Thesis (Ph.D.)--Auburn University, 2005. / Abstract. Vita. Includes bibliographic references.

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Even at 3.3 ppb, seawater contains a uranium supply large enough to power the world’s nuclear fleet for 13,000 years. This large supply has prompted interest in technologies for recovering uranium from seawater. Since the 1960’s, economic models of such technologies have failed to produce an economically competitive strategy when compared to conventional uranium recovery from terrestrial mining. Thus, uranium from seawater is researched as a potential price ceiling because of the large supply but high recovery cost. Such an upper bound is still valuable research because it allows for more certainty in uranium prices for planning, research, development and deployment of nuclear power systems. This thesis explores past cost estimates for uranium recovery from seawater and adds a new cost estimate to the pool of literature. The past estimates showed a development from systems that actively moved seawater to systems that allowed adsorbent to sit passively in seawater. The adsorbent material changed from hydrous titanium oxide to the higher-capacity amidoxime ligand. Capacity was the strongest driver of cost. Early models with the amidoxime ligand used an acrylic substrate or backbone. This substrate was later replaced by polyethylene because of its increased durability and lower cost. However, each of those materials could contribute to the problem of plastics in the ocean. The new technology assessed for cost in this paper attempts to address the plastics concern by replacing the plastic with a high molecular weight chitin nanomat as the substrate for the amidoxime ligand. The cost assessment showed the technology is presently cost prohibitive largely due to the adsorption capacity and chitin nanomat production costs. To increase capacity, the grafting efficiency onto the chitin substrate must be improved in order to achieve capacities comparable to those observed for the amidoxime-polyethylene adsorbent. To reduce chitin nanomat production costs, the ionic liquid (IL) consumption must be reduced and the recyclability of IL must be achieved. / text

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The bertha armyworm (Mamestra configurata) is a major pest of canola and other oilseed crops. A promising control agent for this species is the baculovirus Mamestra configurata nucleopolyhedrovirus (MacoNPV). Baculoviruses are insect-specific viruses. Infections initiate in the host midgut following ingestion of virus particles called occlusion bodies. For a productive infection to occur, the occlusion bodies must dissolve to release the infectious occlusion-derived virions. These virions must pass through the peritrophic matrix, a protein-chitin meshwork that lines the midgut of most insects and provides protection against abrasion and pathogen invasion. The mechanism by which the baculovirus virions transit the peritrophic matrix is unknown. Following the initial infection of midgut cells, a second virion phenotype, the budded virus, is released from infected cells and establishes a systemic infection within the insect. The 11K group of genes, which are conserved among baculovirus species and other insect-infecting viruses, encode proteins with a predicted chitin-binding domain. The degree of conservation of these genes among insect-infecting viruses suggests that they may play a role in insect infectivity. It is possible that the gene products could be involved in an interaction between the baculovirus occlusion-derived virions and the peritrophic matrix or the chitin-secreting cells of the midgut epithelium, and therefore may be involved in initial oral infectivity. The two 11K genes from MacoNPV (ORF 118 and ORF 164), and their homologues in a second species of baculovirus, Autographa californica multiple nucleopolyhedrovirus (AcMNPV [ORF145 and ORF150]) were expressed in a baculovirus expression system. The ability of the proteins, Maco118, Maco164, Ac145, and Ac150, to bind to chitin was assessed in vitro using chitin-coated beads. Each of the four proteins binds to chitin, and hydrophobic interactions mediate the binding. Other binding mechanisms are likely involved, but were not determined in this project. To determine the function of these proteins, a series of gene knockout and repair constructs was produced for AcMNPV ORF 145 and ORF 150 using an established bacmid system. An analysis of the knockout and repair constructs using quantitative real-time polymerase chain reaction showed that deletion of either ORF 145 or ORF 150 had no effect on the rate of budded virus production or viral DNA replication. Oral and injection bioassays were performed in Trichoplusia ni larvae to determine if there were differences in infectivity between the knockout, repair, and wild type constructs. Injection assays, in which budded virus from each construct was injected directly into the insect haemocoel, therefore bypassing the midgut and peritrophic matrix, indicated that there was no statistical difference in infectivity between the knockout, repair, and wild type constructs at a dose of 15 TCID50 U per larva. Oral bioassays, in which larvae were fed occlusion bodies from each virus construct, indicated that there was no statistical difference in mortality rates between the knockout, repair, and wild type constructs. The results from this study indicate that although the baculovirus 11K genes are highly conserved among baculovirus species, and the 11K gene products from MacoNPV and AcMNPV interact with chitin, they are not required for oral infectivity in T. ni larvae, and likely serve another function in the baculovirus infection cycle.

