by Hung-mee Poon. / Includes bibliographical references / Thesis (M.Ph.)--Chinese University of Hong Kong, 1986

Thesis (Sc. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE / Bibliography: leaves 429-434. / by Richard John Quann. / Sc.D.

A combustão do carvão para a produção de energia elétrica tem como consequência a geração de cinzas, que é um dos maiores resíduos gerados no Brasil, em termos de volume (4.109 dm³/ano). Visando a minimização do impacto ambiental causado pelo mau descarte das cinzas, este trabalho teve como objetivo sintetizar e caracterizar zeólitas obtidas a partir de cinza de carvão e aplicar na agricultura como fertilizante potássico. Para isso a cinza utilizada foi obtida no combustor piloto de leito fluidizado operando com carvão da Mina do Leão/RS e empregada para sintetizar material zeolítico a partir do tratamento hidrotérmico alcalino. Foram realizados ensaios experimentais utilizando razão solução/cinzas constante em 6 L mg-1, variando a concentração de hidróxido de potássio (KOH) entre 3 e 5 M, a temperatura entre 100 e 150 ºC e o tempo de reação entre 24 e 72 h. O material sintetizado e a cinza foram caracterizados quanto a sua composição química, mineralógica, morfologia, área superficial específica e capacidade de troca catiônica. Através da caracterização foi observada a formação de duas fases zeolíticas, a chabazita-K e a merlinoíta. A partir da caracterização do material, foi escolhido um dos produtos zeolíticos obtidos para aplicação em solo, como fertilizante de potássio para o cultivo de trigo (Triticum aestivum L.). A condição experimental escolhida foi de 5 M a concentração da solução de KOH, temperatura de 150 ºC e tempo de reação de 24 h. Nesta condição obteve-se apenas uma fase zeolítica identificada, a zeólita merlinoíta, com uma área superficial de 23,37 m² g e uma capacidade de troca catiônica (CTC) de 2,62 meq g 1. Para fins de comparação foi utilizado o fertilizante comercial, cloreto de potássio (KCl), que contém em torno de 60 % de K2O. Foram realizados 35 ensaios experimentais em casa de vegetação da EMBRAPA, utilizando 7 tratamentos (3 doses diferentes de KCl e zeólita 50, 100 e 150 % da dose máxima recomendada e o solo não tratado (testemunha)) em 5 blocos aleatórios. Os experimentos na casa de vegetação foram concluídos com 59 dias de cultivo de trigo e submetidos às análises como determinação da produção de matéria seca da parte aérea e raízes das plantas e análise química do solo e tecido foliar. Verificou-se que a zeólita merlinoíta obtida a partir da cinza de carvão pode ser utilizada como fertilizante, pois teve um desempenho similar ao KCl no crescimento do trigo, não inibindo seu crescimento. Utilizando o tratamento com zeólita 100 % a produção de matéria seca da parte aérea foi de 1,07 ± 0,09 g e raízes 1,6 ± 0,23 g e na análise do tecido foliar teve uma absorção de 3,39 ± 0,31. / Coal combustion for electricity production results in the generation of ash, which is one of the main waste generated in Brazil in terms of volume. Intending the minimization of the environmental impact caused by poor disposal of ashes, this study aimed to synthesize and characterize zeolites obtained from coal ash and apply in agriculture as potassium fertilizer. For this purpose, coal fly ash was obtained from a fluidized bed pilot combustor operating with coal from Mina do Leão/RS and used to synthesize zeolitic material through the alkaline hydrothermal treatment. Experimental tests were performed using the ratio volume of solution/mass of coal fly ash constant at 6 mL mg -1, varying the concentration of potassium hydroxide (KOH) between 3 and 5 M, temperature between 100 and 150 °C and reaction time between 24 and 72 h. The synthesized and coal fly ash material was characterized by their chemical composition, mineralogy, morphology, specific surface area and cation exchange capacity. With the characterization, it was observed the formation of two phases zeolite K-chabazite and merlinoite. By the characterization of the material, it was chosen one of the zeolitic products obtained for application to soil as a potassium fertilizer for the cultivation of wheat (Triticum aestivum L.). The chosen experimental condition was 5 M KOH solution, temperature of 150 °C and 24 h time of reaction. At this condition, only one zeolitic phase was identified, zeolite merlinoite, with a surface area of 23.37 m² g a cation exchange capacity (CEC) of 2.62 meq g-1. For purposes of comparison, the tests in the soil were performed using also a commercial fertilizer, potassium chloride (KCl), containing about 60 % of K2O. A total of 35 experimental trials were carried out in a greenhouse at EMBRAPA, using 7 treatments in 5 random blocks: 50, 100 and 150 % of the maximum recommended dose for KCl and for zeolite and untreated soil (witness). The experiments in the greenhouse were concluded with 59 days of wheat cultivation. The plants were submitted to analysis for dry matter in aerial parts and roots determination. Likewise, soil and foliar tissue were submitted to chemical analysis. It was found that the zeolite Merlinoite obtained from the coal fly ash can be used as a fertilizer because it had a similar performance to KCl in the wheat growth. The treatment with 100% zeolite presented a dry matter production of 1.07 ± 0.09 g for aerial parts and 1.6 ± 0.23 g for roots. Also, the leaf tissue analysis showed a potassium absorption of 3.39 ± 0.31 % m/m in this treatment.

