Chemistry of Globigerinoides ruber shells from ODP Site 160-963

Here we present a high-resolution faunal, floral and geochemical (stable isotopes and trace elements) record from the sediments of Ocean Drilling Program Site 963 (central Mediterranean basin), which shows centennial/millennial-scale resemblance to the high-northern latitude rapid temperature fluctuations documented in the Greenland ice cores between 20 and 70 kyr BP. Oxygen and carbon isotopes, planktic foraminifera and calcareous nannofossil distributions suggest that Dansgaard-Oeschger (D/O) and Heinrich events (HE) are distinctly expressed in the Mediterranean climate record. Moreover, recurrent though subdued oscillations not previously identified in the Lateglacial Mediterranean sediments document a significant centennial-scale climate variability in the basin that is greater than previously thought. Alternations between climate regimes dominated by polar outbreaks during D/O stadials and warm D/O interstadials, with associated intensification of continental runoff, are well expressed in the ODP Site 963. These place the Mediterranean basin as an often overlooked recorder of the interplay between large- and regional- scale climate controls at intermediate latitudes, and of the possible interactions between different components of the climate system. Significant changes in Ba/Ca values measured in Globigerinoides ruber shells from a number of D/O stadials and interstadials suggest enhanced freshwater input from the north-eastern Mediterranean borderland during the D/O interstadials. However, the short duration of 3D stratification events never led to complete oxygen consumption along the water column, but clear effects of sluggish 3D circulation in the basin are testified to by negative excursions in d13C measured in selected species of planktic and benthic foraminifera. HEs are constantly associated with lightening in the d18O record of planktic foraminifera, possibly because of the impact of iceberg melting in the Iberian Margin on Mediterranean thermohaline circulation. Interestingly, in two cases in particular, HE2 and HE5, fresher water inputs also affected deeper horizons of intermediate waters, suggesting a basin-wide impact.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

Quaternary carbonate record of ODP Hole 115-709A

The CaCO3 content in Quaternary deep-sea sediments from Pacific and Atlantic oceans have been suggested to respond differently to glacial/interglacial cycles; CaCO3 contents are highest during glacials in the Pacific but highest during interglacials in the Atlantic Ocean. It is not yet clear as to whether a Pacific or an Atlantic pattern of CaCO3 fluctuations dominates the Indian Ocean. We have analyzed the Ocean Drilling Program (ODP) Site 709A from the western equatorial Indian Ocean for the last 1370 ka to determine the relationships between percentages and fluxes of CaCO3 and Quaternary paleoclimatic changes. We also analyzed the coarse (>25 µm) and fine (<25 µm) fractions of CaCO3 in an attempt at estimating the influence of differences in productivity of foraminifera and calcareous nannofossils in shaping the CaCO3 record. Carbon isotopes and Ba/Al ratios were used as indices of productivity. Percentages and fluxes of CaCO3 in the total sediment and <25 µm fraction do not show any clear relationships to glacial/interglacial cycles derived from d18O of the planktonic foraminifera Globigerinoides ruber. This indicates that CaCO3 fluctuations at this site do not show either a Pacific or an Atlantic pattern of CaCO3 fluctuations. Fluxes of CaCO3 (0.38 to 2.46 g/cm**2/ ka) in total sediment and Ba/Al ratios (0.58 to 3.93 g/cm**2/ka) show six-fold variability through the last 1370 ka, which points out that productivity changes are significant at this site. Fluxes of the fine CaCO3 component demonstrate a 26-fold change (0.02 to 0.52 g/cm**2/ka), whereas the coarse CaCO3 component exhibit eight-fold change (0.13 to 1.07 g/cm**2/ka). This suggests that productivity variations of calcareous nannofossils are greater in comparison with the foraminifera. On the other hand, mean values of coarse CaCO3 fluxes are higher compared to those of fine CaCO3, which reveals that the foraminifera contribute more to the bulk CaCO3 flux than the calcareous nannofossils in the equatorial Indian Ocean.

Age determination of sediment cores from the northern Mid-Atlantic Ridge

We construct age models for a suite of cores from the northeast Atlantic Ocean by means of accelerator mass spectrometer dating of a key core, BOFS 5K, and correlation with the rest of the suite. The effects of bioturbation and foraminiferal species abundance gradients upon the age record are modeled using a simple equation. The degree of bioturbation is estimated by comparing modeled profiles with dispersal of the Vedde Ash layer in core 5K, and we find a mixing depth of roughly 8 cm for sand-sized material. Using this value, we estimate that age offsets between unbioturbated sediment and some foraminifera species after mixing may be up to 2500 years, with lesser effect on fine carbonate (< 10 µm) ages. The bioturbation model illustrates problems associated with the dating of 'instantaneous' events such as ash layers and the 'Heinrich' peaks of ice-rafted detritus. Correlations between core 5K and the other cores from the BOFS suite are made on the basis of similarities in the downcore profiles of oxygen and carbon isotopes, magnetic susceptibility, water and carbonate content, and via marker horizons in X radiographs and ash beds.

