(Table 1, page 168) Iron, manganese, and phosphorus concentrations in Fe-Mn-concretions from the Gulf of Bothnia, northern Baltic Sea

Fe-Mn-concretions of a spheroidal type were found according to electron probe determinations to consist of alternating iron- and manganese-rich layers. This pattern was ascribed to seasonal variations in the physico-chemical conditions governing the precipitation of the hydrous oxides of iron and manganese. Calculations based on the rhythmic growth of the concretions investigated gave a mean accumulation rate of 0.15-0.20 mm/yr. The rather high phosphorus content (average 3.5 % P2O5) of the concretions was found to be concentrated in the iron-rich layers, probably as a result of the scavenging effect of ferric hydroxide.

Geochemistry of Eocene/Oligocene sediments of ODP Site 177-1090

The Agulhas Ridge, off the tip of Africa between the Atlantic and Indian Oceans, is ideally located to capture the evolution of Paleogene-early Neogene circulation patterns associated with global cooling. Multiproxy records of productivity (biogenic barium (Baex), opal, CaCO3 mass accumulation rates (MARs)), nutrient and organic carbon burial (reactive phosphorus (Pr) MARs), and redox state of deep waters (U enrichment) from Ocean Drilling Program (ODP) Site 1090 reflect hydrographic shifts in this region between the middle Eocene and early Oligocene (~9-33 Ma). Several peaks in increased export productivity and burial of organic matter occurred within the late Eocene (~36.5, ~34, and ~33.7 Ma), which along with surface hydrologic conditions favoring opaline organisms over calcareous organisms could have aided in the draw down of pCO2 to a threshold level that facilitated large ice sheet development on Antarctica in the earliest Oligocene. Our multiproxy approach illustrates the importance of vertical as well as spatial hydrographic reorganization in amplifying or driving climatic cooling of the middle Eocene to early Oligocene by facilitating increases in the relative or absolute burial of organic carbon.

Major and trace element composition of clinopyroxenes from an olivine gabbro of ODP Hole 176-735B (Table 1)

Major and trace element profiles of clinopyroxene grains in oceanic gabbros from ODP Hole 735B have been investigated by a combined in situ analytical study with ion probe, and electron microprobe. In contrast to the homogeneous major element compositions, trace elements (REE, Y, Cr, Sr, and Zr) show continuous core to rim zoning profiles. The observed trace element systematics in clinopyroxene cannot be explained by a simple diffusive exchange between melts and gabbros along grain boundaries. A simultaneous modification of the melt composition is required to generate the zoning, although Rayleigh fractional crystallization modelling could mimic the general shape of the profiles. Simultaneous metasomatism between the cumulate crystal and the porous melt during crystal accumulation is the most likely process to explain the zoning. Deformation during solidification of the crystal mush could have caused squeezing out of the incompatible element enriched residual melts (interstitial liquid). Migration of the melt along grain boundaries might carry these melt out of the system. This process named as synkinematic differentiation or differentiation by deformation (Natland and Dick, 2001, doi:10.1016/S0377-0273(01)00211-6) may act as an important magma evolution mechanism in the oceanic crust, at least at slow-spreading ridges.

(Table 1) Grain size, sedimentation rates and accumulation rates of ODP Hole 152-919A coarse-sand ice-rafted debris

At mid- to high-latitude marine sites, ice-rafted debris (IRD) is commonly recognized as anomalously coarse-grained terrigenous material contained within a fine-grained hemipelagic or pelagic matrix (e.g., Conolly and Ewing, 1970; Ruddiman, 1977, doi:10.1130/0016-7606(1977)88<1813:LQDOIS>2.0.CO;2; Krissek, 1989, doi:10.2973/odp.proc.sr.104.114.1989; Jansen et al., 1990; Bond et al., doi:10.1038/360245a0, 1992; Krissek, 1995, doi:10.2973/odp.proc.sr.145.118.1995). The presence of such ice-rafted material is a valuable indicator of the presence of glacial ice at sea level on an adjacent continent, whereas the composition of the IRD can often be used to identify the location of the source area (e.g., Goldschmidt, 1995, doi:10.1016/0025-3227(95)00098-J). Because the amount of core recovered during Leg 163 was very limited, this shore-based, postcruise study focuses on materials recovered at a nearby site during Leg 152. In particular, this study examines sediments recovered at Site 919; these sediments were described as containing a significant ice-rafted component in the Leg 152 Initial Reports volume (Larsen, Saunders, Clift, et al., 1994, doi:10.2973/odp.proc.ir.152.1994). In this study, the sedimentary section from Site 919 has been examined with the goal of providing a detailed history of glaciations on Greenland and other landmasses adjacent to the Norwegian-Greenland Sea; this history ultimately will be calibrated using an oxygen isotope stratigraphy (Flower, 1998, doi:10.2973/odp.proc.sr.152.219.1998), although that calibration has not been completed at this time. Because ice-core studies of the Greenland Ice Sheet (GIS) have shown that the GIS changed dramatically, and in some cases extremely rapidly, during at least the last interglacial stage (GRIP Members, 1993, doi:10.1038/364203a0), a detailed IRD record from the Southeast Greenland margin should provide insight into the longer term behavior of this sensitive component of the Northern Hemisphere climate system.

Age determinations, biomarker analyses, and accumulation rates of three sediment cores from the Fram Strait

A reconstruction of Holocene sea ice conditions in the Fram Strait provides insight into the palaeoenvironmental and palaeoceanographic development of this climate sensitive area during the past 8,500 years BP. Organic geochemical analyses of sediment cores from eastern and western Fram Strait enable the identification of variations in the ice coverage that can be linked to changes in the oceanic (and atmospheric) circulation system. By means of the sea ice proxy IP25, phytoplankton derived biomarkers and ice rafted detritus (IRD) increasing sea ice occurrences are traced along the western continental margin of Spitsbergen throughout the Holocene, which supports previous palaeoenvironmental reconstructions that document a general cooling. A further significant ice advance during the Neoglacial is accompanied by distinct sea ice fluctuations, which point to short-term perturbations in either the Atlantic Water advection or Arctic Water outflow at this site. At the continental shelf of East Greenland, the general Holocene cooling, however, seems to be less pronounced and sea ice conditions remained rather stable. Here, a major Neoglacial increase in sea ice coverage did not occur before 1,000 years BP. Phytoplankton-IP25 indices ("PIP25-Index") are used for more explicit sea ice estimates and display a Mid Holocene shift from a minor sea ice coverage to stable ice margin conditions in eastern Fram Strait, while the inner East Greenland shelf experienced less severe to marginal sea ice occurrences throughout the entire Holocene.

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.

Major and trace element composition in the Central Indian Ocean Basin ferrobasalts (Table 2, 3)

We report the occurrence of ferrobasalts recovered from the Central Indian Ocean Basin crust generated at the Southeast Indian Ridge during a phase of moderate to fast spreading accretion (~110-190 mm/yr, full rate).The rocks are rich in plagioclase, FeO* (13/19 %), and TiO2 (2.27/2.76 %), poor in olivine and MgO (3.44/6.20%), and associated with topographic highs and increased amplitude magnetic anomalies corresponding to chrons A25 and A24. We suggest that secon dary eruptions from ancient N-MORB magma, which may have been trapped at a shallow depth in a horizon of neutral buoyancy, could have produced the ferrobasalts.

Accumulation rates and composition of organic matter in sediments off Peru

Deep-sea sediment samples from three Ocean Drilling Program (ODP) Leg 112 sites on the Peru continental margin were investigated, using a number of organic geochemical and organic petrographic techniques, for amounts and compositions of the organic matter preserved. Preliminary results include mass accumulation rates of organic carbon at Site 679 and characteristics of the organic facies for sediments from Sites 679, 681, and 684. Organic-carbon contents are high, with few exceptions. Particularly high values were determined in the Pliocene interval at Site 684 (4%-7.5%) and in the early Pliocene to Quaternary section of Hole 679D (2%-9%). Older sediments at this site have distinctively lower organic-carbon contents (0.2%-2.5%). Mass accumulation rates of organic matter at Site 679 are 0.02 to 0.07 g carbon/cm**2/k.y. for late Miocene to early Pliocene sediments and higher by a factor of 5 to 10 in the Quaternary sediments. The organic matter in all samples has a predominantly marine planktonic and bacterial origin, with minor terrigenous contribution. Organic particle sizes are strikingly small, so that only a minor portion is covered by visual maceral analysis. Molecular organic-geochemical data were obtained for nonaromatic hydrocarbons, aromatic hydrocarbons (including sulfur compounds), alcohols, ketones, esters, and carboxylic acids. Among the total extractable lipids, long-chain unsaturated ketones from Prymnesiophyte algae strongly predominate among the gas chromatography (GC) amenable components. Steroids are major constituents of the ketone and free- and bound-alcohol fractions. Perylene is the most abundant aromatic hydrocarbon, whereas in the nonaromatic hydrocarbon fractions, long-chain n-alkanes from higher land plants predominate, although the total terrigenous organic matter proportion in the sediments is small.

Geochemical parameters of bottom sediments from the Tajura Rift, Gulf of Aden

Results of a geochemical study of bottom sediments from the Tadjura rift zone are reported. The sediments were analyzed for CaCO3, Si, Al, Ti, Fe, Mn, Cu, Zn, Ni, Co, Cr, V, Zr, Ga, Yb and Y. It was found that formation of chemical composition of the sediments was controlled by factors being appropriate for a near-continental area of the arid climatic zone (aeolian supply of terrigenous material and high biological productivity), as well as by hydrothermal activity in the rift valley. It was shown that high Mn contents were typical for the sediments in study while maximal contents of Fe were found near supposed hydrothermal sources. Total flux of Mn into sediments was been calculated. Diagenetic redistribution gives the main contribution of Mn in surface layer sediments. Speciations of Fe, Mn, Cu, Zn, Ni, Co, and Al were studied. In the surface layer sediments iron and manganese were in hydroxides. Model calculations of contents of chemical elements in sediments of the area in study are given.

Identifying causes for N2O accumulation in a lab-scale sequencing batch reactor performing simultaneous nitrification, denitrification and phosphorus removal

The recently described process of simultaneous nitrification, denitrification and phosphorus removal (SNDPR) has a great potential to save capital and operating costs for wastewater treatment plants. However, the presence of glycogen-accumulating organisms (GAOs) and the accumulation of nitrous oxide (N2O) can severely compromise the advantages of this process. In this study, these two issues were investigated using a lab-scale sequencing batch reactor performing SNDPR over a 5-month period. The reactor was highly enriched in polyphosphate-accumulating organisms (PAOs) and GAOs representing around 70% of the total microbial community. PAOs were the dominant population at all times and their abundance increased, while GAOs population decreased over the study period. Anoxic batch tests demonstrated that GAOs rather than denitrifying PAOs were responsible for denitrification. NO accumulated from denitrification and more than half of the nitrogen supplied in a reactor cycle was released into the atmosphere as NO. After mixing SNDPR sludge with other denitrifying sludge, N2O present in the bulk liquid was reduced immediately if external carbon was added. We therefore suggest that the N2O accumulation observed in the SNDPR reactor is an artefact of the low microbial diversity facilitated by the use of synthetic wastewater with only a single carbon source. (C) 2005 Elsevier B.V. All rights reserved.

The effect of Cu addition and milling contaminations on the microstructure evolution of ball milled Al-Pb alloy during sintering

Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu (x = 0-7.0) bulk alloys were prepared by sintering the mechanically alloyed powders at various temperatures. The microstructure changes of the as consolidated powders in the course of sintering were analyzed by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction analysis and transmission electron microscopy. It has been found that, with respect to the Al-10 wt.%Pb-x wt.%Cu alloy, CuAl2 and Cu9Al4 phases formed in the milling process, and the amount of CuAl2 phase increased while the Cu9Al4 phase disappeared gradually in the sintering process. In both Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu alloys, the sintering process results in the coarsening of Pb phase and the growth rate of Pb phase fulfills the Lifshitz-Slyozov-Wagner equation even though the size of the Pb phase was in nanometer range. The Pb particle exhibits cuboctahedral morphology and has a cubic to cubic orientation relationship with the Al matrix. The addition of Cu strongly depressed the growth rate of Pb. Contamination induced by milling has apparent influence on the microstructure of the sintered alloys. Al7Cu2Fe and aluminium oxide phases were identified in the sintered alloys. The cuboctahedral morphology of Pb particles was broken up by the presence of the oxide phase. (c) 2006 Elsevier B.V. All rights reserved.

Amino acid, peptide and drug transport across monolayers of human intestinal (CAC0-2) cells in vitro

The properties of Caco-2 monolayers were compared on aluminium oxide and nitrocellulose permeable-supports. On nitrocellulose, Caco-2 cells displayed a higher rate of taurocholic acid transport than those cultured on aluminium oxide inserts. In addition, Caco-2 cells grown on these two inserts were not comparable with respect to cell morphology, cell numbers and transepithelial electrical resistance. The low adsorption potential of the aluminium oxide inserts, particularly for high molecular weight or lipophilic ligands, offers a distinct advantage over nitrocellulose inserts for drug transport studies. The carrier-mediated uptake and transport of the imino acid (L-proline) and the acidic amino acids (L-aspartate and L-glutamate) have been studied. At pH7.4, L-proline uptake is mediated via an A-system carrier. Elevated uptake and transport under acidic conditions occurs by activation of a distinct carrier population. Acidic amino acid transport is mediated via a X-AG system. The flux of baclofen, CGP40116 andCGP40117 across Caco-2 monolayers was described by passive transport. The transport of three peptides, thyrotrophin-releasing hormone, SQ29852 and cyclosporin were investigated. Thyrotrophin-releasing hormone transport acrossCaco-2 monolayers was characterised by a minor saturable (carrier-mediated,approximately 25%) pathway, superimposed onto a major non-saturable (diffusional)pathway. SQ29852 uptake into Caco-2 monolayers is described by a major saturable mechanism (Km = 0.91 mM) superimposed onto a minor passive component.However, the initial-rate of SQ29852 transport is consistent with a passive transepithelial transport mechanism. These data highlight the possibility that itsbasolateral efflux is severely retarded such that the passive paracellular transportdictates the overall transepithelial transport characteristics. In addition, modelsuitable for investigating the transepithelial transport of cyclosporin A has been developed. A modification of the conventional Caco-2 model has been developed which has a calcium-free Ap donor-solution and a Bl receiver-solution containing the minimumcalcium concentration required to maintain monolayer integrity (100 μM). The influence of calcium and magnesium on the absorption of [14C]pamidronate was evaluated by comparing its transport across the conventional and minimum calciumCaco-2 models. Ap calcium and magnesium ions retard the Ap-to-Bl flux of pamidronate across Caco-2 monolayers. The effect of self-emulsifying oleic acid-Tween 80 formulations on Caco-2monolayer integrity has been investigated. Oleic acid-Tween 80 (1 0:1) formulations produced a dose-dependent disruption of Caco-2 monolayer integrity. This disruption was related to the oleic acid content of the formulation.

Adhesive bonding of aluminium

Adhesive bonding of aluminium is widely used in the aerospace industry. High initial bood strengths can be obtained, but bond failure occurs atter prolonged exposure to humid enviroments. The thesis contains details ot a test procedure which has been designed and developed for the assessment of different alloys, pretreatments, and adhesives, which will give adhesively bonded aluminium joints of high strength coupled with long term durability. The test involves assembly of lap shear specimens in a precision jig using 250 ballotini spacers in the adhesive to control the bond line thickness. The test is modified by drilling three accurately located holes through the bonded area after assembly of the joint and curing of the adhesive. Further important features at the test, such as fillet control, are detailed. The test was assessed, modified and developed to give a reliable and reproducible method which would discriminate amongst different bonding systems after exposure to humid test environments. This is the first test to have achieved the discrimination necessary for short term assessment of bond systems where long term durability is required. Even better discrimination has been obtained by applying stress in a stress humidity test. Having established accurate, reliable and discriminating test methods they were used to study the durability of structural epoxy adhesive bonds to aluminium as a function of alloy, pretreatment, adhesive and environment. It was established that the long term durability or adhesively bonded aluminium was directly related to the infulence of water migrating within the adhesive. Pretreatments differed in their ability to prevent hydration of the aluminium oxide by the water absorbed within the adhesive.

Calcium carbonate global LGM Burial rate data

Global databases of calcium carbonate concentrations and mass accumulation rates in Holocene and last glacial maximum sediments were used to estimate the deep-sea sedimentary calcium carbonate burial rate during these two time intervals. Sparse calcite mass accumulation rate data were extrapolated across regions of varying calcium carbonate concentration using a gridded map of calcium carbonate concentrations and the assumption that accumulation of noncarbonate material is uncorrelated with calcite concentration within some geographical region. Mean noncarbonate accumulation rates were estimated within each of nine regions, determined by the distribution and nature of the accumulation rate data. For core-top sediments the regions of reasonable data coverage encompass 67% of the high-calcite (>75%) sediments globally, and within these regions we estimate an accumulation rate of 55.9 ± 3.6 x 10**11 mol/yr. The same regions cover 48% of glacial high-CaCO3 sediments (the smaller fraction is due to a shift of calcite deposition to the poorly sampled South Pacific) and total 44.1 ± 6.0 x 10**11 mol/yr. Projecting both estimates to 100 % coverage yields accumulation estimates of 8.3 x 10**12 mol/yr today and 9.2 x 10**12 mol/yr during glacial time. This is little better than a guess given the incomplete data coverage, but it suggests that glacial deep sea calcite burial rate was probably not considerably faster than today in spite of a presumed decrease in shallow water burial during glacial time.