Organic geochemistry of sediments from North Alex Mud Vulcano

Hydrocarbon seeps are ubiquitous at gas-prone Cenozoic deltas such as the Nile Deep Sea Fan (NDSF) where seepage into the bottom water has been observed at several mud volcanoes (MVs) including North Alex MV (NAMV). Here we investigated the sources of hydrocarbon gases and sedimentary organic matter together with biomarkers of microbial activity at four locations of NAMV to constrain how venting at the seafloor relates to the generation of hydrocarbon gases in deeper sediments. At the centre, high upward flux of hot (70 °C) hydrocarbon-rich fluids is indicated by an absence of biomarkers of Anaerobic Oxidation of Methane (AOM) and nearly constant methane (CH4) concentration depth-profile. The presence of lipids of incompatible thermal maturities points to mixing between early-mature petroleum and immature organic matter, indicating that shallow mud has been mobilized by the influx of deep-sourced hydrocarbon-rich fluids. Methane is enriched in the heavier isotopes, with values of d13C ~-46.6 per mil VPDB and dD ~-228 per mil VSMOW, and is associated with high amounts of heavier homologues (C2+) suggesting a co-genetic origin with the petroleum. On the contrary at the periphery, a lower but sustained CH4 flux is indicated by deeper sulphate-methane transition zones and the presence of 13C-depleted biomarkers of AOM, consistent with predominantly immature organic matter. Values of d13C-CH4 ~-60 per mil VPDB and decreased concentrations of 13C-enriched C2+ are typical of mixed microbial CH4 and biodegraded thermogenic gas from Plio-Pleistocene reservoirs of the region. The maturity of gas condensate migrated from pre-Miocene sources into Miocene reservoirs of the Western NDSF is higher than that of the gas vented at the centre of NAMV, supporting the hypothesis that it is rather released from the degradation of oil in Neogene reservoirs. Combined with the finding of hot pore water and petroleum at the centre, our results suggest that clay mineral dehydration of Neogene sediments, which takes place posterior to reservoir filling, may contribute to intense gas generation at high sedimentation rate deltas.

A comparison between multi-proxy and historical data of drift-ice conditions on the East Greenland shelf

The reduction in sea ice along the SE Greenland coast during the last century has severely impacted ice-rafting to this area. In order to reconstruct ice-rafting and oceanographic conditions in the area of Denmark Strait during the last ~150 years, we conducted a multiproxy study on three short (20 cm) sediment cores from outer Kangerdlugssuaq Trough (~300 m water depth). The proxy-based data obtained have been compared with historical and instrumental data to gain a better understanding of the ice sheet-ocean interactions in the area. A robust chronology has been developed based on 210Pb and 137Cs measurements on core PO175GKC#9 (~66.2°N, 32°W) and expanded to the two adjacent cores based on correlations between calcite weight percent records. Our proxy records include sea-ice and phytoplankton biomarkers, and a variety of mineralogical determinations based on the <2 mm sediment fraction, including identification with quantitative x-ray diffraction, ice-rafted debris counts on the 63-150 µm sand fraction, and source identifications based on the composition of Fe oxides in the 45-250 µm fraction. A multivariate statistical analysis indicated significant correlations between our proxy records and historical data, especially with the mean annual temperature data from Stykkishólmur (Iceland) and the storis index (historical observations of sea-ice export via the East Greenland Current). In particular, the biological proxies (calcite weight percent, IP25, and total organic carbon %) showed significant linkage with the storis index. Our records show two distinct intervals in the recent history of the SE Greenland coast. The first of these (ad 1850-1910) shows predominantly perennial sea-ice conditions in the area, while the second (ad 1910-1990) shows more seasonally open water conditions.

