Stable oxygen and carbon isotope composition of benthic foraminifera from the western Mediterranean Sea

The influence of microhabitat, organic matter flux, and metabolism on the stable oxygen and carbon isotope composition of live (Rose Bengal stained) and dead (empty tests) deep-sea benthic foraminifera from the Gulf of Lions (western Mediterranean Sea) have been studied. The total range of observed foraminiferal isotope values exceeds 1.0 per mil for d18O and 2.2 per mil for d13C demonstrating a wide range of coexisting disequilibria relative to d18O of equilibrium calcite (d18OEQ) and d13C of bottom water dissolved inorganic carbon (d13CDIC). The mean d18O values reveal strongest disequilibria for the studied epifaunal to shallow infaunal species (Cibicidoides pachydermus, Uvigerina mediterranea, Uvigerina peregrina) while values approach equilibrium in deep infaunal species (Globobulimina affinis, Globobulimina pseudospinescens). The mean d13C values decrease with increasing average living depths of the different species, thus reflecting a dominant microhabitat (pore water) signal. At the axis of the Lacaze-Duthier Canyon a minimum d13CDIC pore water gradient of approximately -2.1 per mil is assessed for the upper 6 cm of the surface sediment. Although live individuals of U. mediterranea were found in different depth intervals their mean d13C values are consistent with calcification at an average living depth around 1 cm. The deep infaunal occurrence of U. mediterranea specimens suggests association with macrofaunal burrows creating a microenvironment with geochemical characteristics similar to the topmost centimeter. This also explains the excellent agreement between stable isotope signals of live and dead individuals. The ontogenetic enrichment in both d18O and d13C values of U. mediterranea suggests a slow-down of metabolic rates during test growth similar to that previously observed in planktic foraminifera. Enhanced organic carbon fluxes and higher proportion of resuspended terrestrial organic material at the canyon axis are reflected by d13C values of U. mediterranea on average 0.58 per mil lower than those from the open slope. These results demonstrate the general applicability of the d13C signal of this species for the reconstruction of past organic matter fluxes in the Mediterranean Sea. Further studies on live specimens are needed for a more quantitative paleoceanographic approach.

Foraminiferal oxygen and carbon isotope data for DSDP Sites 32-305 and 62-463 and ODP Sites 171-1049 and 171-1050

Oxygen isotope analyses of well-preserved foraminifera from Blake Nose (30°N paleolatitude, North Atlantic) and globally distributed deep-sea sites provide a long-term paleotemperature record for the late Albian-Maastrichtian interval that is difficult to reconcile with the existence of significant Cretaceous ice sheets. Given reasonable assumptions about the isotopic composition of Cretaceous seawater, our results suggest that middle bathyal water temperatures at Blake Nose increased from ~12°C in the late Albian through middle Cenomanian to a maximum of 20°C during the latest Cenomanian and earliest Turonian. Bottom waters were again ~12°C during the middle Campanian and cooled to a minimum of 9°C during the Maastrichtian. Correlative middle bathyal foraminifera from other ocean basins yield paleotemperature estimates that are very similar to those from Blake Nose. Comparison of global bottom-water temperatures and latitudinal thermal gradients suggests that global climate changed from a warm greenhouse state during the late Albian through late Cenomanian to a hot greenhouse phase during the latest Cenomanian through early Campanian, then to cool greenhouse conditions during the mid-Campanian through Maastrichtian.

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.

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.

Sediment and stable carbon isotope record of the Helgoland mud area

The Helgoland mud area in the German Bight is one of the very few sediment depocenters in the North Sea. Despite the shallowness of the setting (<30 m water depth), its topmost sediments provide a continuous and high-resolution record allowing the reconstruction of regional paleoenvironmental conditions for the time since ~400 a.d. The record reveals a marked shift in sedimentation around 1250 a.d., when average sedimentation rates drop from >13 to ~1.6 mm/year. Among a number of major environmental changes in this region during the Middle Ages, the disintegration of the island of Helgoland appears to be the most likely factor which caused the very high sedimentation rates prior to 1250 a.d. According to historical maps, Helgoland used to be substantially bigger at around 800 a.d. than today. After the shift in sedimentation, a continuous and highly resolved paleoenvironmental record reflects natural events, such as regional storm-flood activity, as well as human impacts at work at local to global scales, on sedimentation in the Helgoland mud area.

