Mitigation of High Alkalinity in Leachates of Aged Steel Slag

Steel slag, an abundant by-product of the steel-making industry, after it is aged, has a huge potential for use as an aggregate in road construction. However, the high pH of steel slag seepage (pH≥12) is a major impediment in its beneficial use. Analyses on aged steel slag samples demonstrated that the alkalinity producing capacity of aged steel slag samples strongly correlated to Ca(OH)2 dissolution and that prolonged aging periods have marginal effects on overall alkalinity. Treatment methods that included bitumen-coating, bathing in Al(III) solutions and addition of an alum-based drinking water treatment residual (WTR) were evaluated based on reduction in pH levels and leachate alkalinity. 10% (wt./wt.) alum-based drinking water treatment residual (WTR) addition to slag was determined to be the most successful mitigation method, providing 65−70% reduction in alkalinity both in batch-type and column leach tests, but final leachate pH was only 0.5−1 units lower and leachates were contaminated by dissolved Al(+III) (≥3−4 mM). Based on the interpretation of calculated saturation indices and SEM and EDX analyses, formation of calcium sulfoaluminate phases (i.e., ettringite and monosulfate) was suggested as the mechanism behind alkalinity mitigation upon WTR-modification. The residual alkalinity in WTR-amended slag leachates was able to be completely eliminated utilizing a biosolids compost with high base neutralization capacity. In column leach tests, effluent pH levels below 7 were maintained for 58−74 pore volumes worth of WTR-amended slag leachate using 0.13 kg compost (dry wt.) per 1 kg WTR-amended slag on average; also, dissolved Al(+III) was strongly retained on the compost.

The Generic Approximation Lemma

The approximation lemma is a simplification of the well-known take lemma, and is used to prove properties of programs that produce lists of values. We show how the approximation lemma, unlike the take lemma, can naturally be generalised from lists to a large class of datatypes, and present a generic approximation lemma that is parametric in the datatype to which it applies. As a useful by-product, we find that generalising the approximation lemma in this way also simplifies its proof.

Produção biológica integrada de hidrogénio e metano a partir de resíduos da indústria do biodiesel

Dissertação de Mestrado Integrado em Engenharia da Energia e do Ambiente

GEOTECHNICAL AND ENVIRONMENTAL IMPACTS OF STEEL SLAG IN EMBANKMENTS

Steel slag is a byproduct of iron and steel production by the metallurgical industries. Annually, 21 million tons of steel slag is produced in the United States. Most of the slag is landfilled, which represents a significant economic loss and a waste of valuable land space. Steel slag has great potential for the construction of highway embankments; however, its use has been limited due to its high swelling potential and alkalinity. The swelling potential of steel slags may lead to deterioration of the structural stability of highways, and high alkalinity poses an environmental challenge as it affects the leaching behavior of trace metals. This study seeks a methodology that promotes the use of steel slag in highway embankments by minimizing these two main disadvantages. Accelerated swelling tests were conducted to evaluate the swelling behavior of pure steel slag and water treatment residual (WTR) treated steel slag, where WTR is an alum-rich by-product of drinking water treatment plants. Sequential batch tests and column leach tests, as well as two different numerical analyses, UMDSurf and WiscLEACH, were carried out to check the environmental suitability of the methods. Tests were conducted to study the effect of a common borrow fill material that encapsulated the slag in the embankment and the effects of two subgrade soils on the chemical properties of slag leachate. The results indicated that an increase in WTR content in the steel slag-WTR mixtures yields a decrease in pH and most of the leached metal concentrations, except aluminum. The change in the levels of pH, after passing through encapsulation and subgrade, depends on the natural pHs of materials.