Radiocarbon ages and 230Th data of five sediment cores from the Björn and Gardar Drift, North Atlantic

In locations of rapid sediment accumulation receiving substantial amounts of laterally transported material the timescales of transport and accurate quantification of the transported material are at the focus of intense research. Here we present radiocarbon data obtained on co-occurring planktic foraminifera, marine haptophyte biomarkers (alkenones) and total organic carbon (TOC) coupled with excess Thorium-230 (230Thxs) measurements on four sediment cores retrieved in 1649-2879 m water depth from two such high accumulation drift deposits in the Northeast Atlantic, Björn and Gardar Drifts. While 230Thxs inventories imply strong sediment focussing, no age offsets are observed between planktic foraminifera and alkenones, suggesting that redistribution of sediments is rapid and occurs soon after formation of marine organic matter, or that transported material contains negligible amounts of alkenones. An isotopic mass balance calculation based on radiocarbon concentrations of co-occurring sediment components leads us to estimate that transported sediment components contain up to 12% of fossil organic matter that is free of or very poor in alkenones, but nevertheless appears to consist of a mixture of fresh and eroded fossil material. Considering all available constraints to characterize transported material, our results show that although focussing factors calculated from bulk sediment 230Thxs inventories may allow useful approximations of bulk redeposition, they do not provide a unique estimate of the amount of each laterally transported sediment component. Furthermore, our findings provide evidence that the occurrence of lateral sediment redistribution alone does not always hinder the use of multiple proxies but that individual sediment fractions are affected to variable extents by sediment focussing.

Dissolved organic matter in the Lena River Delta Region, Siberia, Russia

Connectivity between the terrestrial and marine environment in the Artic is changing as a result of climate change, influencing both freshwater budgets and the supply of carbon to the sea. This study characterizes the optical properties of dissolved organic matter (DOM) within the Lena Delta region and evaluates the behavior of DOM across the fresh water-marine gradient. Six fluorescent components (four humic-like; one marine humic-like; one protein-like) were identified by Parallel Factor Analysis (PARAFAC) with a clear dominance of allochthonous humic-like signals. Colored DOM (CDOM) and dissolved organic carbon (DOC) were highly correlated and had their distribution coupled with hydrographical conditions. Higher DOM concentration and degree of humification were associated with the low salinity waters of the Lena River. Values decreased towards the higher salinity Laptev Sea shelf waters. Results demonstrate different responses of DOM mixing in relation to the vertical structure of the water column, as reflecting the hydrographical dynamics in the region. Two mixing curves for DOM were apparent. In surface waters above the pycnocline there was a sharper decrease in DOM concentration in relation to salinity indicating removal. In the bottom water layer the DOM decrease within salinity was less. We propose there is a removal of DOM occurring primarily at the surface layer, which is likely driven by photodegradation and flocculation.

Cloride and bromide concentrations and Br-/Cl- molar ratios in pore fluids at ODP Site 134-833

Other than halite diagenesis and organic matter degradation, Cl- and Br- are considered to be conservative in marine pore fluids. Consequently, Br-/Cl- ratios should remain constant during most diagenetic reactions. Nonetheless, Br-/Cl- molar ratios decrease to 0.00127 (~18% less than seawater value) in pore fluids from Site 833 in the Aoba Basin of the New Hebrides convergent margin despite the lack of halite diagenesis and little organic matter. Sediment at this site is largely volcanic ash, which becomes hydrated with depth as it converts to clay and zeolite minerals. These hydration reactions remove sufficient water to increase the concentrations of most solutes including Cl- and Br-. The resulting concentration gradients drive diffusion, but calculations indicate that diffusion does not decrease the Br-/Cl- ratio. Some Cl- may be leached from the ash, but insufficient amounts are available to cause the observed decrease in Br-/Cl- ratio. The limited source of Cl- suggests that proportionately more Br- than Cl- is lost from the fluids to the diagenetic solids. Similar nonconservative behavior of Cl- and Br- may occur during fluid circulation at ridge crests and flanks, thereby influencing the halide distribution in the crust.

