Grain size analysis on core plugs of sediment core CRP-1 (Table 1, 2)

Twenty four core samples from CRP-1, seven from Quaternary strata (20-43.55 meters below sea floor or mbsf) and seventeen from early Miocene strata (43.55 to 147.69 mbsf), have been analysed for their grain-size distribution using standard sieve and Sedigraph techniques. The results are in good agreement with estimates of texture made as part of the visual core description for the 1 :20 core logs for CRP-1 (Cape Roberts Science Team, 1998). Interpretation of the analyses presented here takes into account the likely setting of the site in Quaternary times as it is today, with CRP-1 high on the landward flank of a well-defined submarine ridge rising several hundred metres above basins on either side. In contrast, seismic geometries for strata deposited in early Miocene times indicate a generally planar sea floor dipping gently seaward. Fossils from these strata indicate shallow water depths (< 100 m), indicating the possibility that waves and tidal currents may have influenced sea floor sediments. The sediments analysed here are considered in terms of 3 textural facies: diamict, mud (silt and clay) and sand. Most of the Quaternary section but only 30% of the early Miocene section is diamict, a poorly sorted mixture of sand and mud with scattered clasts, indicating little wave or current influence on its texture. Although not definitive, diamict textures and other features suggest that the sediment originated as basal glacial debris but has been subsequently modified by minor winnowing, consistent with the field interpretation of this facies as ice-proximal and distal glaciomarine sediment. Sediments deposited directly from glacier ice appear to be lacking. Mud facies sediments, which comprise only 10% of the Quaternary section but a third of the early Miocene section, were deposited below wave base and largely from suspension, and show features (described elsewhere in this volume) indicative of the influence of both glacial and sediment gravity flow processes. Sand facies sediments have a considerable proportion of mud, normally more than 20%, but a well-sorted fine-very fine sand fraction. In the context of the early Miocene coastal setting we interpret these sediments as shoreface sands close to wave base.

Sedimentology on cores off Filchner Shelf Ice, Weddell Sea, Antarctica

Sediment sampling with box corer and gravity corer was conducted along a profile parallel to the Filchner/Rønne Ice Shelf, from 48° to 61°W. Twenty-two sampling locations were determined after evaluation of 12 and 3.5 kHz sub-bottom profiling records. The sediment retrievals show a wide diversity, varying from very well sorted pure sands in the SE of the profile to heavily glacially influenced, pebbly muds close to the foot of the Antarctic Peninsula. In the middle part of the profile mainly soft sediments of muddy to sandy muds were found which were partially influenced by glacially derived dropstones or accumulations of pebble-sized material. The striking changes of surface sediments (marine to glacial) observed along the profile led to an attempt to investigate the concurrence of marine and glacial depositional processes controlling the accumulation of these recent sediments.

Stable oxygen, hydrogene and chlorine isotopes of mid-Atlantic abyssal peridotites

Serpentinized abyssal peridotites sampled by the Ocean Drilling Program Leg 209 along the mid-Atlantic Ridge near the 15°20'N Fracture Zone have been analyzed for oxygen, hydrogen, and chlorine isotope compositions in order to determine isotopic behavior under a wide range of serpentinization conditions and place constraints on fluid history. Oxygen and hydrogen thermometry suggests peak serpentinization temperatures of 300-500°C. Serpentine separates have low deltaD values possibly due to a magmatic fluid component or low-temperature exchange during seafloor weathering. Chlorine geochemistry focused on three holes: 1274A and 1272A (serpentinized peridotites) and 1268A (serpentinite locally altered to talc). Concentrations of both, water-soluble chloride (WSC) and structurally bound chloride (SBC) are significantly lower at Hole 1268A compared to Holes 1274A and 1272A. The delta37Cl values for WSC and SBC of serpentinites in Holes 1274A and 1272A are slightly positive (avg. WSC = 0.20 per mil, n = 22 and avg. SBC = 0.35 per mil, n = 22), representing typical seawater-hydration conditions commonly determined for abyssal peridotite. The SBC of serpentinites from Hole 1268A are also positive (avg. = 0.63 per mil); whereas, the SBC in talc-dominated samples is negative (avg. = -1.22 per mil). The WSC of both talc- and serpentine-dominated samples are also negative (avg. = -0.15 per mil). We interpret the chlorine isotope data to preserve a record of multiple fluid events. As seawater hydrated the peridotite, 37Cl was preferentially incorporated into the forming serpentine and water-soluble salts, yielding similar delta37Cl values on a regional scale as sampled by Holes 1268A, 1274A and 1272A. The resultant pore fluid was left depleted in 37Cl. Locally (Hole 1268A), this evolved fluid was remobilized possibly due to the initiation of hydrothermal circulation in response to emplacement of a mafic magma body. The low delta37Cl pore fluids attained elevated SiO2 and sulfur concentrations due to interaction with the gabbroic intrusion and, when ascending through the surrounding serpentinite, caused formation of isotopically negative talc. This secondary fluid also flushed the preserved serpentinite of its previously formed salts, resulting in negative delta37Cl WSC values. The delta37Cl SBC values of the serpentinite samples remained unmodified by reaction with the secondary fluid.

