14C specific radiocarbon ages and bulk ages accompanied by geochemical proxys from surface sediment samples in the Black Sea

Transfer of organic carbon (OC) from the terrestrial to the oceanic carbon pool is largely driven by riverine and aeolian transport. Before transport, however, terrigenous organic matter can be retained in intermediate terrestrial reservoirs such as soils. Using compound-specific radiocarbon analysis of terrigenous biomarkers their average terrestrial residence time can be evaluated. Here we show compound-specific radiocarbon (14C) ages of terrigenous biomarkers and bulk 14C ages accompanied by geochemical proxy data from core top samples collected along transects in front of several river mouths in the Black Sea. 14C ages of long chain n-alkanes, long chain n-fatty acids and total organic carbon (TOC) are highest in front of the river mouths, correlating well with BIT (branched and isoprenoid tetraether) indices, which indicates contribution of pre-aged, soil-derived terrigenous organic matter. The radiocarbon ages decrease further offshore towards locations where organic matter is dominated by marine production and aeolian input potentially contributes terrigenous organic matter. Average terrestrial residence times of vascular plant biomarkers deduced from n-C29+31 alkanes and n-C28+30 fatty acids ages from stations directly in front of the river mouths range from 900 ± 70 years to 4400 ± 170 years. These average residence times correlate with size and topography in climatically similar catchments, whereas the climatic regime appears to control continental carbon turnover times in morphologically similar drainage areas of the Black Sea catchment. Along-transect data imply petrogenic contribution of n-C29+31 alkanes and input via different terrigenous biomarker transport modes, i.e., riverine and aeolian, resulting in aged biomarkers at offshore core locations. Because n-C29+31 alkanes show contributions from petrogenic sources, n-C28+30 fatty acids likely provide better estimates of average terrestrial residence times of vascular plant biomarkers. Moreover, sedimentary n-C28 and n-C30 fatty acids appear clearly much less influenced by autochthonous sources than n-C24 and n-C26 fatty acids as indicated by increasing radiocarbon ages with increasing chain-length and are, thus, more representative as vascular plant biomarkers.

Alkenones in surface waters of the Nordic seas

Samples of filtered particulate organic matter (POM) were obtained during the summers of 1999 and 2000 from the surface waters of the Nordic seas to monitor the spatial distribution of long-chain alkenones. The aim of the study was to appraise existing alkenone-based climatic proxies in northern high latitudes. Unusually high percentages of the tetraunsaturated alkenone were measured in the polar waters of the East Greenland Current, with C37:4 of up to 77% in 80% of sea-ice cover. Values of percent C37:4 across the Nordic seas showed a strong association with water mass type. Analysis of coccoliths in filters indicated that calcified Emiliania huxleyi could not be discounted as the biological precursor of alkenones in all the water masses. A combined data set of 69 samples of POM revealed a stronger correlation of percent C37:4 to sea surface salinity (SSS; R2 = 0.72) than to sea surface temperature (SST; R2 = 0.50). Values of percent C37:4 in sea surface POM were much higher than those in surficial sediments of the northern North Atlantic. To explain the discrepancy in sedimentary and surface water column percent C37:4, we propose that the alkenone contents in surface sediments underlying arctic and polar waters are a combination of autochthonous and allochthonous inputs of alkenones. Our results show that percent C37:4 can be used to reconstruct the relative extension of arctic/polar water masses in the North Atlantic. However, the results prevent confirmation of percent C37:4 as a paleo-SSS proxy in the Nordic seas, given its multivariate nature in our data set and the decoupling between its range of values in surface waters and sediments.

Specific microbial biomarker signatures from Congo fan sediments of ODP site 175-1075, Congo soils, wetland and estuary sediments

Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30 per mil to -40 per mil for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential of aminoBHPs, in particular aminopentol, to trace and, once better calibrated and understood, quantify past methane sources and fluxes from terrestrial and potentially also marine sources.