Diagenetic alteration of organic matter in DSDP Leg 57 Holes

I analyzed Leg 57 sediments organogeochemically and spectroscopically. Organic carbon and extractable organic matter prevail from the Pliocene to the Miocene. Humic acids occur widely from the Pleistocene to the lower Miocene and one portion of the Oligocene. The absence of humic acids in Oligocene and Cretaceous samples suggests that humic acids had changed to kerogen. Visible spectroscopic data reveal that humic acids in this study have a low degree of condensed aromatic-ring system, which is a feature of anaerobic conditions during deposition, and that chlorophyll derivatives that had at first combined with humic acids moved to the solvent- soluble fraction during diagenesis. The elemental compositions of humic acids show high H/C and O/C ratios, which seem appropriate to a stage before transformation to kerogen. The relation between the linewidths and g-values on the electron spin resonance data indicates that the free radicals in humic acids are quite different from those in kerogen. The low spin concentrations of kerogen and the yields of humic acids up to the lower Miocene demonstrate that organic matter in these sediments is immature. The foregoing indicate the necessity to isolate humic acids even in ancient rocks in the study of kerogen.

Phosphorus concentrations and accumulation rates of ODP Leg 130 sites

Little is known about the fluxes to and from the ocean during the Cenozoic of phosphorus (P), a limiting nutrient for oceanic primary productivity and organic carbon burial on geologic timescales. Previous studies have concluded that dissolved river fluxes increased worldwide during the Cenozoic and that organic carbon burial decreased relative to calcium carbonate burial and perhaps in absolute terms as well. To examine the apparent contradiction between increased river fluxes of P (assuming P fluxes behave like the others) expected to drive increased organic carbon burial and observations indicating decreased organic carbon burial, we determined P accumulation rates for equatorial Pacific sediments from Ocean Drilling Program leg 138 sites in the eastern equatorial Pacific and leg 130 sites on the Ontong Java Plateau in the western equatorial Pacific. Although there are site specific and depth dependent effects on P accumulation rates, there are important features common to the records at all sites. P accumulation rates declined from 50 to 20 Ma, showed some variability from 20 to 10 Ma, and had a substantial peak from 9 to 3 Ma centered at 5-6 Ma. These changes in P accumulation rates for the equatorial Pacific are equivalent to substantial changes in the P mass balance. However, the pattern resembles neither that of weathering flux indicators (87Sr/86Sr and Ge/Si ratios) nor that of the carbon isotope record reflecting changes in organic carbon burial rates. Although these P accumulation rate patterns need confirmation from other regions with sediment burial significant in global mass balances (e.g., the North Pacific and Southern Ocean), it appears that P weathering inputs to the ocean are decoupled from those of other elements and that further exploration is needed of the relationship between P burial and net organic carbon burial.

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.

Abundance of bacteria, cyanobacteria and nanoflagellates at sime series station DYNAPROC

The variability in microbial communities (abundance and biomass), bacterial production and ectoaminopeptidase activity, particulate and dissolved organic carbon (POC, DOC), and particulate and dissolved lipids was examined in spring 1995 in the northwestern Mediterranean, where a transition from the end of a bloom to pre-oligotrophic conditions was observed. Four time series of 36 h each and 4 h sampling intervals were performed at 5 m and at the chlorophyll maximum (30 m) between 11 and 31 May. Simultaneous measurements of pigments, abundance of hetero- and autotrophic flagellates, bacteria and POC enabled the estimation of living POC (defined as autotrophic-C plus heterotrophic-C biomass), and thus the detrital organic carbon. During the first 2 time series (11 to 15 May), the bacterial-C biomass was higher than the autotrophic-C biomass at 5 m (ratio 1.4 and 1.7), whereas the opposite trend was observed in the chlorophyll peak (ratio 0.7 for the first cycle). However, at the end of May, autotrophic-C biomass was equivalent to bacterial-C biomass at both depths studied. The detrital pool remained a more or less constant fraction of the POC (52, 53 and 47% on 11-12 May, 14-15 May and 30-31 May) at the chlorophyll peak, whereas it decreased significantly with time (62 to 53%) at 5 m. Relationships between bacterial activities and evolution of available resources were not systematically evidenced from our 36 h diel cycle data. Nevertheless, at the monthly scale, comparison of bacterial carbon demand (BCD) to potential carbon resources (detrital POC and DOC) showed that bacteria fed differently on the various pools. From ectoaminopeptidase turnover rates and detrital POC, the potential hydrolysis rate of detritus was calculated. Depending on the choice of conversion factors for bacterial production and estimates of hydrolysis turnover rates, it was shown that bacterial hydrolysis of detritus could be one of the DOC accumulation sources. We observed that the percentage of BCD supplied by detrital POC hydrolysis increased in the surface and decreased in the chlorophyll peak. An index of lipid degradation in POC, the lipolysis index, increased during the month at 5 m, also indicating a higher hydrolysis of POC. The opposite trend was observed in the chlorophyll maximum layer. The selective decrease in dissolved lipids in DOC in the chlorophyll maximum layer, particularly free fatty acids, also suggests that bacteria utilized increased fractions of carbon sources from the DOC. We concluded that partitioning between DOC and detritus as resources for bacteria can change during the rapid transition period from mesotrophy to oligotrophy in the northwestern Mediterranean.

