Carbon isotope composition of lipids from bones and host sediments of the Atlantic and Pacific Oceans

Carbon in lipids separated from organic matter of fish and marine mammal bones from bottom of the Pacific and Atlantic oceans has d13C values ranging from -21.6 to -25.8 per mil and is isotopically lighter than that in lipids and total organic matter of host sediments. During fossilization of organic phosphate carbon isotope composition of bound lipids of fish bone becomes lighter and that of bones of mammals becomes heavier, possibly as a result of metabolisms of these organisms and composition of phospholipids in them.

Bulk sediment and diatom silica carbon isotope composition from Antarctic coastal marine sediments

Organic carbon occluded in diatom silica is assumed to be protected from degradation in the sediment. d13C from diatom carbon (d13C(diatom)) therefore potentially provides a signal of conditions during diatom growth. However, there have been few studies based on d13C(diatom). Numerous variables can influence d13C of organic matter in the marine environment (e.g., salinity, light, nutrient and CO2 availability). Here we compare d13C(diatom) and d13C(TOC) from three sediment records from individual marine inlets (Rauer Group, East Antarctica) to (i) investigate deviations between d13C(diatom) and d13C(TOC), to (ii) identify biological and environmental controls on d13C(diatom) and d13C(TOC), and to (iii) discuss d13C(diatom) as a proxy for environmental and climate reconstructions. The records show individual d13C(diatom) and d13C(TOC) characteristics, which indicates that d13C is not primarily controlled by regional climate or atmospheric CO2 concentration. Since the inlets vary in water depths offsets in d13C are probably related to differences in water column stratification and mixing, which influences redistribution of nutrients and carbon within each inlet. In our dataset changes in d13C(diatom) and d13C(TOC) could not unequivocally be ascribed to changes in diatom species composition, either because the variation in d13C(diatom) between the observed species is too small or because other environmental controls are more dominant. Records from the Southern Ocean show depleted d13C(diatom) values (1-4 per mil) during glacial times compared to the Holocene. Although climate variability throughout the Holocene is low compared to glacial/interglacial variability, we find variability in d13C(diatom), which is in the same order of magnitude. d13C of organic matter produced in the costal marine environment seems to be much more sensitive to environmental changes than open ocean sites and d13C is of strongly local nature.

The Toarcian in the Subbetic basin (southern Spain): Bio-events (ammonite and calcareous nannofossils) and carbon-isotope stratigraphy

A detailed carbon-isotope stratigraphic study for the uppermost Pliensbachian lowermost Aalenian interval in the Median Subbetic palaeogeographic domain (External zones of the Betic Cordillera, southern Spain) has been carried out. During the Early Jurassic, the Median Subbetic, which represents a typical basin of the Hispanic Corridor connecting the Tethys and the Eastern Pacific, was located in the westernmost Tethys. The analyzed sections encompass the entire Toarcian stage as represented in the southern Iberian palaeomargin. Rocks are mainly rhythmic sequences of grey marls and marly limestones containing a rich ammonite fauna, nannofossils, and benthic foraminifers-all these provide an accurate biostratigraphic control. The lower and upper Toarcian boundaries are well represented in some of these sections and therefore represent optimal sites to link the carbon-isotope curves to ammonite zones, and to nannofossil events. delta C-13 values of bulk carbonates from the different localities of the Subbetic basin have similar variations from the uppermost Pliensbachian to the lowermost Aalenian, suggesting changes in the original DIC carbon isotope composition along the Hispanic corridor. The transition from Pliensbachian to Toarcian is marked by increasing delta C-13 values from similar to 12 to 2.0 parts per thousand, interrupted in the Serpentinum Zone by a negative shift concomitant with the Toarcian oceanic anoxic event (T-OAE), with the major ammonite extinction event of the Toarcian, and an important turnover of calcareous nannoplankton. The negative shift observed in the Serpentinum Zone confirms the global perturbation of the carbon cycling documented along the Tethys and the palaeo-Pacific in organic material and in marine carbonates. However, the amplitude of the negative excursion (similar to - 1.5 parts per thousand) is not compatible with an isotopic homogeneous seawater DIC and/or CO2 atmospheric reservoirs. The interval from the middle to the top of the Toarcian delta C-13 shows relatively constant values, minor ammonite turnovers, and is associated with increasing diversity of calcareous nannoplankton. (c) 2012 Elsevier B.V. All rights reserved.

