Copper-induced toxicity in aqueous systems depends on its speciation and bioavailability. Dissolved organic matter (DOM) and reduced sulfur species can complex copper, influencing speciation and decreasing bioavailability. DOM composition in estuaries can vary, depending on allochthonous, autochthonous, or wastewater source. At a molecular level, variability in DOM quality potentially results in different copper binding affinities. The aim of this study was to characterize and quantify DOM and reduced sulfur in estuaries and investigate possible correlations between these parameters and the capacity to complex copper, reducing its toxicity. This study will have implications on the development of marine-specific toxicity prediction models. DOM was characterized in seventy-one estuarine samples through DOC concentration and fluorescence measurements, combined with spectral resolution techniques, to quantify humic-, fulvic-, tryptophan-, and tyrosine-like fractions. Reduced sulfur was measured by the chromium-reducible sulfide (CRS) technique. Acute copper toxicity tests were done on a subset of samples expressing extreme DOC, fluorescent allochthonous, autochthonous, and CRS concentrations. The results showed significant differences in DOM quality, independent of DOC concentration. In terms of total fluorescent material, humic-like material ranged from 9.48% to 66.1%, followed by fulvic-like with a range of 14.5% to 63.2%, and 0.00% to 36.5% for tryptophan-like and 0.64% to 25.2% for tyrosine-like material. CRS was widely variable among the samples; concentrations ranging from 0.5 nM to 7800 nM. The toxicity results suggested DOC was a very good predictive measure of copper EC50 in estuaries (r2 = 0.84) independent of DOM quality. Furthermore, CRS was saturated at low copper concentrations indicating strong binding sites for copper, suggesting that while CRS is protective, it does not bind copper at toxicologically relevant concentrations and therefore is not a good predictive measure of copper toxicity.

Copper-induced toxicity in aqueous systems depends on its speciation and bioavailability. Dissolved organic matter (DOM) and reduced sulfur species can complex copper, influencing speciation and decreasing bioavailability. DOM composition in estuaries can vary, depending on allochthonous, autochthonous, or wastewater source. At a molecular level, variability in DOM quality potentially results in different copper binding affinities. The aim of this study was to characterize and quantify DOM and reduced sulfur in estuaries and investigate possible correlations between these parameters and the capacity to complex copper, reducing its toxicity. This study will have implications on the development of marine-specific toxicity prediction models. DOM was characterized in seventy-one estuarine samples through DOC concentration and fluorescence measurements, combined with spectral resolution techniques, to quantify humic-, fulvic-, tryptophan-, and tyrosine-like fractions. Reduced sulfur was measured by the chromium-reducible sulfide (CRS) technique. Acute copper toxicity tests were done on a subset of samples expressing extreme DOC, fluorescent allochthonous, autochthonous, and CRS concentrations. The results showed significant differences in DOM quality, independent of DOC concentration. In terms of total fluorescent material, humic-like material ranged from 9.48% to 66.1%, followed by fulvic-like with a range of 14.5% to 63.2%, and 0.00% to 36.5% for tryptophan-like and 0.64% to 25.2% for tyrosine-like material. CRS was widely variable among the samples; concentrations ranging from 0.5 nM to 7800 nM. The toxicity results suggested DOC was a very good predictive measure of copper EC50 in estuaries (r2 = 0.84) independent of DOM quality. Furthermore, CRS was saturated at low copper concentrations indicating strong binding sites for copper, suggesting that while CRS is protective, it does not bind copper at toxicologically relevant concentrations and therefore is not a good predictive measure of copper toxicity.

Structural topology optimization has been extensively studied in aeronautical, civil, and mechanical engineering applications in order to improve performance of systems. This thesis focuses on an optimal design of damping treatment using topology optimization, and the reduction of computational expense of the topology optimization procedure. This thesis presents mainly two works on topology optimization. In the first work, topology optimization is implemented to optimally design damping treatments in unconstrained-layer damping material. Since the damping effect relies on the placement of damping treatment, and the weight of damping material may be an important factor, the placement of damping material is optimally determined using topology optimization with an allowable maximum. Unconstrained-layer plate and shell structures are modeled. The damping layer on the unconstrained-layer structures is considered as the design domain. Using topology optimization, the damping layer is designed numerically, and then experimentally validated by comparing the damping effects. In the numerical example, the topological damping treatment usually provides much higher damping effects compared to other approaches such as strain energy distribution (SED) and an evolutionary structural optimization (ESO). In the second work, a numerical algorithm, named as reducible design variable method (RDVM) topology optimization, is proposed in order to efficiently reduce the computational expense. Since it usually requires thousands to millions of design variables and up to hundreds of iterations in topology optimization, the major difficulty is its computational expense. The RDVM topology optimization is implemented into static (minimization of compliance) and dynamic (maximization of the fundamental resonance frequency) problems. The RDVM significantly reduces computing time, as confirmed by numerical examples. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2011-07-08 10:10:20.606

AN ABSTRACT OF THE THESIS OF Thara G. Siddaramu, for the Master of Science degree in Civil and Environmental Engineering, presented on February 5, 2011, at Southern Illinois University Carbondale. TITLE: EVALUATION OF DIFFERENT PRETREATMENT APPROACHES FOR DISRUPTING LIGNOCELLULOSIC STRUCTURES MAJOR PROFESSOR: Dr. Yanna Liang There are two major steps in biofuel production- pretreatment of lignocellulosic materials and enzymatic hydrolysis. The present study investigated the ability of two pretreatment methods, namely traditional oven and microwave oven treatments for disrupting lignocellulosic structures. The substrates tested were Jatropha seed cake and sweet sorghum bagasse. In recent years, Jatropha curcas also known as physic nut or purging nut has attracted extensive attention due to its several unique characteristics. Similarly, sweet sorghum has the potential to provide great value to energy sectors and food industries being that the entire plant is rich in various sugars and nutrients. Both crops can adapt to various climates, and can withstand extended drought conditions compared to other crops. Additionally, both Jatropha seed cakes and sweet sorghum bagasse are good sources of lignin and carbohydrates, which could be used for production of biofuels only if the sugars can be unlocked. Several treatment methods such as mechanical, physical, chemical and biological treatments have been reported to breakdown the cellulosic structure of biomass. However, other low cost and quicker methods, such as ovenpretreatment and microwave irradiation have not been evaluated for Jatropha seed cake and Sweet Sorghum Bagasse (SSB), respectively. Composition change of Jatropha seed cake samples was evaluated upon lime pretreatment at 100 oC with different parameters. With a lime dose of 0.2 g and a water content of 10 ml per gram of cake and a treatment period of 1 h, 38.2 ± 0.6% of lignin was removed. However, 65 ± 16% of hemicellulose was also lost under this condition. For all the treatments tested, cellulose content was not affected by lime supplementation. Through further examining total reducing sugar (TRS) release by enzymatic hydrolysis after lime pretreatment, results indicated that 0.1 g of lime and 9 ml of water per gram of cake and 3 h pretreatment produced the maximal 68.9% conversion of cellulose. Without lime pretreatment, the highest cellulose conversion was 33.3%. Finally, this study shows that Jatropha seed cake samples could be hydrolyzed by enzymes. Even though the cellulose content was not high for this Jatropha cake sample, the fractionation by lime presented in this study opened the door for other applications, such as removal of lignin and toxicity for use as animal feed and fertilizer. The microwave radiation pretreatment of SSB was evaluated with or without lime (0.1 g/g bagasse) at 10 ml water/g bagasse for 4 min. TRS release over 72-h enzymatic hydrolysis was different for samples treated differently and at different solid loadings. The TRS concentration was increased by 2 and 5-fold from 0 to 24 hours in non lime-pretreated and lime-pretreated samples, respectively. Further incubation of samples for 48 and 72 h did not result in increased TRS. Comparing different solid loadings of samples treated with or without lime, 1% solid content resulted in 1.4 times higher TRS increase than that of 5% solid concentration. Therefore, lime was effective in disintegrating lignocellulosic structures and making cellulose more accessible for saccharification. Higher solid loadings which can lead to higher sugar concentrations are desired for downstream biofuel production. But, as shown in this study, higher concentration of bagasse samples decreased rate of cellulose hydrolysis due to poorer mixing efficiency and hindrance to interactions between enzymes and solid materials. Thus, an optimal solid content needs to be determined for maximal cellulose hydrolysis and for preparing the hydrolysates for downstream processes, either bioethanol or lipid production.