Chemostratigraphy (CaCO3, TOC, d13Corg) of Sinemurian black shales

The Shales-with-'Beef' and Black Ven Marls of the Charmouth Mudstone Formation (Sinemurian) exposed on the Dorset Coast in southern England (Wessex Basin) show stratigraphic variation in carbonate, organic carbon and organic-carbon isotopes. Little environmental significance is attached to the variation of carbonate except in the case of the tabular and nodular limestones interrupting the sequence that probably record stratigraphic condensation and/or sedimentary stillstands that, in an extreme case, were accompanied by sea-floor erosion to produce the bored and encrusted 'Coinstone'. Relatively high total organiccarbon (TOC) contents are present in the laminated mudstones of the lower turneri Zone (upper brooki and lower birch Subzones) and the obtusum Zone (obtusum and stellare Subzones). Basin stratification related to fresh-water influx was the most likely aid to deoxygenation and enhanced preservation of organic matter. The organic-carbon isotope curve (d13Corg), which shows positive excursions in the upper turneri Zone (upper birchi Subzone) and highest obtusum - raricostatum Zones (highest stellare Subzone, densinodulum and lower raricostatoides Subzones), does not correlate with the TOC stratigraphy and was clearly not controlled by local patterns of organic-matter burial. Long-term (hundreds-of-thousands of years) variations in the carbon-isotope (d13Corg) curve are interpreted as reflecting changing seawater isotopic composition and, in the case of the stratigraphically higher interval, may be related to marine organic-carbon burial on the margins of the proto-Atlantic, as exemplified by the Lusitanian Basin in Portugal. Correlation of the carbon-isotope profile with putative sea-level curves is problematic in detail, although significant local transgressive pulses in the turneri and late raricostatum Zones are approximately coincident with positive d13Corg excursions.

Biomass and stable isotope composition of plankton in five size fractions along a zonal transect (24°N) from the Canary Islands to Florida in January-March 2011

The spatial variability of biomass and stable isotopes in plankton size fractions in the upper 200 m was studied in a high spatial resolution transect along 24°N from Canary Islands to Florida (January - March 2011) during Leg 8 of the Malaspina-2010 expedition (http://www.expedicionmalaspina.es) to determine nitrogen and carbon sources. Plankton samples were collected by vertical tows of a microplankton net (40 mm mesh size) and a mesoplankton net (200 mm mesh size) through the upper 200 m of the water column. Sampling was between 10:00 and 16:00 h GMT. Plankton was separated into five size fractions (40 - 200, 200 - 500, 500 - 1000, 1000 - 2000 and > 2000 mm) by gentle filtration of the samples by a graded series of nylon sieves (2000, 1000, 500, 200 and 40 mm). Large gelatinous organisms were removed before filtration. Aliquots for each size fraction were collected on pre-weighed glass-fibre filters, dried (60°C, 48 h) and stored in a desiccator before determination of biomass (dry weight), carbon and nitrogen content and natural abundance of stable carbon and nitrogen isotopes ashore. Vertical advection of waters predominated in lateral zones while the central Atlantic (30-70°W) was characterized by a strong stratification and oligotrophic surface waters. Plankton biomass was low in the central zone and high in both eastern and western sides, with most of the variability due to either large (>2000 µm) and small plankton (<500 µm). Carbon isotopes reflected mainly the advection the deep water in lateral zones. Stable nitrogen isotopes showed a nearly symmetrical spatial distribution in all fractions, with the lowest values (delta15N <1per mill) in the central zone, and were inversely correlated to carbon stable isotopes (delta13C) and to the abundance of the nitrogen-fixer Trichodesmium. Diazotrophy was estimated to account for >50% of organic nitrogen in the central zone, and even >30% in eastern and western zones. The impact of diazotrophy increased with the size of the organisms, supporting the wide participation of all trophic levels in the processing of recently fixed nitrogen. These results indicate that atmospheric sources of carbon and nitrogen prevail over deep water sources in the subtropical North Atlantic and that the zone influenced by diazotrophy is much larger than reported in previous studies.

