Stable carbon and oxygen isotope ratios of foraminifera from Cretaceous and Paleocene sediments

Detailed analysis of over 200 samples of uppermost Cretaceous and Paleocene sediments from Atlantic Ocean DSDP Sites 384, 86, 95, 152, 144, 20C, 21, 356, 357, and 329 provides new information on the temperature stratification of Paleocene planktonic foraminifera, the temperature and carbon isotopic changes across the Cretaceous/Tertiary boundary, and the fluctuating temperature and carbon isotopic records through the Paleocene ~64.5-54 m.y.). There was a significant temperature rise across the Cretaceous/Tertiary boundary both at the surface and in deep waters of the Atlantic Ocean. This temperature rise occurred before the basal Tertiary 'Globigerina' eugubina Zone, so that in the oldest Paleocene sample yet analyzed from the deep sea (Site 356) temperatures are already three degrees higher at the bottom and at the surface than in the Cretaceous. The temperature rise across the boundaryis more pronounced on the bottom and in samples from higher latitudes. Accompanying the temperature rise across the boundary there is a significant shift in the carbon isotope profile. In the basal Paleocene the foraminifera of the surface zone demonstrate very negative carbon isotope values (unlike in the Cretaceous of today's ocean), while deeper dwelling species have more positive values which then decrease to the bottom. The unusual carbon isotope gradients persist through the first three million years of the Paleocene until towards the top of planktonic foraminiferal Zone P.1 (G. trinidadensis Zone) the foraminifera record a profile more positive at the surface and decreasing towards the bottom (as in today's ocean). During the Paleocene there are two noteworthy rises in surface water temperature; the first around 62-61 m.y. (G. trinidadensis Zone), and the second near the base of the Globorotalia angulata Zone, 60-59 m.y. At this time surface temperatures at low to mid latitudes reached values near 25°C, while at mid-latitude Site 384 temperature highs near 22°C were registered. At a sample spacing of around one per million years, we have only produced some of the detail of these temperature fluctuations. The later Paleocene is generally cooler and there do not seem to be any large variations either through time or latitude. Middle-latitude sites average temperatures near 15°C at the surface, while high lower latitude site temperatures range near 18°C. The most salient feature of the bottom temperature record (based on multispecific samples) through the Paleocene is its lack of fluctuations. There is an overall temperature range of 5°C at these intermediate depth sites (paleodepth estimates between 1500 and 3000 m). Higher values near 13°C accompany the surface temperature peaks around 62 and 60 m.y., while low values near 8°C occur in Zone P.2 (61-60 m.y.). We detected no change in bottom temperature across the paleocene/Eocene boundary in the few samples studied so far. While there are several fluctuations in the carbon isotope values through the early Paleocene, the general trend is one of increasingly positive values at the surface and at depth. This trend culminates in the late Paleocene (upper Zone P.4, about 56-57 m.y.) with a major excursion in the carbon isotope values. At low latitudes the range between the surface and the deepest planktonic foraminifera is a delta13C of 4 per mil as compared with a range of 2 per mil today. The carbon values drop off slightly, but remain strongly positive through the remainder of the Paleocene at most sites. Accompanying the carbon isotope excursion at Site 384 is a productivity increase and a proposed rise in the CCD.

Stable carbon and oxygen isotope ratios of benthic foraminifera from the East Atlantic Ocean

The glacial to interglacial delta13C records of the benthic foraminifera Cibicidoides wuellerstorfi and the Uvigerina peregrina group from deep-sea cores cannot be adjusted by a generally valid constant. The delta13C values of the U. peregrina group largely correlate with the accumulation rates of organic carbon, suggesting a local "habitat effect"; those of C. wuellerstorfi vary independently with respect to the carbon flux and record fluctuations in the delta13C of the ambient bottom water isotopic composition.

Stable carbon isotope ratios of carbon dioxide from EDC and Berkner Island ice cores for 40-50 ka BP

The stable carbon isotopic signature of carbon dioxide (d13CO2) measured in the air occlusions of polar ice provides important constraints on the carbon cycle in past climates. In order to exploit this information for previous glacial periods, one must use deep, clathrated ice, where the occluded air is preserved not in bubbles but in the form of air hydrates. Therefore, it must be established whether the original atmospheric d13CO2 signature can be reconstructed from clathrated ice. We present a comparative study using coeval bubbly ice from Berkner Island and ice from the bubble-clathrate transformation zone (BCTZ) of EPICA Dome C (EDC). In the EDC samples the gas is partitioned into clathrates and remaining bubbles as shown by erroneously low and scattered CO2 concentration values, presenting a worst-case test for d13CO2 reconstructions. Even so, the reconstructed atmospheric d13CO2 values show only slightly larger scatter. The difference to data from coeval bubbly ice is statistically significant. However, the 0.16 per mil magnitude of the offset is small for practical purposes, especially in light of uncertainty from non-uniform corrections for diffusion related fractionation that could contribute to the discrepancy. Our results are promising for palaeo-atmospheric studies of d13CO2 using a ball mill dry extraction technique below the BCTZ of ice cores, where gas is not subject to fractionation into microfractures and between clathrate and bubble reservoirs.

Stable carbon and oxygen isotope ratios of calcareous dinoflagellate cysts and planktic foraminifera from the Campanian/Maastrichtian section of ODP Hole 113-690C in the Weddell Sea (Table 1)

Delta18O and delta13C values for the calcareous dinoflagellate species Orthopithonella? globosa (Fütterer 1984) Lentin and Williams 1985 and Pirumella krasheninnikovii (Bolli 1974) Lentin and Williams 1993 from lates Campanian and earliest Maastrichtian of ODP Hole 690C (Weddell Sea, Antarctic Ocean) have been studied in order to evaluate the species' depth habitat in the water column and their applicability in paleoceanographic studies. The calcareous dinoflagellates show isotopic values comparable to probably shallow-dwelling planktic foraminifera from the same sample in delta18O, but have an offset of about -5 ? to -7? in delta13C. This suggests that calcareous dinoflagellate oxygen isotopes may provide information for paleoceanographic reconstructions of sea-surface water temperatures, whereas their extremely light carbon isotope values are probably due to photosynthetic processes.

(Figure 4) Stable carbon isotopic values and relative contents of biphytanes and sugars from sediment sample from the Peru margin and from the Pakistan margin

Glycolipids are prominent constituents in the membranes of cells from all domains of life. For example, diglycosyl-glycerol dibiphytanyl glycerol tetraethers (2Gly-GDGTs) are associated with methanotrophic ANME-1 archaea and heterotrophic benthic archaea, two archaeal groups of global biogeochemical importance. The hydrophobic biphytane moieties of 2Gly-GDGTs from these two uncultivated archaeal groups exhibit distinct carbon isotopic compositions. To explore whether the isotopic compositions of the sugar headgroups provide additional information on the metabolism of their producers, we developed a procedure to analyze the d13C values of glycosidic headgroups. Successful determination was achieved by (1) monitoring the contamination from free sugars during lipid extraction and preparation, (2) optimizing the hydrolytic conditions for glycolipids, and (3) derivatizing the resulting sugars into aldononitrile acetate derivatives, which are stable enough to withstand a subsequent column purification step. First results of d13C values of sugars cleaved from 2Gly-GDGTs in two marine sediment samples, one containing predominantly ANME-1 archaea and the other benthic archaea, were obtained and compared with the d13C values of the corresponding biphytanes. In both samples the dominant sugar headgroups were enriched in 13C relative to the corresponding major biphytane. This 13C enrichment was significantly larger in the putative major glycolipids from ANME-1 archaea (~15 per mil) than in those from benthic archaea (<7 per mil). This method opens a new analytical window for the examination of carbon isotopic relationships between sugars and lipids in uncultivated organisms.

Stable carbon isotopic analyses of n-alkanes and the calculated C4 plant-derived fractions in the dust samples

Atmospheric dust samples collected along a transect off the West African coast have been investigated for their lipid content and compound-specific stable carbon isotope compositions. The saturated hydrocarbon fractions of the organic solvent extracts consist mainly of long-chain n-alkanes derived from epicuticular wax coatings of terrestrial plants. Backward trajectories for each sampling day and location were calculated using a global atmospheric circulation model. The main atmospheric transport took place in the low-level trade-wind layer, except in the southern region, where long-range transport in the mid-troposphere occurred. Changes in the chain length distributions of the n-alkane homologous series are probably related to aridity, rather than temperature or vegetation type. The carbon preference of the leaf-wax n-alkanes shows significant variation, attributed to a variable contribution of fossil fuel- or marine-derived lipids. The effect of this nonwax contribution on the d13C values of the two dominant n-alkanes in the aerosols, n-C29 and n-C31 alkane, is, however, insignificant. Their d13C values were translated into a percentage of C4 vs. C3 plant type contribution, using a two-component mixing equation with isotopic end-member values from the literature. The data indicate that only regions with a predominant C4 type vegetation, i.e. the Sahara, the Sahel, and Gabon, supply C4 plant-derived lipids to dust organic matter. The stable carbon isotopic compositions of leaf-wax lipids in aerosols mainly reflect the modern vegetation type along their transport pathway. Wind abrasion of wax particles from leaf surfaces, enhanced by a sandblasting effect, is most probably the dominant process of terrigenous lipid contribution to aerosols.

Stable carbon and oxygen isotope record of foraminifera from DSDP Hole 30-289

Sediments accumulate on the sea floor far from land with rates of a few millimetres to a few centimetres per thousand years. Sediments have been accumulating under broadly similar conditions, subject to similar controls, for the past 10 8 years and more. In principle we should be able to study the distribution of climatic variance with frequencies over the range 10**-3 to 10**-7 cycles per year with comparative ease. In fact, nearly all our data are heavily weighted towards the youngest part of the geological record. We study frequencies higher than 10**-4 cycles per year in the special case of a Pleistocene interglacial (the present one), and frequencies in the range 10**-4 to 10**-5 cycles per year in the special case of an ice-age. Although these may be of more direct interest to mankind than earlier periods, it may well be that we will understand the causes of climatic variability better if we can examine their operation over a longer time scale and under different boundary conditions. Rather than review the available data, I have collected some new data to show the feasibility of gathering a data base for examining climatic variability without this usual bias toward the recent. The most widely applicable tool for extracting climatic information from deep-sea sediments is oxygen isotope analysis of calcium carbonate microfossils. It is generally possible to select from the sediment both specimens of benthonic Foraminifera (that is, those that lived in ocean deep water at the sediment-water interface) and specimens of planktonic Foraminifera (that is, those that lived and formed their shells near the ocean surface, and fell to the sediment after death). Thus one is able to monitor conditions at the surface and at depth at simultaneous moments in the geological past. The necessity to analyse calcareous microfossils restricts investigation to calcareous sediments, but even with this restriction in sediment type there are many factors governing the rate of sediment accumulation. On a global scale, sediment accumulates so as to balance the input to the oceans from continental erosion. Even when averaged globally, long-term accumulation rates have varied by almost a factor of ten (Davies et al., 1977, doi:10.1126/science.197.4298.53). At the regional scale, surface productivity and deep-water physical and chemical conditions also affect the sediment accumulation rate. Since all these are susceptible to variation and may well vary in response to climatic change as well as other factors, it is extremely hazardous to attempt to express any climatic variable as a function of time on the basis of measurements originally made as a function of depth in sediment. Although time has been used as a basis for plotting Figs. i-8, these should be regarded as freehand sketches of climatic history rather than as time-series plots.

Stable carbon isotope ratios and accumulation rates of organic carbon and nutrients of DSDP Hole 79-545 (Appendix A)

Future warming is predicted to shift the Earth system into a mode with progressive increase and vigour of extreme climate events possibly stimulating other mechanisms that invigorate global warming. This study provides new data and modelling investigating climatic consequences and biogeochemical feedbacks that happened in a warmer world ~112 Myr ago. Our study focuses on the Cretaceous Oceanic Anoxic Event (OAE) 1b and explores how the Earth system responded to a moderate ~25,000 yr lasting climate perturbation that is modelled to be less than 1 °C in global average temperature. Using a new chronological model for OAE 1b we present high-resolution elemental and bulk carbon isotope records from DSDP Site 545 from Mazagan Plateau off NW Africa and combine this information with a coupled atmosphere-land-ocean model. The simulations suggest that a perturbation at the onset of OAE 1b caused almost instantaneous warming of the atmosphere on the order of 0.3 °C followed by a longer (~45,000 yr) period of ~0.8 °C cooling. The marine records from DSDP Site 545 support that these moderate swings in global climate had immediate consequences for African continental supply of mineral matter and nutrients (phosphorous), subsequent oxygen availability, and organic carbon burial in the eastern subtropical Atlantic, however, without turning the ocean anoxic. The match between modelling results and stratigraphic isotopic data support previous studies [summarized in Jenkyns 2003, doi:10.1098/rsta.2003.1240] in that methane emission from marine hydrates, albeit moderate in dimension, may have been the trigger for OAE 1b, though we can not finally rule out alternative mechanisms. Following the hydrate mechanism a total of 1.15 * 10**18 g methane carbon (delta13C=-60 ?), equivalent to about 10% to the total modern gas hydrate inventory, generated the delta13Ccarb profile recorded in the section. Modelling suggests a combination of moderate-scale methane pulses supplemented by continuous methane emission at elevated levels over ~25,000 yr. The proposed mechanism, though difficult to finally confirm in the geological past, is arguably more likely to occur in a warmer world and apparently perturbs global climate and ocean chemistry almost instantaneously. This study shows that, once set-off, this mechanism can maintain Earth's climate in a perturbed mode over geological time leading to pronounced changes in regional climate.

Stable oxygen and carbon isotopes and sediment geochemistry of sediment core GeoB12616-4

The Indian Ocean is an important component of the global thermohaline circulation system, as its western boundary currents feed the Agulhas Current, an integral part of the Atlantic meridional overturning circulation. However, Indian Ocean intermediate to deep-water variability on glacial-interglacial timescales is still a matter of debate. Here we provide stable carbon and oxygen isotopes and sediment elemental compositions of a sediment core from the edge of the Somali Basin. We demonstrate that throughout the past 600 kyr the intermediate western Indian Ocean was primarily bathed by Southern Ocean sourced Upper Circumpolar Deep Water (UCDW). This Southern Ocean sourced water mass enters the Somali Basin via the Amirante Passage or the Mozambique Channel and represents a downstream equivalent of South Atlantic UCDW. We cannot clearly account for the shortterm passage of Red Sea Water (RSW) at 1500 m water depth along the African continental margin, as previously suggested, on glacial-interglacial timescales.