Thesis (M.S.)--Oregon State University, 2010. / Printout. Includes bibliographical references (leaves 101-116). Also available on the World Wide Web.

Title from PDF of title page (University of Missouri--Columbia, viewed on March 2, 2010). The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Dr. Kent S. Gates, Dissertation Supervisor. Vita. Includes bibliographical references.

Thesis (Ph. D.)--Mississippi State University. Dave C. Swalm School of Chemical Engineering. / Title from title screen. Includes bibliographical references.

Thesis (Ph.D.)--York University, 2005. Graduate Programme in Earth and Space Science. / Typescript. Includes bibliographical references (leaves 181-196). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://wwwlib.umi.com/cr/yorku/fullcit?pNR11647

Thesis (M.S.) University of Missouri-Columbia, 2006. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on August 24, 2007) Includes bibliographical references.

Submitted by Dilene Paulo (dilene.fatima@ufcg.edu.br) on 2018-01-23T14:36:45Z No. of bitstreams: 1 CLARICE OLIVEIRA DA ROCHA – TESE PPGEQ 2014.pdf: 2084559 bytes, checksum: 35cd9fd0fad2c37f97e9a1e07b4e3877 (MD5) / Made available in DSpace on 2018-01-23T14:36:45Z (GMT). No. of bitstreams: 1 CLARICE OLIVEIRA DA ROCHA – TESE PPGEQ 2014.pdf: 2084559 bytes, checksum: 35cd9fd0fad2c37f97e9a1e07b4e3877 (MD5) Previous issue date: 2014-10-10 / CNPq / Propostas têm aparecido visando à remoção do enxofre nos combustíveis por intermédio dos processos de adsorção. Com isso, a utilização desse método para a dessulfurização vem se expondo como um bom potencial de aplicação, tanto do ponto de vista econômico como ambiental. As peneiras moleculares, do tipo silicoaluminofosfato (SAPO), vêm se apresentando como um excelente adsorvente, com uma ótima estabilidade térmica e hidrotérmica e com a impregnação de metais, tornando-se seletiva a adsorção. Assim, sintetizou-se SAPO-5 (microporoso) e SAPO-5M (mesoporoso), impregnados com diferentes teores dos metais de transição, níquel e/ou zinco. Esses adsorventes foram utilizados para a remoção do enxofre presente na mistura modelo (Heptano / Tiofeno). Para isso, foram realizadas técnicas de caracterização como TG, DRX, EDX e BET, bem como um acompanhamento cinético a fim de avaliar a eficiência da adsorção e as isotermas de equilíbrio. Foi confirmado a mesoporosidade do SAPO-5M, uma vez que o mesmo apresentou as isotermas características tipo IV (típica de material mesoporoso). O volume e o diâmetro dos poros do SAPO-5 microporoso e mesoporosos não foram totalmente obstruídos após a impregnação. Para os adsorventes mesoporosos houve um aumento de quatro vezes no diâmetro do poro, em relação ao micro. Embora, tenha apresentado redução na intensidade de difração de raios X após a impregnação, dos óxidos de níquel e/ou de zinco, obteve-se um material cristalograficamente ordenado. Ocorreu total remoção do direcionador, mostrando que a calcinação foi eficiente e o material é estável a altas temperaturas. Ademais, conseguiu-se atenuar a quantidade de enxofre de 500 ppm para cerca de 96,3 ppm, uma redução de 80%, para o adsorvente mesoporoso 0,25%Ni 0,75%Zn/SAPO-5M, cuja capacidade de adsorção de enxofre foi de 40 mg S/gadsorvente. O adsorvente com 1%Zn/SAPO-5, apresentou maior capacidade de adsorção (30 mg S/gadsorvente), dentre os materiais microporosos, conseguindo reduzir o teor de enxofre de 500 ppm para 163 ppm. Para os demais suportes e adsorventes ocorreu uma redução de aproximadamente 31 % do teor de enxofre na mistura modelo. Conclui-se que a síntese do mesoporoso foi eficiente e que o material utilizado se mostrou eficaz na remoção desse contaminante na mistura modelo. / Proposals have appeared aiming at the sulfur removal in fuels by means of adsorption processes. Thus, the use of this method for the desulfurization exposing themselves like a good application potential, both economically and environmentally. The molecular sieves silicoaluminiumfosfate type (SAPO), has been presented as an excellent adsorbent with optimum thermal and hydrothermal stability and metals impregnation, making it selective adsorption. Thus was synthesized SAPO-5 (microporous) and SAPO-5M (mesoporous) impregnated with different amounts of transition metals, nickel and/or zinc. These adsorbents were used for removal of sulfur present in the mixture model (Thiophene / Heptane). For this, characterization techniques as TG, XRD, EDX and BET were performed, as well as a kinetic monitoring to assess the efficiency of adsorption and equilibrium isotherms. It was confirmed mesoporosity of SAPO-5M, since the isotherms showed the same type IV characteristics (typical of mesoporous materials). The volume and pore diameter of the microporous and mesoporous SAPO-5 were not totally blocked after impregnation. For mesoporous adsorbents an increase of four times the pore diameter in relation to the microporous. Although, has shown a reduction in the intensity of X-ray diffraction after the impregnation of the oxides of nickel and/or zinc, gave a crystallographically ordered materials. Complete removal of the template occurred, showing that the calcination was efficient and the material is stable at high temperatures. Furthermore, we were able to attenuate the amount of sulfur 500 ppm to about 96.3 ppm, a reduction of 80% for the mesoporous adsorbent Ni 0.25% 0.75% Zn/SAPO-5M, whose adsorption capacity sulfur was 40 mg S/g of adsorbent. The adsorbent of 1% Zn/SAPO-5 showed higher adsorption capacity (30 mg S/g of adsorbent) among microporous materials, achieving reduced sulfur content from 500 ppm to 163 ppm. For other supports and adsorbent was reduced by approximately 31% of the sulfur content in the mixture model. It is concluded that the synthesis of mesoporous was effective and that the material used is effective in the removal of this contaminant in the mixture model.

