Component NRM directions for sediment core HLY0503-06JPC

The Arctic oceans have been fertile ground for the recording of apparent excursions of the geomagnetic field, implying that the high latitude field had unusual characteristics at least over the last 1-2 Myrs. Alternating field demagnetization of the natural remanent magnetization (NRM) of Core HLY0503-6JPC from the Mendeleev Ridge (Arctic Ocean) implies the presence of primary magnetizations with negative inclination apparently recording excursions in sediments deposited during the Brunhes Chron. Thermal demagnetization, on the other hand, indicates the presence of multiple (often anti-parallel) magnetization components with negative inclination components having blocking temperatures predominantly, but not entirely, below ~ 350 °C. Thermo-magnetic tests, X-ray diffraction (XRD) and scanning electron microscopy (SEM) indicate that the negative inclination components are carried by titanomaghemite, presumably formed by seafloor oxidation of titanomagnetite. The titanomaghemite apparently carries a chemical remanent magnetization (CRM) that is partially self-reversed relative to the detrital remanent magnetization (DRM) carried by the host titanomagnetite. The partial self-reversal could have been accomplished by ionic ordering during oxidation, thereby changing the balance of the magnetic moments in the ferrimagnetic sublattices.

Silicon isotope ratios of ODP Site 177-1089 and sediment core E33-22

Reconstruction of nutrient concentrations in the deep Southern Ocean has produced conflicting results. The cadmium/calcium (Cd/Ca) data set suggests little change in nutrient concentrations during the last glacial period, whereas the carbon isotope data set suggests that nutrient concentrations were higher. We determined the silicon isotope composition of sponge spicules from the Atlantic and Pacific sectors of the Southern Ocean and found higher silicic acid concentrations in the Pacific sector during the last glacial period. We propose that this increase results from changes in the stoichiometric uptake of silicic acid relative to nitrate and phosphate by diatoms, thus facilitating a redistribution of nutrients across the Pacific and Southern Oceans. Our results are consistent with the global Cd/Ca data set and support the silicic acid leakage hypothesis.

Organic and inorganic geochemical measurements of sediment core GeoB7702-3

It has long been known that extreme changes in North African hydroclimate occurred during the late Pleistocene yet many discrepancies exist between sites regarding the timing, duration and abruptness of events such as Heinrich Stadial (HS) 1 and the African Humid Period (AHP). The hydroclimate history of the Nile River is of particular interest due to its lengthy human occupation history yet there are presently few continuous archives from the Nile River corridor, and pre-Holocene studies are rare. Here we present new organic and inorganic geochemical records of Nile Basin hydroclimate from an eastern Mediterranean (EM) Sea sediment core spanning the past 28 ka BP. Our multi-proxy records reflect the fluctuating inputs of Blue Nile versus White Nile material to the EM Sea in response to gradual changes in local insolation and also capture abrupt hydroclimate events driven by remote climate forcings, such as HS1. We find strong evidence for extreme aridity within the Nile Basin evolving in two distinct phases during HS1, from 17.5 to 16 ka BP and from 16 to 14.5 ka BP, whereas peak wet conditions during the AHP are observed from 9 to 7 ka BP. We find that zonal movements of the Congo Air Boundary (CAB), and associated shifts in the dominant moisture source (Atlantic versus Indian Ocean moisture) to the Nile Basin, likely contributed to abrupt hydroclimate variability in northern East Africa during HS1 and the AHP as well as to non-linear behavior of hydroclimate proxies. We note that different proxies show variable gradual and abrupt responses to individual hydroclimate events, and thus might have different inherent sensitivities, which may be a factor contributing to the controversy surrounding the abruptness of past events such as the AHP. During the Late Pleistocene the Nile Basin experienced extreme hydroclimate fluctuations, which presumably impacted Paleolithic cultures residing along the Nile corridor.

