Sedimentological, mineralogical, biogeochemical and micropaleontological parameters on sediment core PS69/849-2, Burton Basin, MacRobertson Shelf, East Antarctica

A multi-proxy study including sedimentological, mineralogical, biogeochemical and micropaleontological methods was conducted on sediment core PS69/849-2 retrieved from Burton Basin, MacRobertson Shelf, East Antarctica. The goal of this study was to depict the deglacial and Holocene environmental history of the MacRobertson Land-Prydz Bay region. A special focus was put on the timing of ice-sheet retreat and the variability of bottom-water formation due to sea ice formation through the Holocene. Results from site PS69/849-2 provide the first paleo-environmental record of Holocene variations in bottom-water production probably associated to the Cape Darnley polynya, which is the second largest polynya in the Antarctic. Methods included end-member modeling of laser-derived high-resolution grain size data to reconstruct the depositional regimes and bottom-water activity. The provenance of current-derived and ice-transported material was reconstructed using clay-mineral and heavy-mineral analysis. Conclusions on biogenic production were drawn by determination of biogenic opal and total organic carbon. It was found that the ice shelf front started to retreat from the site around 12.8 ka BP. This coincides with results from other records in Prydz Bay and suggests warming during the early Holocene optimum next to global sea level rise as the main trigger. Ice-rafted debris was then supplied to the site until 5.5 cal. ka BP, when Holocene global sea level rise stabilized and glacial isostatic rebound on MacRobertson Land commenced. Throughout the Holocene, three episodes of enhanced bottom-water activity probably due to elevated brine rejection in Cape Darnley polynya occured between 11.5 and 9 cal. ka BP, 5.6 and 4.5 cal. ka BP and since 1.5 cal. ka BP. These periods are related to shifts from warmer to cooler conditions at the end of Holocene warm periods, in particular the early Holocene optimum, the mid-Holocene warm period and at the beginning of the neoglacial. In contrast, between 7.7 and 6.7 cal. ka BP, brine rejection shut down, maybe owed to warm conditions and pronounced open-water intervals.

Seasonal changes in sediment core PS1795-2

The Weddell Sea and the associated Filchner-Rønne Ice Shelf constitute key regions for global bottomwater production today. However, little is known about bottom-water production under different climate and icesheet conditions. Therefore, we studied core PS1795, which consists primarily of fine-grained siliciclastic varves that were deposited on contourite ridges in the southeastern Weddell Sea during the Last Glacial Maximum (LGM). We conducted high-resolution X-ray fluorescence (XRF) analysis and grain-size measurements with the RADIUS tool (Seelos and Sirocko, 2005, doi:10.1111/j.1365-3091.2005.00715.x) using thin sections to characterize the two seasonal components of the varves at sub-mm resolution to distinguish the seasonal components of the varves. Bright layers contain coarser grains that can mainly be identified as quartz in the medium-to-coarse silt grain size. They also contain higher amounts of Si, Zr, Ca, and Sr, as well as more ice-rafted debris (IRD). Dark layers, on the other hand, contain finer particles such as mica and clay minerals from the chlorite and illite groups. In addition, Fe, Ti, Rb, and K are elevated. Based on these findings as well as on previous analyses on neighbouring cores, we propose a model of enhanced thermohaline convection in front of a grounded ice sheet that is supported by seasonally variable coastal polynya activity during the LGM. Accordingly, katabatic (i.e. offshore blowing) winds removed sea ice from the ice edge, leading to coastal polynya formation. We suggest that glacial processes were similar to today with stronger katabatic winds and enhanced coastal polynya activity during the winter season. Under these conditions, lighter coarser-grained layers are likely glacial winter deposits, when brine rejection was increased, leading to enhanced bottom-water formation and increased sediment transport. Vice versa, darker finer-grained layers were then deposited during less windier season, mainly during summer, when coastal polynya activity was likely reduced.

Stable oxygen and carbon isotope data for planktic and benthic foraminifera from southern Atlantic of DSDP Hole 74-525A and ODP Hole 113-690C

Published stable isotope records in marine carbonate are characterized by a positive d18O excursion associated with a negative d13C shift during the early Maastrichtian. However, the cause and even the precise timing of these excursions remain uncertain. We have generated high-resolution foraminiferal stable isotope and gray-scale records for the latest Campanian to early Maastrichtian (73-68 Ma) at two Ocean Drilling Program sites, 525 (Walvis Ridge) and 690 (Weddell Sea). We demonstrate that the negative d13C excursion is decoupled from the d18O increase with a lag of about 600 ka. Our d13C records (both planktic and benthic) show an amplitude for the negative excursion of 0.7 per mill that falls between about 72.1 and 70.7 Ma. Our planktic d18O records indicate an overall increase of 1.2 per mill from 73 to 68 Ma at Site 690, whereas at Site 525 they record a slightly smaller increase (1 per mill) that peaks around 70.1 Ma with decreasing values thereafter. Our benthic d18O data indicate an increase of 1.5 per mill at Site 525 and 0.7 per mill at Site 690 between about 71.4 and 69.9 Ma. Benthic d18O values show different baseline values at the two sites before and after the excursion, but the larger increase at Site 525 means that the values attained at the peak of the excursion are similar at the two sites. We interpret this observation in terms of water mass changes. The excursion is interpreted to reflect a cooling of bottom waters in response to the strengthening contribution of intermediate- to deep-water production in the high southern latitudes rather than increased ice volume. The associated carbon cycle perturbations that we observe are interpreted to reflect a weakening of surface water stratification and increased productivity, as supported by our gray value data.

