(Table T1) Mineral composition of oriented clay aggregates from ODP Leg 190 sites

Three sites were cored on the landward slope of the Nankai margin of southwest Japan during Leg 190 of the Ocean Drilling Program. Sites 1175 and 1176 are located in a trench-slope basin that was constructed during the early Pleistocene (~1 Ma) by frontal offscraping of coarse-grained trench-wedge deposits. Rapid uplift elevated the substrate above the calcite compensation depth and rerouted a transverse canyon-channel system that had delivered most of the trench sediment during the late Pliocene (1.06-1.95 Ma). The basin's depth is now ~3000 to 3020 m below sea level. Clay-sized detritus (<2 µm) did not change significantly in composition during the transition from trench-floor to slope-basin environment. Relative mineral abundances for the two slope-basin sites average 36-37 wt% illite, 25 wt% smectite, 22-24 wt% chlorite, and 15-16 wt% quartz. Site 1178 is located higher up the landward slope at a water depth of 1741 m, ~70 km from the present-day deformation front. There is a pronounced discontinuity ~200 m below seafloor between muddy slope-apron deposits (Quaternary-late Miocene) and sandier trench-wedge deposits (late Miocene; 6.8-9.63 Ma). Clay minerals change downsection from an illite-chlorite assemblage (similar to Sites 1175 and 1176) to one that contains substantial amounts of smectite (average = 45 wt% of the clay-sized fraction; maximum = 76 wt%). Mixing in the water column homogenizes fine-grained suspended sediment eroded from the Izu-Bonin volcanic arc, the Izu-Honshu collision zone, and the Outer Zone of Kyushu and Shikoku, but the spatial balance among those contributors has shifted through time. Closure of the Central America Seaway at ~3 Ma was particularly important because it triggered intensification of the Kuroshio Current. With stronger and deeper flow of surface water toward the northeast, the flux of smectite from the Izu-Bonin volcanic arc was dampened and more detrital illite and chlorite were transported into the Shikoku-Nankai system from the Outer Zone of Japan.

DEVELOPMENT OF A MECHANISM AND PROCESS TO CONTINUOUSLY PRODUCE SPHERICAL, TORREFIED BIOMASS PELLETS

A recently developed novel biomass fuel pellet, the Q’ Pellet, offers significant improvements over conventional white pellets, with characteristics comparable to those of coal. The Q’ Pellet was initially created at bench scale using a proprietary die and punch design, in which the biomass was torrefied in-situ¬ and then compressed. To bring the benefits of the Q’ Pellet to a commercial level, it must be capable of being produced in a continuous process at a competitive cost. A prototype machine was previously constructed in a first effort to assess continuous processing of the Q’ Pellet. The prototype torrefied biomass in a separate, ex-situ reactor and transported it into a rotary compression stage. Upon evaluation, parts of the prototype were found to be unsuccessful and required a redesign of the material transport method as well as the compression mechanism. A process was developed in which material was torrefied ex-situ and extruded in a pre-compression stage. The extruded biomass overcame multiple handling issues that had been experienced with un-densified biomass, facilitating efficient material transport. Biomass was extruded directly into a novel re-designed pelletizing die, which incorporated a removable cap, ejection pin and a die spring to accommodate a repeatable continuous process. Although after several uses the die required manual intervention due to minor design and manufacturing quality limitations, the system clearly demonstrated the capability of producing the Q’ Pellet in a continuous process. Q’ Pellets produced by the pre-compression method and pelletized in the re-designed die had an average dry basis gross calorific value of 22.04 MJ/kg, pellet durability index of 99.86% and dried to 6.2% of its initial mass following 24 hours submerged in water. This compares well with literature results of 21.29 MJ/kg, 100% pellet durability index and <5% mass increase in a water submersion test. These results indicate that the methods developed herein are capable of producing Q’ Pellets in a continuous process with fuel properties competitive with coal.

Surface-enhanced Raman spectroscopy of novel psychoactive substances using polymer-stabilized Ag nanoparticle aggregates

A set of seized "legal high'' samples and pure novel psychoactive substances have been examined by surface-enhanced Raman spectroscopy using polymer-stabilized Ag nanoparticle (Poly-SERS) films. The films both quenched fluorescence in bulk samples and allowed identification of mu g quantities of drugs collected with wet swabs from contaminated surfaces.