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A finalidade deste trabalho foi obter suspensões aquosas estáveis de beta-quitina (GA = 79%) explorando o uso de ultrassom de alta intensidade, e preparar filmes autossuportados por casting a partir de suspensões de beta-quitina, soluções aquosas de quitosana (GA = 4,9%) e da combinação de ambas em diferentes proporções. Assim, foram preparados os filmes BQF (100% beta-quitina) e QF (100% quitosana), e os filmes compostos BQ80/Q20, BQ50/Q50, BQ20/Q80, sendo que as porcentagens de beta-quitina e quitosana são indicadas pelos sub-índices empregados na identificação dos referidos filmes. Foi constatado por análises de espectroscopia na região do infravermelho e espectroscopia de ressonância magnética nuclear de hidrogênio que o tratamento de ultrassom não alterou a estrutura de beta-quitina, enquanto a viscosimetria capilar em solução diluída mostrou ligeiro decréscimo (16%) da viscosidade intrínseca, indicando a ocorrência de despolimerização em baixa extensão. As análises de microscopia eletrônica de varredura e microscopia de força atômica mostraram que os filmes com maiores teores de beta-quitina exibiram superfícies mais heterogêneas, granulares e rugosas, enquanto a presença de quitosana resultou em filmes mais homogêneos e significativamente menos rugosos. Assim, os filmes BQF e QF apresentaram valores de rugosidade média quadrática (RMS) 225,0 nm e 21,6 nm , respectivamente. As medidas de ângulo de contato revelaram que o filme QF é o mais hidrofílico (θ ≈ 75,40), enquanto os filmes compostos BQ20/Q80, BQ50/Q50 e BQ80/Q20, que têm teores crescentes de beta-quitina, foram mais hidrofóbicos, apresentando ângulos de contato 87,50, 95,60 e 95,20, respectivamente. As análises termogravimétricas revelaram que o tratamento de ultrassom favorece o intumescimento das partículas de beta-quitina e que o baixo grau de ordem dos filmes contribui para diminuir a estabilidade térmica quando comparada à beta-quitina na forma de pó. As análises de calorimetria exploratória diferencial dos filmes compostos mostraram que a eliminação de água demanda maior energia quanto maior o teor de beta- quitina, evidenciando a ocorrência de fortes interações entre as cadeias de beta-quitina e moléculas de água. Assim, os resultados mostraram que o tratamento de ultrassom permitiu o processamento de beta-quitina/quitosana para a formação de filmes autossustentados sem a utilização de solventes orgânicos, e que os filmes exibem características e propriedades que dependem fortemente de sua composição, i. e. dos teores de beta-quitina e quitosana. / The purpose of this study was to obtain stable aqueous suspensions of beta-chitin (GA = 79%) exploring the use of high intensity ultrasound, and to prepare self-sustained films by casting from suspensions of beta-chitin, chitosan aqueous solutions (GA = 4.9%) and from the combination of both, in different proportions. Thus, the films BQF (100% of beta-chitin) and QF (100% of chitosan) and compound films BQ80/Q20, BQ50/Q50, BQ20/Q80 were prepared, the percentages of beta-chitin and chitosan being indicated by the sub-indices used in the identification of those films. It has been found by infrared spectroscopy and proton nuclear magnetic resonance spectroscopy that the ultrasound treatment did not alter the structure of beta-chitin, while the capillary viscometry in dilute solution showed a slight decrease (16%) of intrinsic viscosity indicating the occurrence of depolymerization at low extension. Atomic force microscopy and scanning electron microscopy showed that the films with higher content of beta-chitin exhibited more heterogeneous, granular and rough surfaces, while the presence of chitosan resulted in significantly more homogeneous and less rough films. Thus, QF and BQF films showed values of mean square roughness (RMS) 225.0 nm and 21.6 nm, respectively. The contact angle measurements showed that QF (θ ≈ 75.40) is the more hydrophilic film, while the composite films BQ20/Q80, and BQ50/Q50, BQ80/Q20, which have increasing contents of beta-chitin were more hydrophobic, exhibiting contact angles 87.50, 95.60 and 95.20, respectively. Thermogravimetric analysis showed that the ultrasound treatment favored the swelling of the particles of chitin and that the low degree of order of the films contributed to decrease the thermal stability when compared to beta-chitin in powder form. The differential scanning calorimetry of the compound films showed that the elimination of water requires more energy the higher the content of beta-chitin, indicating the occurrence of strong interactions between the chains of beta- chitin and water molecules. Thus, the results showed that the ultrasoud treatment allowed the processing beta- chitin/chitosan for the formation of self-sustained films without the use of organic solvents, and that the films exhibited characteristics and properties strongly dependent on their composition, i. e. the content of beta-chitin and chitosan.