Delia radicum L. (Diptera: Anthomyiidae), the cabbage root fly, is a specialist root-feeding insect pest of Brassica crops. The impending withdrawal of chlorpyrifos, one of the main pesticides used against D. radicum, opens new opportunities to research alternative pest management strategies. Manipulating host plant location cues to influence D. radicum adult and larval behaviour, along with induced plant defence responses, offer potential integrative crop protection solutions (Chapter 1). This thesis aimed to identify the semiochemistry underpinning D. radicum larval host plant location, and to investigate whether plant defence induction treatments (methyl jasmonate [MeJA], D-Fructose) and a herbivore induced volatile (dimethyl disulfide [DMDS]) affect D. radicum larval performance and adult oviposition preference. In choice-test bioassays, larvae were inconsistent in their responses to root exudates collected from Brassica host plants (Chapter 2). A combined bioassay and EthoVision® video-tracking approach was developed to record and analyse larval movements in response to volatiles emitted from host and non-host plant roots (Chapter 3). Larvae were significantly attracted to host plant root volatiles. Olfactory stimuli from roots of the non-host plant onion (Allium cepa L. ‘Ailsa Craig’), which share overlapping, yet distinctive volatile profiles to that of Brassica plants, also elicited positive taxis. By analysing the volatile metabolome of broccoli (B. oleracea L. convar. botrytis L. Alef. var. cymosa Duchesne ‘Parthenon’) and onion roots using solid phase micro extraction-gas chromatography-mass spectrometry (SPME-GCMS), a suite of candidate volatile orientation cues were identified. A SPME-based method was developed to non-invasively collect root volatiles in situ from glasshouse- and field-grown broccoli plants pre- and post-D. radicum infestation (Chapters 4, 5 and 6). GC-MS analyses revealed that sulfur compounds, showing characteristic temporal emission patterns, were the principal volatiles released by roots in response to damage. This new method, which has potential for wide application in chemical ecology research, allows the study of volatiles in the soil in situ that are critical for interactions between trophic levels. In EthoVision® bioassays, a major volatile constituent of broccoli roots, DMDS, was attractive to larvae, but toxic at the highest dose tested (Chapter 3). Glasshouse and on-farm experiments using broccoli were conducted to evaluate the efficacy of MeJA, D-Fructose and DMDS against D. radicum compared to commercially available crop protection products (chlorpyrifos [Dursban® WG], spinosad [Tracer®], Steinernema feltiae Filipjev [Nematoda: Steinernematidae] [Entonem] and garlic granules [ECOguard®]). MeJA and garlic reduced larval performance under glasshouse conditions whereas D-Fructose and DMDS did not at the concentrations tested (Chapter 7). In field studies, MeJA combined with reduced rate chlorpyrifos, spinosad, and S. feltiae all showed partial efficacy for controlling D. radicum larvae. Inherent field site, weather and D. radicum population density variability highlighted that glasshouse results cannot always be reproduced in more complex field environments (Chapter 8). Further research is needed into formulation, mode of application and timing to improve efficacy of promising treatments that may help in future integrated pest management (IPM) for this key pest in the absence of existing pesticides.