Influência da temperatura de calcinação do fosfogesso no desempenho de cimentos supersulfatados

The supersulfated cement (CSS) basically consist of up to 90% blast furnace slag, 10-20% of a source of calcium sulfate and a small amount of alkali activator, covered by European standard EN 15743/2010. Because of this SSC are considered "green cement" low environmental impact. The source of calcium sulfate used in the preparation of CSS can be obtained from natural sources, such as gypsum or from alternative sources (industrial products), such as phosphogypsum. The phosphogypsum is a by-product of the fertilizer industry, used in the production of phosphoric acid. In this process the phosphate rock is treated with sulfuric acid to give as the major product phosphoric acid (H3PO4), gypsum and a small amount of hydrofluoric acid. The chemical composition of gypsum is basically calcium sulfate dihydrate (CaSO4.2H2O), similar to gypsum, because it can be used in this type of cement. To become anhydrous, the calcination of gypsum is necessary. The availability of the source of calcium sulfate to react with the slag is dependent on its solubility that is directly related to its calcination temperature. The solubility of the anhydrous gypsum decreases with increasing calcination temperature. This study investigated the influence of temperature of calcination of phosphogypsum on the performance of CSS. Samples were prepared with 10 and 20% of phosphogypsum calcinated at 350 to 650 ° C using KOH as an alkaline activator at three different concentrations (0.2, 0.5 and 0.8%). The results showed that all mortars presented the minimum values required by EN 15743/2010 for 7 and 28 days of hydration. In general CSS containing 10% phosphogypsum showed slightly better compressive strength results using a lower calcination temperature (350 °C) and curing all ages. The CSS containing 20% of calcined gypsum at 650 °C exhibit satisfactory compressive strenght at 28 days of hydration, but at later ages (56 to 90 days) it strongly reduced. This indicates that the calcination temperature of phosphogypsum has a strong influence on the performance of the CSS.

Modulação da capacidade antioxidante e de detoxificação no peixe Cyprinus carpio (Cyprinidae) após tratamento com nanocápsulas de ácido lipóico

O metabolismo aeróbico é muito eficiente no processo de geração de energia, no entanto, é uma fonte de produção de espécies reativas de oxigênio (ERO). Para a prevenção dos efeitos potencialmente danosos dessas ERO, os organismos desenvolveram um sistema de defesa antioxidante (SDA), que inclui compostos enzimáticos e não enzimáticos. O ácido lipóico (AL) é uma molécula lipo e hidro solúvel, com capacidade de atravessar membranas celulares. Ele possui propriedades antioxidantes, auxiliando na eliminação de ERO, induzindo a expressão de genes importantes nas defesas antioxidantes, quelando metais e interagindo com outros antioxidantes. Trabalhos prévios demonstraram que nanocápsulas poliméricas de ácido lipóico favoreceram a proteção deste antioxidante, aumentando sua estabilidade físico- química em comparação com formulações contendo ácido lipóico livre. O objetivo deste estudo foi avaliar e comparar o efeito do AL livre e do AL em nanocápsulas sobre a atividade de enzimas antioxidantes (glutamato-cisteína ligase, GCL e glutationa-S- transferase, GST), a concentração de glutationa reduzida (GSH) e sub-produtos da peroxidação lipídica (malondealdeído, método TBARS) e da expressão de genes que codificam para as diferentes formas da enzima GST (alfa e pi). Para isso o peixe Cyprinus carpio (Cyprinidae) foi exposto a uma dose de 40 mg/kg a diferentes formas de AL (livre e em nanocápsulas) por injeção intraperitoneal (duas injeções, sendo a primeira no tempo 0 e a segunda após 24 h), sendo logo sacrificados a diferentes tempos da primeira injeção (48 h, 96 h e uma semana), sendo dissecados o cérebro, fígado e músculo dos peixes de cada tratamento. Os resultados obtidos indicam que os órgãos respondem de forma diferente. A curto prazo, o fígado foi o principal órgão a apresentar respostas antioxidantes após tratamento com AL, enquanto que a longo prazo o cérebro e o músculo se mostraram mais responsivos em termos antioxidantes quando 6 comparado ao fígado. Foi também importante a forma em que o AL é administrado, livre ou em nanocápsulas, sendo observado que um mesmo órgão em um mesmo tempo de exposição pode responder de forma diferente de acordo com o tipo de AL que está sendo utilizado. Além disso, o efeito antioxidante do AL nanoencapsulado parece ser mais efetivo quando utilizado a longo prazo, sugerindo que a forma nanoencapsulada libera o antioxidante em forma mais lenta. Os resultados também indicam que a composição da nanocápsulas deve ser levada em consideração, uma vez que foi observado um efeito antioxidante significativo nos tratamentos que continham apenas a nanocápsulas, sem o AL. Sugere-se que este efeito ocorra devido à produção endógena do próprio antioxidante em questão, favorecida pela composição da própria nanocápsula, que possui ácido octanóico, substrato para a síntese de AL. Também se observou um efeito pró-oxidante em alguns tratamentos onde foi utilizada esta formulação, sugerindo que alguns componentes da nanocápsula, como por exemplo, o surfactante que é utilizado para estabilizar a suspensão, possam aumentar a suscetibilidade dos órgãos ao estresse oxidativo.

