Chemical and isotopic analysis of bulk organic matter and hydrocarbon biomarkers from IODP Holes 311-U1327C, 311-U1328B and 311-U1328C

The chemical and isotopic compositions of sedimentary organic matter (SOM) from two mid-slope sites of the northern Cascadia margin were investigated during Integrated Ocean Drilling Program (IODP) Expedition 311 to elucidate the organic matter origins and identify potential microbial contributions to SOM. Gas hydrate is present at both locations (IODP Sites U1327 and U1328), with distinct patterns of near-seafloor structural accumulations at the cold seep Site U1328 and deeper stratigraphic accumulations at the slope-basin Site U1327. Source characterization and evidence that some components of the organic matter have been diagenetically altered are determined from the concentrations and isotopic compositions of hydrocarbon biomarkers, total organic carbon (TOC), total nitrogen (TN) and total sulfur (TS). The carbon isotopic compositions of TOC (d13C TOC = -26 to -22 per mil) and long-chain n-alkanes (C27, C29 and C31, d13C = -34 to -29 per mil) suggest the organic matter at both sites is a mixture of 1) terrestrial plants that employ the C3 photosynthetic pathway and 2) marine algae. In contrast, the d15N TN values of the bulk sediment (+4 to +8 per mil) are consistent with a predominantly marine source, but these values most likely have been modified during microbial organic matter degradation. The d13C values of archaeal biomarker pentamethylicosane (PMI) (-46.4 per mil) and bacterial-sourced hopenes, diploptene and hop-21-ene (-40.9 to -34.7 per mil) indicate a partial contribution from methane carbon or a chemoautotrophic pathway. Our multi-isotope and biomarker-based conclusions are consistent with previous studies, based only on the elemental composition of bulk sediments, that suggested a mixed marine-terrestrial organic matter origin for these mid-slope sites of the northern Cascadia margin.

Age determination of sediment core MD99-2201

A marine sediment core from the leeward margin of Great Bahama Bank (GBB) was subjected to a multiproxy study. The aragonite dominated core MD992201 comprises the past 7230 years in a decadal time resolution and shows sedimentation rates of up to 13.8 m/kyr. Aragonite mass accumulation rates, age differences between planktonic foraminifera and aragonite sediments, and temperature distribution are used to deduce changes in aragonite production rates and paleocurrent strengths. Aragonite precipitation rates on GBB are controlled by exchange of carbonate ions and CO2 loss due to temperature-salinity conditions and biological activity, and these are dependent on the current strength. Paleocurrent strengths on GBB show high current velocities during the periods 6000-5100 years BP, 3500-2700 years BP, and 1600-700 years BP; lower current speeds existed during the time intervals 5100-3500 years BP, 2700-1600 years BP, and 700-100 years BP. Bahamian surface currents are directly linked to the North Atlantic atmospheric circulation, and thus periods with high (low) current speeds are proposed to be phases of strong (weak) atmospheric circulation.

Temperature proxies of sediment cores from the Sea of Marmara

Reconstructing ocean temperature values is a major target in paleoceanography and climate research. However, most temperature proxies are organism-based and thus suffer from an "ecological bias". Multiproxy approaches can potentially overcome this bias but typically require more investment in time and resources, while being susceptible to errors induced by sample preparation steps necessary before analysis. Three lipid-based temperature proxies are widely used: UK'37 (based on long chain alkenones from phytoplanktonic haptophytes), TEX86 [based on glycerol dialkyl glycerol tetraethers (GDGTs) from pelagic archaea] and LDI (based on long chain diols from phytoplanktonic eustigmatophytes). So far, separate analytical methods, including gas chromatography (GC) and liquid chromatography (LC), have been used to determine these proxies. Here we present a sensitive method for determining all three in a single normal phase high performance LC-atmospheric pressure chemical ionization mass spectrometry (NP-HPLC-APCI-MS) analysis. Each of the long chain alkenones and long chain diols was separated and unambiguously identified from the accurate masses and characteristic fragmentation during multiple stage MS analysis (MS2). Comparison of conventional GC and HPLC-MS methods showed similar results for UK'37 and LDI, respectively, using diverse environmental samples and an Emiliania huxleyi culture. Including the three sea surface temperature (SST) proxies; the NP-HPLC-APCI-MS method in fact allows simultaneous determination of nine paleoenvironmental proxies. The extent to which the ecology of the source organisms (ecological bias) influences lipid composition and thereby the reconstructed temperature values was demonstrated by applying the new method to a sediment core from the Sea of Marmara, covering the last 21 kyr BP. Reconstructed SST values differed considerably between the proxies for the Last Glacial Maximum (LGM) and the period of Sapropel S1 formation at ca. 10 kyr BP, whereas the trends during the late Holocene were similar. Changes in the composition of alkenone-producing species at the transition from the LGM to the Bølling/Allerød (B/A) were inferred from unreasonably high UK'37-derived SST values (ca. 20 °C) during the LGM. We ascribe discrepancies between the reconstructed temperature records during S1 deposition to habitat change, e.g. a different depth due to changes in nutrient availability.