Isotopic ratios of methane, ethane, carbon dioxide, inorganic carbon and organic matter from ODP Leg 164 sites

The isotopic characteristics of CH4 (d13C values range from -101.3 per mil to -61.1 per mil PDB, and dD values range from -256 per mil to -136 per mil SMOW) collected during Ocean Drilling Program (ODP) Leg 164 indicate that the CH4 was produced by microbial CO2 reduction and that there is not a significant contribution of thermogenic CH4 to the sampled sediment gas from the Blake Ridge. The isotopic values of CO2 (d13C range -20.6 per mil to +1.24 per mil PDB) and dissolved inorganic carbon (DIC; d13C range -37.7 per mil to +10.8 per mil PDB) have parallel profiles with depth, but with an offset of 12.5 per mil. Distinct downhole variations in the carbon isotopic composition of CH4 and CO2 cannot be explained by closed-system fractionation where the CO2 is solely derived from the locally available sedimentary organic matter (d13C -2.0 per mil ± 1.4 per mil PDB) and the CH4 is derived from CO2 reduction. The observed isotopic profiles reflect the combined effects of upwards gas migration and decreased microbial activity with depth.

Stable isotope ratios of foraminifera and sea surface temperature estimation of sediment core W2804A-14

Carbon isotopically based estimates of CO2 levels have been generated from a record of the photosynthetic fractionation of 13C (epsilon p) in a central equatorial Pacific sediment core that spans the last ~255 ka. Contents of 13C in phytoplanktonic biomass were determined by analysis of C37 alkadienones. These compounds are exclusive products of Prymnesiophyte algae which at present grow most abundantly at depths of 70-90 m in the central equatorial Pacific. A record of the isotopic compostion of dissolved CO2 was constructed from isotopic analyses of the planktonic foraminifera Neogloboquadrina dutertrei, which calcifies at 70-90 m in the same region. Values of epsilon p, derived by comparison of the organic and inorganic delta values, were transformed to yield concentrations of dissolved CO2 (c e) based on a new, site-specific calibration of the relationship between epsilon p and c e. The calibration was based on reassessment of existing epsilon p versus c e data, which support a physiologically based model in which epsilon p is inversely related to c e. Values of PCO2, the partial pressure of CO2 that would be in equilibrium with the estimated concentrations of dissolved CO2, were calculated using Henry's law and the temperature determined from the alkenone-unsaturation index UK 37. Uncertainties in these values arise mainly from uncertainties about the appropriateness (particularly over time) of the site-specific relationship between epsilon p and 1/c e. These are discussed in detail and it is concluded that the observed record of epsilon p most probably reflects significant variations in Delta pCO2, the ocean-atmosphere disequilibrium, which appears to have ranged from ~110 µatm during glacial intervals (ocean > atmosphere) to ~60 µatm during interglacials. Fluxes of CO2 to the atmosphere would thus have been significantly larger during glacial intervals. If this were characteristic of large areas of the equatorial Pacific, then greater glacial sinks for the equatorially evaded CO2 must have existed elsewhere. Statistical analysis of air-sea pCO2 differences and other parameters revealed significant (p < 0.01) inverse correlations of Delta pCO2 with sea surface temperature and with the mass accumulation rate of opal. The former suggests response to the strength of upwelling, the latter may indicate either drawdown of CO2 by siliceous phytoplankton or variation of [CO2]/[Si(OH)4] ratios in upwelling waters.