Geochemistry and stable carbon isotope composition of kerogen of DSDP Site 124-767

Celebes Basin sediments from Ocean Drilling Program Site 767 (Leg 124) containing both marine and terrestrial organic matter have been investigated through palynofacies and geochemical analyses. The main degradation processes affecting or having affected organic matter are recorded in the sedimentary column as shown by ammonium, phosphate and sulfate pore-water profiles, and by petrographic and geochemical analyses of sediments. In the upper part of the sedimentary section (down to 200 mbsf), the decrease of the ratio of total organic carbon to sulfur (TOC/S) with depth, generally related to the sulfate reduction process, is accompanied by an increase of framboidal pyrite content in the marine organic matter, and by an increasing amount of amorphous marine organic matter relative to the total organic matter. However, as the terrestrial organic input also varies with depth, dilution effects are superimposed on diagenesis. This continental supply affects the TOC/S ratio by increasing total organic carbon and decreasing the ability of the bulk organic matter to be metabolized through sulfate reduction. A positive relationship between the TOC/P ratio and the amount of degraded organic matter of marine origin clearly displays the effect of an organic source on the composition of the sediment. Each lithostratigraphic unit possesses its own characteristics in terms of composition and preservation of organic matter. The effects of diagenesis can only be appreciated within a single lithostratigraphic unit and mainly affect the less-resistant marine organic matter.

Sedimentology and Cd/Ca ratios of benthic foraminifera from ODP Site 172-1060 in the western Nort Atlantic

The Western Boundary Undercurrent (WBUC), off eastern America, is an important component of the Atlantic Meridional Overturning circulation and is the principal route for southward transport of North Atlantic waters and southward return of Southern Source Water (SSW). Here a direct flow speed proxy (mean grain size of the sortable silt) is used to infer the vigour of flow of the palaeo-WBUC at Blake Outer Ridge, (ODP Site 1060, depth 3481 m) during Marine Isotope Stage (MIS) 3. The overall shape of the flow speed proxy record shows a complex pattern of variability, with generally more vigorous flow and larger-scale flow variations between 35 and 60 ka than in the younger part of MIS 3 and MIS 2 (b35 ka). Six events of reduced bottom flow vigour (Slow Events, SEs) occur. These appear uncorrelated with Heinrich events, but are instead synchronous with the warming phases of Antarctic Warm Events A-1 to A-4 (with one new one, A-1a and one poorly defined, 'A-0'). This indicates that Antarctic climate exerts a stronger control on deep flow vigour in the North Atlantic during MIS 3 than Northern Hemisphere climate. The correspondence of SEs with Antarctic warming suggests a weaker WBUC flow due to reduced volume flux at SSW source or reduced SSW density. Because the variability of the lower limb of the WBUC was not connected to sharp North Atlantic changes in temperature, it is unlikely that the Dansgaard/Oeschger cycles were associated with a mode of MOC variation involving wholeocean overturn, but more likely with perturbations of only the shallow Glacial Gulf Stream-Glacial Northern Source Intermediate Water cell. Nutrient proxies (benthic carbon isotopes and Cd/Ca of Uvigerina peregrina) at this site show similar trends to the GRIP delta18O record. This correlation has previously been attributed mainly to hydrographic and flow changes but is here shown to be better explained by variations in surface ocean productivity and subsequent decomposition of 12C rich organic material on the sea floor.

Radiocarbon ages and stable isotope measurements on sediment cores of the subarctic Pacific and its marginal seas

Under modern conditions only North Pacific Intermediate Water is formed in the northwest Pacific Ocean. This situation might have changed in the past. Recent studies with general circulation models indicate a switch to deep-water formation in the northwest Pacific during Heinrich Stadial 1 (17.5-15.0 ka) of the last glacial termination. Reconstructions of past ventilation changes based on paleoceanographic proxy records are still insufficient to test whether a deglacial mode of deep-water formation in the North Pacific Ocean existed. Here we present deglacial ventilation records based on radiocarbon-derived ventilation ages in combination with epibenthic stable carbon isotopes from the northwest Pacific including the Okhotsk Sea and Bering Sea, the two potential source regions for past North Pacific ventilation changes. Evidence for most rigorous ventilation of the intermediate-depth North Pacific occurred during Heinrich Stadial 1 and the Younger Dryas, simultaneous to significant reductions in Atlantic Meridional Overturning Circulation. Concurrent changes in d13C and ventilation ages point to the Okhotsk Sea as driver of millennial-scale changes in North Pacific Intermediate Water ventilation during the last deglaciation. Our records additionally indicate that changes in the d13C intermediate-water (700-1750 m water depth) signature and radiocarbon-derived ventilation ages are in antiphase to those of the deep North Pacific Ocean (>2100 m water depth) during the last glacial termination. Thus, intermediate- and deep-water masses of the northwest Pacific have a differing ventilation history during the last deglaciation.

