominantly controlled by a balance between biological production and respiration. In particular, variability in metabolic DIC throughout stations in the well-mixed southern North Sea indi- cates the presence of an external carbon source, which is traced to the European continental coastline using naturally occurring radium isotopes (224Ra and 228Ra). 228Ra is also shown to be a highly effective tracer of North Sea total alkalinity (AT) compared to the more conventional use of salinity. Coastal inputs of meta- bolic DIC and AT are calculated on a basin-wide scale, and ratios of these inputs suggest denitrification as a primary metabolic pathway for their formation. The AT input paralleling the metabolic DIC release prevents a significant decline in pH as compared to aerobic (i.e., unbuffered) release of metabolic DIC. Finally, long- term pH trends mimic those of riverine nitrate loading, highlighting the importance of coastal AT production via denitrification in regulating pH in the southern North Sea.

Benthic foraminifera and stable isotope composition in Paleocene-Eocene sediments

In the late Paleocene to early Eocene, deep sea benthic foraminifera suffered their only global extinction of the last 75 million years and diversity decreased worldwide by 30-50% in a few thousand years. At Maud Rise (Weddell Sea, Antarctica; Sites 689 and 690, palaeodepths 1100 m and 1900 m) and Walvis Ridge (Southeastern Atlantic, Sites 525 and 527, palaeodepths 1600 m and 3400 m) post-extinction faunas were low-diversity and high-dominance, but the dominant species differed by geographical location. At Maud Rise, post-extinction faunas were dominated by small, biserial and triserial species, while the large, thick-walled, long-lived deep sea species Nuttallides truempyi was absent. At Walvis Ridge, by contrast, they were dominated by long-lived species such as N. truempyi, with common to abundant small abyssaminid species. The faunal dominance patterns at the two locations thus suggest different post-extinction seafloor environments: increased flux of organic matter and possibly decreased oxygen levels at Maud Rise, decreased flux at Walvis Ridge. The species-richness remained very low for about 50 000 years, then gradually increased. The extinction was synchronous with a large, negative, short-term excursion of carbon and oxygen isotopes in planktonic and benthic foraminifera and bulk carbonate. The isotope excursions reached peak negative values in a few thousand years and values returned to pre-excursion levels in about 50 000 years. The carbon isotope excursion was about -2 per mil for benthic foraminifera at Walvis Ridge and Maud Rise, and about -4 per mil for planktonic foraminifera at Maud Rise. At the latter sites vertical gradients thus decreased, possibly at least partially as a result of upwelling. The oxygen isotope excursion was about -1.5 per mil for benthic foraminifera at Walvis Ridge and Maud Rise, -1 per mil for planktonic foraminifera at Maud Rise. The rapid oxygen isotope excursion at a time when polar ice-sheets were absent or insignificant can be explained by an increase in temperature by 4-6°C of high latitude surface waters and deep waters world wide. The deep ocean temperature increase could have been caused by warming of surface waters at high latitudes and continued formation of the deep waters at these locations, or by a switch from dominant formation of deep waters at high latitudes to formation at lower latitudes. Benthic foraminiferal post-extinction biogeographical patterns favour the latter explanation. The short-term carbon isotope excursion occurred in deep and surface waters, and in soil concretions and mammal teeth in the continental record. It is associated with increased CaC03-dissolution over a wide depth range in the oceans, suggesting that a rapid transfer of isotopically light carbon from lithosphere or biosphere into the ocean-atmosphere system may have been involved. The rapidity of the initiation of the excursion (a few thousand years) and its short duration (50 000 years) suggest that such a transfer was probably not caused by changes in the ratio of organic carbon to carbonate deposition or erosion. Transfer of carbon from the terrestrial biosphere was probably not the cause, because it would require a much larger biosphere destruction than at the end of the Cretaceous, in conflict with the fossil record. It is difficult to explain the large shift by rapid emission into the atmosphere of volcanogenic CO2, although huge subaerial plateau basalt eruptions occurred at the time in the northern Atlantic. Probably a complex combination of processes and feedback was involved, including volcanogenic emission of CO2, changing circulation patterns, changing productivity in the oceans and possibly on land, and changes in the relative size of the oceanic and atmospheric carbon reservoirs.

Microfossil, stable isotope, and facies of a near-continuous core from the Gippsland Basin

Fossil, facies, and isotope analyses of an early high-paleolatitude (55°S) section suggests a highly unstable East Antarctic Ice Sheet from 32 to 27 Myr. The waxing and waning of this ice sheet from 140% to 40% of its present volume caused sea level changes of ±25 m (ranging from -30 to +50 m) related to periodic glacial (100,000 to 200,000 years) and shorter interglacial events. The near-field Gippsland sea level (GSL) curve shares many similarities to the far-field New Jersey sea level (NJSL) estimates. However, there are possible resolution errors due to biochronology, taphonomy, and paleodepth estimates and the relative lack of lowstand deposits (in NJSL) that prevent detailed correlations with GSL. Nevertheless, the lateral variations in sea level between the GSL section and NJSL record that suggest ocean siphoning and antisiphoning may have propagated synchronous yet variable sea levels.