Water chemistry and sediment age of lake Terrasovoje, Amery Oasis, East Antarctica

The late Quaternary palaeoenvironmental history of the southern Windmill Islands, East Antarctica, has been reconstructed using diatom assemblages from two long, well-dated sediment cores taken in two marine bays. The diatom assemblage of the lowest sediment layers suggests a warm climate with mostly open water conditions during the late Pleistocene. During the following glacial, the Windmill Islands were covered by grounded ice preventing any in situ bioproductivity. Following deglaciation, a sapropel with a well-preserved diatom assemblage was deposited from ~10?500 cal yr BP. Between ~10?500 and ~4000 cal yr BP, total organic carbon (Corg) and total diatom valve concentrations as well as the diatom species composition suggest relatively cool summer temperatures. Hydrological conditions in coastal bays were characterised by combined winter sea-ice and open water conditions. This extensive period of glacial retreat was followed by the Holocene optimum (~4000 to ~1000 cal yr BP), which occurred later in the southern Windmill Islands than in most other Antarctic coastal regions. Diatom assemblages in this period suggest ice-free conditions and meltwater-stratified waters in the marine bays during summer, which is also reflected in high proportions of freshwater diatoms in the sediments. The diatom assemblage in the upper sediments of both cores indicates Neoglacial cooling from ~1000 cal yr BP, which again led to seasonally persistent sea-ice on the bays. The Holocene optimum and cooling trends in the Windmill Islands did not occur contemporaneously with other Antarctic coastal regions, showing that the here presented record reflects partly local environmental conditions rather than global climatic trends.

Trace-element geochemistry of tholeiitic basalts from DSDP Hole 55-433C

Hole 433C, a multiple re-entry hole drilled in 1862 meters of water on Suiko Seamount in the central Emperor Seamounts, penetrated 387.5 meters of lava flows overlain by 163.0 meters of sediments. The recovered volcanic rocks consist of three flow units (1-3) of alkalic basalt underlain by more than 105 flows or flow lobes (Flow Units 4-67) of tholeiitic basalt. This study reports trace-element, including rare-earth element (REE), data for 25 samples from 24 of the least altered tholeiitic flows. These data are used to evaluate the origin and evolution of tholeiitic basalts from Suiko Seamount and to evaluate changes in the mantle source between the time when Suiko Seamount formed, 64.7 ± 1.1 m.y. ago (see Dalrymple et al., 1980), and the present day. Stearns (1946), Macdonald and Katsura (1964) and Macdonald (1968) have established that chemically distinct lavas erupt during four eruptive stages of development of a Hawaiian volcano. These stages, from initial to final, are shield-building, caldera-filling, post-caldera, and post-erosional. The lavas of the shield-building stage are tholeiitic basalts, which erupt rapidly and in great volume. The shield-building stage is quickly followed by caldera collapse and by the caldera-filling stage, during which the caldera is filled by tholeiitic and alkalic lavas. During the post-caldera stage, a relatively thin veneer of alkalic basalts and associated differentiated lavas are erupted, sometimes accompanied by minor eruptions of tholeiitic lava. After a period of volcanic quiescence and erosion, lavas of the nephelinitic suite, which include both alkalic basalts and strongly SiO2-undersaturated nephelinitic basalts, may erupt from satellite vents during the post-erosional stage. Many Hawaiian volcanoes develop through all four stages; but individual volcanoes have become extinct before the cycle is complete. We interpret the tholeiitic lavas drilled on Suiko Seamount to have erupted during either the shield-building or the caldera-filling stage, and the overlying alkalic flows to have erupted during either the caldera-filling or the post-caldera stage (see Kirkpatrick et al., 1980).