With the pressure on the construction industry to lower CO2 emissions it has become increasingly important to utilise materials that supplement Portland cement (CEM I) in concrete. These include additions such as ground granulated blast-furnace slag (GGBS) and fly ash, which have found greater use due to the benefits they provide to many properties of the material (in addition to environmental impact). While studies have investigated these materials in binary blends with CEM I, little work has examined the effect of combining materials in ternary blend concretes. A wide-ranging study was, therefore, set up to examine this for the range of more commonly available additions. This thesis reports on research carried out to investigate the effects of cement combinations based on CEM I / GGBS with either fly ash or limestone. The experimental programme investigated these materials in both paste and concrete and covered fresh properties, compressive strength, permeation and durability properties (using standard water curing for the latter three) and considered, for the hardened properties, how these may be balanced with environmental cost. The mixes covered a range of w/c ratios (0.35. 0.50 and 0.65), which was the main basis of comparison, and combinations of CEM I with GGBS (at levels of 35%, 55% and 75%), and fly ash and LS part-replacing this (at levels of 10 to 20 % and 10 to 35% respectively), after consideration of the relevant standards and related research. The initial phase of the study examined the characteristics of the materials, which indicated that they conformed to appropriate standards and were typical of those used in the application. Studies with cement paste (0.35 and 0.50 w/c ratio) indicated that there were reductions in water demand with the use of addition materials (binary and ternary) compared to CEM I. The setting times of the cement pastes were also affected, generally increasing with GGBS level for the binary mixes, although the effect was influenced by w/c ratio. Whilst fly ash and limestone delayed setting at the higher w/c ratio, the opposite occurred as this reduced, compared to the binary mixes. It was also found that the yield stress increased with GGBS level and further with the addition of ternary materials (particularly limestone) compared to CEM I. The superplastiser (SP) dosage requirement in concrete was found to decrease with increasing w/c ratio, and ternary additions reduced this compared to binary and CEM I concrete with the effect most noticeable at low w/c ratio. Early strength development was less than CEM I for binary concretes and differences increased with GGBS level. Improvements with the introduction of fly ash compared to the binary concretes were noted with increasing GGBS levels and w/c ratio. In general, the addition of LS gave reduced early strength for all concretes. Although at the 35% GGBS level binary concretes achieved similar strength to those of CEM I, the others generally gave reductions at all ages to 180 days, with differences increasing with GGBS level. However, with increasing w/c ratio and GGBS level improved strength development of ternary concretes, was noted compared to those of CEM I from 28 days. Permeation (absorption (initial surface absorption and sorptivity) and permeability (water penetration and air permeability)) and durability properties (accelerated carbonation and chloride ingress) of the test concrete were also investigated. At 28 days, for low GGBS levels, the binary concretes gave reduced absorption properties compared to CEM I, while the reverse occurred at high level. The effect of the ternary concretes gave further improvements at the lower GGBS levels and with increasing w/c ratio and curing time compared to CEM I. At the higher GGBS level the effect of the ternary additions was less noticeable but, in the case of limestone, improvements were still seen with increasing w/c ratio compared to CEM I. Similar effects were noted for the sorptivity results. The air permeability results gave higher values at 28 days for the binary and ternary concretes compared to CEM I, but significant improvements in the long-term at the lower GGBS level across the range of w/c ratios compared to CEM I concrete. Similar trends were found with water penetration tests. Accelerated carbonation increased with GGBS level for binary concretes compared to CEM I. These differences increased further with the introduction of fly ash and LS, particularly the former. In contrast rapid chloride tests indicated improvements with increasing GGBS levels compared to CEM I and further benefits with the inclusion of fly ash and limestone. Embodied CO2 (ECO2) was calculated based on published British Cement Association (BCA) values for each component of the mix and was shown to reduce with increasing w/c ratio and addition level in concrete. For concrete of an equal strength of 40N/mm2 the ECO2 could be almost halved (reduced from 343 kg/m3 for the CEM I to 176 kg/m3) for the ternary concretes at higher GGBS levels. These combination concretes also gave enhanced durability with regard to chloride ingress and at the lower w/c ratio comparable properties to CEM I in the case of carbonation. Overall, the results suggest that there is potential for ternary concretes to be used in the concrete industry given their ability to reduce ECO2, without compromising strength, permeation and durability properties of concrete.

The Leishmania spp. are kinetoplastid protozoan parasites that cause a spectrum of highly prevalent and neglected tropical diseases known as leishmaniasis. The parasites must undergo two life forms during their life cycle: the extracellular promastigote life stage within the sand fly vector, and the intracellular amastigote life stage after internalization of host phagocytic cells. In the extracellular life stage, Leishmania promastigotes reside and develop to their infectious metacyclic form solely in the gut lumen of the sand fly, a process known as metacyclogenesis. During this process, other organisms that co-inhabit the sand fly gut, collectively known as the microbiome, influence parasite development. Based on the hypothesis that vector gut microbiota influence the development of parasite virulence, we sequenced midgut microbiomes of the sand fly Lutzomyia longipalpis with or without L. infantum infection. Sucrose fed sand flies contained a highly diverse, stable midgut microbiome. Blood feeding caused a decrease in bacterial richness, which eventually recovered. However, bacterial richness progressively decreased in L. infantum-infected sand flies. Furthermore, parasites altered the relative abundance of several bacterial phylogenies, including Pseudomonas and Serratia. Importantly, antibiotic-mediated perturbation of the midgut microbiome rendered sand flies unable to support parasite growth and consequent development to infectious metacyclic forms, and revealing the level of microbial diversity may induce flies resistant to infection. Together, these data suggest the sand fly midgut microbiome is a critical factor for Leishmania growth and differentiation prior to disease transmission. During the intracellular amastigote life form, macrophages are the primary cell type to phagocytize parasites. The effect of secreted factors such as exosomes from Leishmania-infected human cells and their effect on the immune response has not been extensively investigated. In this thesis, we characterized the proteome of primary human donor monocyte-derived macrophage (MDM) exosomes during L. infantum infection compared to donor-matched uninfected controls, and determined their impact on naïve MDMs measured by cytokine gene expression and resistance to subsequent parasite infection. Proteomic comparisons of infected and uninfected MDM exosomes were made using stable isotopic dimethyl labeling LC-MS/MS technology. A total of 484 human proteins were identified between four donors. Proteins significantly less abundant in exosomes derived from infected MDMs were matrix metalloprotease 9, galectin-3 binding protein, and several Annexins and histone proteins. Proteins more abundant included galectin-1, galectin-9, and serotransferrin and transferrin receptor 1. Interestingly, class I and class II MHC protein chains were differentially abundant in our samples. Furthermore, we observed several Leishmania spp. proteins in exosomes from infected MDMs as well. Naïve MDMs pretreated with exosomes from infected or uninfected MDM for 4 hours were not more resistant to L. infantum infection nor displayed increased gene expression of the pro-inflammatory cytokines IL-1α, IL-1β, IL-6, IL-8 or TNF-α. To date, the work presented in this thesis is the first to comprehensively identify the proteome in primary human MDM exosomes during Leishmania spp. infection, and to determine the impact of these exosomes on the immune response of other naïve human MDMs.

Doctor of Philosophy(PhD), / Until recently, Northwestern Australia was thought to be relatively free of serious fruit fly pests. Although a noxious strain, present in Darwin since 1985, was widely believed to be an infestation of the Queensland fruit fly, Bactrocera tryoni, from the East coast, the fruit flies present outside this area were believed to be the benign endemic species, B. aquilonis. However, during the year 2000, infestations of fruit flies were discovered on major commercial crops in both Western Australia and the Northern Territory. It was not known whether these outbreaks were due to an invasion of the major pest species, Bactrocera tryoni, a change in the behaviour of B. aquilonis, or a hybridisation event between the two species. Finding the source of these outbreaks has been complicated by the fact that, since B. tryoni and B. aquilonis are virtually indistinguishable morphologically, it was not known which species are present in the region. Traditionally any tryoni complex fly caught in the Northwest was called B. aquilonis based solely on location. In order to get a good population profile of the region, an extensive trapping program was set up to include flies from urban areas, commercial crops and natural areas where the benign strain is thought to remain. Tests of genetic differentiation and clustering analyses revealed a high degree of homogeneity in the Northwest samples, suggesting that just one species is present in the region. The Northwest samples were genetically differentiated from the Queensland samples but only to a small degree (FST =0.0153). MtDNA sequencing results also showed a small degree of differentiation between these regions. A morphological study of wing shape indicated that there are some minor identifiable morphological differences between East coast and Northwest laboratory reared flies. This difference was greater than that seen between B. jarvisi populations across the same geographic range. The results suggest that the flies caught in the Northwest are a separate population of B. tryoni. Soon after pest flies were discovered in Darwin, a population became established in Alice Springs. This population had a low genetic diversity compared with Queensland and Darwin populations, and showed evidence of being heavily founded. In 2000, an outbreak was discovered in the nearby town of Ti Tree. Due to the geographic and genetic similarity of these populations, Alice Springs was determined to be the source of the Ti Tree outbreak. To investigate the founding of these populations, a program was developed to estimate the propagule size. Using a simulation method seven different statistics were tested for estimating the propagule size of an outbreak population. For outbreaks originating from populations with high genetic diversity, the number of alleles was a good estimator of propagule size. When, however, the genetic diversity of the source population was already reduced, allele frequency measures, particularly the likelihood of obtaining the outbreak population from the source population, gave more accurate estimates. Applying this information to the Alice Springs samples, it was estimated that just five flies were needed to found the major population in and around Alice Springs. For Ti Tree, the propagule size was estimated to be 27 flies (minimum 10). In 2000, a much larger outbreak occurred in the developing horticultural region of Kununurra in northern Western Australia. An important question for the management of the problem is whether there is an established fly population or the flies are reinvading each year. This population was found to have a large amount of gene flow from the Northern Territory. Within the Kununurra samples, one group of flies was genetically differentiated from all the other samples. This group came from a small geographic area on the periphery of Kununurra and appeared to be the result of an invasion into this area at the time when the population was building up following the dry season. A further threat to the Northwest horticultural regions comes from B. jarvisi. A recent increase in the host range of this species has lead to speculation that it may become a greater pest in Northwestern Australia. At the present time, protocols for the population monitoring and disinfestation of this species are not in place. Here it is shown that B. jarvisi eggs are more heat tolerant than B. tryoni eggs and that monitoring of B. jarvisi populations is possible using cue lure traps placed according to fruiting time and location of their favoured host, Planchonia careya.

