Stable isotope analysis and biomarkers of carbonates from the Columbia River in southwestern Washington, USA

Exotic limestone masses with silicified fossils, enclosed within deep-water marine siliciclastic sediments of the Early to Middle Miocene Astoria Formation, are exposed along the north shore of the Columbia River in southwestern Washington, USA. Samples from four localities were studied to clarify the origin and diagenesis of these limestone deposits. The bioturbated and reworked limestones contain a faunal assemblage resembling that of modern and Cenozoic deep-water methane-seeps. Five phases make up the paragenetic sequence: (1) micrite and microspar; (2) fibrous, banded and botryoidal aragonite cement, partially replaced by silica or recrystallized to calcite; (3) yellow calcite; (4) quartz replacing carbonate phases and quartz cement; and (5) equant calcite spar and pseudospar. Layers of pyrite frequently separate different carbonate phases and generations, indicating periods of corrosion. Negative d13Ccarbonate values as low as -37.6 per mill V-PDB reveal an uptake of methane-derived carbon. In other cases, d13Ccarbonate values as high as 7.1 per mill point to a residual, 13C-enriched carbon pool affected by methanogenesis. Lipid biomarkers include 13C-depleted, archaeal 2,6,10,15,19-pentamethylicosane (PMI; d13C: -128 per mill), crocetane and phytane, as well as various iso- and anteiso-carbon chains, most likely derived from sulphate-reducing bacteria. The biomarker inventory proves that the majority of the carbonates formed as a consequence of sulphate-dependent anaerobic oxidation of methane. Silicification of fossils and early diagenetic carbonate cements as well as the precipitation of quartz cement - also observed in other methane-seep limestones enclosed in sediments with abundant diatoms or radiolarians - is a consequence of a preceding increase of alkalinity due to anaerobic oxidation of methane, inducing the dissolution of silica skeletons. Once anaerobic oxidation of methane has ceased, the pH drops again and silica phases can precipitate.

Grain-size distribution, sedimentation rate and x-ray fluorescence data of four sediment cores off the Senegal River estuary

Fine-grained sediment depocenters on continental shelves are of increased scientific interest since they record environmental changes sensitively. A north-south elongated mud depocenter extends along the Senegalese coast in mid-shelf position. Shallow-acoustic profiling was carried out to determine extent, geometry and internal structures of this sedimentary body. In addition, four sediment cores were retrieved with the main aim to identify how paleoclimatic signals and coastal changes have controlled the formation of this mud depocenter. A general paleoclimatic pattern in terms of fluvial input appears to be recorded in this depositional archive. Intervals characterized by high terrigenous input, high sedimentation rates and fine grain sizes occur roughly contemporaneously in all cores and are interpreted as corresponding to intensified river discharge related to more humid conditions in the hinterland. From 2750 to 1900 and from 1000 to 700 cal a BP, wetter conditions are recorded off Senegal, an observation which is in accordance with other records from NW-Africa. Nevertheless, the three employed proxies (sedimentation rate, grain size and elemental distribution) do not always display consistent inter-core patterns. Major differences between the individual core records are attributed to sediment remobilization which was linked to local hydrographic variations as well as reorganizations of the coastal system. The Senegal mud belt is a layered inhomogeneous sedimentary body deposited on an irregular erosive surface. Early Holocene deceleration in the rate of the sea-level rise could have enabled initial mud deposition on the shelf. These favorable conditions for mud deposition occur coevally with a humid period over NW-Africa, thus, high river discharge. Sedimentation started preferentially in the northern areas of the mud belt. During mid-Holocene, a marine incursion led to the formation of an embayment. Afterwards, sedimentation in the north was interrupted in association with a remarkable southward shift in the location of the active depocenter as it is reflected by the sedimentary architecture and confirmed by radiocarbon dates. These sub-recent shifts in depocenters location are caused by migrations of the Senegal River mouth. During late Holocene times, the weakening of river discharge allowed the longshore currents to build up a chain of beach barriers which have forced the river mouth to shift southwards.