Organic d13C values, kerogen atomic C/N ratios and relative weights of some kerogen pyrolysis products of ODP Hole 112-682A (Table 1)

Carbon isotopic composition of predominantly marine kerogen in latest Oligocene mudstones of the Peru Margin ODP 682A Hole shows an about 3.5? increase with decreasing age. Py-GC and elemental (C=N ratio) analysis of the kerogen plus sulphur isotopic study together with earlier knowledge on geological setting and organic geochemistry results in a better understanding of depositionary environment and allows to separation of the influence of concentration of water dissolved carbon dioxide (ce) on kerogen delta13C from that of other factors (bacterial degradation, sea surface temperature, DIC delta13C, productivity, and admixture of land plant OM). Based on this analysis, the major part of the kerogen shift is considered as a result of the latest Oligocene decrease of marine photosynthetic carbon isotopic fractionation in the Peru Margin photic zone, which in turn possibly reflects a simultaneous drop in atmospheric CO2 level. Uncertainties in the evaluation of the factors affecting the marine photosynthetic carbon isotopic fractionation and the extent of ocean-atmosphere disequilibrium do not permit calculation of the decrease of the atmospheric CO2.

AMS C-14 ages of coretops collected on RRS Charles Darwin cruise CD159, July 2004, N. Atlantic, for the NERC RAPID programme

Material and data were collected at 41 sites in the subpolar North Atlantic Ocean between Scotland and Newfoundland, during the RRS CharlesDarwin CD159 cruise in July 2004 (McCave, 2005). Sites were selected to reflect the major inputs of water that becomes the North Atlantic Deep Water (NADW); the Iceland-Scotland Overflow Water (ISOW), the Denmark Strait Overflow Water (DSOW) and the Labrador Sea Water (LSW). Areas cored were the south Iceland Rise, SE Greenland slope/rise and Eirik Drift, and the Labrador margin. A total of 29 box cores, 19 piston cores, 6 kasten cores, 9 short gravity cores and 20 CTD casts as well as 28 surface water samples were collected during the cruise. Here we present sediment core-top sample ages. The cores were sampled at 1 or 0.5 cm intervals and we used the top 1 or 2 cm, depending on availability of foraminifera in the samples. Sediment samples were disaggregated on an end-over-end wheel, wet sieved at >63 um, and dry sieved to 63-150 and >150 um. Accelerator Mass Spectrometer (AMS) radiocarbon dating was done for each core top based on between 900-1600 monospecific planktonic foraminifera (Globigerina bulloides or Neogloboquadrina pachyderma (sinistral)). All dates were of modern or late Holocene age except site RAPID-08-5B (9806 ± 38 uncorrected 14C years BP) and site RAPID-14-10B (11543 ± 40 uncorrected 14C years BP). The >150 um fraction was split until approximately 300 foraminifera remained and counted for number of lithic grains, benthic foraminifera, planktonic foraminifera and foraminifera fragments. In all but the shallowest sample (Greenland rise, 761m water depth) benthic foraminifera constituted less than 2% of the total >150 um fraction of the sample.

(Table 2) Stable carbon and nitrogen isotope ratios and molar C/N ratio for euchaetid and aetideid copepods during POLARSTERN cruise ANT-XXIII/5

Stable isotope (SI) ratios of carbon (d13C) and nitrogen (d15N) were measured in omnivorous and carnivorous deep-sea copepods of the families Euchaetidae and Aetideidae across the Atlantic sector of the Southern Ocean to establish their trophic positions. Due to high and variable C/N ratios related to differences in lipid content, d13C was corrected using a lipid-normalisation model. d15N signals ranged from 3.0-6.9 per mil in mesopelagic species to 7.0-9.5 per mil in bathypelagic congeners. Among the carnivorous Paraeuchaeta species, the epi- to mesopelagic species Paraeuchaeta antarctica had lower d15N values than the mesopelagic P. rasa and bathypelagic P. barbata. The same trend was observed among omnivorous Aetideidae, but was not significant. In the most abundant species P. antarctica, individuals from the western Atlantic had higher d13C and d15N values than specimens at the eastern stations. These longitudinal changes in d13C and d15N values were attributed to regional differences in hydrography and sea surface temperature (SST), in particular related to a northward extension of the Antarctic Polar Front (APF) at the easternmost stations. The results indicate that even in a mesopelagic carnivorous species, the changes in surface stable isotope signatures are pronounced.