<p>Leishmaniasis is a disease affecting more than 12 million people worldwide. It is caused by the protozoan parasite Leishmania, which is transmitted to humans and dog hosts through bites of infected sand flies belonging to genus Phlebotomine. Several studies have shown Polymerase Chain Reaction (PCR) to be effective for the diagnosis of VL in clinical samples compared to the classical methods. The aims of this study were first to compare four different sample preparation methods for the PCR diagnosis of visceral leishmaniasis (VL) using peripheral blood samples and furthermore to find a method that is sensitive, rapid, cost benefit, simple and easy to perform. Two preparation methods were compared for the isolation of leukocytes (with Ficoll and Tris –EDTA buffer) and two DNA isolation methods (with Proteinase K and QIAgen kit). From the methods that were compared, lysis of erythrocytes with TE and the QIAgen kit seems to be the most suitable to use.</p>

We have simulated the behavior of several artificial flies, interacting visually with each other. Each fly is described by a simple tracking system (Poggio and Reichardt, 1973; Land and Collett, 1974) which summarizes behavioral experiments in which individual flies fixate a target. Our main finding is that the interaction of theses implemodules gives rise to a variety of relatively complex behaviors. In particular, we observe a swarm-like behavior of a group of many artificial flies for certain reasonable ranges of our tracking system parameters.

Coal fly ash is a by-product of coal combustion that has drawn renewed public scrutiny due to the negative environmental impacts from accidental release of this waste material from storage facilities. Historically, the leaching of toxic elements from coal fly ash into the environment has always been a major environmental concern. Despite extensive efforts into the characterization of coal fly ash, effective models for the fate and transport of toxic fly ash constituents have remained lacking, making it difficult to perform accurate environmental impact assessment for coal fly ash. To close this critical knowledge gap, the overall objective of this study was to develop a predictive model for the leaching of toxic elements from fly ash particles. First, physical properties of coal fly ash were characterized to evaluate their contribution to elemental transport. Unburned carbon was shown to contribute to the sorption of arsenic to fly ash, which slowed the release of arsenic from fly ash. In parallel, leaching properties of various elements were determined to differentiate species of varying leaching capacities, demonstrating that the majority of toxic elements were not mobile under environmentally relevant conditions. Subsequently, a mechanistic model for the dissolution of fly ash elements was developed and validated with batch kinetics studies. Furthermore, elemental dissolution was integrated with hydrodynamic modeling to describe the leaching of toxic elements from fly ash in dry disposal facilities, which was validated by column studies. The mechanistic model developed and validated in this research represents the first such model that successfully characterized the complex processes underlying the release and transport of toxic elements in coal fly ash, providing a valuable tool to predict the environment impact of coal fly ash and develop more effective management practices for both the industry and regulators.