Geochemistry of ODP Sites 123-765 and 123-766

The sediments of the Argo and Gascoyne abyssal plains are generally lean in organic matter, are immature, and contain hydrocarbons trapped during sediment deposition rather than those generated during sediment catagenesis. TOC concentrations in the Argo Abyssal Plain Cenozoic sediments are 0.5 wt%, and organic matter appears to be from mixed marine and reworked, degraded, organic matter sources, with the latter being contributed by turbidity flows from the nearby continental margin. TOC concentrations within the Cenozoic sediments of the Gascoyne Abyssal Plain are mostly undetectable (<0.1 wt%). Biomarker distributions determined by gas chromatography (GC) and gas chromatography-mass spectrometry (GCMS) indicate that organic matter extracted from the Lower Cretaceous sediments from both sites is predominantly marine with varying contributions from terrestrial organic matter. The specific marine biomarker, 24-n-propylcholestane is in relatively high abundance in all samples. In addition, the relatively high abundance of the 4-methylsteranes with the 23,24-dimethyl side chain (in all samples) indicates significant dinoflagellate contributions and marine organic matter. The ratios of n-C27/n-C17 reflect relative contributions of marine vs. terrestrial organic matter. TOC, while generally low at Argo, is relatively high near the Barremian/Aptian boundary (one sample has a TOC of 5.1 wt%) and the Aptian/Albian boundary (up to 1.3 wt% TOC), and two samples from the Barremian and Aptian sections contain relatively high proportions of terrestrial organic carbon. TOC values in the Lower Cretaceous sediments from Gascoyne Abyssal Plain are low (<0.1 wt%) near the Aptian/Barremian boundary. TOC values are higher in older sediments, with maxima in the upper Barremian (1.02 wt%), the Barremian/Hauterivian (0.6 wt%), and Valanginian (1.8 wt%). Sediments from the upper Barremian contain higher amounts of terrestrial organic carbon than older sediments.

Organic geochemistry of two sediment cores from the Kara Sea

Within the Russian-German research project on "Siberian River Run-off (SIRRO)" devoted to the freshwater discharge and its influence on biological, geochemical, and geological processes in the Kara Sea, sedimentological and organic-geochemical investigations were carried-out on two well-dated sediment cores from the Yenisei Estuary area. The main goal of this study was to quantify the terrigenous organic carbon accumulation based on biomarker and bulk accumulation rate data, and its relationship to Yenisei river discharge and climate change through Holocene times. The biomarker data at both cores clearly indicate the predominance of terrigenous organic matter, reaching 70 to 100% and 50 to 80% of the total organic carbon within and directly north of the estuary, respectively. During the last about 9 Cal. kyrs. BP represented in the studied sediment section, siliciclastic sediment and (terrigenous) organic carbon input was strongly influenced by postglacial sea-level rise and climate-related changes in river discharge. The mid-Holocene Climatic Optimum is documented by maximum river discharge between 8.2 and 7.3 Cal. kyrs. BP. During the last 2000 years river discharge probably became reduced, and accumulation of both terrigenous and marine organic carbon increased due to increased coagulation of fine-grained material.