Stable isotope record of the Okhotsk Sea

Stable isotope data on benthic foraminifera from more than 30 cores on the northern Emperor Seamounts and in the Okhotsk Sea are synthesized in paleohydrographic profiles spanning the depth range 1000-4000 m. Holocene (core-top) benthic foraminiferal d18O and d13C data are calibrated to modern hydrographic properties through measurements of d13C of SumCO2 and d18O of seawater. Cibicidoides stable isotope ratios are close to the d13C and equilibrium d18O of seawater, whereas Uvigerina d18O and d13C are variably offset from Cibicidoides. Glacial maximum d13C of Cibicidoides displays a different vertical profile than that of the Holocene. When results are adjusted by +0.32 per mil to account for the secular change in d13C during the last glacial maximum, the data coincide with the modern seawater and foraminiferal curves deeper than ~2 km. However, at shallower depths d13C gradually increases by as much as 1 per mil above the modern value. Furthermore, above 2 km the benthic d18O decreases by ~0.5 per mil. These results are consistent with a benthic front at ~2 km in the North Pacific (see Herguera et al., 1992), but they differ from interpretations based on trace metal data which indicate a source of nutrient-depleted deep water during glaciation. The isotopic data suggest that during glaciation there was a better ventilated watermass at intermediate depths in the far northwestern Pacific, it was relatively fresher than deep waters there, and deep waters were as nutrient-rich as today.

Radiocarbon ages and clay minerals in sediment cores obtained during a 2009 Jan Mayen cruise to the Norwegian Sea

The origin of two acoustic sediment units has been studied based on lithological facies, chronology and benthic stable isotope values as well as on foraminifera and clay mineral assemblages in six marine sediment cores from Kveithola, a small trough west of Spitsbergenbanken on the western Barents Sea margin. We have identified four time slices with characteristic sedimentary environments. Before c. 14.2 cal. ka, rhythmically laminated muds indicate extensive sea ice cover in the area. From c. 13.9 to 14.2 cal. ka, muds rich in ice-rafted debris were deposited during the disintegration of grounded ice on Spitsbergenbanken. From c. 10.3 to 13.1 cal. ka, sediments with heterogeneous lithologies suggest a shifting influence of suspension settling and iceberg rafting, probably derived from a decaying Barents Sea Ice Sheet in the inner-fjord and land areas to the north of Kveithola. Holocene deposition was episodic and characterized by the deposition of calcareous sands and shell debris, indicative of strong bottom currents. We speculate that a marked erosional boundary at c. 8.2 cal. ka may have been caused by the Storegga tsunami. Whilst deposition was sparse during the Holocene, Kveithola acted as a sediment trap during the preceding deglaciation. Investigation of the deglacial sediments provides unprecedented details on the dynamics and timing of glacial retreat from Spitsbergenbanken.

Geochemistry, isotopes, trace elements and fluid inclusion geothermometry at DSDP Hole 83-504B

Stockwork-like metal sulfide mineralizations were found at 910-928 m below seafloor (BSF) in the pillow/dike transition zone of Hole 504B. This is the same interval where most physical properties of the 5.9-m.y.-old crust of the Costa Rica Rift change from those characteristic of Layer 2B to those of Layer 2C. The pillow lavas, breccias, and veins of the stockwork-like zone were studied by transmitted and reflected light microscopy, X-ray diffraction, and electron microprobe analysis. Bulk rock oxygen isotopic analyses as well as isolated mineral oxygen and sulfur isotopic analyses and fluid inclusion measurements were carried out. A complex alteration history was reconstructed that includes three generations of fissures, each followed by precipitation of characteristic hydrothermal mineral parageneses: (1) Minor and local deposition of quartz occurred on fissure walls; adjacent wall rocks were silicified, followed by formation of chlorite and minor pyrite I in the veins, whereas albite, sphene, chlorite and chlorite-expandable clay mixtures, actinolite, and pyrite replaced igneous phases in the host rocks. The hydrothermal fluids responsible for this first stage were probably partially reacted seawater, and their temperatures were at least 200-250° C. (2) Fissures filled during the first stage were reopened and new cracks formed. They were filled with quartz, minor chlorite and chlorite-expandable clay mixtures, traces of epidote, common pyrite, sphalerite, chalcopyrite, and minor galena. During the second stage, hydrothermal fluids were relatively evolved metal- and Si-rich solutions whose temperatures ranged from 230 to 340° C. The fluctuating chemical composition and temperature of the solutions produced a complex depositional sequence of sulfides in the veins: chalcopyrite I, ± Fe-rich sphalerite, chalcopyrite II ("disease"), Fe-poor sphalerite, chalcopyrite III, galena, and pyrite II. (3) During the last stage, zeolites and Mg-poor calcite filled up the remaining spaces and newly formed cracks and replaced the host rock plagioclase. Analcite and stilbite were first to form in veins, possibly at temperatures below 200°C; analcite and earlier quartz were replaced by laumontite at 250°C, whereas calcite formation temperature ranged from 135 to 220°C. The last stage hydrothermal fluids were depleted in Mg and enriched in Ca and 18O compared to seawater and contained a mantle carbon component. This complex alteration history paralleling a complex mineral paragenesis can be interpreted as the result of a relatively long-term evolution of a hydrothermal system with superimposed shorter term fluctuations in solution temperature and composition. Hydrothermal activity probably began close to the axis of the Costa Rica Rift with the overall cooling of the system and multiple fracturing stages due to movement of the crust away from the axis and/or cooling of a magmatic heat source.

40Ar-39Ar geochronological studies on rocks at DSDP Leg 58 Holes

The technique of 40Ar-39Ar step-heating dating was applied to three rock samples from core of DSDP Site 443, one sample from Site 445, and four samples at Site 446. All sites were drilled during DSDP Leg 58. At Site 443 (Shikoku Basin), about 116 meters of basalt basement was drilled. Three samples were chosen for dating from different levels in the basalt; two samples are aphyric basalt, and the other is subophitic dolerite. At Site 445 (Daito Ridge), no basement rock was drilled; however, conglomeratic sandstone was cored in the lower part of the hole. 40Ar-39Ar dating was applied to a basalt pebble in the conglomerate. At Site 446 (Daito Basin), the lower cored sequence is clay stone interlayered with 16 basalt sills. Four samples were chosen from sills at different levels.

Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.

Pollen analysis of a sediment profile from Gabelsee in Germany

The article shows that pollen analysis plays an important role in the prediction of potential settlement areas and, furthermore, can offer a crude determination of settlement duration. Especially when the archaeological data fails to offer a possibility of dating, pollen analysis in connection with 14C can importantly broaden the knowledge base. As in the present case, the results of the Archaeo-Prognosis mapping and the pollen analysis of the Gabelsee are compared and, within this vicinity, confirmend. = Der Beitrag zeigt, dass die Pollenanalyse eine wichtige Rolle für die Vorhersage von potenziellen Siedlungsflächen spielen und darüber hinaus eine grobe Berechnung der Siedlungsdauer bieten kann. Insbesondere wenn die archäologische Datenbasis keine genaue Datierung zulässt, ermöglicht die Pollenanalyse in Verbindung mit der 14C-Datierung eine wichtige Erweiterung der Kenntnisse. Im vorliegenden Fall konnten die Ergebnisse der Archäoprognosekarte mit denjenigen der Pollenanalyse des Gabelsees verglichen und für diesen lokalen Raum bestätigt werden.

Age datums, and abundance of Discoaster brouweri and Coccolithus pelagicus in ODP Site 180-1115 sediments

The relative abundance of warm-water Discoaster brouweri vs. cool-water Coccolithus pelagicus provides a useful proxy for interpreting Pliocene surface water temperature trends at Ocean Drilling Program Site 1115 (Solomon Sea). Surface waters were mostly warm during the early Pliocene with a slightly cooler interval centered on 4.5 Ma. A more pronounced cool interval occurred at ~3.2 Ma. The early and mid-Pliocene cool periods may reflect Antarctic glacial growth. A mid-Pliocene warm interval occurred from ~3.1 to 2.8 Ma. Temperature began to decline beginning ~2.7 Ma, marking the onset of Northern Hemisphere glaciation. This long-term decline in surface water temperature is interrupted by a brief warming event at ~2.3 Ma.

Iridium and other element concentrations and magnetostratigraphy across the Cretaceous/Tertiarty boundary in ODP Hole 122-761C

Samples from Ocean Drilling Program Hole 761C, collected on both sides of the Cretaceous/Tertiary boundary have been analyzed for their chemical and mineralogical content. The sediment consists of nannofossil ooze with variable amounts of clay. The boundary is marked by a color change associated with a nearly step-like decrease of the carbonate fraction. Paleomagnetic data and the drop of the carbonate content indicate that a strong reduction of the sedimentation rate occurred at the boundary and persisted for million of years. An iridium anomaly of 80 ng/cm**2, together with overabundances of Cr and Fe, are found in close coincidence with the planktonic crisis. These enrichments can be explained by the infall of =0.16 g/cm2 of Cl-like chondritic material. Co and Ni enrichments and a great quantity of Ni-rich magnetites are also observed in the basal Danian. These elements and minerals excepted, the composition of the insoluble fraction appears to be nearly unchanged across the boundary. Chemical and mineralogical observations support a cosmic origin for the Cretaceous/Tertiary event but do not reveal the presence of any significant impact ejecta.

Radiocarbon dating on four sediment profiles from Bunger Hills, East Antarctica

Radiocarbon dating was carried out on the total organic carbon of 19 lacustrine and marine sediment samples from the Bunger Hills. The results indicate that radiocarbon contamination is negligible throughout two sediment sequences from a fresh water lake. In contrast, two sequences from marine basins are irregularly influenced by the Antarctic Marine Reservoir Effect, which today amounts to more than 1000 years, depending on the degree of dilution with meltwater. All sediments were deposited during Holocene time.

Magnetic properties of ODP Hole 116-717C

Dark gray and black mud turbidites cored on ODP Leg 116 commonly yielded large magnetic susceptibility peaks. What is more, these peaks displayed different shapes suggesting variations in sedimentological processes. Consequently, a detailed study of the magnetic properties of two of these turbidites was undertaken to better understand the source of their unusual magnetism. Physical properties were measured as was the demagnetization behavior of sample natural remanent magnetizations (NRMs). Subsequently, an anhysteretic remanent magnetization (ARM) and saturation isothermal remanent magnetization (SIRM) were imparted to the samples, demagnetized, and various grain size tests based on the behavior of these remanences were applied. Finally, magnetic concentrates from two samples were examined with a scanning electron microscope with the capability to do energy dispersive X-ray (EDX) analysis. The turbidites stand out from surrounding layers because of their high susceptibilities, NRMs, ARMs, SIRMs, and ratios of ARM and SIRM to susceptibility. Their alternating field and thermal demagnetization properties and IRM acquisition curves are consistent with titanomagnetite grains as the primary magnetic mineral with some amount of hematite present. These properties are very similar to those published for samples from the Deccan flood basalts and suggest this formation as a possible source of the magnetic grains. Magnetic granulometry tests implied that the magnetic particles behave dominantly as single-domain and pseudo-single-domain grains. Moreover, they also implied that the large variation in susceptibility observed in the black mud turbidites results from a tenfold increase in the concentration of titanomagnetite grains. Electron microscope, EDX, and SIRM analyses revealed detrital titanomagnetites with typical sizes around 8-10 µm, but as large as 20-25 µm. These are probably the dominant magnetic grains in the black mud turbidites; however, ARM and susceptibility frequency-dependence suggested that there may also be a submicrometer fraction present. Most of the observed titanomagnetite grains are tabular and some display exsolution lamellae, accounting for the pseudo-single-domain behavior despite their moderate sizes. We hypothesize that the magnetic mineral concentration variations are brought about by sedimentological factors. The heavier magnetic minerals may tend to sink to the bottom of a turbidite; however, sometimes turbidite turbulence may act to keep these tabular, medium-size grains in suspension longer than some other larger or more equidimensional grains. Consequently, the susceptibility peak shape may reflect the turbidite current velocities as well as other sedimentological factors.