A Review of ENSO Influence on the North Atlantic. A Non-Stationary Signal

The atmospheric seasonal cycle of the North Atlantic region is dominated by meridional movements of the circulation systems: from the tropics, where the West African Monsoon and extreme tropical weather events take place, to the extratropics, where the circulation is dominated by seasonal changes in the jetstream and extratropical cyclones. Climate variability over the North Atlantic is controlled by various mechanisms. Atmospheric internal variability plays a crucial role in the mid-latitudes. However, El Niño-Southern Oscillation (ENSO) is still the main source of predictability in this region situated far away from the Pacific. Although the ENSO influence over tropical and extra-tropical areas is related to different physical mechanisms, in both regions this teleconnection seems to be non-stationary in time and modulated by multidecadal changes of the mean flow. Nowadays, long observational records (greater than 100 years) and modeling projects (e.g., CMIP) permit detecting non-stationarities in the influence of ENSO over the Atlantic basin, and further analyzing its potential mechanisms. The present article reviews the ENSO influence over the Atlantic region, paying special attention to the stability of this teleconnection over time and the possible modulators. Evidence is given that the ENSO–Atlantic teleconnection is weak over the North Atlantic. In this regard, the multidecadal ocean variability seems to modulate the presence of teleconnections, which can lead to important impacts of ENSO and to open windows of opportunity for seasonal predictability.

Evaporation maps for ternary non-ideal liquid mixtures

This thesis deals with the evaporation of non-ideal liquid mixtures using a multicomponent mass transfer approach. It develops the concept of evaporation maps as a convenient way of representing the dynamic composition changes of ternary mixtures during an evaporation process. Evaporation maps represent the residual composition of evaporating ternary non-ideal mixtures over the full range of composition, and are analogous to the commonly-used residue curve maps of simple distillation processes. The evaporation process initially considered in this work involves gas-phase limited evaporation from a liquid or wetted-solid surface, over which a gas flows at known conditions. Evaporation may occur into a pure inert gas, or into one pre-loaded with a known fraction of one of the ternary components. To explore multicomponent masstransfer effects, a model is developed that uses an exact solution to the Maxwell-Stefan equations for mass transfer in the gas film, with a lumped approach applied to the liquid phase. Solutions to the evaporation model take the form of trajectories in temperaturecomposition space, which are then projected onto a ternary diagram to form the map. Novel algorithms are developed for computation of pseudo-azeotropes in the evaporating mixture, and for calculation of the multicomponent wet-bulb temperature at a given liquid composition. A numerical continuation method is used to track the bifurcations which occur in the evaporation maps, where the composition of one component of the pre-loaded gas is the bifurcation parameter. The bifurcation diagrams can in principle be used to determine the required gas composition to produce a specific terminal composition in the liquid. A simple homotopy method is developed to track the locations of the various possible pseudo-azeotropes in the mixture. The stability of pseudo-azeotropes in the gas-phase limited case is examined using a linearized analysis of the governing equations. Algorithms for the calculation of separation boundaries in the evaporation maps are developed using an optimization-based method, as well as a method employing eigenvectors derived from the linearized analysis. The flexure of the wet-bulb temperature surface is explored, and it is shown how evaporation trajectories cross ridges and valleys, so that ridges and valleys of the surface do not coincide with separation boundaries. Finally, the assumption of gas-phase limited mass transfer is relaxed, by employing a model that includes diffusion in the liquid phase. A finite-volume method is used to solve the system of partial differential equations that results. The evaporation trajectories for the distributed model reduce to those of the lumped (gas-phase limited) model as the diffusivity in the liquid increases; under the same gas-phase conditions the permissible terminal compositions of the distributed and lumped models are the same.

