Miocene stable isotope record of benthic foraminifera from IODP Site 320-U1336

Stable carbon and oxygen isotopes (d13C and d18O) of foraminiferal tests are amongst the most important tools in paleoceanography but the extent to which recrystallization can alter the isotopic composition of the tests is not well known. Here, we compare three middle Miocene (16-13 Ma) benthic foraminiferal stable isotope records from eastern equatorial Pacific sites with different diagenetic histories to investigate the effect of recrystallization. To test an extreme case, we analyzed stable isotope compositions of benthic foraminifera from Integrated Ocean Drilling Program Site U1336, for which the geochemistry of bulk carbonates and associated pore waters indicate continued diagenetic alteration in sediments > 14.7 Ma. Despite this diagenetic overprinting, the amplitudes and absolute values of the analyzed U1336 stable isotopes agree well with high resolution records from better preserved Sites U1337 and U1338 nearby. Our results suggest that although benthic foraminiferal tests of all three sites show some degree of textural changes due to recrystallization, they have retained their original stable isotope signatures. The good agreement of the benthic foraminiferal stable isotope records demonstrates that recrystallization occurred extremely rapidly (<100 kyr) after deposition. This is confirmed by the preservation of orbital cyclicities in U1336 stable isotope data and d18O values being different to inorganic calcite that would precipitate from U1336 pore waters during late recrystallization. The close similarity of the benthic foraminiferal stable isotope records between the sites allows the well resolved paleo-magnetic results of Site U1336 to be transferred to Sites U1337 and U1338 improving the global Geological Timescale.

CO2 concentration and stable isotope ratios of three Antarctic ice cores covering the period from 149.4 - 1.5 kyr before 1950

We present new d13C measurements of atmospheric CO2 covering the last glacial/interglacial cycle, complementing previous records covering Terminations I and II. Most prominent in the new record is a significant depletion in d13C(atm) of 0.5 permil occurring during marine isotope stage (MIS) 4, followed by an enrichment of the same magnitude at the beginning of MIS 3. Such a significant excursion in the record is otherwise only observed at glacial terminations, suggesting that similar processes were at play, such as changing sea surface temperatures, changes in marine biological export in the Southern Ocean (SO) due to variations in aeolian iron fluxes, changes in the Atlantic meridional overturning circulation, upwelling of deep water in the SO, and long-term trends in terrestrial carbon storage. Based on previous modeling studies, we propose constraints on some of these processes during specific time intervals. The decrease in d13C(atm) at the end of MIS 4 starting approximately 64 kyr B.P. was accompanied by increasing [CO2]. This period is also marked by a decrease in aeolian iron flux to the SO, followed by an increase in SO upwelling during Heinrich event 6, indicating that it is likely that a large amount of d13C-depleted carbon was transferred to the deep oceans previously, i.e., at the onset of MIS 4. Apart from the upwelling event at the end of MIS 4 (and potentially smaller events during Heinrich events in MIS 3), upwelling of deep water in the SO remained reduced until the last glacial termination, whereupon a second pulse of isotopically light carbon was released into the atmosphere.

Radiocarbon, stable isotopic compositions and seawater chemical properties of Black Sea core-top sediments and CTD stations

Chloropigments and their derivative pheopigments preserved in sediments can directly be linked to photosynthesis. Their carbon and nitrogen stable isotopic compositions have been shown to be a good recorder of recent and past surface ocean environmental conditions tracing the carbon and nitrogen sources and dominant assimilation processes of the phytoplanktonic community. In this study we report results from combined compound-specific radiocarbon and stable carbon and nitrogen isotope analysis to examine the time-scales of synthesis and fate of chlorophyll-a and its degradation products pheophytin-a, pyropheophytin-a, and 132,173-cyclopheophorbide-a-enol until burial in Black Sea core-top sediments. The pigments are mainly of marine phytoplanktonic origin as implied by their stable isotopic compositions. Pigment ?15N values indicate nitrate as the major uptake substrate but 15N-depletion towards the open marine setting indicates either contribution from N2-fixation or direct uptake of ammonium from deeper waters. Radiocarbon concentrations translate into minimum and maximum pigment ages of approximately 40 to 1200 years. This implies that protective mechanisms against decomposition such as association with minerals, storage in deltaic anoxic environments, or eutrophication-induced hypoxia and light limitation are much more efficient than previously thought. Moreover, seasonal variations of nutrient source, growth period, and habitat and their associated isotopic variability are likely at least as strong as long-term trends. Combined triple isotope analysis of sedimentary chlorophyll and its primary derivatives is a powerful tool to delineate biogeochemical and diagenetic processes in the surface water and sediments, and to assess their precise time-scales.