Hydrolysis of cellulosic biomass is an important and ongoing subject of research due to generating precursors for biofuel synthesis. This work involves hydrolysis of microcrystalline cellulose and Arundo donax to glucose. Methods for acid hydrolysis include the use of sulfuric acid, phosphomolybdic acid, blue molybdenum using low concentrations at 40-100 °C. For comparison purposes, enzymatic hydrolysis was also carried out using cellulase. Products were quantified by measuring total organic carbon and reducible sugars using dinitrosalicylic acid. Use of phosphomolybdic acid, blue molybdenum and sulfuric acid even at 6.0 M did not increase the amount of glucose compared to using water only. Interestingly, enzymatic hydrolysis of powdered Arundo donax without pretreatment was successful and resulted in statistically similar amounts of glucose compared to using microcrystalline cellulose. Efforts are ongoing to understand the enzyme kinetics in the hydrolysis of Arundo donax and potentially increase the yield of glucose using chemical and microbiological pretreatment.

This dissertation is an investigation into the classification of all hyperbolic manifolds which admit a reducible Dehn filling and a toroidal Dehn filling with distance 3. The first example was given by Boyer and Zhang. They used the Whitehead link. Eudave-Muñoz and Wu gave an infinite family of such hyperbolic manifolds using tangle arguments. I show in this dissertation that these are the only hyperbolic manifolds admitting a reducible Dehn filling and a toroidal Dehn filling with distance 3. The main tool to prove this is to use the intersection graphs on surfaces introduced and developed by Gordon and Luecke. / text

Families of operators that are triangularizable must necessarily satisfy a number of spectral mapping properties. These necessary conditions are often sufficient as well. This thesis investigates such properties in finite dimensional and infinite dimensional Banach spaces. In addition, we investigate whether approximate spectral mapping conditions (being "close" in some sense) is similarly a sufficient condition.

Families of operators that are triangularizable must necessarily satisfy a number of spectral mapping properties. These necessary conditions are often sufficient as well. This thesis investigates such properties in finite dimensional and infinite dimensional Banach spaces. In addition, we investigate whether approximate spectral mapping conditions (being "close" in some sense) is similarly a sufficient condition.

In this study it was aimed to analyse refining processes such as decreasing reducible oxide content of ladle slag with affecting parameters in low carbon aluminum killed grades and for the research Erdemir low carbon steel grades 7112K and 7110K are selected. There was a negative correlation between reducible oxide amount in ladle slag and desulphurization capacity of ladle slag with metal-slag reaction and steel internal cleanliness. To refine these properties of slag, aluminium dross, which was aluminium production discard and has a metallic content around %30-35 was used and after ladle treatment operation, decrease in reducible oxides such as FetO, MnO, SiO2, P2O5 was analysed. After the study it was observed that 653 kg. of converter slag leaked during tapping of steel and SiO2 ve P2O5 content of ladle slag had negligible change after ladle treatment. According to the results, it is observed that initial %10-12 (FetO + MnO) content was reduced to % 4.5-5.0 (FetO + MnO) after ladle treatment with use of aluminium dross. Beside of this, in order to see the effect of this slag reduction on steel cleanliness, low carbon aluminium killed grades were compared with ultra-low carbon aluminium killed grades having (FetO + MnO) content of %16-17 in slag. It was seen that reoxidation of aluminium (loss of dissolved aluminium) during continuous casting for ULC (ultra-low carbon) gradesis 144 ppm but for LC grades it was 94 ppm and it was being expected that ULC steel group would have higher inclusion content after casting.

We give conditions which, given two Bernoulli trial measures, determine whether there exists a homeomorphism of Cantor space which sends one measure to the other, answering a question of Oxtoby. We then provide examples, relating these results to the notions of good and refinable measures on Cantor space.