Pricing derivatives with stochastic volatility

This Ph.D. thesis contains 4 essays in mathematical finance with a focus on pricing Asian option (Chapter 4), pricing futures and futures option (Chapter 5 and Chapter 6) and time dependent volatility in futures option (Chapter 7). In Chapter 4, the applicability of the Albrecher et al.(2005)'s comonotonicity approach was investigated in the context of various benchmark models for equities and com- modities. Instead of classical Levy models as in Albrecher et al.(2005), the focus is the Heston stochastic volatility model, the constant elasticity of variance (CEV) model and the Schwartz (1997) two-factor model. It is shown that the method delivers rather tight upper bounds for the prices of Asian Options in these models and as a by-product delivers super-hedging strategies which can be easily implemented. In Chapter 5, two types of three-factor models were studied to give the value of com- modities futures contracts, which allow volatility to be stochastic. Both these two models have closed-form solutions for futures contracts price. However, it is shown that Model 2 is better than Model 1 theoretically and also performs very well empiri- cally. Moreover, Model 2 can easily be implemented in practice. In comparison to the Schwartz (1997) two-factor model, it is shown that Model 2 has its unique advantages; hence, it is also a good choice to price the value of commodity futures contracts. Fur- thermore, if these two models are used at the same time, a more accurate price for commodity futures contracts can be obtained in most situations. In Chapter 6, the applicability of the asymptotic approach developed in Fouque et al.(2000b) was investigated for pricing commodity futures options in a Schwartz (1997) multi-factor model, featuring both stochastic convenience yield and stochastic volatility. It is shown that the zero-order term in the expansion coincides with the Schwartz (1997) two-factor term, with averaged volatility, and an explicit expression for the first-order correction term is provided. With empirical data from the natural gas futures market, it is also demonstrated that a significantly better calibration can be achieved by using the correction term as compared to the standard Schwartz (1997) two-factor expression, at virtually no extra effort. In Chapter 7, a new pricing formula is derived for futures options in the Schwartz (1997) two-factor model with time dependent spot volatility. The pricing formula can also be used to find the result of the time dependent spot volatility with futures options prices in the market. Furthermore, the limitations of the method that is used to find the time dependent spot volatility will be explained, and it is also shown how to make sure of its accuracy.

Avaliação agronômica da aplicação do resíduo da indústria processadora de goiabas em pomar comercial de goiabeiras

Dada a escassez de informações na literatura e a importância do manejo adequado de resíduos orgânicos na agricultura, objetivou-se avaliar os efeitos da aplicação do resíduo da indústria processadora de goiabas em um Argissolo Vermelho-Amarelo, determinando-se as alterações provocadas na química do solo, no estado nutricional de goiabeiras e na produção de frutos. As doses de resíduo aplicadas no pomar foram estabelecidas em função dos teores de N no resíduo. O delineamento empregado foi o de blocos casualizados, com cinco tratamentos e quatro repetições, sendo as doses do resíduo (moído) de 0, 9, 18, 27 e 36 t ha-1 (peso do material seco). Foram feitas três aplicações do resíduo: em 2006, 2007 e 2008. O resíduo da indústria processadora de goiabas promoveu aumento nos teores de P no solo; as goiabeiras apresentaram aumento dos teores de N, Ca, Mg e Mn; a produção de frutos foi alterada positiva e significativamente no terceiro ano do experimento.