Embedding colloidal nanoparticles inside mesoporous silica using gas expanded liquids for high loading recyclable catalysts

The ability to tune the structural and chemical properties of colloidal nanoparticles (NPs), make them highly advantageous for studying activity and selectivity dependent catalytic behaviour. Incorporating pre-synthesized colloidal NPs into porous supports materials remains a challenge due to poor wetting and pore permeability. In this report monodisperse, composition controlled AgPd alloy NPs were synthesised and embedded into SBA-15 using supercritical carbon dioxide and hexane. Supercritical fluid impregnation resulted in high metal loading without the requirement for surface pre-treatments. The catalytic activity, reaction profiles and recyclability of the alloy NPs embedded in SBA-15 and immobilised on non-porous SiO2 are evaluated. The NPs incorporated within the SBA-15 porous network showed significantly greater recyclability performance compared to non-porous SiO2.

THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

MEDIUM-CHAIN-LENGTH POLY(3-HYDROXYALKANOATE) NANOPARTICLE SUSPENSIONS

The main goal of this thesis was to prepare medium-chain-length poly-3-hydroxyalkanoate (mcl-PHA) nanoparticle suspensions at high solids content (≥ 10 % w/v). A two-stage emulsification-solvent evaporation process was employed to produce poly-3-hydroxydecanoate (PHD) suspensions. The formulation and processing conditions including ultrasonication time and amplitude, selection of solvent, and selection of surfactants and their concentrations were investigated to make concentrated suspensions (10 and 30 % (w/v)) of PHD with particles less than 300 nm. Among the ionic surfactants tested to stabilize the suspension, the anionic, sodium dodecyl sulphate (SDS), and the cationic, dodecyltrimethylammonium bromide (DTAB) surfactants produced the smallest particle sizes (~100 nm). However, more stabilized nanoparticles were obtained when the ionic surfactant, SDS, was combined with any of the non-ionic surfactants tested, with polyoxyethylene octyl phenyl ether (Triton X-100) or polyoxyethylene (20) sorbitan monooleate (Tween 80) resulting in a slight increase in zeta potential over 30 days while the zeta potential with other non-ionic surfactants decreased. Mcl-PHA containing 11 and 18 % of carboxyl groups was synthesized via free radical addition reaction of 11-mercaptoundecanoic acid to the pendant double bonds of unsaturated poly-3-hydroxynonanoate (PHNU). Colloidal suspensions prepared by ultrasonication needed a surfactant to maintain stability, even at 0.4 % solids of mcl-PHA containing 11 % carboxylation (PHNC-1) unlike the stable suspensions prepared without surfactants by the titration method. Similar particle sizes (155.6 ± 8.4 to 163.4 ± 11.3 nm) and polydispersity indices (0.42 ± 0.03 to 0.49 ± 0.04) were obtained when several non-ionic surfactants were tested to minimize particle agglomeration, with the smallest particles obtained with Triton X-100. When Triton X-100 was combined with a variety of ionic surfactants, smaller nanoparticles (97.1 ± 1.1 to 121.7 ± 5.7 nm) with a narrower particle size distribution (0.21 ± 0.001 to 0.25 ± 0.003) were produced. The SDS and Triton X-100 combination was chosen to evaluate other mcl-PHAs at 10 % (w/v) solids content. Slightly smaller nanoparticles were formed with carboxylated mcl-PHAs compared to mcl-PHAs having aliphatic pendant side chains. Mcl-PHA consisting of 18 % carboxylation (PHNC-2) formed a much smaller nanoparticles and higher zeta potential.

Co-production of bio-oil and propylene through the hydrothermal liquefaction of polyhydroxybutyrate producing cyanobacteria

A polyhydroxybutyrate (PHB) producing cyanobacteria was converted through hydrothermal liquefaction (HTL) into propylene and a bio-oil suitable for advanced biofuel production. HTL of model compounds demonstrated that in contrast to proteins and carbohydrates, no synergistic effects were detected when converting PHB in the presence of algae. Subsequently, Synechocystis cf. salina, which had accumulated 7.5wt% PHB was converted via HTL (15% dry weight loading, 340°C). The reaction gave an overall propylene yield of 2.6%, higher than that obtained from the model compounds, in addition to a bio-oil with a low nitrogen content of 4.6%. No propylene was recovered from the alternative non-PHB producing cyanobacterial strains screened, suggesting that PHB is the source of propylene. PHB producing microorganisms could therefore be used as a feedstock for a biorefinery to produce polypropylene and advanced biofuels, with the level of propylene being proportional to the accumulated amount of PHB.