Standing stocks and carbon isotopes of live benthic foraminifera from the South Atlantic

Live (Rose Bengal stained) and dead benthic foraminifera of surface and subsurface sediments from 25 stations in the eastern South Atlantic Ocean and the Atlantic sector of the Southern Ocean were analyzed to decipher a potential influence of seasonally and spatially varying high primary productivity on the stable carbon isotopic composition of foraminiferal tests. Therefore, stations were chosen so that productivity strongly varied, whereas conservative water mass properties changed only little. To define the stable carbon isotopic composition of dissolved inorganic carbon (d13CDIC) in ambient water masses, we compiled new and previously published d13CDIC data in a section running from Antarctica through Agulhas, Cape and Angola Basins, via the Guinea Abyssal Plain to the Equator. We found that intraspecific d13C variability of all species at a single site is constantly low throughout their distribution within the sediments, i.e. species specific and site dependent mean values calculated from all subbottom depths on average only varied by +/-0.09 per mil. This is important because it makes the stable carbon isotopic signal of species independent of the particular microhabitat of each single specimen measured and thus more constant and reliable than has been previously assumed. So-called vital and/or microhabitat effects were further quantified: (1) d13C values of endobenthic Globobulimina affinis, Fursenkoina mexicana, and Bulimina mexicana consistently are by between -1.5 and -1.0 per mil VPDB more depleted than d13C values of preferentially epibenthic Fontbotia wuellerstorfi, Cibicidoides pachyderma, and Lobatula lobatula. (2) In contrast to the Antarctic Polar Front region, at all stations except one on the African continental slope Fontbotia wuellerstorfi records bottom water d13CDIC values without significant offset, whereas L. lobatula and C. pachyderma values deviate from bottom water values by about -0.4 per mil and -0.6 per mil, respectively. This adds to the growing amount of data on contrasting cibicid d13C values which on the one hand support the original 1:1-calibration of F. wuellerstorfi and bottom water d13CDIC, and on the other hand document severe depletions of taxonomically close relatives such as L. lobatula and C. pachyderma. At one station close to Bouvet Island at the western rim of Agulhas Basin, we interpret the offset of -1.5 per mil between bottom water d13CDIC and d13C values of infaunal living Bulimina aculeata in contrast to about -0.6 +/- 0.1 per mil measured at eight stations close-by, as a direct reflection of locally increased organic matter fluxes and sedimentation rates. Alternatively, we speculate that methane locally released from gas vents and related to hydrothermal venting at the mid-ocean ridge might have caused this strong depletion of 13C in the benthic foraminiferal carbon isotopic composition. Along the African continental margin, offsets between deep infaunal Globobulimina affinis and epibenthic Fontbotia wuellerstorfi as well as between shallow infaunal Uvigerina peregrina and F. wuellerstorfi, d13C values tend to increase with generally increasing organic matter decomposition rates. Although clearly more data are needed, these offsets between species might be used for quantification of biogeochemical paleogradients within the sediment and thus paleocarbon flux estimates. Furthermore, our data suggest that in high-productivity areas where sedimentary carbonate contents are lower than 15 weight %, epibenthic and endobenthic foraminiferal d13C values are strongly influenced by 13C enrichment probably due to carbonate-ion undersaturation, whereas above this sedimentary carbonate threshold endobenthic d13C values reflect depleted pore water d13CDIC values.

Organic carbon concentrations and isotope ratios of sediments from the Laptev Sea

Stable carbon isotope ratios in the organic fraction of surface sediments from the Laptev Sea shelf were analyzed in order to study the modern distribution pattern of terrestrial organic matter. The delta13Corg signature of the surface sediments range from -26.6? near the coastal margin to -22.8? in the north towards the outer shelf. Characterizing the possible sources of organic matter by their delta13Corg signature reveals that the terrestrial influence reaches further north in the eastern than in the western Laptev Sea. Downcore records of the delta13Corg, measured on three AMS 14C-dated cores from water depths between 46 and 77 m, specify the spatial and temporal changes in the deposition of terrestrial organic matter on the Laptev Sea shelf during the past 12.7 ka. The major depositional changes of terrestrial organic matter occurred between 11 and 7 ka and comprised the main phase of the southward retreat of the coastline and of the river depocenters due to the postglacial sea level rise.