Concrete deterioration due to sulfide-bearing aggregates

Dans la région de Trois-Rivières (Québec, Canada), plus de 1 000 bâtiments résidentiels et commerciaux montrent de graves problèmes de détérioration du béton. Les problèmes de détérioration sont liés à l’oxydation des sulfures de fer incorporés dans le granulat utilisé pour la confection du béton. Ce projet de doctorat vise à mieux comprendre les mécanismes responsables de la détérioration de béton incorporant des granulats contenant des sulfures de fer, et ce afin de développer une méthodologie pour évaluer efficacement la réactivité potentielle de ce type de granulats. Un examen pétrographique détaillé de carottes de béton extraites de fondations résidentielles montrant différents degré d’endommagement a été réalisé. Le granulat problématique contenant des sulfures de fer a été identifié comme un gabbro à hypersthène incorporant différentes proportions (selon les différentes localisations dans les deux carrières d’origine) de pyrrhotite, pyrite, chalcopyrite et pentlandite. Les produits de réaction secondaires observés dans les échantillons dégradés comprennent des formes minérales de "rouille", gypse, ettringite et thaumasite. Ces observations ont permis de déterminer qu’en présence d’eau et d’oxygène, la pyrrhotite s’oxyde pour former des oxyhydroxides de fer et de l’acide sulfurique qui provoquent une attaque aux sulfates dans le béton. Tout d’abord, la fiabilité de l’approche chimique proposée dans la norme européenne NF EN 12 620, qui consiste à mesurer la teneur en soufre total (ST,% en masse) dans le granulat pour détecter la présence (ou non) de sulfures de fer, a été évaluée de façon critique. Environ 50% (21/43) des granulats testés, représentant une variété de types de roches/lithologies, a montré une ST > 0,10%, montrant qu’une proportion importante de types de roches ne contient pas une quantité notable de sulfure, qui, pour la plupart d’entre eux, sont susceptibles d’être inoffensifs dans le béton. Ces types de roches/granulats nécessiteraient toutefois d’autres tests pour identifier la présence potentielle de pyrrhotite compte tenu de la limite de ST de 0,10 % proposée dans les normes européennes. Basé sur une revue exhaustive de la littérature et de nombreuses analyses de laboratoire, un test accéléré d’expansion sur barres de mortier divisé en deux phases a ensuite été développé pour reproduire, en laboratoire, les mécanismes de détérioration observés à Trois-Rivières. Le test consiste en un conditionnement de 90 jours à 80°C/80% RH, avec 2 cycles de mouillage de trois heures chacun, par semaine, dans une solution d’hypochlorite de sodium (eau de javel) à 6% (Phase I), suivi d’une période pouvant atteindre 90 jours de conditionnement à 4°C/100 % HR (Phase II). Les granulats ayant un potentiel d’oxydation ont présenté une expansion de 0,10 % au cours de la Phase I, tandis que la formation potentielle de thaumasite est détectée par le regain rapide de l’expansion suivi par la destruction des échantillons durant la Phase II. Un test de consommation d’oxygène a également été modifié à partir d’un test de Drainage Minier Acide, afin d’évaluer quantitativement le potentiel d’oxydation des sulfures de fer incorporés dans les granulats à béton. Cette technique mesure le taux de consommation d’oxygène dans la partie supérieure d’un cylindre fermé contenant une couche de matériau compacté afin de déterminer son potentiel d’oxydation. Des paramètres optimisés pour évaluer le potentiel d’oxydation des granulats comprennent une taille de particule inférieure à 150 μm, saturation à 40 %, un rapport de 10 cm d’épaisseur de granulat par 10 cm de dégagement et trois heures d’essai à 22ᵒC. Les résultats obtenus montrent que le test est capable de discriminer les granulats contenant des sulfures de fer des granulats de contrôle (sans sulfures de fer) avec un seuil limite fixé à 5% d’oxygène consommé. Finalement, un protocole d’évaluation capable d’estimer les effets néfastes potentiels des granulats à béton incorporant des sulfures de fer a été proposé. Le protocole est divisé en 3 grandes phases: (1) mesure de la teneur en soufre total, (2) évaluation de la consommation d’oxygène, et (3) un test accéléré d’expansion sur barres de mortier. Des limites provisoires sont proposées pour chaque phase du protocole, qui doivent être encore validées par la mise à l’essai d’un plus large éventail de granulats.