Fatty acid and stable isotope composition of calanoid copepods in the open eastern Atlantic Ocean during POLARSTERN cruise ANT-XXIX/1

The majority of global ocean production and total export production is attributed to oligotrophic oceanic regions due to their vast regional expanse. However, energy transfers, food-web structures and trophic relationships in these areas remain largely unknown. Regional and vertical inter- and intra-specific differences in trophic interactions and dietary preferences of calanoid copepods were investigated in four different regions in the open eastern Atlantic Ocean (38°N to 21°S) in October/November 2012 using a combination of fatty acid (FA) and stable isotope (SI) analyses. Mean carnivory indices (CI) based on FA trophic markers generally agreed with trophic positions (TP) derived from d15N analysis. Most copepods were classified as omnivorous (CI ~0.5, TP 1.8 to ~2.5) or carnivorous (CI >=0.7, TP >=2.9). Herbivorous copepods showed typical CIs of <=0.3. Geographical differences in d15N values of epi- (200-0 m) to mesopelagic (1000-200 m) copepods reflected corresponding spatial differences in baseline d15N of particulate organic matter from the upper 100 m. In contrast, species restricted to lower meso- and bathypelagic (2000-1000 m) layers did not show this regional trend. FA compositions were species-specific without distinct intra-specific vertical or spatial variations. Differences were only observed in the southernmost region influenced by the highly productive Benguela Current. Apparently, food availability and dietary composition were widely homogeneous throughout the oligotrophic oceanic regions of the tropical and subtropical Atlantic. Four major species clusters were identified by principal component analysis based on FA compositions. Vertically migrating species clustered with epi- to mesopelagic, non-migrating species, of which only Neocalanus gracilis was moderately enriched in lipids with 16% of dry mass (DM) and stored wax esters (WE) with 37% of total lipid (TL). All other species of this cluster had low lipid contents (< 10% DM) without WE. Of these, the tropical epipelagic Undinula vulgaris showed highest portions of bacterial markers. Rhincalanus cornutus, R. nasutus and Calanoides carinatus formed three separate clusters with species-specific lipid profiles, high lipid contents (>=41% DM), mainly accumulated as WE (>=79% TL). C. carinatus and R. nasutus were primarily herbivorous with almost no bacterial input. Despite deviating feeding strategies, R. nasutus clustered with deep-dwelling, carnivorous species, which had high amounts of lipids (>=37% DM) and WE (>=54% TL). Tropical and subtropical calanoid copepods exhibited a wide variety of life strategies, characterized by specialized feeding. This allows them, together with vertical habitat partitioning, to maintain high abundance and diversity in tropical oligotrophic open oceans, where they play an essential role in the energy flux and carbon cycling.

Organic carbon and humic substances contents, carbon isotope composition and peroxidase activity in sediments from DSDP Sites 15-147 and 75-532

Sediment samples from the Cariaco Trench (DSDP Leg 15) and the Walvis Ridge (DSDP Leg 75) ranging in age from Holocene to Upper Miocene (approximately 8 million years BP) and in depth from 5 to 258 m were extracted with basic sodium pyrophosphate and the extract analyzed for enzymic activity. Since no dehydrogenase, alkaline phosphatase or esterase activity was found, it is estimated from these data that the maximum bacterial population does not exceed 1000 cells per gram dry sediment. Peroxidase activity was, however, found in most samples: this showed marked dependence on the humic substance concentration (expressed as percent of the organic carbon content) and increased with depth at a rate of 33 units per meter. To explain this observation, we favor an hypothesis based on the presence of active humic-enzyme association. The humic substances absorb and stabilize peroxidase which is liberated throughout the sediment column by lysis of cells. The association of the enzyme with the humic substances protects it from biodegradation and denaturation. This hypothesis agrees with laboratory experiments which show the enhanced stability of humic-enzyme complexes towards degradation by biological, chemical and thermal effects.

Late Cretaceous-Early Neogene oxygen and carbon isotope record of the Indian Ocean

Stable isotopic data of calcareous nannofossil, monogeneric and monospecific planktic and benthic foraminifera from five Indian Ocean DSDP sites (212, 217, 220, 237, and 253), leads to the following paleoclimatic and paleoceanographic conclusions: - The latest Cretaceous oxygen isotopic record implies a cooling (3-4°C) during the Maastrichtian. At the Cretaceous/Tertiary boundary only a minor warming (about 2°C) has been recorded. The parallel delta13C decrease of more than 1? indicates a significant decrease in productivity. - During the latest Paleocene a positive delta13C excursion was detected in Sites 217 and 237. This transient enrichment in delta13C may be due to productivity changes on continents and/or a change in the storage rate of organic matter in marginal basins or shelf areas. - The most striking feature in the oxygen isotopic record is noted at the Early/Middle Eocene transition. The shift towards more positive values (which were probably enhanced to a certain extent by a preceding diagenetic alteration) delineates a dramatic climatic deterioration at high and mid latitudes during the earlier Tertiary. - Near the Eocene/Oligocene boundary a cooling is evident within the latest Eocene interval. During the earliest Oligocene time a hiatus at Sites 217 and 253 partially obscures the climatic record. - Several climatic fluctuations have been noted during the Oligocene: a cooling at the base of Zone NP 23, a warming at the top of Zone NP 23 through NP 24, and a cooling during Zone NP 25. - The Miocene oxygen isotopic record is dominated by changes in surface and bottom water environments during Zone NN5. The decreasing and then increasing delta18O values, together with the subsequent steepening of the vertical delta18O gradient, point towards major climatic instabilities. These events coincide with the Mid-Miocene build-up of Antarctic ice-sheets. During the latest Miocene to the earliest Pliocene the delta18O record of planktic foraminifera indicates a significant warming of the Indian Ocean at mid-latitudes. - The delta13C record during the Oligocene and Miocene reveals several cycles (delta13C enrichments: NP 24, NN2, NN5, NN9, and base NN 11) which are most likely related to changes in storage rates of organic matter and biological productivity due to climatic changes and transgression/regression cycles. In addition, changes in the circulation patterns may also have influenced the carbon isotopic record.

Natural remanent magnetization (NRM) from ODP Site 1263 covering magnetochron C20r and C21n and high-resolution bulk carbon isotope (d13C) records from Sites 702 and 1263

To explore cause and consequences of past climate change, very accurate age models such as those provided by the astronomical timescale (ATS) are needed. Beyond 40 million years the accuracy of the ATS critically depends on the correctness of orbital models and radioisotopic dating techniques. Discrepancies in the age dating of sedimentary successions and the lack of suitable records spanning the middle Eocene have prevented development of a continuous astronomically calibrated geological timescale for the entire Cenozoic Era. We now solve this problem by constructing an independent astrochronological stratigraphy based on Earth's stable 405 kyr eccentricity cycle between 41 and 48 million years ago (Ma) with new data from deep-sea sedimentary sequences in the South Atlantic Ocean. This new link completes the Paleogene astronomical timescale and confirms the intercalibration of radioisotopic and astronomical dating methods back through the Paleocene-Eocene Thermal Maximum (PETM, 55.930 Ma) and the Cretaceous-Paleogene boundary (66.022 Ma). Coupling of the Paleogene 405 kyr cyclostratigraphic frameworks across the middle Eocene further paves the way for extending the ATS into the Mesozoic.

Stable carbon and oxygen isotope compositions of bulk rock samples analyzed from the Zumaia section

Astronomical tuning of sedimentary records to precise orbital solutions has led to unprecedented resolution in the geological time scale. However, the construction of a consistent astronomical time scale for the Paleocene is controversial due to uncertainties in the recognition of the exact number of 405-kyr eccentricity cycles and accurate correlation between key records. Here, we present a new Danian integrated stratigraphic framework using the land-based Zumaia and Sopelana hemipelagic sections from the Basque Basin and deep-sea records drilled during Ocean Drilling Program (ODP) Legs 198 (Shatsky Rise, North Pacific) and 208 (Walvis Ridge, South Atlantic) that solves previous discrepancies. The new coherent stratigraphy utilises composite images from ODP cores, a new whole-rock d13C isotope record at Zumaia and new magnetostratigraphic data from Sopelana. We consistently observe 11 405-kyr eccentricity cycles in all studied Danian successions. We achieve a robust correlation of bioevents and stable isotope events between all studied sections at the ~100-kyr short-eccentricity level, a prerequisite for paleoclimatic interpretations. Comparison with and subsequent tuning of the records to the latest orbital solution La2011 provides astronomically calibrated ages of 66.022 ± 0.040 Ma and 61.607 ± 0.040 Ma for the Cretaceous-Paleogene (K-Pg) and Danian-Selandian 105 (D-S) boundaries respectively. Low sedimentation rates appear common in all records in the mid-Danian interval, including conspicuous condensed intervals in the oceanic records that in the past have hampered the proper identification of cycles. The comprehensive interbasinal approach applied here reveals pitfalls in time scale construction, filtering techniques in particular, and indicates that some caution and scrutiny has to be applied when building orbital chronologies. Finally, the Zumaia section, already hosting the Selandian Global Boundary Stratotype Section and Point (GSSP), could serve as the global Danian unit stratotype in the future.