Chitin is known as an effective biosorbent, which is used to preconcentrate PCP for further treatment. In order to reuse and recover the biosorbent, magnetic separation is a cost-effective alternative to separate the PCP-adsorbed biosorbent (i.e. chitin) from the treated water. Therefore, chitin is immobilized by magnetite prior PCP adsorption. From the immobilization results, the solution pH, temperature, agitation rate do not show great effect on the immobilization of chitin and magnetite. Second, magnetite-immobilized chitin can be formed as quickly as 5 min. Moreover, the interaction of chitin and magnetite is very strong since it is not easy to separate by vigorous shaking, high temperature and changing pH. Although the underlying mechanism of magnetite and chitin is still obscure, the biosorbent is proved to have high stability and reusability. In addition, both Langmuir and Freundlich models indicate that immobilization of chitin by magnetite is favorable with the Langmuir model being the major one. / For PCP adsorption study, it is found that magnetite-immobilized chitin can retain the PCP adsorption ability as free chitin. In accordance with the results, the PCP adsorption of magnetite-immobilized chitin is influenced by altering the parameters of biosorbent concentration, solution pH, temperature, agitation rate, contact time and initial PCP concentration. In general, higher amount of biosorbent gives higher removal efficiency (RE) but lower removal capacity (RC) as more binding sites are available for PCP. The PCP removal is enhanced by lowering pH since uncharged PCP is favorable for adsorption. It is speculated that hydrophobic interaction, hydrogen bonding and electrostatic interaction are involved. In addition, the biosorption efficiency is impeded by high temperature. Evidence shows that the adsorption might be due to the exothermic force such as hydrogen bonding. The biosorption is described as biphasic mechanism with the fast initial phase followed by slow equilibrium phase. For the PCP (10 mg/L) adsorption, the optimized conditions are: 1,500 mg/L of magnetite-immobilized chitin, initial pH 6, 25°C, 200 rpm and 60 min. The RE is 57.9% and RC is 5.4 mg/g. However, the increase in the amount of immobilized chitin (24,000 mg/L) can increase the RE up to 98%. By considering the Langmuir and Freundlich isotherms, the adsorption might be heterogenous, as the correlation coefficient from Freundlich model is higher. / Pentachlorophenol (PCP), a highly chlorinated aromatic organic compound, was widely used as a biocide and is now restrictly used as a wood preservative. PCP is toxic and ubiquitous environmental pollutant. In the present study, integrated treatment of biosorption and photocatalytic oxidation (PCO) using magnetite-immobilized chitin is employed to completely degrade PCP. / To thoroughly remove PCP, PCO is also employed after the biosorption. One hundred % of PCP removal is achieved after 5 h irradiation time, in 100 mL solution at initial pH 9 with 20 mM of H2O2 and 200 mg/L of TiO2. The intermediates of PCP are identified as 2,3,5,6-tetrachlorohydroquinone (TeHQ) and 2,3,5,6-tetrachlorophenol (TeCP) by GC/MS analysis. In addition, the toxicity of sample is monitored by the solid-phase and aqueous-phase Microtox RTM tests, which the toxicity increases and then decreases along the irradiation time. The biosorbent shows no great changes on chitin content and functional groups after PCO. In addition, the results imply that magnetite-immobilized chitin has a good potential to be reused at least for four cycles with high RE and DE. Therefore, the combination of biosorption and PCO treatment was feasible for PCP removal and the system is economic and convenient for repeated use. / by Pang, King Man. / "Oct 2007." / Source: Dissertation Abstracts International, Volume: 69-08, Section: B, page: 4636. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (p. 186-212). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Microbial action on particulate chitin was analyzed in an eastcentral Indiana borrow pit lake. Experiments were conducted to determine the effects of water depth, particle size, mesh size of nylon bag containing chitin, and season on the decomposition process. The majority of chitinolytic bacteria isolated were classified as actinomycetes and pseudomonads. Results indicate that the sediment-water interface is the most active site of chitin mineralization in the lake environment. The samples seeded during summer showed the fastest rate of decomposition with greater than 50% weight loss after two weeks and greater than 95% weight loss after 7 weeks incubation in situ. The highest rate of decomposition (43.6 mg/g/day) occurred during this period. Samples seeded during the spring showed considerably slower activity with only a 25`o weight loss after 9 weeks incubation in situ. Fall samples showed a 30% weight loss after 9 weeks incubation in situ. The rate of degradation was highly correlated with water temperature. Significantly higher rates were-.noted with smaller particle size but no significant difference was evidenced with varying mesh size fran 10 to 100 in. The majority of chitinolytic bacteria isolated were Gram negative; Pseudanonas, Chranobacterium, Flavobacterium, and Serratia spp. Gram positive organisms showing chitin hydrolysis were predominantly actinomycetes. An active chitinolytic culture of Pseudcmonas sp. was used for enzyme studies. This culture was purified using (NH4)2SO4 precipitation, anion exchange chromatography and hydroxylapatite chromatography.Ball State UniversityMuncie, IN 47306

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