Downstream processing of reverse osmosis brine: Characterisation of potential scaling compounds

Reverse osmosis (RO) brine produced at a full-scale coal seam gas (CSG) water treatment facility was characterized with spectroscopic and other analytical techniques. A number of potential scalants including silica, calcium, magnesium, sulphates and carbonates, all of which were present in dissolved and non-dissolved forms, were characterized. The presence of spherical particles with a size range of 10-1000nm and aggregates of 1-10 microns was confirmed by transmission electron microscopy (TEM). Those particulates contained the following metals in decreasing order: K, Si, Sr, Ca, B, Ba, Mg, P, and S. Characterization showed that nearly one-third of the total silicon in the brine was present in the particulates. Further, analysis of the RO brine suggested supersaturation and precipitation of metal carbonates and sulphates during the RO process should take place and could be responsible for subsequently capturing silica in the solid phase. However, the precipitation of crystalline carbonates and sulphates are complex. X-ray diffraction analysis did not confirm the presence of common calcium carbonates or sulphates but instead showed the presence of a suite of complex minerals, to which amorphous silica and/or silica rich compounds could have adhered. A filtration study showed that majority of the siliceous particles were less than 220nm in size, but could still be potentially captured using a low molecular weight ultrafiltration membrane. © 2015 Elsevier Ltd.

Poly(epsilon-caprolactone)nanocapsules as carrier systems for herbicides: Physico-chemical characterization and genotoxicity evaluation

The toxicity of herbicides used in agriculture is influenced by their chemical stability, solubility, bioavailability, photodecomposition, and soil sorption. Possible solutions designed to minimize toxicity include the development of carrier systems able to modify the properties of the compounds and allow their controlled release. Polymeric poly(epsilon-caprolactone) (PCL) nanocapsules containing three triazine herbicides (ametryn, atrazine, and simazine) were prepared and characterized in order to assess their suitability as controlled release systems that could reduce environmental impacts. The association efficiencies of the herbicides in the nanocapsules were better than 84%. Assessment of stability (considering particle diameter, zeta potential, polydispersity, and pH) was conducted over a period of 270 days, and the particles were found to be stable in solution. In vitro release kinetics experiments revealed controlled release of the herbicides from the nanocapsules, governed mainly by relaxation of the polymer chains. Microscopy analyses showed that the nanocapsules were spherical, dense, and without aggregates. In the infrared spectra of the PCL nanocapsules containing herbicides, there were no bands related to the herbicides, indicating that interactions between the compounds had occurred. Genotoxicity tests showed that formulations of nanocapsules containing the herbicides were less toxic than the free herbicides. The results indicate that the use of PCL nanocapsules is a promising technique that could improve the behavior of herbicides in environmental systems. (C) 2012 Elsevier B.V. All rights reserved.

Magnetic and Acoustic Investigations of Turbulent Spherical Couette Flow

Title of dissertation: MAGNETIC AND ACOUSTIC INVESTIGATIONS OF TURBULENT SPHERICAL COUETTE FLOW Matthew M. Adams, Doctor of Philosophy, 2016 Dissertation directed by: Professor Daniel Lathrop Department of Physics This dissertation describes experiments in spherical Couette devices, using both gas and liquid sodium. The experimental geometry is motivated by the Earth's outer core, the seat of the geodynamo, and consists of an outer spherical shell and an inner sphere, both of which can be rotated independently to drive a shear flow in the fluid lying between them. In the case of experiments with liquid sodium, we apply DC axial magnetic fields, with a dominant dipole or quadrupole component, to the system. We measure the magnetic field induced by the flow of liquid sodium using an external array of Hall effect magnetic field probes, as well as two probes inserted into the fluid volume. This gives information about possible velocity patterns present, and we extend previous work categorizing flow states, noting further information that can be extracted from the induced field measurements. The limitations due to a lack of direct velocity measurements prompted us to work on developing the technique of using acoustic modes to measure zonal flows. Using gas as the working fluid in our 60~cm diameter spherical Couette experiment, we identified acoustic modes of the container, and obtained excellent agreement with theoretical predictions. For the case of uniform rotation of the system, we compared the acoustic mode frequency splittings with theoretical predictions for solid body flow, and obtained excellent agreement. This gave us confidence in extending this work to the case of differential rotation, with a turbulent flow state. Using the measured splittings for this case, our colleagues performed an inversion to infer the pattern of zonal velocities within the flow, the first such inversion in a rotating laboratory experiment. This technique holds promise for use in liquid sodium experiments, for which zonal flow measurements have historically been challenging.