Contents and stable carbon isotope compositions of biomarkers indicative for AOM-communities dominated by different ANME groups in two carbonate samples from Hydrate Hole pockmark

Different types of seep carbonates were recovered from the 'Kouilou pockmarks' on the Congo deep-sea fan in approximately 3100 m water depth. The carbonate aggregates are represented by pyritiferous nodules, crusts and slabs, tubes, and filled molds. The latter are interpreted to represent casts of former burrows of bivalves and holothurians. The nodules consisting of high-Mg-calcite apparently formed deeper within the sediments than the predominantly aragonitic crusts and slabs. Nodule formation was caused by anaerobic oxidation of methane dominantly involving archaea of the phylogenetic ANME-1 group, whereas aragonitic crusts resulted from the activity of archaea of the ANME-2 cluster. Evidence for this correlation is based on the distribution of specific biomarkers in the two types of carbonate aggregates, showing higher hydroxyarchaeol to archaeol ratios in the crusts as opposed to nodules. Formation of crusts closer to the seafloor than nodules is indicated by higher carbonate contents of crusts, probably reflecting higher porosities of the host sediment during carbonate formation. This finding is supported by lower d18O values of crusts, agreeing with precipitation from pore waters similar in composition to seawater. The aragonitic mineralogy of the crusts is also in accord with precipitation from sulfate-rich pore waters similar to seawater. Moreover, the interpretation regarding the relative depth of formation of crusts and nodules agrees with the commonly observed pattern that ANME-1 archaea tend to occur deeper in the sediment than members of the ANME-2 group. Methane represents the predominant carbon source of all carbonates (d13C values as low as -58.9 per mil V-PDB) and the encrusted archaeal biomarkers (d13C values as low as -140 per mil V-PDB). Oxygen isotope values of some nodular carbonates, ranging from + 3.9 to + 5.1per mil V-PDB, are too high for precipitation in equilibrium with seawater, probably reflecting the destabilization of gas hydrates, which are particularly abundant at the Kouilou pockmarks.

Stable carbon isotope record of planktonic foraminifera and organic matter from sediment cores in the Gulf of Aqaba

The stable carbon isotopic composition of the planktonic foraminifera Globigerinoides sacculifer and G. ruber (white) and sedimentary organic matter from the northern Gulf of Aqaba have been investigated to estimate changes in delta13CDIC in surface waters during the last 1,000 years. The high sedimentation rates at the core sites (about 54 cm/Kyear) provide high temporal resolution (~10 years). Recent sediments at the top of the cores reflect conditions younger than 1950. The delta13C records of the planktonic foraminifera from three multicores display similar trends, showing a uniform and consistent pattern before the 1750s, and a gradual decrease of approximately 0.63? over the last two centuries. This decrease seems to track the decrease of delta13CDIC in surface waters, which is mainly caused by the increase of anthropogenic input of 13C-depleted CO2 into the atmosphere. Similarly, a trend towards lighter values of the carbon isotopic composition of sedimentary organic matter (delta13Corg) during the last 200 years supports the interpretation obtained from the planktonic foraminiferal delta13C. Furthermore, direct measurements of seawater show that delta13C of the dissolved inorganic carbon (DIC) in the northern Gulf of Aqaba has decreased by about 0.44 per mil during the period 1979-2000. The average annual decrease is 0.021 per mil, which is similar to that observed globally. The delta13C values of planktonic foraminifera combined with organic matter delta13C from marine sediments are good indicators for reconstructing past changes in atmospheric CO2 concentrations from the northern Gulf of Aqaba.

Seawater carbonate chemistry, stable carbon isotope fractionation and growth rate during experiments with marine phytoplankton community, 1999

Stable carbon isotope fractionation (%) of 7 marine phytoplankton species grown in different irradiance cycles was measured under nutrient-replete conditions at a high light intensity in batch cultures. Compared to experiments under continuous light, all species exhibited a significantly higher instantaneous growth rate (pi), defined as the rate of carbon fixation during the photo period, when cultivated at 12:12 h. 16:8 h, or 186 h light:dark (L/D) cycles. Isotopic fractionation by the diatoms Skeletonema costatum, Asterionella glacialis, Thalassiosira punctigera, and Coscinodiscus wailesii (Group I) was 4 to 6% lower in a 16:8 h L/D cycle than under continuous light, which we attribute to differences in pi. In contrast, E, in Phaeodactylum tn'cornutum, Thalassiosira weissflogii, and in the dinoflagellate Scrippsiella trochoidea (Group 11) was largely insensitive to day length-related differences in instantaneous growth rate. Since other studies have reported growth-rate dependent fractionation under N-limited conditions in P. tricornutum, pi-related effects on fractionation apparently depend on the factor controlling growth rate. We suggest that a general relationship between E, and pi/[C02,,,] may not exist. For 1 species of each group we tested the effect of variable CO2 concentration, [COz,,,], on isotopic fractionation. A decrease in [CO2,,,] from ca 26 to 3 pm01 kg-' caused a decrease in E, by less than 3%0 This indicates that variation in h in response to changes in day length has a similar or even greater effect on isotopic fractionation than [COz,,,] m some of the species tested. In both groups E, tended to be higher in smaller species at comparable growth rates. In 24 and 48 h time series the algal cells became progressively enriched in 13C during the day and the first hours of the dark period, followed by l3C depletion in the 2 h before beginning of the following Light period. The daily amplitude of the algal isotopic composition (613C), however, was <1.5%0, which demonstrates that diurnal variation in Fl3C is relatively small.