Age determinations for ODP Sites in the Norwegian-Greenland Sea

Records of biogenic and terrigenous components have been obtained from the interval corresponding to the last 2.6 m.y. of ODP Sites 643 and 644 in order to reconstruct surface and deep water regimes in the Norwegian Sea. Surface water regimes record long lasting moderate glacial conditions during the interval 2.6 1.0 Ma. Small intrusions of Atlantic water episodically penetrated into the Norwegian Sea forming a narrow tongue along the eastern margin, which is documented at Site 644. The polar front was most probably situated between the Site 644 and 643 locations on the outer Voring Plateau during these time intervals. Deep water regimes reflect long-term persistent corrosive bottom waters, most probably due to a weakly undersaturated water column and a low rate of carbonate shell production in surface waters. Deep water production in the Norwegian-Greenland Sea may have operated in a different way, e.g. brine formation during winter sea ice growth. Bottom waters were oxygenated throughout the entire period, and deep water was exchanged persistently with the North Atlantic. Increased glacial/interglacial enviromental contrasts are documented, reflecting a strengthening of the Norwegian Current and intensified glaciations on the surrounding land masses during the interval 1.0 0.6 Ma. During this time a major shift in the mode of deep water production occurred. Tile onset of large amplitudes in glacial/interglacial environmental conditions with maximum contrasts in surface water regimes, different modes of deep water production, and intensified exchange with the North Atlantic marks the last 0.6 Ma. A broad development of the Norwegian Current is observed during peak interglacials, while during glacials seasonally variable sea ice cover and iceberg drift dominate surface water conditions.

Beryllium-10, mineralogy and grain size distribution of DSDP Hole 68-502B (Table 1)

We present a high-resolution 10Be profile from deep sea sediments (sampled from Hole 502B in the Caribbean sea) that strongly resembles the 10Be record in ice core profiles, particularly the Vostok core from Antarctica. This high-resolution profile revealed occurrences of enhanced 10Be concentrations at about 23-24, 37-39 and 60-65 ka. The excellent match between these peaks appearing in a georeservoir profile other than in polar ice, strengthens the implications that can be inferred from 10Be and provide global markers for chronological correlation of climatic events. The position at low latitude of the studied sediment section is, unlike the case with the high latitude polar regions, excellent for exposing causes of modulation in 10Be production. We interpret the source of the pattern and enhancements, particularly the 37-39 ka peak, of 10Be to be global and do not strictly relate to climatic conditions and/or production rates specific to the polar regions.

Quantitative silicoflagellate data from the southern Indic Ocean from ODP Holes 188-1165B, 120-748B and 120-751A

In the modern marine environment the silicoflagellate genus Dictyocha is rare, or absent, south of the Antarctic polar front (APF); the genus Distephanus, in contrast, is dominant. In sediments recovered from ODP Site 1165, 1600 km south of the front, however, three intervals where Dictyocha is abundant are interpreted to represent Pliocene warm events. Comparison of our data with Ciesielski and Weaver's [1974] modern core top silicoflagellate relationship with sea surface temperature (SST) indicates that at Site 1165 mean annual SST was approximately 5°C at 3.7 Ma (event I), and approximately 4°C at 4.3-4.4 Ma (event II) and 4.55-4.8 Ma (event III). Event I represents a 5.5°C warming, and events II and III represents a 4.5°C warming relative to modern mean annual SST. Dictyocha is absent from other Site 1165 Pliocene intervals, which suggests that cooler SST (<2°C) prevailed. The warm events detected at Site 1165 may represent times when North Atlantic Deep Water production and ocean heat transport into the Southern Ocean exerted maximum influence.