Texture, geochemistry, isotope composition, petrography and epoch at DSDP Site 93-603

Abundant Fe-Mn carbonate concretions (mainly siderite, manganosiderite, and rhodochrosite) were found in the hemipelagic claystones of Site 603 on the eastern North American continental rise. They occur as nodules, micronodules, or carbonate-replaced burrow fills and layers at a subbottom depth of between ~ 120 (Pliocene) and 1160 m (Albian-Cenomanian). In general, the Fe-Mn carbonate concretions form from CO3- produced by the microbiological degradation of organic matter in the presence of abundant Fe + or Mn + and very low S- concentrations. However, there is also some evidence for diagenetic replacement of preexisting calcite by siderite. The carbon isotope composition of diagenetic Fe-Mn carbonate nodules is determined by CO2 reduction during methanogenesis. Carbonate nodules in Cretaceous sediments at sub-bottom depths of 1085 and 1160 m have distinctly lower d13C values (- 12.2 and - 12.9 per mil) than Neogene siderites, associated with abundant biogenic methane in the pore space (-8.9 to 1.7 per mil between 330 and 780 m depth). Since no isotopic zonation could be detected within individual nodules, we assume that the isotopic composition reflects more or less geochemical conditions at the present burial depth of the carbonate nodules. Carbonates did not precipitate within the zone of sulfate reduction (approximately 0.01 to 10 m), where all of the pyrite was formed. The oxygen isotope composition indicates precipitation from seawater-derived interstitial waters. The d18O values decrease with increasing burial depth from + 5.1 to - 1.2 per mil, suggesting successively higher temperatures during carbonate formation.

Last Glacial Maximum carbon isotopic composition

We present Holocene and last glacial maximum (LGM) oxygen and carbon isotope measurements on Planulina wuellerstorfi in six southeast Pacific cores. Sedimentation rates are low in this part of the ocean, and measurements were made on individual foraminiferal shells in order to identify the Holocene and glacial individuals on the basis of their extreme d18O. The new d13C data were combined with previous P. wuellerstorfi data for interpretation of global thermohaline circulation. Data from the Southern Ocean were examined closely for regional coherency and a few anomalous d13C values suspected of having productivity overprint were removed. The resulting global d13C distributions and gradients indicate that the deep water circulation was similar during the Holocene and LGM. This interpretation brings d13C data to a better agreement with Cd/Ca data and marks a sharp contrast with a widely held view based on d13C measurements that the glacial Southern Ocean was the terminus of the thermohaline circulation. The proposed presence of glacial North Atlantic Deep Water does not necessarily contradict the postulated presence of Glacial North Atlantic Intermediate Water.

Stable isotope composition of Holocene benthic foraminifers from the Eastern Mediterranean Sea

Temporal and regional changes in paleoproductivity and paleoceanography in the eastern Mediterranean Sea during the past 12 kyr were reconstructed on the basis of the stable oxygen and carbon isotope composition of the epibenthic Planulina ariminensis and the shallow endobenthic Uvigerina mediterranea from three sediment cores of the Aegean Sea and Levantine Basin. The Younger Dryas is characterized by high d18O values, indicating enhanced salinities and low temperatures of deep water masses at all investigated sites. With the onset of the Holocene, d18O records show a continuous decrease towards the onset of sapropel S1 formation, mainly caused by a freshening and warming of surface waters at deep water formation sites. In the middle and late Holocene, the similarity of d18O values from the southern Aegean Sea and Levantine Basin suggests the influence of isotopically identical deep water masses. By contrast, slightly higher d18O values are observed the northern Aegean Sea, which probably point to lower temperatures of North Aegean deep waters. The epifaunal d13C records reveal clear changes in sources and residence times of eastern Mediterranean deep waters associated with period of S1 formation. Available data for the early and late phase of sapropel S1 formation and for the interruption around 8.2 kyr display drops by 0.5 and 1.5 per mil, indicating the slow-down of deep water circulation and enhanced riverine input of isotopically light dissolved inorganic carbon from terrestrial sources into the eastern Mediterranean Sea. The decrease in epifaunal d13C signals is particularly expressed in the southern Aegean Sea and Levantine Basin, while it is less pronounced in the northern Aegean Sea. This points to a strong reduction in deep water exchange rates in the southern areas, but the persistence of local deep water formation in the northern Aegean Sea. The d13C values of U. mediterranea records reveal temporal and regional differences in paleoproductivity during the past 12 kyr, with rather eutrophic and mesotrophic conditions in the North Aegean Sea and southeast Levantine Basin, respectively, while the South Aegean Sea is characterized by rather oligotrophic conditions. After S1 formation, increasing d13C values reflect a progressive decrease in surface water productivity in the eastern Mediterranean Sea during the middle and late Holocene. In the northern Aegean Sea, this time interval is marked by repetitive changes in organic matter fluxes documented by significant fluctuations in the d13C signal of U. mediterranea on millennial- to multi-centennial time scales. These fluctuations can be linked to short-term changes in river runoff driven by northern hemisphere climatic variability.