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Desenvolvimento de uma célula a combustível de glicerol direto em meio alcalino

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Direct catalytic macrolactonization and application of the phase separation strategy in complex molecule synthesis

Les macrolactones sont des squelettes structuraux importants dans de nombreuses sphères de l’industrie chimique, en particulier dans les marchés pharmaceutiques et cosmétiques. Toutefois, la stratégie traditionnelle pour la préparation de macrolactones demeure incommode en requérant notamment l’ajout (super)stœchiométrique d’agents activateurs. Conséquemment, des quantités stœchiométriques de sous-produits sont générées; ils sont souvent toxiques, dommageables pour l’environnement et nécessitent des méthodes de purification fastidieuses afin de les éliminer. La présente thèse décrit le développement d’une macrolactonisation efficace catalysée au hafnium directement à partir de précurseurs portant un acide carboxylique et un alcool primaire, ne générant que de l’eau comme sous-produit et ne nécessitant pas de techniques d’addition lente et/ou azéotropique. Le protocole a également été adapté à la synthèse directe de macrodiolides à partir de mélanges équimolaires de diols et de diacides carboxyliques et à la synthèse de dimères tête-à-queue de seco acides. Des muscs macrocycliques ainsi que des macrolactones pertinentes à la chimie médicinale ont pu être synthétisés avec l’approche développée. Un protocole pour l’estérification directe catalysée au hafnium entre des acides carboxyliques et des alcools primaires a aussi été développé. Différentes méthodes pour la macrolactonisation catalytique directe entre des alcools secondaires et des acides carboxyliques ont été étudiées. En outre, la stratégie de séparation de phase en macrocyclisation en débit continu a été appliquée lors de la synthèse totale formelle de la macrolactone ivorenolide A. Les étapes-clés de la synthèse incluent une macrocyclisation par le couplage d’alcynes de Glaser-Hay et une réaction de métathèse d’alcènes Z-sélective.

Learning English is Fun! Incidental vocabulary acquisition of music and traditional class ninth graders via listening to pop songs

Finnish youth are constantly exposed to music and lyrics in English in their free time. It is likely that this has a positive effect on vocabulary learning. Learning vocabulary while simultaneously accompanied with melodies is likely to result in better learning outcomes. The present thesis covers a study on the vocabulary learning of traditional and music class ninth graders in a south-western upper comprehensive school in Finland, mainly concentrating on vocabulary learning as a by-product of listening to pop music and learning vocabulary through semantic priming. The theoretical background presents viable linguistic arguments and theories, which provide clarity for why it would be possible to learn English vocabulary via listening to pop songs. There is conflicting evidence on the benefits of music on vocabulary learning, and this thesis sets out to shed light on the situation. Additionally, incorporating pop music in English classes could assist in decreasing the gap between real world English and school English. The thesis is a mixed method research study consisting of both quantitative and qualitative research materials. The methodology comprises vocabulary tests both before and after pop music samples and a background questionnaire filled by students. According to the results, all students reported liking listening to music and they clearly listened to English pop music the most. A statistically significant difference was found when analysing the results of the differences in pre- and post-vocabulary tests. However, the traditional class appeared to listen to mainstream pop music more than the students in the music class, and thus it seems likely that the traditional class benefited more from vocabulary learning occurring via listening to pop songs. In conclusion, it can be established that it is possible to learn English vocabulary via listening to pop songs and that students wish their English lectures would involve more music-related vocabulary exercises in the future. Thus, when it comes to school learning, pop songs should be utilised in vocabulary learning, which could also in turn result in more diverse learning and the students could, more easily than before, relate to the themes and topics of the lectures. Furthermore, with the help of pop songs it would be possible to decrease the gap between school English and real-world English.