Stable isotope record and composition of planktonic foraminifera from ODP Site 172-1056

The stable isotopic composition of two planktonic foraminifer species (Globigerinoides sacculifer and Neogloboquadrina dutertrei) and two benthic foraminifer species (Cibicidoides wuellerstorfi and Uvigerina peregrina) was measured at sub-orbital resolution through the marine isotope stages (MISs) 10, 11, and 12 (345-460 ka) at Site 1056 on the Blake-Bahama Outer Ridge. Planktonic foraminifers were counted for the interval 405-450 ka at 2-4-kyr resolution. Site 1056 (32°29'N, 76°20'W) is located on the continental slope (water depth: 2167 m) beneath the Gulf Stream. The average rate of sediment accumulation through the interval is 11.4 cm/kyr, but sediment accumulation is much more rapid during glacial intervals (15-17 cm/kyr). The decline in percent carbonate during glacial intervals, and its rise during interglacials, indicates that the increased sediment supply is of terrigenous origin. Low carbonate values and low benthic delta13C, which are both associated with a weak Western Boundary Undercurrent and low North Atlantic Deep Water production, persist for 6 kyr after the benthic delta18O record indicates that ice volume has begun to decrease. Recovery of carbonate and benthic delta13C values is abrupt and rapid. Millennial-scale variation (~3-4 kyr) is apparent in the glacial intervals of the planktonic delta18O records and is more pronounced in a Delta delta18O record, which represents the temperature range in the photic zone. Semi-precessional (10-12-kyr) cycles are apparent in the planktonic deltadelta13C record. The millennial-scale cycles are largely caused by an increase in G. sacculifer delta18O and represent surface warming. They are interpreted as representing periodic increases in westward intensification of the gyre. The semi-precessional cycles are driven by changes in the N. dutertrei delta13C and represent fluctuations in the Gulf Stream itself and therefore likely have a tropical origin. Planktonic foraminifer census counts did not show an expected response to one of the largest glacial/interglacial transitions of the late Pleistocene. The most obvious change was an increase in faunal diversity during MIS 12.2, the interval of maximum delta18O values. This suggests that cool slope water and warm subtropical gyre water penetrated a more sluggish Gulf Stream with greater frequency at this time. The millennial-scale maxima in the Delta delta18O record are accompanied by decreases in diversity, which is consistent with the interpretation of surface warming during these events.

Lack of an osmotic constraint on intake rate of the eastern curlew Numenius madagascariensis

Rates of food intake in animals consuming abundant prey can be constrained by the rates of digestion or excretion of ingested substances, such as salt, particularly so in the animals that regularly migrate between freshwater and saltwater environments. We tested this hypothesis in a long-distance migrant shorebird, the eastern curlew Numenius madagascariensis (suborder Charadrii), foraging on intertidal decapods in eastern Australia. We predicted that if food intake rates are constrained osmotically, individuals with access to freshwater and less saline prey (FW group) would have higher rates of food and water intake than individuals with seawater-only access (SW group). Food intake rates did not differ between the FW and SW groups (0.14 g ash-free dry mass min(-1)), nor did the water influx rates (0.75 g min(-1)). Salt intake rates were lower at FW sites (19.3 versus 23.3 mg NaCl min(-1)) and overall they were similar to those of marine birds. Food intake rate in the eastern curlew appeared limited by digestive rather than by osmoregulatory capacity.

On the statistical analysis of the GS-NS0 cell proteome: Imputation, clustering and variability testing

We have undertaken two-dimensional gel electrophoresis proteomic profiling on a series of cell lines with different recombinant antibody production rates. Due to the nature of gel-based experiments not all protein spots are detected across all samples in an experiment, and hence datasets are invariably incomplete. New approaches are therefore required for the analysis of such graduated datasets. We approached this problem in two ways. Firstly, we applied a missing value imputation technique to calculate missing data points. Secondly, we combined a singular value decomposition based hierarchical clustering with the expression variability test to identify protein spots whose expression correlates with increased antibody production. The results have shown that while imputation of missing data was a useful method to improve the statistical analysis of such data sets, this was of limited use in differentiating between the samples investigated, and highlighted a small number of candidate proteins for further investigation. (c) 2006 Elsevier B.V. All rights reserved.

Computer simulation of liquid flow patterns on distillation trays

This thesis describes work carried out to improve the fundamental modelling of liquid flows on distillation trays. A mathematical model is presented based on the principles of computerised fluid dynamics. It models the liquid flow in the horizontal directions allowing for the effects of the vapour through the use of an increased liquid turbulence, modelled by an eddy viscosity, and a resistance to liquid flow caused by the vapour being accelerated horizontally by the liquid. The resultant equations are similar to the Navier-Stokes equations with the addition of a resistance term.A mass-transfer model is used to calculate liquid concentration profiles and tray efficiencies. A heat and mass transfer analogy is used to compare theoretical concentration profiles to experimental water-cooling data obtained from a 2.44 metre diameter air-water distillation simulation rig. The ratios of air to water flow rates are varied in order to simulate three pressures: vacuum, atmospheric pressure and moderate pressure.For simulated atmospheric and moderate pressure distillation, the fluid mechanical model constantly over-predicts tray efficiencies with an accuracy of between +1.7% and +11.3%. This compares to -1.8% to -10.9% for the stagnant regions model (Porter et al. 1972) and +12.8% to +34.7% for the plug flow plus back-mixing model (Gerster et al. 1958). The model fails to predict the flow patterns and tray efficiencies for vacuum simulation due to the change in the mechanism of liquid transport, from a liquid continuous layer to a spray as the liquid flow-rate is reduced. This spray is not taken into account in the development of the fluid mechanical model. A sensitivity analysis carried out has shown that the fluid mechanical model is relatively insensitive to the prediction of the average height of clear liquid, and a reduction in the resistance term results in a slight loss of tray efficiency. But these effects are not great. The model is quite sensitive to the prediction of the eddy viscosity term. Variations can produce up to a 15% decrease in tray efficiency. The fluid mechanical model has been incorporated into a column model so that statistical optimisation techniques can be employed to fit a theoretical column concentration profile to experimental data. Through the use of this work mass-transfer data can be obtained.

Bacterial associations with salmonid eggs

Rainbow trout eggs Salmo gairdneri, Richardson, were incubated under a range of different environmental conditions. Recovery of bacteria from egg surfaces revealed that increased water temperature, slow water flow rates and high egg density all significantly increased egg surface bacterial populations. Live eggs were mainly colonized by Cytophaga sp., pseudomonas fluorescens and Aeromonas hydrophila. In contrast, dead eggs supported considerable numbers of fluorescent Pseudomonas sp. Analysis of potential nutrient sources for bacteria colonizing live egg surfaces revealed that small amounts of amino acids, phosphate and potassium may be lost by incubating eggs. Subsequently these nutrients were shown to be capable of supporting limited bacterial growth and reproduction. Dead eggs `leaked' increased amounts of the above nutrients which in turn supported higher bacterial numbers. In addition, biochemical analysis of eggs revealed amino acids and fatty acids that might be utilized by bacteria colonizing dead egg surfaces. Assessment of adhesion properties of bacteria frequently recovered from egg surfaces revealed high cell surface hydrophobicity as an important factor in successful egg colonization. Analysis of egg mortalities from groups of rainbow trout and brown trout (S.trutta L.) eggs maintained under two different incubation systems revealed that potentially a close correlation existed between egg surface bacterial numbers and mortalities in the egg during incubation. Innoculation of newly-fertilized eggs with bacteria demonstrated that groups of eggs supporting high numbers of P.fluorescens suffered significantly higher mortalities during the early part of their incubation. Exposure of incubating eggs to oxolinic acid, chlortetracycline and chloramphenicol demonstrated that numbers of bacteria on egg surfaces could be significantly reduced. However, as no corresponding increase in egg hatching success was revealed, the treatment of incubating eggs with antibiotics or antimicrobial compounds can not be recommended. In commercial hatcheries bacteria are only likely to be responsible for egg deaths during incubation when environmental conditions are unfavourable. High water temperatures, slow water flow rates and high egg density all lead to increased bacterial number of egg surfaces, reduced water circulation and low levels of dissolved oxygen. Under such circumstances sufficient amounts of dissolved oxygen may not be available to support developing embryos.

New solid base catalysts for biodiesel synthesis

The application of heterogeneous catalysts for the manufacture of renewable biodiesel fuels offers an exciting, alternative clean chemical technology to current energy intensive processes employing soluble base catalysts. We recently synthesised tuneable MgO nanocrystals as efficent solid base catalysts for biodiesel synthesis, and have developed a simple X-ray spectroscopic method to quantitatively determine surface basicity, thereby providing a rapid screening tool for predicting the reactivity of new solid base catalysts. Promotion of these MgO nanocrystals through Cs doping dramatically enhances biodiesel production rates due to the formaion of a mixed Cs Mg(CO ) phase. These MgO derived nanocatalysts permit energy efficent, continuous processing of diverse, sustainable oil feedstocks in flow reactors.

Trained Neural Network Characterizing Variables for Predicting Organic Retention by Nanofiltration Membranes

Many organic compounds cause an irreversible damage to human health and the ecosystem and are present in water resources. Among these hazard substances, phenolic compounds play an important role on the actual contamination. Utilization of membrane technology is increasing exponentially in drinking water production and waste water treatment. The removal of organic compounds by nanofiltration membranes is characterized not only by molecular sieving effects but also by membrane-solute interactions. Influence of the sieving parameters (molecular weight and molecular diameter) and the physicochemical interactions (dissociation constant and molecular hydrophobicity) on the membrane rejection of the organic solutes were studied. The molecular hydrophobicity is expressed as logarithm of octanol-water partition coefficient. This paper proposes a method used that can be used for symbolic knowledge extraction from a trained neural network, once they have been trained with the desired performance and is based on detect the more important variables in problems where exist multicolineality among the input variables.