Free radical polymerization is the most common polymerization technique that is used for the manufacturing of polymers, due to the ease of the polymerization initiation, wide latitude of the material design for a large variety of monomers, and the excellent process robustness for commercial production. In the 1990’s, research activities for the precise control of radical polymerization process resulted in the discovery of ‘Living Radical Polymerization’. The discoveries opened the door for the next generation of radical polymerizations. Extensive research has been conducted to understand the mechanisms and kinetics for numerous practical applications, particularly for polymerization in bulk and solution systems. However, despite the interest of industry, the mechanistic understanding in aqueous dispersed systems such as emulsion and miniemulsion polymerization is far behind the aforementioned two systems. There are still major challenges from the production viewpoint. One reason for the poor understanding is the complexity of the heterogeneous system, which includes multiple　reaction phases that are accompanied by the segregation and transfer of the reaction species among different phases. The purpose of this research was to investigate living radical polymerization or “Stable Free Radical Polymerization” (SFRP) in aqueous dispersed systems to obtain better mechanistic understanding of how the heterogeneous nature of the system interacts with the novel living radical chemistry. The theoretical and experimental feasibility of the SFRP emulsion process were studied in this research, in particular, focusing on the compartmentalization effect. Particle size influence on the polymerization kinetics and the polymer livingness was experimentally confirmed, and compared to bulk polymerization. In addition, a comprehensive mathematical model including all major chemical and physical events was developed to further our mechanistic understanding. Based on the results from the experimental and modeling studies, it was shown that rate reduction in the smaller particles is the primary cause of difficulty in implementing a conventional emulsion process (i.e. ab initio emulsion polymerization). Finally, for overcoming this difficulty, a new approach using a combination of TEMPO with highly hydrophobic 4-stearoyl TEMPO was proposed for a coagulum free ab initio emulsion process. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2010-02-18 09:49:52.336

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Earth’s climate system has experienced significant changes throughout its history. Tropical, glacial and interglacial conditions have persisted across the globe during the Tertiary, and the present interglacial period with strong seasonality and episodes of warming and cooling has existed for the last several thousand years. However, rapid warming during the last century has highlighted the importance of understanding past climate behaviour, in order to predict the likely effects of such warming on our future climate. This has led to the use of proxies, such as sediment cores, tree rings, ice and carbonates, which provide high resolution palaeoclimate archives. Studies using a variety of proxies from around the globe have developed a network of site specific climate information, offering insights of climate fluctuations on a millennial scale, and identifying changing oceanic conditions as a major influence on global climate change. Coral skeletons are particularly sensitive recorders of ambient seawater conditions as they record fluctuations of oxygen and carbon in their aragonitic skeletons, which are caused by perturbations of sea surface temperature (SST) and sea surface salinity (SSS). Therefore, tropical oceans themselves provide a crucial record of climate change. Many of the coupled atmospheric-oceanographic processes that drive the global climate system occur in the Indo-Pacific, making it a particularly important region for data collection. Porites corals from the Indo-Pacific have been studied in detail and have revealed high resolution SST and SSS records, yet comprehensive investigations using other coral species are minimal. This study expands upon the current understanding of coral proxies by investigating three coral species of different ages, and provides new insights into the palaeoclimate history of the Indo-Pacific. Goniastrea retiformis, Platygyra pini and Platygyra lamellina corals have been retrieved from Timor Leste in the Indo-Pacific, and analysed using stable and radiogenic isotopic techniques. Sclerochronology was used to determine that the 4.5 year old, modern G. retiformis coral was living from 2006-mid 2010. Uranium-thorium (U/Th) analysis provided a mid Holocene age of 4.5 ± 0.092 (2σ) ka for the fossil P. pini. Uranium-lead (U/Pb) techniques were used to obtain a 2.7 ± 0.34 (2σ) Ma age for the fossil P. lamellina. A rigorous diagenetic screening process of X-ray diffraction (XRD), petrographic analysis of thin sections, and scanning electron microscopy (SEM) has been carried out to ascertain the extent of preservation in each coral. X-ray images allow annual density bands to be located and unique micromilling paths were developed for the three samples. This enabled us to obtain the first δ¹⁸O and δ¹³C stable isotope results for a G. retiformis coral, and the first fossil coral results for the Platygyra genus. Cross spectral analysis has been used to verify the periodicity of seasonal fluctuations visible in the data, and confirmed that these coral species are suitable for use as climate proxies. G. retiformis is an abundant reef coral distributed throughout the tropical Pacific, and has a robust skeletal configuration making it suitable for use as a climate proxy. The 4.5 year long record has revealed that δ¹⁸O and δ¹³C values range from -4.62‰ ± 0.03‰ (2σ) to -6.11‰ ± 0.02‰ (2σ), and 1.57‰ to -2.53‰, with means of -5.35‰ and -1.02‰, respectively. These values are in agreement with the average δ¹⁸O range of -5.1 to -5.6‰ in modern corals throughout the Indo-Pacific, predominantly of the Porites genus. Statistical analysis of the isotopic data has revealed a quasi-biennial signal in G. retiformis, typical of the temporal interaction between El Niño Southern Oscillation (ENSO) and the South Asian monsoon. Results have also been compared to the Southern Oscillation Index (SOI) in order to assess potential relationships between coral isotopes and ENSO. This has shown an accurate record of El Niño and La Niña events for the first half of the ~ 4.5 year record, from 2006 to mid 2008. Climate processes such as local rainfall and the Indian Ocean Dipole (IOD) are also reflected in the record, to varying extents. The use of Platygyra corals as climate proxies is limited to three investigations using modern samples, despite the fact that this genus has a much broader latitudinal range than the extensively studied Porites genus. This thesis provides the first examination of fossil samples, and provides analysis of both pristine and altered specimens. The 4.5 ka P. pini coral has allowed investigation of the palaeoclimate record in a sample that has been exposed to diagenesis. XRD, petrographic and SEM analyses have revealed widespread secondary aragonite growth, dissolution and secondary calcite within the coral, which would have occurred due to marine and freshwater diagenesis. However, primary growth textures have been retained in some areas of the coral. δ¹⁸O and δ¹³C values range from -3.47‰ ± 0.03‰ (2σ) to -5.45‰ ± 0.02‰ (2σ), and 3.43‰ to -0.49‰, with means of -4.82‰ and 1.12‰, respectively. These values are significantly more positive that the mean δ¹⁸O of four Platygyra corals from the Pacific region, which range from -4.82‰ to -5.10‰. There are two reasonable explanations for this. Secondary aragonite, which is detected throughout the milled section of coral, causes positive shifts in coral δ¹⁸O, an effect which is likely to have altered the geochemical record of this particular coral. But the fact that SST in the southern Indo Pacific Warm Pool (IPWP) during the mid Holocene were 1.2° C cooler than present must also be acknowledged, as cooler temperatures also impart a shift toward higher δ¹⁸O, due to equilibrium fractionation processes. SST reconstruction using the temperature dependence equation from a modern Platygyra coral reveals an SST range of 18.5-27.6° C, and mean of 24.7° C. The present day mean annual SST of 28° C suggests that mid Holocene temperatures less than 26.8° C are unrealistically cool, highlighting the fact that isotopic fractionation during diagenesis has affected coral chemistry. However, the presence of interannual periodicity indicates that ENSO was operating, and the magnitude of isotopic fluctuation through the 10 year record is similar to that found in modern and other Holocene corals. We suggest that although absolute isotopic and SST values are unreliable, prohibiting the extraction of high resolution climate records, insights into the behaviour of broad scale, seasonal and interannual climate processes may still be obtained. A strong annual periodicity has been detected when analysing the stable isotopic values recorded in the 2.7 Ma P. lamellina coral. This indicates that seasonal SST fluctuations were the dominant influence on this coral. Ranges of -4.67‰ ± 0.03‰ (2σ) to -5.48‰ ± 0.02‰ (2σ) and 0.88‰ to -1.12‰ for δ¹⁸O and δ¹³C, respectively, are similar to modern Platygyra coral results, suggesting that this coral has been preserved in pristine condition. Palaeo-SSTs have been reconstructed using a modern Platygyra temperature dependence equation, providing a range of 24-27.7° C and a mean of 25.9° C. Foraminiferal data from sediment cores in the greater Indo-Pacific suggest that mean annual SSTs at this time were ~ 2-3° C cooler than present. The coral record I present supports this statement, providing new insights into our understanding of tropical palaeoclimates. This coral has been entrained within a turbidite deposit on the sea floor that has subsequently been uplifted during the emergence of Timor, with U/Pb dating allowing further constraints of the stratigraphic age of the deposit. Tectonic narrowing is postulated to have caused major changes to the Indonesian Throughflow (ITF) from 4-2 Ma, and been a driver of major global climate change beginning in the late Pliocene. This means that fossil Platygyra corals Timor Leste could provide unique time slices of information about this important time in global climate history. This study confirms that G. retiformis, P. pini and P. lamellina corals are excellent candidates for further, detailed investigations. They provide the opportunity to develop new coral proxies which are both abundant throughout the tropics and distributed over a wide latitudinal range. Their prevalence in both modern and fossil reefs means that once modern samples of each species have been calibrated against modern SST and SSS, these corals will provide reliable, quantitative palaeoclimate proxies, with potential for data capture throughout the Indo-Pacific and mid latitudes. Geochemical coral archives are a crucial tool in the study of climate processes, and we believe that these species are ideally suited to enhancing and refining our current understanding of earth’s climate system.

Determining sustainable water resource utilization rates is an important problem faced by regulatory agencies all around the world. One of the key parameters in determining accurate water budgeting schemes is the rate of water resource replenishment, or ‘recharge’ in groundwater systems. Fundamental questions regarding groundwater recharge include: What is the source of recharge? What is the spatial distribution of recharge? What is the annual average recharge rate, from potentially disparate sources in disparate areas? Answers to these questions can be gained through combining physical and chemical hydrogeological research tools, including stable isotopic compositions. Land-use intensification, including significant increases in dairying, has placed a priority on developing water resource management practices throughout New Zealand. Here we present the first compilation of delta oxygen-18 and delta hydrogen-2 values from individual precipitation events, local surface waters, depression springs, and groundwaters from the greater-Christchurch area. A variety of analytical methods were used in an effort to evaluate the potential use of stable isotopic compositions as tracers of surface-groundwater interaction in the local hydrologic cycle. The results of this thesis found the isotopic variability of Christchurch precipitation to be highly varied. Back-trajectory analysis of single precipitation events exhibit pathways arriving from three principal sources: the Southern Pacific Ocean, the Tasman Sea, and the Tropical Pacific Ocean. Separately, delta oxygen-18 and delta hydrogen-2 values values from these sources show three distinct local meteoric water lines, which are determined to be largely affected by the environmental conditions present in these areas at the time water vapour formation. Intra-storm variation of extra-tropical cyclones support these findings as significant changes in deuterium excess as moisture sources change with southward movement of the low pressure system. Three line-conditioned tests were subsequently developed to compare the relationship between monthly surface rainfall, surface water, and groundwater samples to the respective moisture origins. Surface rainfall, rainfall infiltration, surface waters, and groundwaters all exhibit the least amount of deviation from the Southern Pacific Ocean local meteoric water line. These observations suggest the principle moisture source to Christchurch to be from west-south westerly flow from the mid-latitudes. However, these similarities do not make partitioning their relative contributions to the groundwater system easy. Previous physical and isotopic investigations have shown the dominant sources of recharge to the Christchurch Groundwater System (CGS) are alpine rivers and local precipitation of which there is statistically significant difference with respect to delta oxygen-18 values. A binary single-isotope mixing model allows for quantification of the relative contributions of alpine river and precipitation derived inputs to local depression springs. The isotopic model indicates that approximately 80% of spring discharge was derived from alpine rivers, in good agreement with recently published physical mass balance model results. Deep groundwater flow paths however show groundwater to flow from the Central Canterbury Plains to the CGS. Potentially including losses from the upper Waimakariri River reaches. If included, this places a net recharge amount to the CGS water budget, which if using losses from only the lower Waimakariri River, there is a net loss. Losses from the upper reaches and subsequent groundwater flow into the CGS are likely as there have been no observed declines in groundwater levels even though there is currently a net loss by only using recharge components within the CGS. Ultimately, recharge from groundwater movement from the Central Canterbury Plains may play significant role; however, a much more sophisticated geochemical model is needed to test these theories and determine contributions. This research demonstrates the utility of stable isotopes as tracers of hydrogeological processes, particularly in shallow groundwater, and their potential contributions to the water resource allocation decision making process.

Recently, the growth and condition of Lake Whitefish (Coregonus clupeaformis), an important commercial fishery commodity, has declined in some areas of the Great Lakes. As Lake Whitefish are benthic feeders, historically the bulk of their diet was made up of the energy rich Diporeia hoyi, an amphipod whose abundances declined concurrently with reductions in Lake Whitefish growth and condition. Lake Whitefish populations from lakes Michigan, Erie and Superior have been used to determine whether there is a plausible link between the declines in Lake Whitefish condition and Diporeia abundance as indicated by stable isotope analysis, dietary and condition indices for Lake Whitefish. The first study was Lake Michigan specific and tested the hypothesis that condition, in terms of relative weight, percent lipid and docosahexaenoic acid (DHA), improved as the proportion of high quality prey (e.g., Diporeia) in the diet increased. Samples of spawning whitefish from four regions (northwest, Naubinway, Elk Rapids and southeast) around Lake Michigan had distinct mean carbon and nitrogen isotope signatures. The signatures indicated Lake Whitefish may be using a variety of prey items, especially the Naubinway population where fish occupy the largest isotopic niche space. Relative weight was significantly higher in the southeast and lower for all northern regions. The mean measured lipid from Lake Whitefish dorsal skinless muscle biopsies was highest for northwest region fish. DHA was significantly different among studied regions, with higher mean values in Elk Rapids and the northwest. No linear relationships between stable isotope measures and condition metrics were found. These results suggest that Lake Whitefish are coping with declining Diporeia abundances by feeding on alternate prey. Results do not substantiate the hypothesis of a relationship between condition and prey use, although Lake Whitefish from Elk Rapids and the northwest had high quality prey and good condition. The second study incorporated eight spawning populations around lakes Michigan, Erie and Superior to determine if there were differences in energy available to female Lake Whitefish. The hypotheses tested were three fold: (1) observed differences in growth and reproduction among populations were driven by energy availability, (2) populations with low energy reserves exhibit reproductive trade-offs and (3) high energy reserves are related to Diporeia consumption. Lake Whitefish from lakes Erie and Superior both displayed high growth and no trade-offs between egg size and number. Populations from Lake Michigan all had low investment in growth, significantly lower gonadosomatic index (GSI) and four of these populations displayed significant trade-offs between egg size and number. Growth and GSI tended to increase with mean total lipid stored in muscle and populations displaying reproductive trade-offs had significantly lower muscle lipid, however, these trends were not evident when using DHA as a measure of good nutrition. No relationship was evident between Diporeia consumption and populations with high muscle lipid stores. Overall, my results suggest that while changes in the availability of prey resources has had an effect on Lake Whitefish populations, the impact of declining abundances of Diporeia alone cannot explain the systemic changes in Lake Whitefish condition across the Great Lakes basin.

In this thesis, we are interested in using the Padé approximants and asymptotic series to approximate the density functions of the stable distributions. The paper specifically discusses the selection of the optimal degree and central point of Padé approximants as well as how to connect the Padé approximants and asymptotic series as a piecewise function. Based on such approximation, a computational algorithm is developed to estimate the maximum likelihood estimator with confidence interval of the parameters, using quasi-Newton method. Simulations are conducted to evaluate the performance of this algorithm, and comparisons are made to Nolan's integral method to show that the method introduced in the thesis is fast and reliable in approximation and estimation.

Thesis (Ph. D.)--University of California, San Diego, 1998. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--Drexel University, 2005. / Includes abstract and vita. Includes bibliographical references (leaves 191-199).

Tree-rings are natural archives of the climate variation experienced by trees during their life span. Because trees actively discriminate against 13C versus 12C in atmospheric carbon dioxide due to environmental forcing inducing higher assimilation of 12C in optimal conditions for growth, the ratio between these two isotopes represents a record of climate variability occurring at the time of the wood formation. Therefore, the delta13C can be used to reconstruct palaeoclimate from when the trees sampled were living. As the instrumental period from meteorological methods to measure climate is relatively short (last 150 years), the calibration between delta13C time series and climatic data can be used to improve the understanding of climate variability through longer periods. The main objective of this study is to produce a consistent methodology for the reconstruction of climate and environmental forcing on trees from the high resolution delta13C time series over the period 1997-2009 at three study sites in Europe where extensive eddy covariance measurements have been conducted. This atmospheric measurement technique permits a very fine resolution to observe the exchange of gases between the atmosphere and a land surface with additional applications in meteorology. At Hyytiala, dendrometer and microcore measurements were used to test if a methodology can be developed to predict the occurrence of radial growth during years when dendrological data are missing. The modeling of the intra-annual rate of growth is then performed via the Gompertz equation. Integration of cell life time to match climate information with time delta13C series is also assessed. The delta13C signature from both inter- and intra-annual resolution are tested against three weather variables: photosynthetically active radiation, temperature and precipitation. The results show stronger linear responses from the delta13C time series of the most northern site (Hyytiala, Finland) to the weather variables while the two other study sites (Norunda, Sweden and Loobos, the Netherlands) did not show significant linear relationships at both annual and intra-annual resolution. The approach developed in this study represents a first step in developing a generic method accessible for non-specialists in dendroclimatology for the use of delta13C time series as climate archives.

This work expands the investigation into the behaviour of verdazyl radicals and N-alkylated tetrazines as ligands. These new ligands were coordinated to various metals as a means of exploring new properties in the metal-verdazyl and metal-tetrazine products. The synthesis of N,N’-diphenyl Kuhn and 6-oxo verdazyl radicals bearing a 2-pyridyl group at the C3 position was accomplished. Palladium(II) dichloride complexes of each of these radicals were prepared in order to study the differences in the structural, electronic, and electrochemical properties compared to corresponding complexes of the previously reported N,N’-dialkyl-6-oxoverdazyl ligands. The N,N’-diphenyl verdazyl ligands are structurally bulkier than their dialkyl counterparts resulting in increased interaction between the ligand and palladium as observed in the solid state. The radical complexes were investigated by EPR and shown to exhibit a small amount of spin density on the palladium atoms with most of the spin density remaining on the ligands. The UV-Visible spectra had a noticeable red-shift in the absorbance maxima of the complexes compared to the free ligands. The electrochemistry of the new palladium-verdazyl complexes showed that there was a positive increase to the reduction and oxidation potentials when compared to the free ligands. An N-benzyl tetrazine and its Ru(hfac)2 complex were synthesized from their corresponding radical species utilizing Mn2(CO)10 to photogenerate benzyl radicals. This method was found to give high yields of the tetrazine and its metal complex. Spectroscopic, structural, and electrochemical properties of the tetrazine and its Ru(hfac)2 complex are reported. These compounds were investigated in regards to the activation energy associated with the homolytic cleavage of the C-N bond in the inert solvent, tert-butylbenzene. The activation energy of C-N bond of the tetrazine was 155 kJmol-1 while its Ru(hfac)2 complex was 138 kJmol-1; this resulted in the rate of dissociation being a factor of ~40 greater for the Ru(hfac)2 complex at 393 K. This work presents the potential of coordination compounds in tuning the properties of molecules associated with the stable free radical polymerization process. / Graduate / 0488 / 0485 / cooper_johnston@hotmail.com