(Table 1) List of studied samples with vestimentiferan tubes

Vestimentiferan tube worms are prominent members of modern methane seep communities and are totally reliant as adults on symbiotic sulphide-oxidizing bacteria for their nutrition. The sulphide is produced in the sediment by a biochemical reaction called the anaerobic oxidation of methane (AOM). A well-studied species from the Gulf of Mexico shows that seep vestimentiferans 'mine' sulphide from the sediment using root-like, thin walled, permeable posterior tube extensions, which can also be used to pump sulphate and possibly hydrogen ions from the soft tissue back into the sediment to increase the local rate of AOM. The 'root-balls' of exhumed seep vestimentiferans are intimately associated with carbonate nodules, which are a result of AOM. We have studied vestimentiferan specimens and associated carbonates from seeps at the Kouilou pockmark field on the Congo deep-sea fan and find that some of the posterior 'root' tubes of living specimens are enclosed with carbonate indurated sediment and other, empty examples are partially or completely replaced by the carbonate mineral aragonite. This replacement occurs from the outside of the tube wall inwards and leaves fine-scale relict textures of the original organic tube wall. The process of mineralization is unknown, but is likely a result of post-mortem microbial decay of the tube wall proteins by microorganisms or the precipitation from locally high flux of AOM derived carbonate ions. The aragonite-replaced tubes from the Kouilou pockmarks show similar features to carbonate tubes in ancient seep deposits and make it more likely that many of these fossil tubes are those of vestimentiferans. These observations have implications for the supposed origination of this group, based on molecular divergence estimates.

Low-temperature magnetic remanence and hysteresis measurements on sediment core GeoB4901-8 from the Niger deep-sea fan

Low-temperature (LT) magnetic remanence and hysteresis measurements, in the range 300-5 K, were combined with energy dispersive spectroscopy (EDS) in order to characterize the magnetic inventory of strongly diagenetically altered sediments originating from the Niger deep-sea fan. We demonstrate the possibility of distinguishing between different compositions of members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series on a set of five representative samples, two from the upper suboxic and three from the lower sulfidic anoxic zone of gravity core GeoB 4901. Highly sensitive LT magnetic measurements were performed on magnetic extracts resulting in large differences in the magnetic behavior between samples from the different layers. This emphasizes that both Fe-Ti oxide phases occur in different proportions in the two geochemical environments. Most prominent are variations in the coercivity sensitive parameter coercive field (BC). At room-temperature (RT) hysteresis loops for all extracts are narrow and yield low coercivities (6-13 mT). With decreasing temperature the loops become more pronounced and wider. At 5 K an approximately 5-fold increase in BC for the suboxic samples contrasts a 20-25-fold increase for the samples from the anoxic zone. We demonstrate that this distinct increase in BC at LT corresponds to the increasing proportion of the Ti-rich hemoilmenite phase, while Fe-rich (titano-)magnetite dominates the magnetic signal at RT. This trend is also seen in the room-temperature saturation isothermal remanent magnetization (RT-SIRM) cycles: suboxic samples show remanence curves dominated by Fe-rich mineral phases while anoxic samples display curves clearly dominated by Ti-rich particles. We show that the EDS intensity ratios of the characteristic Fe Kalpha and Ti Kalpha lines of the Fe-Ti oxides may be used to differentiate between members of the magnetite-ulvöspinel and ilmenite-hematite solid solution series. Furthermore it is possible to calculate an approximate composition for each grain if the intensity ratios of natural particles are linked to well-known standards. Thus, element spectra with high Fe/Ti intensity ratios were found to be rather typical of titanomagnetite while low Fe/Ti ratios are indicative of hemoilmenite. The EDS analyses confirm the LT magnetic results, Fe-rich magnetic phases dominate in the upper suboxic environment whereas Ti-rich magnetic phases comprise the majority of particles in the lower anoxic domain: The mineral assemblage of the upper suboxic environments is composed of magnetite (~19%), titanomagnetite (~62%), hemoilmenite (~17%) and ~2% other particles. In the lower anoxic sediments, reductive diagenetic alteration has resulted in more extensive depletion of the (titano-)magnetite phase, resulting in a relative enrichment of the hemoilmenite phase (~66%). In these strongly anoxic sediments stoichiometric magnetite is barely preserved and only ~5% titanomagnetite was detected. The remaining ~28% comprises Ti-rich particles such as pseudobrookite or rutile.