Heavy metals and carbon isotope concentrations in recent Baltic Sea sediments

Recent sediment cores of the western Baltic Sea were analyzed for heavy metal and carbon isotope contents. The sedimentation rate was determined from radiocarbon dates to be 1.4 mm/yr. The 'recent age' of the sediment was about 850 yr. Within the upper 20 cm of sediment, certain heavy metals became increasingly enriched towards the surface; Cd, Pb, Zn and Cu increased 7-, 4-, 3- and 2-fold, respectively, whereas Fe, Mn, Ni and Co remained unchanged. Simultaneously, the radiocarbon content decreased by about 14 per cent. The enrichment in heavy metals as well as the decrease in the 14C-concentration during the last 130 ± 30yr parallels industrial growth as reflected in European fossil fuel consumption within that same period of time. The near-surface sediments are affected by residues released from fossil fuels at the rate of about 30 g/m**2 yr for the past two decades. The residues have a pronounced effect on the heavy metal and carbon isotope composition of the most Recent sediments allowing estimates to be made for sedimentation, erosion and heavy metal pollution.

The South Atlantic carbon isotope record of planktic foraminifera

We reviewed the paleoceanographic application of the carbon isotope composition of planktic foraminifera. Major controls on the distribution of d13C of dissolved CO2 (d13CSCO2) in the modern ocean are photosynthesis-respiration cycle, isotopic fractionation during air-sea exchange, and circulation. The carbon isotope composition of surface waters is not recorded without perturbations by planktic foraminifera. Besides d13CSCO2 of the surrounding seawater, the d13C composition of planktic foraminifera is affected by vital effects, the water depth of calcification and postdepositional dissolution. We compared several high-resolution (>10cm/ka) carbon isotope records from the Southern Ocean, the Benguela upwelling system, and the tropical Atlantic. In the Southern Ocean, carbon isotope values are about 1.2 per mil lower during the LGM and up to 1.7 per mil lower during the last deglaciation, when compared to the Holocene. These depletions might be explained with a combination of a subsurface nutrient enrichment and reduced air-sea exchange due to an increased stratification of surface waters. In the Benguela Upwelling system, waters originating in the south are upwelled. While the deglacial minimum is transferred and recorded in its full extent in the d13C record of Globigerina bulloides, glacial values show only little changes. This might suggest, that the lower glacial d13C values of high-latitude surface waters are not upwelled off Namibia, or that G. bulloides records post-upwelling conditions, when increased seasonal production has already increased surface-water d13C. Synchronous to the d13C depletions in high latitudes, low d13C values were recorded in Globigerinoides sacculifer during the LGM and during the last deglaciation in the nutrient-depleted western equatorial Atlantic. Hence, part of the glacial-interglacial variability presumably transferred from high to low latitudes seems to be related to changes in thermodynamic fractionation. The variability in d13C is lowest in the northernmost core M35003-4 from the eastern Caribbean, implying that the Antarctic Intermediate Water might have acted as a conduit to transfer the deglacial minimum to tropical surface waters.

Stable isotope composition of atmospheric carbon monoxide : a modelling study

Stable isotope composition of atmospheric carbon monoxide: A modelling study.rnrnThis study aims at an improved understanding of the stable carbon and oxygen isotope composition of the carbon monoxide (CO) in the global atmosphere by means of numerical simulations. At first, a new kinetic chemistry tagging technique for the most complete parameterisation of isotope effects has been introduced into the Modular Earth Submodel System (MESSy) framework. Incorporated into the ECHAM/MESSy Atmospheric Chemistry (EMAC) general circulation model, an explicit treatment of the isotope effects on the global scale is now possible. The expanded model system has been applied to simulate the chemical system containing up to five isotopologues of all carbon- and oxygen-bearing species, which ultimately determine the δ13C, δ18O and Δ17O isotopic signatures of atmospheric CO. As model input, a new stable isotope-inclusive emission inventory for the relevant trace gases has been compiled. The uncertainties of the emission estimates and of the resulting simulated mixing and isotope ratios have been analysed. The simulated CO mixing and stable isotope ratios have been compared to in-situ measurements from ground-based observatories and from the civil-aircraft-mounted CARIBIC−1 measurement platform.rnrnThe systematically underestimated 13CO/12CO ratios of earlier, simplified modelling studies can now be partly explained. The EMAC simulations do not support the inferences of those studies, which suggest for CO a reduced input of the highly depleted in 13C methane oxidation source. In particular, a high average yield of 0.94 CO per reacted methane (CH4) molecule is simulated in the troposphere, to a large extent due to the competition between the deposition and convective transport processes affecting the CH4 to CO reaction chain intermediates. None of the other factors, assumed or disregarded in previous studies, however hypothesised to have the potential in enriching tropospheric CO in 13C, were found significant when explicitly simulated. The inaccurate surface emissions, likely underestimated over East Asia, are responsible for roughly half of the discrepancies between the simulated and observed 13CO in the northern hemisphere (NH), whereas the remote southern hemisphere (SH) compositions suggest an underestimated fractionation during the oxidation of CO by the hydroxyl radical (OH). A reanalysis of the kinetic isotope effect (KIE) in this reaction contrasts the conventional assumption of a mere pressure dependence, and instead suggests an additional temperature dependence of the 13C KIE, which is driven by changes in the partitioning of the reaction exit channels. This result is yet to be confirmed in the laboratory.rnrnApart from 13CO, for the first time the atmospheric distribution of the oxygen mass-independent fractionation (MIF) in CO, Δ17O, has been consistently simulated on the global scale with EMAC. The applicability of Δ17O(CO) observations to unravelling changes in the tropospheric CH4-CO-OH system has been scrutinised, as well as the implications of the ozone (O3) input to the CO isotope oxygen budget. The Δ17O(CO) is confirmed to be the principal signal for the CO photochemical age, thus providing a measure for the OH chiefly involved in the sink of CO. The highly mass-independently fractionated O3 oxygen is estimated to comprise around 2% of the overall tropospheric CO source, which has implications for the δ18O, but less likely for the Δ17O CO budgets. Finally, additional sensitivity simulations with EMAC corroborate the nearly equal net effects of the present-day CH4 and CO burdens in removing tropospheric OH, as well as the large turnover and stability of the abundance of the latter. The simulated CO isotopologues nonetheless hint at a likely insufficient OH regeneration in the NH high latitudes and the upper troposphere / lower stratosphere (UTLS).rn