Compositional and isotopic data on core MD84641

The organic carbon isotopic record of the sapropels(S1 and S3-S10) and intercalated marl oozes has been determined in a 12-m piston core from the eastern Mediterranean. The d13C_organic values are systematically lighter (mean=-21.0±0.82 per mil) in all sapropels and heavier (mean=-18.8±1.07 per mil) in the marl oozes. These differences are not due to variable marine and terrestrial organic matter mixtures because all values are heavier than modern plankton in the Mediterranean, there is no relationship between the C_organic/N ratios and the isotopic values, and published information on the abundance and distribution of organic biomarkers shows that terrestrial material constitutes a minor fraction of the total organic matter. Temperature effects on isotope fractionation are also discounted because the change in d13C_organic values between glacial and interglacial horizons is in the opposite sense. Diagenesis, which can produce relatively small changes in the carbon isotopic composition of sedimentary organic matter under certain circumstances, is unlikely to have caused the observed differences because this mechanism would cause an enrichmet in 12C, implying that all values were even heavier originally, and there is no secular trend in the d13C_organic record. The observed differences in d13C_organic between the two lithologies are probably produced by changes in the isotopic composition and the concentration of dissolved CO2. First, freshwater flooding during the formation of the sapropels caused the isotopic composition of the dissolved inorganic carbon in the surface waters of the Mediterranean to become lighter because of the 13C deficiency in fresh waters. Hence photosynthesis would have produced isotopically lighter organic material. Second, changes in atmospheric pCO2 between glacial and interglacial periods, as shown by the Vostok ice core, caused marked changes in the concentration of free dissolved CO2 in the mixed layer; lower values during glacial maxima caused a smaller fractionation of the carbon isotopes by phytoplankton, whereas levels were less limiting during the interglacials. Concentrations of dissolved CO2 could also have been much higher during the deposition of the sapropels because of the supply of regenerated CO2 to the mixed layer by upwelling, and this could have further lightened the d13C_organic values in the sapropels themselves. Carbon isotope records may provide an alternative method for estimating atmospheric pCO2 levels over longer time periods than can be obtained from ice cores.

Organic geochemistry records from two Palaeocene-Eocene Thermal Maximum sections in Denmark

Analysis of sediments deposited at different latitudes around the world during the Palaeocene-Eocene Thermal Maximum (PETM; ~56 Ma) have revealed a globally profound warming phase, regionally varying from 5-8 °C. Such records from Europe have not yet been obtained. We studied the variations in sea surface and continental mean annual air temperatures (SST and MAT, respectively) and the distribution patterns and stable carbon isotopes of higher plant derived n-alkanes in two proximal PETM sections (Fur and Store Bælt, Denmark) from the epicontinental North Sea Basin. A negative carbon isotope excursion (CIE) of 4-7 per mil was recorded in land plant derived n-alkanes, similar to what has been observed for other PETM sections. However, differences observed between the two proximal sites suggest that local factors, such as regional vegetation and precipitation patterns, also influenced the CIE. The presence of S-bound isorenieratene derivatives at the onset of the PETM and increased organic carbon contents points to a rapid shift in depositional environment; from well oxygenated to anoxic and sulfidic. These euxinic conditions are comparable with those during the PETM in the Arctic Ocean. SSTs inferred from TEX86 show relatively low temperatures followed by an increase of ~7 °C across the PETM. At the Fur section, a remarkably similar temperature record was obtained for MAT using the MBT'/CBT proxy. However, the MAT record of the Store Bælt section did not reveal this warming.

Gas composition, concentration and stable isotope ratios (Table 2, 3, 4)

The deployment of CCS (carbon capture and storage) at industrial scale implies the development of effective monitoring tools. Noble gases are tracers usually proposed to track CO2. This methodology, combined with the geochemistry of carbon isotopes, has been tested on available analogues. At first, gases from natural analogues were sampled in the Colorado Plateau and in the French carbogaseous provinces, in both well-confined and leaking-sites. Second, we performed a 2-years tracing experience on an underground natural gas storage, sampling gas each month during injection and withdrawal periods. In natural analogues, the geochemical fingerprints are dependent on the containment criterion and on the geological context, giving tools to detect a leakage of deep-CO2 toward surface. This study also provides information on the origin of CO2, as well as residence time of fluids within the crust and clues on the physico-chemical processes occurring during the geological story. The study on the industrial analogue demonstrates the feasibility of using noble gases as tracers of CO2. Withdrawn gases follow geochemical trends coherent with mixing processes between injected gas end-members. Physico-chemical processes revealed by the tracing occur at transient state. These two complementary studies proved the interest of geochemical monitoring to survey the CO2 behaviour, and gave information on its use.