Sustentabilidade ambiental e humana da produção de alimentos: uma análise comparativa entre agricultura biológica e convencional

A produção e o consumo de alimentos produzidos em agricultura biológica (AB) apoiam-se na ideia da sua superior qualidade nutricional e em supostos efeitos benéficos na saúde humana, bem como no menor impacto ambiental da AB relativamente à agricultura convencional (AC). Mas serão mesmo as dietas baseadas nestes alimentos significativamente mais saudáveis para as pessoas e o ambiente e, portanto, mais sustentáveis que as dietas baseadas no modo convencional? O objetivo deste trabalho é apresentar uma síntese da informação publicada na última década referente a análises comparativas entre AB e AC, através de um conjunto de indicadores de qualidade ambiental e de saúde humana. Foram consultados diversos estudos, privilegiando aqueles que recorreram a um conjunto de indicadores de qualidade ambiental e de saúde humana. A nível ambiental, os estudos apontam para que, apesar das práticas biológicas terem, em geral, impactes menos negativos por unidade de área que as práticas convencionais, o mesmo não se verifica por unidade de produto. Os estudos sobre o impacto comparativo na biodiversidade mostram a tendência benéfica da AB, apesar de as diferenças se afigurarem pouco consistentes. A presença de resíduos de pesticidas e metais pesados em alimentos biológicos é significativamente menor que nos convencionais. A nível nutricional, os vegetais e frutas biológicos apresentam consistentemente conteúdos mais elevados em metabolitos secundários que os convencionais. Todavia, os estudos disponíveis sobre efeitos na saúde são pouco conclusivos quanto a diferenças consistentes entre modos de produção. Evidências científicas suportam a ideia geral de que a AB tende a constituir um modo de produção de alimentos ambiental e humanamente mais sustentável que a AC, embora as diferenças sejam consistentes apenas em alguns indicadores.

Digestibilidade Aparente de Ingredientes pela Tilápia do Nilo (Oreochromis niloticus)

Avaliou-se a digestibilidade aparente do milho, amido de milho, milho extrusado, germe de milho, sorgo, farelo de trigo, farelo de arroz, glúten 21, glúten 60, farelo de soja, farelo de canola, farelo de algodão, farinha de peixe, farinha de carne, farinha de vísceras de aves, farinha de sangue e farinha de penas. Confeccionaram-se 18 rações, marcadas com 0,10% de óxido de crômio III, uma delas, basal purificada, e as demais, contendo os ingredientes. Os peixes, 100 juvenis com 100±10 g, foram alojados em cinco tanques-rede para facilitar o manejo de alimentação e a coleta de fezes e permaneceram, durante o dia, em cinco aquários (250 L) de alimentação, recebendo refeições à vontade das 8 às 17h30. Após, foram transferidos para cinco aquários (300 L) de coleta de fezes, onde permaneceram até a manhã do dia subseqüente. O coeficiente de digestibilidade aparente dos ingredientes foi calculado com base no teor de óxido crômio da ração e das fezes. Com base nos resultados, concluiu-se que, entre os ingredientes energéticos, o milho apresentou o melhor coeficiente de digestibilidade aparente, seguindo-se o milho extrusado, o farelo de trigo e o farelo de arroz; dos ingredientes protéicos - vegetal, o glúten 60 e o glúten 21, seguidos do farelo de canola, apresentou os melhores coeficientes e dos protéicos - animal, destacou-se a farinha de vísceras de aves, seguida da farinha de peixes, enquanto os piores coeficientes foram proporcionados pela farinha de penas e farinha de sangue.

Obtenção de álcool alílico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de óleo de mamona

In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ° C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (υ C = C) 1470 -1600 cm -1 and (υ CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals