Polar desert environments are limiting in plant available nutrients, mainly nitrogen (N) and phosphorus (P) that severely limit plant growth and establishment. Cryogenic activity regularly patterns the ground into a patchwork of frost boils – sorted circles that are associated with an increase in moisture, fertility and plant cover. Within some frost boils, the accumulation of ice-rich soil at the permafrost table can cause an upward flow of soil organic carbon (SOC) enriched permafrost material into the active layer. These diapiric intrusions are predicted to fuel microbial activity and enrich the horizon in N and P; however, the enrichment of the diapir horizon and accessibility by plants has yet to be studied. The aim of this research was to characterize the N distribution within diapir horizons located in frost boils and the effect of these intrusions on vascular plant N uptake in a polar desert ecosystem of the Canadian High Arctic. Natural abundance and enriched isotope 15N techniques were used to trace the flow of N through the soil-plant system. Surface and diapir horizons contained the highest total C and total N content within frost boils. Natural abundance δ15N analysis indicated that uptake by Salix arctica plants located on frost boils in the absence of a diapir horizon were sourcing N from the surface. However, when diapir nutrients became available, S. arctica plants began sourcing N from the diapir horizon and underlying low SOC sources in the soil, while reducing uptake from the surface. The altered foraging strategy of S. arctica in response to diapir horizon formation was further indicated by significant uptake of atom%15N nutrients that were injected directly into diapir horizons. These findings suggest diapir horizons are enriched in N and accessible by plants roots as an important nutrient source that is instrumental in their survival within frost boils of a polar desert ecosystem in the high arctic.

The Arctic—warming at twice the rate of the rest of the planet—is a source of striking imagery of amplified environmental change in our time, and has come to serve as a spatial setting for climate crisis discourse. The recent alterations in the Arctic environment have also been perceived by some observers as an opportunity to expand economic exploitation. Heightened geopolitical interest in the region and its resources, contradicted by calls for the protection of fragile Far North ecosystems, has rendered the Arctic an arena for negotiating human interactions with nature, and for reflecting upon the planetary risks and possibilities associated with the advent and expansion of the Anthropocene—the proposed new epoch in Earth history in which humankind is said to have gained geological agency and become the dominant force over the Earth system. With the Arctic serving as a nexus of crosscutting analytical themes spanning contemporary history (the late twentieth and the early twenty-first century until 2015), this dissertation examines defining characteristics of the Anthropocene and how the concept, which emerged from the Earth system science community, impacts ideas and assumptions in historiography, social sciences and the environmental humanities, including the fields of environmental history, crisis management and security studies, political geography, and science and technology studies (STS). The primary areas of empirical analysis and theoretical investigation encompass constructivist perspectives and temporal conceptions of environmental and climate crisis; the role of science and expertise in performing politics and shaping social discourse; the geopolitical significance of telecoupling—a concept that reflects the interconnectedness of the Anthropocene and supports stakeholder claims across wide spatial scales; and implications of the recent transformation in humankind’s long duration relationship with the natural world. Several dissertation themes were observed in practice at the international science community of Ny-Ålesund on Svalbard, where global change is made visible through a concentration of scientific activity. Ny-Ålesund is furthermore a place of geopolitics, where extra-regional states attempt to enhance their legitimacy as Arctic stakeholders through the performance of scientific research undertakings, participation in governance institutions, and by establishing a physical presence in the Far North. This dissertation concludes that this small and remote community represents an Anthropocene node of global environmental change, Earth system science, emergent global governance, geopolitics, and stakeholder construction in an increasingly telecoupled world.

The Arctic is a region undergoing unprecedented and unequivocal climate change. The seas of this extreme region form a major component of the oceanic thermohaline conveyor and natural carbon cycle. Using a combination of recent and historical datasets this study examines the distribution, diversity, photophysiology and primary productivity of phytoplankton in the Atlantic sector of the Arctic Ocean. CHEMTAX analysis reveals a diverse phytoplankton community structure in the Greenland Sea comprising six main phytoplankton groups. The influence of sea-ice and water column stratification are key factors in the presence or absence of groups such as haptophytes and prasinophytes. Group-specific differences are observed in spectral absorption and photophysiological parameters. However, the influence of environmental factors has a stronger influence than taxonomic composition on photophysiology. A clear division between the photoacclimatory response of algal communities beneath sea-ice and those of open-ocean stations is predominantly due to ‘E_k independent’ photoacclimation beneath sea-ice. This occurs due to the combined effect of sea-ice decreasing irradiance entering the water column and a positive correlation between P_m ^B and temperature. This variation in photophysiology is important for primary production models as a sensitivity analysis shows that errors in these parameters propagate to give the largest final errors in primary production values. The importance of other model parameters varies with the level of biomass in the water column and the presence or absence of sea ice. Accelerated ice-melt and an increase in open water due to climate change are likely to increase primary production in the Atlantic Arctic alongside an altered distribution of phytoplankton groups, with an increase in the importance of prasinophytes or haptophytes.

Protein sequences may evolve to avoid highly hydrophobic local regions of sequence, in part because such sequences promote nonnative aggregation. Hydrophobic local sequences are avoided in proteins even in buried regions, where native structure requirements tend to favor them. In this dissertation, I describe three explorations of this hydrophobic suppression. In Chapter 2, I examine the occurrence of hydrophobic and polar residues in completely buried β-strand elements, and find evidence for hydrophobic suppression that decreases as a β-strand becomes more exposed. In Chapter 3, I present a generalized study of the tendency of local sequences to deviate from the hydropathy (hydrophobicity) expected based on their solvent exposure. First, I examined the hydropathy of local and nonlocal sequence groups over a large range of solvent exposures, within folded protein domains in the ASTRAL Compendium database; second, I calculated the tendency of residues within 10 positions of a nonpolar or polar reference residue to deviate from the hydropathy expected based on their structural environment. Both analyses suggested that protein sequences exhibit 'local hydropathic balance' across a range of 6-7 residues, meaning that polar and nonpolar residues are more dispersed in the sequence than expected based on solvent exposure patterns. This balance occurs in all major fold classes, domain sizes and protein functions. An unexpected finding was that it partly arises from a tendency of buried or exposed residues to be flanked by polar or nonpolar residues, respectively. This relationship may result from evolutionary selection for folding efficiency, which might be enhanced by reduced local competition for buried or exposed sites during folding. Finally, in Chapter 4, I present several exploratory analyses, including a decision-tree approach, to visualize the influence of a large number of sequence-structure properties on residue hydrophobicity. Overall, the work in this dissertation confirms that hydrophobic suppression and local hydropathic balance in general are intrinsic properties of folded proteins. I speculate that local hydropathic balance results from selection for reduced aggregation propensity, increased folding efficiency and increased native state specificity. The concept of local hydropathic balance might be used to improve the properties of designed and engineered proteins.

Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: 2,7-dimethylocta-3,5-diyne-2,7-diol forms inclusion complexes with various guests molecules, where the guest molecules are polar-ordered. A Cambridge Structural Database (CSD) search revealed ten inclusion complexes where the guest molecules were polar-ordered. Using Density Functional Theory (DFT) computational methods (in the absence of the host), we evaluated the intra-channel and lateral guest-guest interactions between the guest molecules. Two polar-ordered inclusion complexes ((1,4,7-cyclohexane-1,2,4,5,7,8-hexaoxonane)·CHCl3 and (2,4,6-(endolongifolyl)-1,3,5-trioxane)·CDCl3) were singled out in the CSD search for further studies along with 2,7-dimethylocta-3,5-diyne-2,7-diol. Synthesis of any 1,2,4,5,7,8-hexaoxonane and 1,3,5-trioxane derivatives was attempted to establish whether the polar-ordering ability extends into the family of compounds. We managed to produce three new polar-ordered inclusion complexes with 2,7-dimethylocta-3,5-diyne-2,7-diol (ClC(CH3)3, BrC(CH3)3 and IC(CH3)3), thus extending the series to six guest polar-ordered systems. We were only able to synthesise 1,4,7-cyclohexane-1,2,4,5,7,8-hexaoxonane and produce the CHCl3 inclusion complex and one new polar-ordered inclusion complex (CHBr3). Three 1,3,5-trioxanes was synthesised (the cyclohexyl, cyclohex-3-en-1-yl and cyclopentyl derivatives), which did not include any solvents. However, these 1,3,5-trioxanes also form polar-ordered crystals. These compounds and inclusion complexes were analysed by means of single crystal X-ray diffraction to determine their crystal structures. All the crystal structures could be solved and refined to adequate accuracy (except for 2,4,6-tri(cyclopentyl)-1,3,5-trioxane) with no disorder of the guest molecules (where applicable) and their polar-ordering property investigated. Due to their vast molecular differences, these compounds were studied separately by means of visual crystal structure analysis and computational modelling techniques (Density functional theory, molecular mechanics, molecular dynamics and molecular quench dynamics). / AFRIKAANSE OPSOMMING: 2,7-dimetielokta-3,5-diyn-2,7-diol vorm insluitingskomplekse met verskeie molekules as gaste, waar die gas-molekules polêr georden is. 'n Cambridge Struktuur Databasis (CSD) soektog lewer tien insluitings komplekse waarvan die gas-molekules polêr georden is. Deur gebruik te maak van Digtheidsfunksionele teorie (DFT) berekeninge (in die afwesigheid van die gasheer) het ons die inter-kanaal en wedersydse gas-gas interaksies tussen die gas molekules geëvalueer. Twee polêr geordende insluitingskomplekse ((1,4,7-sikloheksaan-1,2,4,5,7,8-heksaoksonaan)·CHCl3 en (2,4,6-(endolongifolyl)-1,3,5-trioksaan)·CDCl3) is uitgesonder uit die CSD soektog vir verdere studies saam met 2,7-dimetielokta-3,5-diyn-2,7-diol. Aanslag was gemaak om enige 1,2,4,5,7,8-heksaoksonaan en 1,3,5-trioksaan derivate te sintetiseer en vas te stel of die polêre ordensvermoë oor die familie van verbindings strek. Ons het daarin geslaag om drie nuwe polêr geordende insluitingskomplekse op te lewer met 2,7-dimetielokta-3,5-diyn-2,7-diol (Cl(CH3)3, BrC(CH3)3 en I(CH3)3), en sodoende die reeks uitgebrei na ses gaste wat polêr geordende insluitingskomplekse vorm. Net 1,4,7-sikloheksaan-1,2,4,5,7,8-heksaoksonaan kon gesintetiseer word en dit lewer twee polêr geordende insluitingskomplekse (CHCl3 en CHBr3 (nuut)). Drie 1,3,5-trioksane is gesintetiseer (die sikloheksiel, sikloheks-3-een-1-iel en siklopentiel derivate) en het nie enige oplosmiddels (gaste) ingesluit nie. Nietemin vorm hiedie 1,3,5-trioksane ook polêr geordende kristalle. Hierdie verbindings en insluitingskomplekse is geanaliseer deur middel van enkelkristal X-straal diffraksie om hul kristalstrukture te bepaal. Alle kristalstrukture was opgelos en verwerk tot voldoende akkuraatheid (behalwe vir 2,4,6-tri(siklopentiel)-1,3,5-trioxane) met geen wanorde in die gas molekuul posisies nie (waar van toepassing) en hul polêre ordensvermoë is ondersoek. As gevolg van groot verskille in hul molekulêre strukture, is hierdie verbindings afsonderlik bestudeer deur middel van molekulêre modellerings metodes (Digtheidsfunksionele teorie, molekulêre meganika, molekulêre dinamika en molekulêre stakings dinamika).

Pc3-4 waves are recorded as geomagnetic pulsations with periods of 6-100s. They are generated at the bowshock and propagate to mid and auroral latitudes as Alfvén waves along closed magnetic field lines. At these latitudes Pc3-4 waves have been studied on the ground using magnetometers and in the ionosphere using HF radar. These waves have also been observed using magnetometers at polar latitudes even though there is no known propagation mechanism to the “open” field lines of the polar cap regions. In this work we used PolarDARN stations at Rankin Inlet and Inuvik to attempt the first study of Pc3-4 waves in the polar cap regions using radar. In ground scatter data, Doppler velocity oscillations with frequencies in the Pc3-4 range were found to be a common daytime occurrence. The oscillations are spatially coherent and in phase along the beam’s line of sight, matching lower latitude observations. However, upon further study it became apparent that the characteristics of the oscillations are different from those known for Pc3-4 waves. The observed oscillations have a diurnal trend that shows peaks in activity at 7:00 and 14:00MLT, where Pc3-4 oscillations have a diurnal peak at 10:30-11:00 MLT. In addition, poor coherence was observed between oscillations in radar and ground magnetic field variations at the nearby Taloyoak magnetometer. Further confounding the problem, we found that although the oscillations were coherent along the line-of-sight of the radar, poor coherence is observed when comparing oscillations in different beams separated by similar spatial scales. This finding counters both the spatial coherence observed along the beam’s line of sight and the spatial coherence of Pc3-4 waves at auroral latitudes. We conclude that it is unlikely that the observed oscillations are the result of Pc3-4 ULF waves. We instead propose that the observed Doppler velocity oscillations are caused by a change in the ionization along the ray’s path due to auroral particle precipitation.

Research during the last two decades has established that variability of the winter polar stratospheric vortex can significantly influence the troposphere, affecting the likelihood of extreme weather events and the skill of long-range weather forecasts. This influence is particularly strong following the rapid breakdown of the vortex in events known as sudden stratospheric warmings (SSWs). This thesis addresses some outstanding issues in our understanding of the dynamics of this stratospheric variability and its influence on the troposphere. First, a geometrical method is developed to characterise two-dimensional polar vortex variability. This method is also able to identify types of SSW in which the vortex is displaced from the pole and those in which it is split in two; known as displaced and split vortex events. It shown to capture vortex variability at least as well as previous methods, but has the advantage of being easily applicable to climate model simulations. This method is subsequently applied to 13 stratosphere-resolving climate models. Almost all models show split vortex events as barotropic and displaced vortex events as baroclinic; a difference also seen in observational reanalysis data. This supports the idea that split vortex events are caused by a resonant excitation of the barotropic mode. Models show consistent differences in the surface response to split and displaced vortex events which do not project stongly onto the annular mode. However, these differences are approximately co-located with lower stratospheric anomalies, suggesting that a local adjustment to stratospheric potential vorticity anomalies is the mechanism behind the different surface responses. Finally, the predictability of the polar stratosphere and its influence on the troposphere is assessed in a stratosphere-resolving seasonal forecast system. Little skill is found in the prediction of the strength of the Northern Hemisphere vortex at lead times beyond one month. However, much greater skill is found for the Southern Hemisphere vortex during austral spring. This allows for forecasts of interannual changes in ozone depletion to be inferred at lead times much beyond previous forecasts. It is further demonstrated that this stratospheric skill descends with time and leads to an enhanced surface skill at lead times of more than three months.

Because the surface plays an important role in the electrical and optical properties of GaN devices, an improved understanding of surface effects should help optimize device performance. In this work, atomic force microscopy (AFM) and related techniques have been used to characterize three unique sets of n-type GaN samples. The sample sets comprised freestanding bulk GaN with Ga polar and N polar surfaces, epitaxial GaN films with laterally patterned Ga- and N-polar regions on a common surface, and truncated, hexagonal GaN microstructures containing Ga-polar mesas and semipolar facets. Morphology studies revealed that bulk Ga-polar surfaces treated with a chemical-mechanical polish (CMP) were the flattest of the entire set, with rms values of only 0.4 nm. Conducting AFM (CAFM) indicated unexpected insulating behavior for N-polar GaN bulk samples, but showed expected forward and reverse-bias conduction for periodically patterned GaN samples. Using scanning Kelvin probe microscopy, these same patterned samples demonstrated surface potential differences between the two polarities of up to 0.5 eV, where N-polar showed the expected higher surface potential. An HCl cleaning procedure used to remove the surface oxide decreased this difference between the two regions by 0.2 eV. It is possible to locally inject surface charge and measure the resulting change in surface potential using CAFM in conjunction with SKPM. After injecting electrons using a 10 V applied voltage between sample and tip, the patterned polarity samples reveal that the N-polar regions become significantly more negatively charged as compared to Ga-polar regions, with up to a 2 eV difference between charged and uncharged N polar regions. This result suggests that the N-polar regions have a thicker surface oxide that effectively stores charge. Removal of this oxide layer using HCl results in significantly decreased surface charging behavior. A phenomenological model was then developed to fit the discharging behavior of N-polar GaN with good agreement to experimental data. Surface photovoltage (SPV) measurements obtained using SKPM further support the presence of a thicker surface oxide for N polar GaN based on steady state and restoration SPV behaviors. Scanning probe microscopy techniques have therefore been used to effectively discriminate between the surface morphological and electrical behaviors of Ga- vs. N-polar GaN.

Pour une meilleure compréhension en gestion de la qualité de l’environnement le dosage des contaminants dans les différents compartiments naturels reste un premier pas vers l’élucidation de la dynamique des polluants et de leurs impacts sur les écosystèmes. Cependant les stratégies d’échantillonnage usuellement utilisées n’ont pas changé depuis l’avènement de la chimie analytique. Ces techniques consistent en général à prélever une certaine quantité de l’échantillon (eau, air, solide) afin d’en extraire les substances d’intérêt pour les doser. La question de la représentativité de telles pratiques se pose alors ; en effet pour un site donné la contamination peut être très variable au cours du temps et sur de faibles distances. La compréhension fine de la contamination d’un milieu en utilisant de telles techniques impose alors la multiplication des prélèvements dans le temps et l’espace.Depuis les années 80 mais surtout depuis le début des années 2000, des outils d’échantillonnage passif ont été mis au point dans de nombreux domaines permettant d’avoir un suivi de la contamination intégré dans le temps à moindre coût. Ces nouvelles approches consistent à prélever l’échantillon en continu et in-situ sans apport d’énergie, fournissant ainsi une valeur moyenne de la contamination.Afin de pouvoir utiliser ces dispositifs, un certain nombre de développements en laboratoire doivent être au préalable menés afin de déterminer les constantes cinétiques nécessaires pour déduire la contamination du milieu échantillonné à partir des résidus séquestrés par les échantillonneurs. Ainsi, dans le cadre de ces travaux, une sélection d’échantillonneurs existants ont été testés et adaptés en laboratoire puis évalués en conditions réelles sur divers sites environnementaux.Les développements en laboratoire ont eu pour objet de mettre au point différentes configurations d’outils dans le but d’être applicables au plus grand nombre de molécules et ce de la manière la plus quantitative possible. A titre d’exemple, des dispositifs adaptés ont été mis au point pour l’échantillonnage de molécules très polaires qui auparavant n’étaient pas efficacement échantillonnées par les dispositifs existants. Sur site, les outils d’échantillonnage ont principalement été mis en œuvre dans le cadre de programmes de recherche plus vastes et ont à ce titre pu être testés sur de grands terrains d’étude (Bassin d’Arcachon et Estuaire de la Gironde) et être comparés aux techniques d’échantillonnage ponctuels qui font actuellement référence. Les résultats fournis par les outils sont proches de ceux obtenus par échantillonnage ponctuel. Cependant l’aspect quantitatif apparaît probablement encore améliorable soit par l’usage de nouveaux composés référence de performance soit par mise au point de dispositifs plus robustes et faiblement impactés dans leurs performances par les conditions environnementales. / For a better understanding and management of the environmental quality, contaminant analysis in the various compartments is a natural first step in the understanding of the dynamics of pollutants and of their impacts on ecosystems. However sampling strategies commonly used have not changed since the advent of analytical chemistry. These techniques in general consist of taking a certain amount of sample (water, air, solid) to extract the substances of interest to assay. The issue of representativeness of such sampling practices arises since for a given site the contamination can vary over time and over short distances. Detailed understanding of the contamination of an ecosystem using such sampling techniques requires the multiplication of samples over time and space.Since the 80’s and more especially the beginning of 2000, passive sampling tools have been developed in many areas. They provide an integrated monitoring of contamination over time at low cost. These new approaches are based on the fact that the sample are taken continuously in-situ and without energy supply, thus providing an average value of the contamination.To use these devices, a number of laboratory developments must first be conducted to determine the kinetic constants to deduce the necessary characteristics of the environmental contamination. Thus, as part of this work, a selection of existing samplers has been tested and adapted in laboratory experiments and evaluated in real conditions at various environmental sites.Laboratory developments have been conducted to develop different configuration tools in order to be used for a wide range of pollutants with the best quantitative capacity. For example, suitable devices have been developed for sampling highly polar molecules which previously were not strongly sampled by existing devices.On-site, sampling tools were mainly implemented in the framework of broader research programs and consequently have been tested during large field studies (Bassin d'Arcachon, Gironde Estuary) to compare their performance to grab sampling techniques. The results provided by the tools are similar to those obtained by grab sampling. However, the quantitative aspect appears still improvable either by the use of new performance reference compounds or by using devices more robust and slightly affected in their performance by environmental conditions.

No description available.