Neodymium isotopic record of planktonic foraminifera in sediment core MD81-LC21

A well developed sapropel (S5) was deposited in the eastern Mediterranean during the Last Interglacial (Eemian), 124-119 ka. Freshwater contributions to the basin at this time can be traced using the isotopic composition of Nd in planktonic foraminifera. This enables differentiation between radiogenic sources to the south, under the influence of the African monsoon, and unradiogenic sources to the north, relating to the mid-latitude westerlies. Here we compare new Nd data, from a core in the southeast Aegean Sea, with published data from the Ionian and Levantine Seas. Shifts towards more radiogenic Nd in the lower and middle parts of sapropel S5 are most pronounced in the Ionian Sea record, with epsioln-Nd and d18O G. ruber co-varying more closely here than in the Levantine and Aegean Seas. This is consistent with a freshwater source proximal to the Ionian Sea site, likely indicating a substantial reactivation of rivers flowing northward from the central Saharan watershed. The lack, during S5 deposition, of a noticeable shift towards more unradiogenic Nd in the Aegean record would exclude a large influx of water from the northern borders of the eastern Mediterranean during sapropel deposition. These findings support a scenario whereby the Last Interglacial eastern Mediterranean was influenced strongly by the remote effects of an intensified African monsoon, with more local precipitation in the northern borders contributing relatively little to the sea surface composition.

Organic and inorganic geochemistry and archaeal community composition of hypersaline sediments from Orca Basin, RV Atlantis Expedition AT18-02

Among the most extreme habitats on Earth, dark, deep, anoxic brines host unique microbial ecosystems that remain largely unexplored. As the terminal step of anaerobic degradation of organic matter, methanogenesis is a potentially significant but poorly constrained process in deep-sea hypersaline environments. We combined biogeochemical and phylogenetic analyses as well as incubation experiments to unravel the origin of methane in hypersaline sediments of Orca Basin in the northern Gulf of Mexico. Substantial concentrations of methane (up to 3.4 mM) coexisted with high concentrations of sulfate (16-43 mM) in two sediment cores retrieved from the northern and southern parts of Orca Basin. The strong depletion of 13C in methane (-77 to -89 per mill) pointed towards a biological source. While low concentrations of competitive substrates limited the significance of hydrogenotrophic and acetoclastic methanogenesis, the presence of non-competitive methylated substrates (methanol, trimethylamine, dimethyl sulfide, dimethylsulfoniopropionate) supported the potential for methane generation through methylotrophic methanogenesis. Thermodynamic calculations demonstrated that hydrogenotrophic and acetoclastic methanogenesis were unlikely to occur under in situ conditions, while methylotrophic methanogenesis from a variety of substrates was highly favorable. Likewise, carbon isotope relationships between methylated substrates and methane supported methylotrophic methanogenesis as the major source of methane. Stable isotope tracer and radiotracer experiments with 13C bicarbonate, acetate and methanol as well as 14C-labeled methylamine indicated that methylotrophic methanogenesis was the predominant methanogenic pathway. Based on 16S rRNA gene sequences, halophilic methylotrophic methanogens related to the genus Methanohalophilus dominated the benthic archaeal community in the northern basin but also occurred in the southern basin. High abundances of methanogen lipid biomarkers such as intact polar and polyunsaturated hydroxyarchaeols were detected in sediments from the northern basin, with lower abundances in the southern basin. Strong 13C-depletion of saturated and monounsaturated hydroxyarchaeol were consistent with methylotrophic methanogenesis as the major methanogenic pathway. Collectively, the availability of methylated substrates, thermodynamic calculations, experimentally determined methanogenic activity as well as lipid and gene biomarkers strongly suggested methylotrophic methanogenesis as predominant pathway of methane formation in the presence of sulfate in Orca Basin sediments.

Charge transport in a quantum electromechanical system

We describe a quantum electromechanical system comprising a single quantum dot harmonically bound between two electrodes and facilitating a tunneling current between them. An example of such a system is a fullerene molecule between two metal electrodes [Park et al., Nature 407, 57 (2000)]. The description is based on a quantum master equation for the density operator of the electronic and vibrational degrees of freedom and thus incorporates the dynamics of both diagonal (population) and off diagonal (coherence) terms. We derive coupled equations of motion for the electron occupation number of the dot and the vibrational degrees of freedom, including damping of the vibration and thermo-mechanical noise. This dynamical description is related to observable features of the system including the stationary current as a function of bias voltage

A method for screening the temperature dependence of three-dimensional crystal formation

Temperature is an important parameter controlling protein crystal growth. A new temperature-screening system (Thermo-screen) is described consisting of a gradient thermocycler fitted with a special crystallization-plate adapter onto which a 192-well sitting-drop crystallization plate can be mounted (temperature range 277-372 K; maximum temperature gradient 20 K; interval precision 0.3 K). The system allows 16 different conditions to be monitored simultaneously over a range of 12 temperatures and is well suited to conduct wide (similar to 20 K) and fine (similar to 3 K) temperature-optimization screens. It can potentially aid in the determination of temperature phase diagrams and run more complex temperature-cycling experiments for seeding and crystal growth.

Fracture load and marginal fit of shrinkage-free ZrSiO4 all-ceramic crowns after chewing simulation

The aim of this in vitro study was to evaluate the fracture load and marginal accuracy of crowns made from a shrinkage-free ZrSiO4 ceramic cemented with glass-ionomer or composite cement after chewing simulation. Thirty-two human mandibular molars were randomly divided into two groups. All teeth were prepared for and restored with shrinkage-free ZrSiO4 ceramic crowns (Everest HPC (R), KaVo). The crowns of group A (N = 16) were luted to the teeth using KetacCem (R) and group B (N = 16) were adhesively cemented using Panavia (R) 21EX. Measurements of the marginal accuracy before and after cementation were made using replicas and an image analysis system. All specimens were exposed to 1.2 million cycles of thermo-mechanical fatigue in a chewing simulator. Surviving specimens were subsequently loaded until fracture in a static testing device. Fracture loads (N) were recorded. All specimens survived chewing simulation. The mean fracture loads (+/- s.d.) were Group A, 1622 N (+/- 433); group B, 1957 N (+/- 806). There was no significant difference between the two groups (P > 0.05). The marginal gap values before cementation were (mean +/- s.d.): Group A, 32.7 mu m (+/- 6.8); group B, 33.0 mu m (+/- 6.7).The mean marginal gap values after cementation were (+/- s.d.): Group A, 44.6 mu m (+/- 6.7); group B, 46.6 mu m (+/- 7.7). The marginal openings were significantly higher after cementation for both groups (P < 0.05). All test groups demonstrated fracture load and marginal accuracy values within the range of clinical acceptability.

Random vibration of the functionally graded laminates in thermal environments

This work deals with the random free vibration of functionally graded laminates with general boundary conditions and subjected to a temperature change, taking into account the randomness in a number of independent input variables such as Young's modulus, Poisson's ratio and thermal expansion coefficient of each constituent material. Based on third-order shear deformation theory, the mixed-type formulation and a semi-analytical approach are employed to derive the standard eigenvalue problem in terms of deflection, mid-plane rotations and stress function. A mean-centered first-order perturbation technique is adopted to obtain the second-order statistics of vibration frequencies. A detailed parametric study is conducted, and extensive numerical results are presented in both tabular and graphical forms for laminated plates that contain functionally graded material which is made of aluminum and zirconia, showing the effects of scattering in thermo-clastic material constants, temperature change, edge support condition, side-to-thickness ratio, and plate aspect ratio on the stochastic characteristics of natural frequencies. (c) 2005 Elsevier B.V. All rights reserved.

Treatment of ocular allergies:nonpharmacologic, pharmacologic and immunotherapy

Ocular allergy is a significant and growing issue worldwide but for many patients, it is often not differentiated from systemic conditions, such as hay fever. Management of seasonal and perennial allergic conjunctivitis is often poor. Management is principally through avoidance measures (blocking or hygiene), nonpharmaceutical (such as artificial tears and cold compresses) and pharmaceutical (such as topical antihistamines and prophylactic mast cell stabilizers). Vernal and atopic keratoconjunctivitis are more severe and generally need treatment with NSAIDs, steroids and immunomodulators. Giant papillary conjunctivitis can be related to allergy but also is often contact lens related and in such cases can be managed by a period of abstinence and replacement of the lens or a change in lens material and/or design. Immunotherapy can be efficacious in severe, persistent cases of contact lens or allergic conjunctivitis.

Sulphide ore minerals:surface chemical properties

The surfaces of iron-containing sulphide minerals were oxidised by a range of inorganic oxidants, and the resultant surface alteration products studied using various spectroscopic techniques. The characterisation of surface oxidation is relevant to the alteration of ores in nature and their behaviour during flotation and leaching, of importance to the metallurgical industry. The sulphides investigated included pyrite (FeS2), hexagonal pyrrhotine (Fe9S10), monoclinic pyrrhotine (Fe7Se), violarite (FeNi2S4), pentlandite ((FeiNi)9Se), chalcopyrite (CuFeS2) and arsenopyrite (FeAsS). The surfaces were oxidised by various methods including acid (sulphuric), alkali (ammonium hydroxide), hydrogen peroxide, steam, electrochemical and air/oxygen (in a low-temperature (150ºC) furnace), The surfaces were examined using surface sensitive chemical spectroscopic methods including x-ray photoelectron spectroscopy (ms), Auger electron spectroscopy (LES) and conversion electron Mössbauer spectroscopy (CEKS). Physical characterisation of the surfaces was undertaken using scanning electron microscopy (SM), spectral reflectance measurements and optical microscopy. Bulk characterisation of the sulphide minerals was undertaken using x-ray diffraction and electron microprobe techniques. Observed phases suggested to form in most of the sulphide surfaces include Fe204, Fe1-x0, Fe202, Fe00H, Fe(OH)3, with iron II & III oxy-sulphates. The iron sulphides show variable extents of oxidation, indicating pyrite to be the most stable. Violarite shows stability to oxidation, suggested to result from both its stable spinel crystal structure, and from the rapid formation of sulphur at the surface protecting the sub-surface from further oxidation. The phenomenon of sub-surface enrichment (in metals), forming secondary sulphides, is exhibited by pentlandite and chalcopyrite, forming violarite and copper sulphides respectively. The consequences of this enrichment with regard to processing and leaching are discussed. Arsenopyrite, often a hindrance in ore processing, exhibits the formation of arsenic compounds at the surface, the dissolution of which is discussed in view of the possible environmental hazard caused by the local pollution of water systems. The results obtained allow a characterisation of the sulphides in terms of their relative stability to oxidation, and an order of stability of the sulphide surfaces is proposed. Models were constructed to explain the chemical compositions of the surfaces, and the inter-relationships between the phases determined at the surface and in the sub-surface. These were compared to the thermo-chemically predicted phases shown in Eh/pH and partial pressure diagrams! The results are discussed, both in terms of the mineralogy and geochemistry of natural ores, and the implications for extraction and processing of these ore minerals.

Novel high water content hydrogels

Hydrogels may be described as cross-linked hydrophilic polymers that swell but do not dissolve in water. The production of high water content hydrogels was the subject of investigation. Based upon copolymer compositions that had already achieved commercial success as biomaterials, new monomers were added or substituted in and the effects observed. The addition of N-isopropyl acrylamide to an acrylamide-based composition that had previously been designed to become a contact lens, produced materials that showed smart effects in that the water content showed dependence on the temperature of the hydrating solution. Such thermo-responsive materials have potential uses in drug delivery, ultrafiltration and cell culture surfaces. Proteoglycans in nature have an important role to play in structural support where a highly hydrophilic structure maintains lubricious surfaces. Certain functional groups that impart this hydrophilicity are present in certain sulphonate monomers, Bis(3-sulphopropyl ester) itaconate, dipotassium salt (SPI), 3-Sulphopropyl ester acrylate, potassium salt (SPA) and Sodium 2-(acrylamido)-2-methyl propane sulphonate (NaAMPS). These monomers were incorporated into a HEMA-based copolymer that had been designed initially as a contact lens and the resulting effects examined. Highly hydrophilic materials resulted that showed reduced protein deposition over the neutral core material. It is postulated that a sulphonate group would have a larger number of hydration shells around it than for example methacrylic acid, leading to more dynamic exchange and so reducing the adsorption of biological solutes. A cationic monomer was added to bring back the net anionic nature of the sulphonate hydrogels and the effects studied. Ionic interactions were found to cause a reduction in the water content of the resulting materials as the mobility of the network decreased, leading to stiffer but less extensible materials. The presence of a net dominant charge, whether negative or positive, appeared to act to reduce protein deposition, but increasing equivalence in the amount of both charges served to present a more 'neutral' surface and deposition subsequently increased. The grafting of hydrophilic hydrogel layers onto silicone elastomer was attempted and the results evaluated using dynamic contact angle measurements. Following plasma oxidation to reduce the surface energy barrier to aqueous grafting chemistry, it was found that the wettability of the modified elastomers could be significantly enhanced by such treatment. The SPA-grafted material in particular hinted at an osmotic drive for rehydration that may be exploited in biomaterials.

Grewia polysaccharide gum as a pharmaceutical excipient

Grewia gum is obtained from the inner stem bark of the edible plant Grewia mollis Juss (Fam. Tiliaceae) which grows widely in the middle belt region of Nigeria, and is also cultivated. The dried and pulverised inner stem bark is used as a thickening agent in some food delicacies in that region of the country. This ability of the material to increase solution viscosity has generated a lot of interest and is the catalysing momentum for this research. Such materials have been used as stabilizers or suspending agents in cosmetics, foods and liquid medications, and as mucoadhesives and controlled release polymeric matrices in solid dosage forms. The physicochemical characterization of candidate excipients forms an essential step towards establishing suitability for pharmaceutical application. For natural gums, this usually requires isolation of the gum from the storage site by extraction processes. Grewia polysaccharide gum was extracted and dried using techniques such as air-drying, freeze-drying or spray-drying. Component analysis of the gum showed that it contains five neutral sugars: glucose, galactose, rhamnose, arabinose and xylose. The gum contains traces of elements such as zinc, magnesium, calcium and phosphorus. At low substance weight, the gum hydrates in aqueous medium swelling and dispersing to give a highly viscous dispersion with pseudoplasmic flow behaviour. The method by which drying is achieved can have significant effect on some physicochemical properties of the gum. Consequently, the intrinsic viscosity and molecular weight, and parameters of powder flow were shown to differ with the method of drying. The gum has good thermal stability. In comparison with established excipients, grewia gum may be preferable to gum Arabic or sodium carboxymethylcellulose as a suspending agent in ibuprofen suspension formulations. The release retardant property of the gum was superior to guar and Metolose® in ibuprofen matrices. Similarly, carboxy methylcellulose, Methocel®, gum Arabic or Metolose® may not be preferable to grewia gum when controlled release of a soluble drug like cimetidine is indicated. The mucoadhesive performance of the gum compared favourably with excellent mucoadhesives such as hydroxypropyl methylcellulose, carboxymethylcellulose, guar and carbopol 971 P.

The oxidation behaviour of sintered iron

The oxidation behaviour of porous, sintered iron was studied by thermo-gravimetric analysis (TGA), at temperatures between 300oC and 700oC, in a flowing atmosphere of 20% O2/80% N2. Samples for TGA tests were compacted from pure iron powder, at 150MPa to 550MPa, and vacuum sintered at 1120oC. The mass gain of samples during oxidation was recorded continuously for a period of 24 hours. It was found that the oxidation mass gain of PM samples depended on the permeability of the pore structure and the temperature. At low temperatures, the oxidising gas was able to permeate through the pore structure, causing the oxidation of a large active surface area. At high temperatures the active surface area was smaller, because oxygen diffusing into the pore structure, from the external atmosphere, was adsorbed by pore surfaces close to the external surface of the compact. Although the weight of the external oxide scale on compacts increased with increasing oxidation temperature, the absence of oxide in the core porosity in compacts oxidised at higher temperatures resulted in smaller mass gains than were observed for compacts oxidised at lower temperatures. The heat generated by the oxidation of the large active surface areas of porous samples was studied by thermo-calorimetric analysis (TCA). It was determined that this phenomenon could raise the core temperature of samples significantly above the ambient furnace temperature, and affecting the morphology of the oxide scale formed. The effects (on oxidation behaviour at 500oC) of small, elemental alloy additions of Al, Cu, P and Si to pure iron powder were studied. It was found that elements that promote pore rounding during sintering caused a significant reduction in the mass gain rate of the PM alloys, compared to the PM pure iron. The oxidation resistance due to these elements prevented pore closure by oxide growth, so that the active surface area of these PM alloys remained high. The PM alloys were also studied by thermo-mechanical analysis (TMA, dilatometry), to determine their dimensional stability during sintering and subsequent elevated temperature service. The oxidation experiment was augmented with optical and electron microscopy, and X-ray analysis of alloy and scale compositions.

The mechanisms of melt stabilisation of polyolefins

The effects of melt stabilisers on the oxidative degradation of polyolefins (polypropylene, low density polyethylene) have been studied under a variety of processing conditions . The changes in the both chemical and physical properties of unstabilised polymers occurring during processing were found to be strongly dependent on the amount of oxygen present in the mixer. 2 ,6 ,3' ,5' -tetra-tert-butyl-4'-phenoxy-4-methylene-2, 5-cyclohexadiene-1- one (galvinoxyl), iodine, nitroxyl radicals and cupric stearate were found to be very efficient melt stabilisers particularly when processed in a restricted amount of air. The mechanisms of their melt stabilising action have been investigated and a common cyclical regenerative mechanism involving both chain-breaking electron acceptor (CB-A) and chain-breaking electron donor (CB-D) antioxidant activity was found to be involved in each case. 2,6,3',5'-tetra-tert-butyl-4'-hydroxy phenyl-4-rrethylene-2,5-cyclohexadiene- 1-one (hydrogalvinoxy1), 4-hydroxy, 2,2,6, 6-tetra methyl-N-hydroxy piperidine and hydrogen iodide were formed together with olefinic unsaturation in the substrates during the melt processing of the polymers containing galvinoxyl, 4-hydroxy, 2,2,6, 6-tetra methyl piperidine oxyl and iodine respectively. No bonding of the melt stabilisers to the polymers was found to occur. Cupric stearate was found to undergo a similar redox reaction during its action as a melt stabiliser with the formation of unsaturation in the polymer. Evidence for the above processes is presented. The behaviours of melt stabilisers in the subsequent thermal and photooxidation of polyolefins have also been studied. Galvinoxyl which is very effective under both mild and severe processing canditions has been found to be an effective antioxidant during thermal oxidation (oven ageing) and it is also moderately good. as a photo-stabiliser. Iodine and cupric stearate acted efficiently during melt stabilisation of polymers, however they were both ineffective as thermo-oxidative antioxidants and UV stabilisers. Although the melt stabilisation effectiveness of stable nitroxyl radicals (e.g. 4-hydroxy, 2,2,6,6-tetra methyl piperidineoxyl and Bis- (2,2,6 ,6-tetra methyl-4- piperidinyl-N-oxyl) sebacate) is not as high as that of galvinoxyl during processing particularly in excess of air, they have been found to be much more efficient as UV stabilisers for polyolefins. The reasons for this are discussed.