Inverse Spectral Methods in Acoustic Normal Mode Velocimetry of High Reynolds Number Spherical Couette Flows

Experimental geophysical fluid dynamics often examines regimes of fluid flow infeasible for computer simulations. Velocimetry of zonal flows present in these regimes brings many challenges when the fluid is opaque and vigorously rotating; spherical Couette flows with molten metals are one such example. The fine structure of the acoustic spectrum can be related to the fluid’s velocity field, and inverse spectral methods can be used to predict and, with sufficient acoustic data, mathematically reconstruct the velocity field. The methods are to some extent inherited from helioseismology. This work develops a Finite Element Method suitable to matching the geometries of experimental setups, as well as modelling the acoustics based on that geometry and zonal flows therein. As an application, this work uses the 60-cm setup Dynamo 3.5 at the University of Maryland Nonlinear Dynamics Laboratory. Additionally, results obtained using a small acoustic data set from recent experiments in air are provided.

Fabrication of Mg foams for biomedical applications by means of a replica method based upon spherical carbon particles

Interest in Mg foams is increasing due to their potential use as biomaterials. Fabrication methods determine to a great extent their structure and, in some cases, may pollute the foam. In this work Mg foams are fabricated by a replica method that uses as skeleton packed spheres of active carbon, a material widely utilized in medicine. After Mg infiltration, carbon particles are eliminated by an oxidizing heat treatment. The latter covers Mg with MgO which improves performance. In particular, oxidation retards degradation of the foam, as the polarization curves of the Mg foam with and without oxide indicate. The sphericity and regularity of C particles allows control of the structure of the produced open-cell foams.

Effect of third-order aberrations on dynamic accommodation

We investigate the potential for the third-order aberrations coma and trefoil to provide a signed cue to accommodation. It is first demonstrated theoretically (with some assumptions) that the point spread function is insensitive to the sign of spherical defocus in the presence of odd-order aberrations. In an experimental investigation, the accommodation response to a sinusoidal change in vergence (1–3 D, 0.2 Hz) of a monochromatic stimulus was obtained with a dynamic infrared optometer. Measurements were obtained in 10 young visually normal individuals with and without custom contact lenses that induced low and high values of r.m.s. trefoil (0.25, 1.03 μm) and coma (0.34, 0.94 μm). Despite variation between subjects, we did not find any statistically significant increase or decrease in the accommodative gain for low levels of trefoil and coma, although effects approached or reached significance for the high levels of trefoil and coma. Theoretical and experimental results indicate that the presence of Zernike third-order aberrations on the eye does not seem to play a crucial role in the dynamics of the accommodation response.

Prediction of fluidization behaviour and a quasi-stationary approach to drying kinetics of irregular particulate food materials

Changes in fluidization behaviour behaviour was characterised for parallelepiped particles with three aspect ratios, 1:1, 2:1 and 3:1 and spherical particles. All drying experiments were conducted at 500C and 15 % RH using a heat pump dehumidifier system. Fluidization experiments were undertaken for the bed heights of 100, 80, 60 and 40 mm and at 10 moisture content levels. Due to irregularities in shape minimum fluidisation velocity of parallelepiped particulates (potato) could not fitted to any empirical model. Also a generalized equation was used to predict minimum fluidization velocity. The modified quasi-stationary method (MQSM) has been proposed to describe drying kinetics of parallelepiped particulates at 30o C, 40o C and 50o C that dry mostly in the falling rate period in a batch type fluid bed dryer.

Micro-structure differences in kaolinite suspensions

SEM observations of the aqueous suspensions of kaolinite from Birdwood (South Australia) and Georgia (USA) show noticeable differences in number of physical behaviour which has been explained by different microstructure constitution.. Birdwood kaolinite dispersion gels are observed at very low solid loadings in comparison with Georgia KGa-1 kaolinite dispersions which remain fluid at higher solids loading. To explain this behaviour, the specific particle interactions of Birdwood kaolinite, different from interaction in Georgia kaolinite have been proposed. These interactions may be brought about by the presence of nano-bubbles on clay crystal edges and may force clay particles to aggregate by bubble coalescence. This explains the predominance of stair step edge-edge like (EE) contacts in suspension of Birdwood kaolinite. Such EE linked particles build long strings that form a spacious cell structure. Hydrocarbon contamination of colloidal kaolinite particles and low aspect ratio are discussed as possible explanations of this unusual behaviour of Birdwood kaolinite. In Georgia KGa-1 kaolinite dispersions instead of EE contact between platelets displayed in Birdwood kaolinite, most particles have edge to face (EF) contacts building a cardhouse structure. Such an arrangement is much less voluminous in comparison with the Birdwood kaolinite cellular honeycomb structure observed previously in smectite aqueous suspensions. Such structural characteristics of KGa-1 kaolinite particles enable higher solid volume fractions pulps to form before significantly networked gel consistency is attained.