Iron and manganese in bottom sediments and interstitial waters sampled in the White Sea on August 21-30, 2003

Iron and manganese in bottom sediments studied along the sublatitudinal transect from Kandalaksha to Arkhangelsk are characterized by various contents and speciations depending on sedimentation environment, grain size of sediments, and diagenetic processes. The latter include redistribution of reactive forms leading to enrichment in Fe and Mn of surface sediments, formation of films, incrustations, and ferromanganese nodules. Variations in total Fe content (2-8%) are accompanied by changes in concentration of its reactive forms (acid extraction) and concentration of dissolved Fe in interstitial waters (1-14 µM). Variations in Mn content in bottom sediments (0.03-3.7%) and interstitial waters (up to 500 µM) correspond to high diagenetic mobility of this element. Changes in oxidation degree of chemical elements result in redox stratification of sediment strata with maximum concentrations of Fe, Mn, and sulfides. Organic matter of bottom sediments with considerable terrestrial constituent is oxidized by bottom water oxygen mainly at the sediment surface or in anaerobic conditions within the sediment strata. The role of inorganic components in organic matter oxidation changes from surface layer bottom sediments (where manganese oxyhydroxide dominates among oxidants) to deeper layers (where sulfate of interstitial water serves as the main oxidant). Differences in river runoff and hydrodynamics are responsible for geochemical asymmetry of the transect. The deep Kandalaksha Bay serves as a sediment trap for manganese (Mn content in sediments varies within 0.5-0.7%), whereas the sedimentary environment in the Dvina Bay promotes its removal from bottom sediments (Mn 0.05%).

Age determination and n-Alkane concentration of Arctic Ocean sediment cores

We have reconstructed the surface water environment of the Arctic Ocean over the last ? 50,000 years using measurements of the organic nitrogen and carbon isotope ratios, carbonate and total organic carbon concentrations (TOC), and terrestrial biomarkers (lignin and long-chain n-alkanes) in four multicores. Variations in nitrogen isotope ratios that are concordant with TOC and carbonate concentrations (representing foraminifera and excluding ice-rafted-debris) reflect differences in relative nutrient utilization of phytoplankton in the surface waters. However, d15N variations also appear to be dependent on the stratification of the water column and therefore potentially track the exchange of nutrients between deep and surface waters. Low Last Glacial Maximum (LGM) d15N values and higher Holocene values are opposite to those recorded in the Southern Ocean. The Arctic Ocean with higher nutrient utilization today compared to the LGM therefore acts as a counterpart to the Southern Ocean, although the global impact on carbon dioxide variations compared to the Southern Ocean is probably low.

Benthic foraminiferal fauna and isotope record in Holocene sediments of the northwest Indian Ocean

Historically, the Holocene has been considered an interval of relatively stable climate. However, recent studies from the northern Arabian Sea (Netherlands Indian Ocean Program 905) suggested high-amplitude climate shifts in the early and middle Holocene based on faunal and benthic isotopic proxy records. We examined benthic foraminiferal faunal and stable isotopic data from Ocean Drilling Program (ODP) Site 723 and total organic carbon data from ODP Site 724, Oman Margin (808 and 593 m water depths, respectively). At Site 723 the mid-Holocene shift in d18O values of infaunal benthic species Uvigerina peregrina (1.4 per mil) is 3 times larger than that of epifaunal benthic species Cibicides kullenbergi recorded at Site NIOP 905 off Somalia. However, none of the five other benthic species we measured at Hole 723A exhibits such a shift in d18O. We speculate that the late Holocene d18O decrease in U. peregrina represents species-specific changes in ecological habitat or food preference in response to changes in surface and deep ocean circulation. While the stable isotopic data do not appear to indicate a middle Holocene climatic shift, our total organic carbon and benthic faunal assemblage data do indicate that the early Holocene deep Arabian Sea was influenced by increased ventilation perhaps by North Atlantic Deep Water and/or Circumpolar Deep Water incursions into the Indian Ocean, leading to remineralization of organic matter and a relatively weak early Holocene oxygen minimum zone in the northwest Arabian Sea in spite of strong summer monsoon circulation.