Co-production of bio-oil and propylene through the hydrothermal liquefaction of polyhydroxybutyrate producing cyanobacteria

A polyhydroxybutyrate (PHB) producing cyanobacteria was converted through hydrothermal liquefaction (HTL) into propylene and a bio-oil suitable for advanced biofuel production. HTL of model compounds demonstrated that in contrast to proteins and carbohydrates, no synergistic effects were detected when converting PHB in the presence of algae. Subsequently, Synechocystis cf. salina, which had accumulated 7.5wt% PHB was converted via HTL (15% dry weight loading, 340°C). The reaction gave an overall propylene yield of 2.6%, higher than that obtained from the model compounds, in addition to a bio-oil with a low nitrogen content of 4.6%. No propylene was recovered from the alternative non-PHB producing cyanobacterial strains screened, suggesting that PHB is the source of propylene. PHB producing microorganisms could therefore be used as a feedstock for a biorefinery to produce polypropylene and advanced biofuels, with the level of propylene being proportional to the accumulated amount of PHB.

Characterisation of Large Disturbance Rotor Angle and Voltage Stability in Interconnected Power Networks with Distributed Wind Generation

Wind generation in highly interconnected power networks creates local and centralised stability issues based on their proximity to conventional synchronous generators and load centres. This paper examines the large disturbance stability issues (i.e. rotor angle and voltage stability) in power networks with geographically distributed wind resources in the context of a number of dispatch scenarios based on profiles of historical wind generation for a real power network. Stability issues have been analysed using novel stability indices developed from dynamic characteristics of wind generation. The results of this study show that localised stability issues worsen when significant penetration of both conventional and wind generation is present due to their non-complementary characteristics. In contrast, network stability improves when either high penetration of wind and synchronous generation is present in the network. Therefore, network regions can be clustered into two distinct stability groups (i.e. superior stability and inferior stability regions). Network stability improves when a voltage control strategy is implemented at wind farms, however both stability clusters remain unchanged irrespective of change in the control strategy. Moreover, this study has shown that the enhanced fault ride-through (FRT) strategy for wind farms can improve both voltage and rotor angle stability locally, but only a marginal improvement is evident in neighbouring regions.

New biomass derived carbon catalysts for biomass valorization

Due to diminishing petroleum reserves, unsteady market situation and the environmental concerns associated with utilization of fossil resources, the utilization of renewables for production of energy and chemicals (biorefining) has gained considerable attention. Biomass is the only sustainable source of organic compounds that has been proposed as petroleum equivalent for the production of fuels, chemicals and materials. In fact, it would not be wrong to say that the only viable answer to sustainably convene our future energy and material requirements remain with a bio-based economy with biomass based industries and products. This has prompted biomass valorization (biorefining) to become an important area of industrial research. While many disciplines of science are involved in the realization of this effort, catalysis and knowledge of chemical technology are considered to be particularly important to eventually render this dream to come true. Traditionally, the catalyst research for biomass conversion has been focused primarily on commercially available catalysts like zeolites, silica and various metals (Pt, Pd, Au, Ni) supported on zeolites, silica etc. Nevertheless, the main drawbacks of these catalysts are coupled with high material cost, low activity, limited reusability etc. – all facts that render them less attractive in industrial scale applications (poor activity for the price). Thus, there is a particular need to develop active, robust and cost efficient catalytic systems capable of converting complex biomass molecules. Saccharification, esterification, transesterification and acetylation are important chemical processes in the valorization chain of biomasses (and several biomass components) for production of platform chemicals, transportation fuels, food additives and materials. In the current work, various novel acidic carbons were synthesized from wastes generated from biodiesel and allied industries, and employed as catalysts in the aforementioned reactions. The structure and surface properties of the novel materials were investigated by XRD, XPS, elemental analysis, SEM, TEM, TPD and N2-physisorption techniques. The agro-industrial waste derived sulfonic acid functionalized novel carbons exhibit excellent catalytic activity in the aforementioned reactions and easily outperformed liquid H2SO4 and conventional solid acids (zeolites, ion-exchange resins etc). The experimental results indicated strong influence of catalyst pore-structure (pore size, pore-volume), concentration of –SO3H groups and surface properties in terms of the activity and selectivity of these catalysts. Here, a large pore catalyst with high –SO3H density exhibited the highest esterification and transesterification activity, and was successfully employed in biodiesel production from fatty acids and low grade acidic oils. Also, a catalyst decay model was proposed upon biodiesel production and could explain that the catalyst loses its activity mainly due to active site blocking by adsorption of impurities and by-products. The large pore sulfonated catalyst also exhibited good catalytic performance in the selective synthesis of triacetin via acetylation of glycerol with acetic anhydride and out-performed the best zeolite H-Y with respect to reusability. It also demonstrated equally good activity in acetylation of cellulose to soluble cellulose acetates, with the possibility to control cellulose acetate yield and quality (degree of substitution, DS) by a simple adjustment of reaction time and acetic anhydride concentration. In contrast, the small pore and highly functionalized catalysts obtained by hydrothermal method and from protein rich waste (Jatropha de-oiled waste cake, DOWC), were active and selective in the esterification of glycerol with fatty acids to monoglycerides and saccharification of cellulosic materials, respectively. The operational stability and reusability of the catalyst was found to depend on the stability of –SO3H function (leaching) as well as active site blocking due to adsorption of impurities during the reaction. Thus, our results corroborate the potential of DOWC derived sulfated mesoporous active carbons as efficient integrated solid acid catalysts for valorization of biomass to platform chemicals, biofuel, bio-additive, surfactants and celluloseesters.

Assessing the influence of abiotic factors and leaf-level properties on the stability of growing-season canopy greenness in a deciduous forest

Maps depicting spatial pattern in the stability of summer greenness could advance understanding of how forest ecosystems will respond to global changes such as a longer growing season. Declining summer greenness, or “greendown”, is spectrally related to declining near-infrared reflectance and is observed in most remote sensing time series to begin shortly after peak greenness at the end of spring and extend until the beginning of leaf coloration in autumn,. Understanding spatial patterns in the strength of greendown has recently become possible with the advancement of Landsat phenology products, which show that greendown patterns vary at scales appropriate for linking these patterns to proposed environmental forcing factors. This study tested two non-mutually exclusive hypotheses for how leaf measurements and environmental factors correlate with greendown and decreasing NIR reflectance across sites. At the landscape scale, we used linear regression to test the effects of maximum greenness, elevation, slope, aspect, solar irradiance and canopy rugosity on greendown. Secondly, we used leaf chemical traits and reflectance observations to test the effect of nitrogen availability and intrinsic water use efficiency on leaf-level greendown, and landscape-level greendown measured from Landsat. The study was conducted using Quercus alba canopies across 21 sites of an eastern deciduous forest in North America between June and August 2014. Our linear model explained greendown variance with an R2=0.47 with maximum greenness as the greatest model effect. Subsequent models excluding one model effect revealed elevation and aspect were the two topographic factors that explained the greatest amount of greendown variance. Regression results also demonstrated important interactions between all three variables, with the greatest interaction showing that aspect had greater influence on greendown at sites with steeper slopes. Leaf-level reflectance was correlated with foliar δ13C (proxy for intrinsic water use efficiency), but foliar δ13C did not translate into correlations with landscape-level variation in greendown from Landsat. Therefore, we conclude that Landsat greendown is primarily indicative of landscape position, with a small effect of canopy structure, and no measureable effect of leaf reflectance. With this understanding of Landsat greendown we can better explain the effects of landscape factors on vegetation reflectance and perhaps on phenology, which would be very useful for studying phenology in the context of global climate change

Temporal and spatial variation in temperature experienced by macrofauna at main endeavour Hydrothermal vent field

A significant focus of hydrothermal vent ecological studies has been to understand how species cope with various stressors through physiological tolerance and biochemical resistance. Yet, the environmental conditions experienced by vent species have not been well characterized. This objective requires continuous observations over time intervals that can capture environmental variability at scales that are relevant to animals. We used autonomous temperature logger arrays (four roughly parallel linear arrays of 12 loggers spaced every 10–12 cm) to study spatial and temporal variations in the thermal regime experienced by hydrothermal vent macrofauna at a diffuse flow vent. Hourly temperatures were recorded over eight months from 2010 to 2011 at Grotto vent in the Main Endeavour vent field on the Juan de Fuca Ridge, a focus area of the Ocean Networks Canada cabled observatory. The conspicuous animal assemblages in video footage contained Ridgeia piscesae tubeworms, gastropods (primarily Lepetodrilus fucensis), and polychaetes (polynoid scaleworms and the palm worm Paralvinella palmiformis). Two dimensional spatial gradients in temperature were generally stable over the deployment period. The average temperature recorded by all arrays, and in some individual loggers, revealed distinctive fluctuations in temperature that often corresponded with the tidal cycle. We postulate that this may be related to changes in bottom currents or fluctuations in vent discharge. A marked transient temperature increase lasting over a period of days was observed in April 2011. While the distributions and behavior of Juan de Fuca Ridge vent invertebrates may be partially constrained by environmental temperature and temperature tolerance, except for the one transient high-temperature event, observed fluid temperatures were generally similar to the thermal preferences for some species, and typically well below lethal temperatures for all species. Average temperatures of the four arrays ranged from 4.1 to 11.0 °C during the deployment, indicating that on an hourly timescale the temperature conditions in this tubeworm community were fairly moderate and stable. The generality of these findings and behavioural responses of vent organisms to predictable rhythmicity and non-periodic temperature shifts are areas for further investigation

A joint electromagnetic and seismic study of an active pockmark within the hydrate stability field at the Vestnesa Ridge, West Svalbard margin

We acquired coincident marine controlled-source electromagnetic (CSEM), high-resolution seismic reflection and ocean-bottom seismometer (OBS) data over an active pockmark in the crest of the southern part of the Vestnesa Ridge, to estimate fluid composition within an underlying fluid-migration chimney. Synthetic model studies suggest resistivity obtained from CSEM data can resolve gas or hydrate saturation greater than 5% within the chimney. Acoustic chimneys imaged by seismic reflection data beneath the pockmark and on the ridge flanks, were found to be associated with high-resistivity anomalies (+2-4 m). High-velocity anomalies (+0.3 km/s), within the gas hydrate stability zone (GHSZ) and low-velocity anomalies (-0.2 km/s) underlying the GHSZ, were also observed. Joint analysis of the resistivity and velocity anomaly indicates pore saturation of up to 52% hydrate with 28% free gas, or up to 73% hydrate with 4% free gas, within the chimney beneath the pockmark assuming a non-uniform and uniform fluid distribution respectively. Similarly, we estimate up to 30% hydrate with 4% free gas or 30% hydrate with 2% free gas within the pore space of the GHSZ outside the central chimney assuming a non-uniform and uniform fluid distribution respectively. High levels of free-gas saturation in the top part of the chimney are consistent with episodic gas venting from the pockmark.

Stability of Reconstituted and Diluted Mitomycin C Solutions in Polypropylene Syringes and Glass VialsAbstract

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Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.