Paleotemperatures, stable isotopes and alkenones of samples from the South Atlantic

Carbon dioxide is one of the most important greenhouse gases which are increasing in atmospheric concentration due to human activities. For using natural CO2 dynamics as a key to understanding the climatic consequences of anthropogenic pCO2 rise, the ocean plays an important role due to its much larger carbon pool compared to the atmosphere. By studying the ratio of stable carbon isotopes in organic matter from marine sediments, it is possible to estimate the partial pressure of CO2 in surface waters during ancient times. The organic compound C37:2 alkenone, whose sole origin is from autotrophic marine algae, was chosen for d13C analysis and its isotopic composition used to reconstruct past PCO2 levels in the surface layer of the eastern Angola Basin for the last 200,000 years. In addition to the variation of ancient concentrations of dissolved CO2 ([CO2(aq)] = ce), the effect of carbon demand which depends on algal growth rate was considered. Here to, carbon isotopic fractionation of C37:2 alkenones (ep) in core-top sediments from the equatorial and the South Atlantic was calibrated against pre-industrial [CO2(aq)] and phosphate concentrations in surface waters. From these data, a variable b = (25 per mil - ep) * ce which reflects intracellular carbon demand was calculated. This variable b correlates with the ambient concentration of seawater phosphate and depends on growth rates. The bulk sediment d15N was used as a proxy parameter for calculating ancient b-values, taking into account that d15N in core-top sediments is correlated to phosphate concentration in modern surface waters. On this basis, the alkenone d13C record of GeoB1016-3 documents a permanent oceanic source for atmospheric carbon dioxide during the last 200,000 years. As a consequence of using d15N derived b-values instead of b = constant, the Angola Basin appears to have been an even stronger CO2 source during glacial periods than at present. Qualitatively similar results were reported by Jasper et al. (1994) for the central Equatorial Pacific. These observations suggest that enhanced productivity of low-latitude upwelling areas during glacial periods is not responsible for the lower CO2 content of the glacial atmosphere.

Distribution of major carbon pools in a cyanobacterial mat from Salin de Giraud, Camargue, France

The fine-scale depth distribution of major carbon pools and their stable carbon isotopic signatures (d13C) were determined in a cyanobacterial mat (Salin-de-Giraud, Camargue, France) to study early diagenetic alterations and the carbon preservation potential in hypersaline mat ecosystems. Particular emphasis was placed on the geochemical role of extracellular polymeric substances (EPS). Total carbon (Ctot), organic carbon (Corg), total nitrogen (Ntot), total hydrolysable amino acids (THAA), carbohydrates, cyanobacteria-derived hydrocarbons (8-methylhexadecane, n-heptadec-5-ene, n-heptadecane) and EPS showed highest concentrations in the top millimetre of the mat and decreased with depth. The hydrocarbons attributed to cyanobacteria showed the strongest decrease in concentration with depth. This correlated well with the depth profiles of oxygenic photosynthesis and oxygen, which were detected in the top 0.6 and 1.05 mm, respectively, at a high down-welling irradiance (1441 µmol photons m**-2 s**-1). At depths beneath the surface layer, the Corg was composed mainly of amino acids and carbohydrates. A resistance towards microbial degradation could have resulted from interactions with diverse functional groups present in biopolymers (EPS) and with minerals deposited in the mat. A 13C enrichment with depth for the total carbon pool (Ctot) was observed, with d13C values ranging from -16.3 permil at the surface to -11.3 permil at 9-10 mm depth. Total lipids depicted a d13C value of -17.2 permil in the top millimetre and then became depleted in 13C with depth (-21.7 to -23.3 permil). The d13C value of EPS varied only slightly with depth (-16.1 to -17.3 permil) and closely followed the d13C value of Corg at depths beneath 4 mm. The EPS represents an organic carbon pool of preservation potential during early stages of diagenesis in recent cyanobacterial mats as a result of a variety of possible interactions. Their analyses might improve our understanding of fossilized microbial remains from mat ecosystems.

A relationship between aerosol transport and compound-specific d13C land plant biomarker and pollen records

We examined near-surface, late Holocene deep-sea sediments at nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) along the Southwest African continental margin. Contents, distribution patterns and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) are indicators of land plant vegetation of different biosynthetic types, which can be correlated with concentrations and distributions of pollen taxa in the same sediments. Calculated clusters of wind trajectories and satellite Aerosol Index imagery afford information on the source areas for the lipids and pollen on land and their transport pathways to the ocean sites. This multidisciplinary approach on an almost continental scale provides clear evidence of latitudinal differences in lipid and pollen composition paralleling the major phytogeographic zonations on the adjacent continent. Dust and smoke aerosols are mainly derived from the western and central South African hinterland dominated by deserts, semi-deserts and savannah regions rich in C4 and CAM plants. The northern sites (Congo Fan area and northern Angola Basin), which get most of their terrestrial material from the Congo Basin and the Angolan highlands, may also receive some material from the Chad region. Very little aerosol from the African continent is transported to the most southerly sites in the Cape Basin. As can be expected from the present position of the phytogeographic zones, the carbon isotopic signatures of the n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. The results of the study suggest that this combination of pollen data and compound-specific isotope geochemical proxies can be effectively applied in the reconstruction of past continental phytogeographic developments.

Isotope measurements from late Paleocene - early Eocene of 5 cores from Atlantic and Pacific Ocean

High-resolution stable carbon isotope records for upper Paleocene - lower Eocene sections at Ocean Drilling Program Sites 1051 and 690 and Deep Sea Drilling Project Sites 550 and 577 show numerous rapid (40 - 60 kyr duration) negative excursions of up to 1 per mill. We demonstrate that these transient decreases are the expected result of nonlinear insolation forcing of the carbon cycle in the context of a long carbon residence time. The transients occur at maxima in Earth's orbital eccentricity, which result in high-amplitude variations in insolation due to forcing by climatic precession. The construction of accurate orbital chronologies for geologic sections older than ~ 35 Ma relies on identifying a high-fidelity recorder of variations in Earth's orbital eccentricity. We use the carbon isotope records as such a recorder, establishing a robust orbitally tuned chronology for latest Paleocene-earliest Eocene events. Moreover, the transient decreases provide a means of precise correlation among the four sites that is independent of magnetostratigraphic and biostratigraphic data at the <10^5-year scale. While the eccentricity-controlled transient decreases bear some resemblance to the much larger-amplitude carbon isotope excursion (CIE) that marks the Paleocene/Eocene boundary, the latter event is found to occur near a minimum in the ~400-kyr eccentricity cycle. Thus the CIE occurred during a time of minimal variability in insolation, the dominant mechanism for forcing climate change on 104-year scales. We argue that this is inconsistent with mechanisms that rely on a threshold climate event to trigger the Paleocene/Eocene thermal maximum since any threshold would more likely be crossed during a period of high-amplitude climate variations.

Chemobiostratigraphy of the Cretaceous/Paleocene boundary at ODP Hole 120-750A

An integrated biostratigraphic and stable isotope investigation was conducted on a high-latitude sequence across the Cretaceous/Paleogene (K/P) boundary recovered in Hole 750A in the southern Indian Ocean. The sequence consists of nannofossil chalk and is discontinuous across the boundary; missing is an estimated 0.3-m.y. late Maestrichtian and early Danian interval. Nonetheless, because calcareous nannofossil Zones NP1 and NP2 are well-developed, micropaleontological studies of the sequence have yielded a detailed record of Danian high-latitude microplankton evolution. In addition, stable carbon isotope analyses of planktonic and benthic foraminifer and bulk samples provide a record of late Maestrichtian and early Danian surface- and deep-water carbon isotope variations. Together, the carbon isotope and carbonate accumulation records serve as an index of regional marine net productivity across the boundary. Earliest Danian nannoplankton assemblages consisted mainly of persistent genera that were generally rare or absent in the Upper Cretaceous at Hole 750A. However, by 0.5-0.6 m.y. after the boundary, newly evolving Danian taxa became dominant. The turnover in nannofossil assemblages was accompanied by significant changes in rates of net productivity as gauged by carbon isotope distributions and carbonate accumulation rates. During the period dominated by persistent taxa, net productivity was extremely low, as reflected by the absence of vertical delta13C gradients and reduced carbonate accumulation rates. Later in the Danian, as new species evolved and flourished, vertical delta13C gradients reappeared and carbonate accumulation rates increased, signaling partial recovery of net productivity in this region. The absolute timing and magnitude of late Maestrichtian and early Danian biotic and geochemical changes in the southern Indian Ocean were similar to those recorded in other pelagic K/P boundary sequences from low- and mid-latitude Atlantic and Pacific sites, indicating that these events were ubiquitous.

Age determination and grwoth rates of stalagmites and stalactites from the Okshola cave, Fauske, northern Norway

The sensitivity of terrestrial environments to past changes in heat transport is expected to be manifested in Holocene climate proxy records on millennial to seasonal timescales. Stalagmite formation in the Okshola cave near Fauske (northern Norway) began at about 10.4 ka, soon after the valley was deglaciated. Past monitoring of the cave and surface has revealed stable modern conditions with uniform drip rates, relative humidity and temperature. Stable isotope records from two stalagmites provide time-series spanning from c. 10380 yr to AD 1997; a banded, multi-coloured stalagmite (Oks82) was formed between 10380 yr and 5050 yr, whereas a pristine, white stalagmite (FM3) covers the period from ~7500 yr to the present. The stable oxygen isotope (delta18Oc), stable carbon isotope (delta13Cc), and growth rate records are interpreted as showing i) a negative correlation between cave/surface temperature and delta18Oc, ii) a positive correlation between wetness and delta13Cc, and iii) a positive correlation between temperature and growth rate. Following this, the data from Okshola show that the Holocene was characterised by high-variability climate in the early part, low-variability climate in the middle part, and high-variability climate and shifts between two distinct modes in the late part. A total of nine Scandinavian stalagmite delta18Oc records of comparable dating precision are now available for parts or most of the Holocene. None of them show a clear Holocene thermal optimum, suggesting that they are influenced by annual mean temperature (cave temperature) rather than seasonal temperature. For the last 1000 years, delta18Oc values display a depletion-enrichment-depletion pattern commonly interpreted as reflecting the conventional view on climate development for the last millennium. Although the delta18Oc records show similar patterns and amplitudes of change, the main challenges for utilising high-latitude stalagmites as palaeoclimate archives are i) the accuracy of the age models, ii) the ambiguity of the proxy signals, and iii) calibration with monitoring data.

Cenomanian/Turonian sea surface temperatures of the equatorial Atlantic reconstructed from geochemical data

Oceanic anoxic event 2 (OAE-2) occurring during the Cenomanian/Turonian (C/T) transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 Myr. However, the impact of this major perturbation on and interaction with global climate remains unclear. Here we report new high-resolution records of sea surface temperature (SST) based on TEX86 and d 18O of excellently preserved planktic foraminifera and stable organic carbon isotopes across the C/T transition from black shales located offshore Suriname/French Guiana (Demerara Rise, Ocean Drilling Program Leg 207 Site 1260) and offshore Senegal (Cape Verde Basin, Deep Sea Drilling Project Leg 41 Site 367). At Site 1260, where both SST proxy records can be determined, a good match between conservative SST estimates from TEX86 and d 18O is observed. We find that late Cenomanian SSTs in the equatorial Atlantic Ocean (33°C) were substantially warmer than today (27°-29°C) and that the onset of OAE-2 coincided with a rapid shift to an even warmer (35°-36°C) regime. Within the early stages of the OAE a marked (4°C) cooling to temperatures lower than pre-OAE conditions is observed. However, well before the termination of OAE-2 the warm regime was reestablished and persisted into the Turonian. Our findings corroborate the view that the C/T transition represents the onset of the interval of peak Cretaceous warmth. More importantly, they are consistent with the hypotheses that mid-Cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide (CO2) and that major OAEs were capable of triggering global cooling through the negative feedback effect of organic carbon-burial-led CO2 sequestration. Evidently, however, the factors that gave rise to the observed shift to a warmer climate regime at the onset of OAE-2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 Myr.