Environmental magnetism, geochemical measurements and colour reflectance of two sediment cores: GeoB4905-4 off Cameroon and GeoB4906-3 off Gabon

We combine environmental magnetism, geochemical measurements and colour reflectance to study two late Quaternary sediment cores: GeoB 4905-4 at 2° 30 N off Cameroon and GeoB 4906-3 at 0° 44 N off Gabon. This area is suitable for investigating precipitation changes over Central and West Africa because of its potential to record input of aeolian and fluvial sediments. Three magnetozones representing low and high degree of alteration of the primary rock magnetic signals were identified. The magnetic signature is dominated by fine-grained magnetite, while residual haematite prevails in the reduced intervals, showing increase in concentration and fine grain size at wet intervals. Our records also show millennial-scale changes in climate during the last glacial and interglacial cycles. At the northern location, the past 5.5 ka are marked by high-frequency oscillations of Ti and colour reflectance, which suggests aeolian input and hence aridity. The southern location remains under the influence of the Intertropical Convergence Zone and thus did not register aeolian signals. The millennial-scale climatic signals indicate that drier and/or colder conditions persisted during the late Holocene and are synchronous with the 900 a climatic cycles observed in Northern Hemisphere ice core records.

Age model, lipids, and iron/calcium-ratios of sediment core GeoB9307-3

Hide Intense debate persists about the climatic mechanisms governing hydrologic changes in tropical and subtropical southeast Africa since the Last Glacial Maximum, about 20,000 years ago. In particular, the relative importance of atmospheric and oceanic processes is not firmly established. Southward shifts of the intertropical convergence zone (ITCZ) driven by high-latitude climate changes have been suggested as a primary forcing, whereas other studies infer a predominant influence of Indian Ocean sea surface temperatures on regional rainfall changes. To address this question, a continuous record representing an integrated signal of regional climate variability is required, but has until now been missing. Here we show that remote atmospheric forcing by cold events in the northern high latitudes appears to have been the main driver of hydro-climatology in southeast Africa during rapid climate changes over the past 17,000 years. Our results are based on a reconstruction of precipitation and river discharge changes, as recorded in a marine sediment core off the mouth of the Zambezi River, near the southern boundary of the modern seasonal ITCZ migration. Indian Ocean sea surface temperatures did not exert a primary control over southeast African hydrologic variability. Instead, phases of high precipitation and terrestrial discharge occurred when the ITCZ was forced southwards during Northern Hemisphere cold events, such as Heinrich stadial 1 (around 16,000 years ago) and the Younger Dryas (around 12,000 years ago), or when local summer insolation was high in the late Holocene, i.e., during the last 4,000 years.

Compilation of d18O data, living planktic foraminifera

Most of the isotopic paleotemperature equations used for paleoceanographic reconstructions have been derived from culture experiments or inorganic precipitates of calcium carbonate. To test these equations in the modern ocean, we measured the oxygen isotope composition of planktonic foraminifera (Globigerinoides ruber, Globigerinoides sacculifer, Globigerina bulloides and Neogloboquadrina pachyderma) collected from Atlantic and Southern Ocean surface waters, and added published plankton tow data from the Pacific, Indian and Arctic Oceans. The resulting species-specific regression equations of the temperature:d18O relationships for G. ruber, G. sacculifer and G. bulloides are statistically indistinguishable. The equations derived for G. sacculifer and G. bulloides agree with relationships obtained from laboratory experiments, in which these species were cultured at pH values close to modern surface waters. The equation derived from N. pachyderma has a significantly lower slope and offset than the other three species but produces a regression equation that is nearly identical to the one for the epifaunal benthic foraminifer Cibicides sp. Our work on plankton tow and pumped samples indicates that culture-derived equations appear to be more appropriate for predicting the absolute d18O of the species examined compared to equations derived from inorganic precipitates. However, over the oceanic temperature range, the slopes of the equations we derive for living species agree with the slopes obtained from inorganic precipitates.

Biogeochemical processes in anoxic sediment from Lake Plußsee, Germany

In anoxic environments, volatile methylated sulfides like methanethiol (MT) and dimethyl sulfide (DMS) link the pools of inorganic and organic carbon with the sulfur cycle. However, direct formation of methylated sulfides from reduction of dissolved inorganic carbon has previously not been demonstrated. When studying the effect of temperature on hydrogenotrophic microbial activity, we observed formation of DMS in anoxic sediment of Lake Plußsee at 55 °C. Subsequent experiments strongly suggested that the formation of DMS involves fixation of bicarbonate via a reductive pathway in analogy to methanogenesis and engages methylation of MT. DMS formation was enhanced by addition of bicarbonate and further increased when both bicarbonate and H2 were supplemented. Inhibition of DMS formation by 2-bromoethanesulfonate points to the involvement of methanogens. Compared to the accumulation of DMS, MT showed the opposite trend but there was no apparent 1:1 stoichiometric ratio between both compounds. Both DMS and MT had negative d13C values of -62 per mil and -55 per mil, respectively. Labeling with NaH**13CO3 showed more rapid incorporation of bicarbonate into DMS than into MT. The stable carbon isotopic evidence implies that bicarbonate was fixed via a reductive pathway of methanogenesis, and the generated methyl coenzyme M became the methyl donor for MT methylation. Neither DMS nor MT accumulation were stimulated by addition of the methyl-group donors methanol and syringic acid or by the methyl-group acceptor hydrogen sulphide. The source of MT was further investigated in a H2**35S labeling experiment, which demonstrated a microbially-mediated process of hydrogen sulfide methylation to MT that accounted for only <10% of the accumulation rates of DMS. Therefore, the major source of the 13C-depleted MT was neither bicarbonate nor methoxylated aromatic compounds. Other possibilities for isotopically depleted MT, such as other organic precursors like methionine, are discussed. This DMS-forming pathway may be relevant for anoxic environments such as hydrothermally influenced sediments and fluids and sulfate-methane transition zones in marine sediments.

Mineralogical and stable isotope analyses of carbonates from the eastern Black Sea

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area ("Batumi seep area") located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups. X-ray diffractometry revealed the presence of two different authigenic carbonate phases, i.e. pure aragonitic rims associated with vital microbial mats and high-Mg calcite cementing the hemipelagic sediment. As indicated by the CT images, the initial sediment has been strongly deformed, first plastic then brittle, leading to brecciation of the progressively cemented sediment. The aragonitic rims on the other hand, represent a presumably recent carbonate growth phase since they cover the already deformed sediment. The stable oxygen isotope signature indicates that the high-Mg calcite cement incorporated pore water mixed with substantial hydrate water amounts. This points at a dominant role of high gas/fluid flux from decomposing gas hydrates leading to the deformation and cementation of the overlying sediment. In contrast, the aragonitic rims do not show an influence of 18O-enriched hydrate water. The differences in d18O between the presumably recent aragonite precipitates and the older high-Mg cements suggest that periods of hydrate dissociation and vigorous fluid discharge alternated with times of hydrate stability and moderate fluid flow. These results indicate that shallow-buried gas hydrates are prone to episodic decomposition with associated vigorous fluid flow. This might have a profound impact on the seafloor morphology resulting e.g. in the formation of carbonate pavements and pockmark-like structures but might also affect the local carbon cycle.

Long sedimentary records of sediment cores from the Chilean margin

The Antarctic Intermediate Water (AAIW) is a key player in global-scale oceanic overturning processes and an important conduit for heat, fresh water, and carbon transport. The AAIW past variability is poorly understood mainly due to the lack of sedimentary archives at intermediate water depths. We present records of benthic stable isotopes from sediments retrieved with the seafloor drill rig MARUM-MeBo at 956 m water depth off northern Chile (GeoB15016, 27°29.48'S, 71°07.58'W) that extend back to 970 ka. The sediments at this site are presently deposited at the boundary between AAIW and Pacific Deep Water (PDW). For previous peak interglacials, our results reveal similar benthic d13C values at site GeoB15016 and of a newly generated stack of benthic d13C from various deep Pacific cores representing the "average PDW." This suggests, unlike today, the absence of AAIW at the site and the presence of nearly pure PDW. In contrast, more positive d13C values at site GeoB15016 compared to the stack imply a considerable AAIW contribution during cold phases of interglacials and especially during glacials. Besides, we used three short sediment cores to reconstruct benthic d13C values from the AAIW core during the last glacial and found a d13C signature similar to today's. Assuming that this was the case also for the past 970 kyr, we demonstrate that sea level changes and latitudinal migrations of the AAIW formation site can only account for about 50% of the full range of past d13C increases at site GeoB15016 during cold periods. Other processes that could explain the remaining of the positive d13C anomalies are increases in glacial AAIW production and/or deeper convection of the AAIW with respect to preceding interglacials.

Individual dinoflagellate cysts species of surface sediment samples from the Mediterranean Sea

To determine the relationship between the spatial dinoflagellate cyst distribution and oceanic environmental conditions, 34 surface sediments from the Eastern and Western Mediterranean Sea have been investigated for their dinoflagellate cyst content. Multivariate ordination analyses identified sea-surface temperature, chlorophyll-a , nitrate concentration, salinity, and bottom oxygen concentration as the main factors affecting dinoflagellate cyst distribution in the region. Based on the relative abundance data, two associations can be distinguished that can be linked with major oceanographic settings. (1) An offshore eastern Mediterranean regime where surface sediments are characterized by oligotrophic, warm, saline surface water, and high oxygen bottom water concentrations (Impagidinium species, Nematosphaeropsis labyrinthus, Pyxidinopsis reticulata and Operculodinium israelianum). Based on the absolute abundance, temperature is positively related to the cyst accumulation of Operculodinium israelianum. Temperature does not form a causal factor influencing the accumulation rate of the other species in this association. Impagidinium species and Nematosphaeropsis labyrinthus show a positive relationship between cyst accumulation and nitrate availability in the upper waters. (2) Species of association 2 have highest relative abundances in the Western Mediterranean Sea, Strait of Sicily/NW Ionian Sea, and/or the distal ends of the Po/Nile/Rhône River plumes. At these stations, surface waters are characterized by (relative to the other regime) higher productivity associated with lower sea-surface temperature, salinity, and lower bottom water oxygen concentrations (Selenopemphix nephroides, Echinidinium spp., Selenopemphix quanta, Quinquecuspis concreta, Brigantedinium spp. and Lingulodinium machaerophorum). Based on both the absolute and relative abundances, Selenopemphix nephroides is suggested to be a suitable indicator to trace changes in the trophic state of the upper waters. The distribution of Lingulodinium machaerophorum is related to the presence of river-influenced surface waters, notably the Nile River. We suggest that this species might form a suitable marker to trace past variations in river discharge, notably from the Nile.

Gridded bathymetry from multibeam echosounder EM122 data of the cruise MSM34/2 (2013)

Bathymetry based on data recorded during MSM34-2 between 27.12.2013 and 18.01.2014 in the Black Sea. The main objective of this cruise was the mapping and imaging of the gas hydrate distribution and gas accumulations as well as possible gas migration pathways. Objectives of Cruise: Gas hydrates have been the focus of scientific and economic interest for the past 15-20 years, mainly because the amount of carbon stored in gas hydrates is much greater than in other carbon reservoirs. Several countries including Japan, Korea and India have launched vast reasearch programmes dedicated to the exploration for gas hydrate resources and ultimately the exploitation of the gas hydrates for methane. The German SUGAR project that is financed the the Ministry of Education and Research (BmBF) and the Ministry of Economics (BmWi) aims at developing technology to exploit gas hydrate resources by injecting and storing CO2 instead of methane in the hydrates. This approach includes techniques to locate and quantify hydrate reservoirs, drill into the reservoir, extract methane from the hydrates by replacing it with CO2, and monitor the thus formed CO2-hydrate reservoir. Numerical modeling has shown that any exploitation of the gas hydrates can only be succesful, if sufficient hydrate resources are present within permeable reservoirs such as sandy or gravelly deposits. The ultimate goal of the SUGAR project being a field test of the technology developed within the project, knowledge of a suitable test site becomes crucial. Within European waters only the Norwegian margin and the Danube deep-sea fan show clear geophysical evidence for large gas hydrate accumulations, but only the Danube deep-sea fan most likely contains gas hydrates within sandy deposits. The main objective of cruise MSM34 therefore is locating and characterising suitable gas hydrate deposits on the Danube deep-sea fan.

Quantification and molecular characterization of dissolved organic sulfur in water samples obtained during POLARSTERN cruise ANT-XXV (PS73) to the East Atlantic and the Southern Ocean

Although sulfur is an essential element for marine primary production and critical for climate processes, little is known about the oceanic pool of non-volatile dissolved organic sulfur (DOS). We present a basin-scale distribution of solid phase extractable DOS in the East Atlantic Ocean and the Atlantic sector of the Southern Ocean. While molar DOS versus dissolved organic nitrogen (DON) ratios of 0.11 ± 0.024 in Atlantic surface water resembled phytoplankton stoichiometry (S/N ~ 0.08), increasing dissolved organic carbon (DOC) versus DOS ratios and decreasing methionine-S yield demonstrated selective DOS removal and active involvement in marine biogeochemical cycles. Based on stoichiometric estimates, the minimum global inventory of marine DOS is 6.7 Pg S, exceeding all other marine organic sulfur reservoirs by an order of magnitude.

Age model and stable oxygen isotope analyses of sediment core GeoB8507-3

The present study is the first study on the stable oxygen isotope composition of the photosynthetic calcareous-walled dinoflagellate species Thoracosphaera heimii off NW Africa during the last 45,000 yr. T. heimii based temperature estimates of sediment core GeoB 8507-3 were compared with those obtained from the stable oxygen isotopes of the planktic foraminifera Globigerina bulloides and Globigerinoides ruber (pink), and the Mg/Ca ratio of G. ruber (pink). We show that the isotopic composition of T. heimii and the temperature estimates based on the equation for inorganically precipitated calcite provide comparable results to those obtained from G. ruber (pink) isotopes and Mg/Ca ratios with exception of the Early Holocene and the Younger Dryas. The recently proposed palaeotemperature equation of Zonneveld et al. (2007), however, provides unrealistic temperature reconstructions that are about 16 °C lower than those based on planktic foraminifera. Thus, this equation needs to be revised. The difference between T. heimii and G. bulloides isotopic and temperature reconstructions can be ascribed to differences in the ecology of both species, especially with regard to their depth habitat and/or seasonal production in the research area. All temperature proxies suggest comparable conditions during the last glacial and Holocene. Small differences between the reconstructed temperature values of T. heimii and the other proxies can be explained by differences in seasonal production of the individual species. The relatively low temperatures recorded by T. heimii at about 15,000 to 8,000 yr BP are interpreted to reflect an increase in duration and/or intensity of the upwelling in the vicinity of the core site in comparison to the last glacial, with an abrupt and strong decrease of upwelling intensity and/or duration during the Early Holocene and the Younger Dryas.