Geochemistry, grain sizes and radiocarbon age of sediment core Lz1005 from Amery Oasis, East Antarctica

The clay mineralogical composition of a 552 cm long sediment core from Lake Terrasovoje in Amery Oasis, East Antarctica, was analysed and compared with that in surface sediments from other locations in the vicinity. The lower part of the sediment core is formed by sub- and proglacial sediments with a dominance of smectite and illite, and lower amounts of kaolinite and chlorite. The upper part of the core is deposited after 12 500 cal yr bp and mainly composed of illite and kaolinite, with low amounts of smectite and chlorite, such as found in samples from rock outcrops and covering sediments throughout Amery Oasis. The clay composition in the lower section of core Lz1005 suggest that the basin of Lake Terrasovoje was filled by a 150-200 m thickened Nemesis Glacier prior to 12 500 cal yr bp rather than by local ice caps.

Grain size composition of sediment cores from the Weddell Sea, Antarctica

Sedimentary processes in the southeastern Weddell Sea are influenced by glacial-interglacial ice-shelf dynamics and the cyclonic circulation of the Weddell Gyre, which affects all water masses down to the sea floor. Significantly increased sedimentation rates occur during glacial stages, when ice sheets advance to the shelf edge and trigger gravitational sediment transport to the deep sea. Downslope transport on the Crary Fan and off Dronning Maud and Coats Land is channelized into three huge channel systems, which originate on the eastern-, the central and the western Crary Fan. They gradually turn from a northerly direction eastward until they follow a course parallel to the continental slope. All channels show strongly asymmetric cross sections with well-developed levees on their northwestern sides, forming wedge-shaped sediment bodies. They level off very gently. Levees on the southeastern sides are small, if present at all. This characteristic morphology likely results from the process of combined turbidite-contourite deposition. Strong thermohaline currents of the Weddell Gyre entrain particles from turbidity-current suspensions, which flow down the channels, and carry them westward out of the channel where they settle on a surface gently dipping away from the channel. These sediments are intercalated with overbank deposits of high-energy and high-volume turbidity currents, which preferentially flood the left of the channels (looking downchannel) as a result of Coriolis force. In the distal setting of the easternmost channel-levee complex, where thermohaline currents are directed northeastward as a result of a recirculation of water masses from the Enderby Basin, the setting and the internal structures of a wedge-shaped sediment body indicate a contourite drift rather than a channel levee. Dating of the sediments reveals that the levees in their present form started to develop with a late Miocene cooling event, which caused an expansion of the East Antarctic Ice Sheet and an invigoration of thermohaline current activity.

Stable isotope ratios, carbon content and primary production of three sediment cores from the subantarctic eastern Atlantic

We present three new benthic foraminiferal delta13C, delta18O, and total organic carbon time series from the eastern Atlantic sector of the Southern Ocean between 41°S and 47°S. The measured glacial delta13C values belong to the lowest hitherto reported. We demonstrate a coincidence between depleted late Holocene (LH) delta13C values and positions of sites relative to ocean surface productivity. A correction of +0.3 to +0.4 [per mil VPDB] for a productivity-induced depletion of Last Glacial Maximum (LGM) benthic delta13C values of these cores is suggested. The new data are compiled with published data from 13 sediment cores from the eastern Atlantic Ocean between 19°S and 47°S, and the regional deep and bottom water circulation is reconstructed for LH (4-0 ka) and LGM (22-16 ka) times. This extends earlier eastern Atlantic-wide synoptic reconstructions which suffered from the lack of data south of 20°S. A conceptual model of LGM deep-water circulation is discussed that, after correction of southernmost cores below the Antarctic Circumpolar Current (ACC) for a productivity-induced artifact, suggests a reduced formation of both North Atlantic Deep Water in the northern Atlantic and bottom water in the southwestern Weddell Sea. This reduction was compensated for by the formation of deep water in the zone of extended winter sea-ice coverage at the northern rim of the Weddell Sea, where air-sea gas exchange was reduced. This shift from LGM deep-water formation in the region south of the ACC to Holocene bottom water formation in the southwestern Weddell Sea, can explain lower preformed d13CDIC values of glacial circumantarctic deep water of approximately 0.3 per mil to 0.4 per mil. Our reconstruction brings Atlantic and Southern Ocean d13C and Cd/Ca data into better agreement, but is in conflict, however, with a scenario of an essentially unchanged thermohaline deep circulation on a global scale. Benthic delta18O-derived LGM bottom water temperatures, by 1.9°C and 0.3°C lower than during the LH at deepest southern and shallowest northern sites, respectively, agree with the here proposed reconstruction of deep-water circulation in the eastern South Atlantic Ocean.

(Table 1) Grain size and color of sediments at DSDP Core 92-599-3

Size analyses were performed on pelagic sediments from Core 599-3, which exhibited paleontologic and lithologic evidence of reworking. The results show that darker, transported layers above sharp contacts are 0.33 phi coarser than the underlying lighter, in situ layers. The reworking is of unknown origin, but it coincides with periods of enhanced bottom currents and heightened tectonic activity during the latest Miocene.

Long chain alkyl diol distribution in Arabian Sea surface sediments

Oxygen exposure has a large impact on lipid biomarker preservation in surface sediments and may affect the application of organic proxies used for reconstructing past environmental conditions. To determine its effect on long chain alkyl diol and keto-ol based proxies, the distributions of these lipids was studied in nine surface sediments from the Murray Ridge in the Arabian Sea obtained from varying water depths (900 to 3000 m) but in close lateral proximity and, therefore, likely receiving a similar particle flux. Due to substantial differences in bottom water oxygen concentration (<3 to 77 µmol/L) and sedimentation rate, substantial differences exist in the time the biomarker lipids are exposed to oxygen in the sediment. Long chain alkyl diol and keto-ol concentrations in the surface sediments (0-0.5 cm) decreased progressively with increasing oxygen exposure time, suggesting increased oxic degradation. The 1,15-keto-ol/diol ratio (DOXI) increased slightly with oxygen exposure time as diols had apparently slightly higher degradation rates than keto-ols. The ratio of 1,14- vs. 1,13- or 1,15-diols, used as upwelling proxies, did not show substantial changes. However, the C30 1,15-diol exhibited a slightly higher degradation rate than C28 and C30 1,13-diols, and thus the Long chain Diol Index (LDI), used as sea surface temperature proxy, showed a negative correlation with the maximum residence time in the oxic zone of the sediment, resulting in ca. 2-3.5 °C change, when translated to temperature. The UK'37 index did not show significant changes with increasing oxygen exposure. This suggests that oxic degradation may affect temperature reconstructions using the LDI in oxic settings and where oxygen concentrations have varied substantially over time.

Thermal processing of miscanthus, sugarcane bagasse, sugarcane trash and their acid hydrolysis residues

The research presented in this thesis was developed as part of DIBANET, an EC funded project aiming to develop an energetically self-sustainable process for the production of diesel miscible biofuels (i.e. ethyl levulinate) via acid hydrolysis of selected biomass feedstocks. Three thermal conversion technologies, pyrolysis, gasification and combustion, were evaluated in the present work with the aim of recovering the energy stored in the acid hydrolysis solid residue (AHR). Mainly consisting of lignin and humins, the AHR can contain up to 80% of the energy in the original feedstock. Pyrolysis of AHR proved unsatisfactory, so attention focussed on gasification and combustion with the aim of producing heat and/or power to supply the energy demanded by the ethyl levulinate production process. A thermal processing rig consisting on a Laminar Entrained Flow Reactor (LEFR) equipped with solid and liquid collection and online gas analysis systems was designed and built to explore pyrolysis, gasification and air-blown combustion of AHR. Maximum liquid yield for pyrolysis of AHR was 30wt% with volatile conversion of 80%. Gas yield for AHR gasification was 78wt%, with 8wt% tar yields and conversion of volatiles close to 100%. 90wt% of the AHR was transformed into gas by combustion, with volatile conversions above 90%. 5volO2%-95vol%N2 gasification resulted in a nitrogen diluted, low heating value gas (2MJ/m3). Steam and oxygen-blown gasification of AHR were additionally investigated in a batch gasifier at KTH in Sweden. Steam promoted the formation of hydrogen (25vol%) and methane (14vol%) improving the gas heating value to 10MJ/m3, below the typical for steam gasification due to equipment limitations. Arrhenius kinetic parameters were calculated using data collected with the LEFR to provide reaction rate information for process design and optimisation. Activation energy (EA) and pre-exponential factor (ko in s-1) for pyrolysis (EA=80kJ/mol, lnko=14), gasification (EA=69kJ/mol, lnko=13) and combustion (EA=42kJ/mol, lnko=8) were calculated after linearly fitting the data using the random pore model. Kinetic parameters for pyrolysis and combustion were also determined by dynamic thermogravimetric analysis (TGA), including studies of the original biomass feedstocks for comparison. Results obtained by differential and integral isoconversional methods for activation energy determination were compared. Activation energy calculated by the Vyazovkin method was 103-204kJ/mol for pyrolysis of untreated feedstocks and 185-387kJ/mol for AHRs. Combustion activation energy was 138-163kJ/mol for biomass and 119-158 for AHRs. The non-linear least squares method was used to determine reaction model and pre-exponential factor. Pyrolysis and combustion of biomass were best modelled by a combination of third order reaction and 3 dimensional diffusion models, while AHR decomposed following the third order reaction for pyrolysis and the 3 dimensional diffusion for combustion.

Methane and stable isotope record of ice core EDML from Dronning Maud Land, Antarctica

Precise knowledge of the phase relationship between climate changes in the two hemispheres is a key for understanding the Earth's climate dynamics. For the last glacial period, ice core studies have revealed strong coupling of the largest millennial-scale warm events in Antarctica with the longest Dansgaard-Oeschger events in Greenland through the Atlantic meridional overturning circulation. It has been unclear, however, whether the shorter Dansgaard-Oeschger events have counterparts in the shorter and less prominent Antarctic temperature variations, and whether these events are linked by the same mechanism. Here we present a glacial climate record derived from an ice core from Dronning Maud Land, Antarctica, which represents South Atlantic climate at a resolution comparable with the Greenland ice core records. After methane synchronization with an ice core from North Greenland, the oxygen isotope record from the Dronning Maud Land ice core shows a one-to-one coupling between all Antarctic warm events and Greenland Dansgaard-Oeschger events by the bipolar seesaw. The amplitude of the Antarctic warm events is found to be linearly dependent on the duration of the concurrent stadial in the North, suggesting that they all result from a similar reduction in the meridional overturning circulation.

Seawater carbonate chemistry and processes during experiments with coccolithophores (Emiliania huxleyi and Gephyrocapsa oceanica), 2000

The formation of calcareous skeletons by marine planktonic organisms and their subsequent sinking to depth generates a continuous rain of calcium carbonate to the deep ocean and underlying sediments1. This is important in regulating marine carbon cycling and ocean-atmosphere CO2 exchange2. The present rise in atmospheric CO2 levels3 causes significant changes in surface ocean pH and carbonate chemistry4. Such changes have been shown to slow down calcification in corals and coralline macroalgae5,6, but the majority of marine calcification occurs in planktonic organisms. Here we report reduced calcite production at increased CO2 concentrations in monospecific cultures of two dominant marine calcifying phytoplankton species, the coccolithophorids Emiliania huxleyi and Gephyrocapsa oceanica . This was accompanied by an increased proportion of malformed coccoliths and incomplete coccospheres. Diminished calcification led to a reduction in the ratio of calcite precipitation to organic matter production. Similar results were obtained in incubations of natural plankton assemblages from the north Pacific ocean when exposed to experimentally elevated CO2 levels. We suggest that the progressive increase in atmospheric CO2 concentrations may therefore slow down the production of calcium carbonate in the surface ocean. As the process of calcification releases CO2 to the atmosphere, the response observed here could potentially act as a negative feedback on atmospheric CO2 levels.