Carbon and oxygen stable isotope composition of bulk sediment and abundance of Braarudospahaera in ODP Site 122-762 (Table 1)

Nannofossil assemblages enriched in Braarudosphaera occur in lower Oligocene to lower Miocene sediments at Ocean Drilling Program Sites 762 and 763 on the central Exmouth Plateau. Braarudosphaerids appear here rather abruptly in the lower Oligocene (in Zone NP21). They reach their greatest numbers in the lower Oligocene (in Zones NP22 and NP23), where they comprise up to 10% of some samples. Braarudosphaera bigelowii is the overwhelmingly dominant species, occurring together with rare specimens of B. discula and Micrantholithus pinguis. The holococcoliths Peritrachelina joidesa and Lantemithus minutus are also associated with the Braarudosphaera enrichment. There are two populations of B. bigelowii: one of normal size (10-14 µm) and one of large specimens (20-22 µm). The larger braarudosphaerids are more common than the smaller forms. Braarudosphaera-rich sediments are absent at Wombat Plateau sites during the same time interval. We attribute this to latitudinal control, because the Wombat sites are about 4° north of the central Exmouth Plateau sites. We believe that the occurrence of braarudosphaerids is related to an Oligocene to early Miocene oceanographic event on the Exmouth Plateau. We suspect that mid-ocean up welling of cool, low-salinity, nutrient-rich water along a divergent zone created the Braarudosphaera-nch sediments in the South Atlantic and Indian oceans.

Stable carbon and oxygen isotope composition of Late Cretaceous benthic foraminifera from the southern South Atlantic

The stable carbon and oxygen isotope composition of different benthic foraminiferal species of the latest Campanian and earliest Maastrichtian from Ocean Drilling Project Hole 690C (Weddell Sea, southern South Atlantic, ~1800 m paleowater depth) have been investigated. The total range of measured isotope values of all samples exceeds ~4 per mil for delta 13C and 1.1 per mil for delta 18O. Carbon isotope values of proposed deep infaunal species are generally similar or only slightly lower when compared to proposed epifaunal to shallow infaunal species. Interspecific differences vary between samples probably reflecting temporal changes in organic carbon fluxes to the sea floor. Constantly lower delta 13C values for Pullenia marssoni and Pullenia reussi suggest the deepest habitat for these species. The strong depletion of delta 13C values by up to 3 per mil within lenticulinids may be attributed to a deep infaunal microhabitat, strong vital effects, or different feeding strategy when compared to other species or modern lenticulinids. The mean delta 18O values reveal a strong separation of epifaunal to shallow infaunal and deep infaunal species. Epifaunal to shallow infaunal species are characterized by low delta 18O values, deep infaunal species by higher values. This result possibly reflects lower metabolic rates and longer life cycles of deep infaunal species or the operating of a pore water [CO3]2- effect on the benthic foraminiferal stable isotopes. Pyramidina szajnochae shows an enrichment of oxygen isotopes with test size comprising a total of 0.6 per mil between 250 and 1250 µm shell size. Although delta 13C lacks a corresponding trend these data likely represent the presence of changes in metabolic rates during ontogenesis. These results demonstrate the general applicability of multi-species stable isotope measurements of pristine Cretaceous benthic foraminifera to reconstruct past microhabitats and to evaluate biological and environmental effects on the stable isotope composition.