Em função de seu importante papel funcional e de sua posição de transição entre o ambiente marinho e terrestre, os ecossistemas estuarinos vêm sendo objeto de estudo das mais diversas áreas do conhecimento. Entretanto, poucos são os estudos destinados ao entendimento da biogeoquímica e gênese de seus solos. Os compostos de ferro e enxofre são tidos como de importância chave para os ciclos biogeoquímicos ativos nestes ambientes, principalmente pelo fato de a redução bacteriana do sulfato (RBS) ser considerada como a forma de respiração preponderante nestes locais. O ciclo biogeoquímico destes elementos se encontra, entretanto, governado pelas variações físico-químicas do meio devido a variações incessantes em função da freqüência de inundação pelas marés, das diferentes estações climáticas e da atividade da fauna e da flora presentes nestes ambientes. Diante do escasso número de informações sobre estes solos pretende-se, em um estudo biogeoquímico detalhado dos solos de mangue do Estado de São Paulo, gerar informações adicionais sobre a gênese destes solos e avaliar os efeitos das variações sazonais, da atividade biológica (plantas e macro-fauna) e das distintas posições fisiográficas dentro dos manguezais, sobre a biogeoquímica do Fe e S. Para isso, foram realizadas análises morfológicas, químicas, mineralógicas (DRX e MEV), determinações na água intersticial (pH, salinidade, concentrações de Mn2+, Fe2+, HS-, SO4 2-e Cl-) e na fase sólida (COT, Fe total, S total, Mn total, AVS, C biomassa microbiana, densidade de raízes vivas e mortas, porcentagem de areia e extração seqüencial das diferentes formas de Fe) em diferentes perfis sob vegetação de mangue do Estado de São Paulo (Guarujá e Cananéia). Com base nas evidências obtidas neste estudo fica evidente a ação de processos pedogenéticos nos substratos de mangue (adição de matéria orgânica, translocação de Fe2+ e de partículas minerais e a transformação de elementos como Fe e S) os quais devem, portanto, ser denominados, entendidos e estudados como solos e não como sedimentos. Os resultados sugerem a oxidação das frações pirítica e AVS pela ação do sistema radicular das plantas e pela atividade da macro-fauna, principalmente caranguejos, evidenciando ainda a presença de um ciclo sazonal na biogeoquímica do Fe e S o qual se mostra, em grande parte, governado pela ação das plantas e da macro-fauna. Foram encontradas diferenças drásticas entre as condições geoquímicas da água intersticial dos solos e sedimentos de mangue estudados, sendo estas devidas a um maior dinamismo dos processos biogeoquímicos atuantes nos solos, ocasionado pelo efeito das plantas (oxidação, liberação de exudatos pelas raízes). Os resultados obtidos apontam que a participação e a intensidade de cada um dos processos ligados à decomposição da matéria orgânica nos solos de mangue podem variar em função das distintas posições fisiográficas, devido a seus efeitos sobre a freqüência e duração de inundação e composição granulométrica dos solos. Os resultados indicam também, que a ocorrência ou a dominância de um processo sobre os demais afeta de forma significativa a composição das fases sólida e líquida dos solos de mangue, no que se refere ao Fe e S. / Due to the important functional role of mangrove forest communities and their transitional position between marine and terrestrial environments, these ecosystems have been the object of study by a variety of scientific disciplines; however, there are only a few published studies on the genesis and biogeochemistry of its soils. Iron and sulfur compounds play a key role on the active biogeochemical cycles in these environments, mainly because sulfate reduction is considered the preponderant respiration process in these sites. The biogeochemical cycles of these elements are, however, ruled by physicochemical variations constantly generated by tide flooding, different climatic seasons and fauna and flora activity. Considering the scarce information about these soils, a detailed biogeochemical study of mangrove sites located in the State of São Paulo was undertaken to generate additional information on the genesis of these soils and also to evaluate the effects of seasonal variations, biological activity (plants and macrofauna) and physiographic positions on Fe and S biogeochemistry. Morphological, chemical and mineralogical data (XRD and SEM) were examined for evidence of pedogenic processes; interstitial water (pH, salinity, concentrations of Mn2+, Fe2+, HS-, SO4 2-e Cl-) and solid phase (TOC, total Fe, total S, total Mn, AVS, microbial biomass C, density of living and dead roots, sand percentage and sequential extraction of Fe) analysis were undertaken in different soil profiles under mangrove vegetation from São Paulo State (Guarujá and Cananéia) to asses Fe and S biogeochemistry. The evidences presented in this study indicate that pedogenic processes (addition of organic material; translocation of Fe2+ and mineral particles; transformation of elements such as Fe and S) have occurred in mangrove substrates and that these substrates are more properly referred to, understood and studied as soils and not sediments. Results also evidence that pyrite and AVS oxidation is taking place in response to plants and macro-fauna activity and that the seasonal cycle of Fe and S biogeochemistry is mostly ruled by plants and macro-fauna. Results indicate important differences between physicochemical conditions of the pore water in the vegetated (soils) and non-vegetated (sediment) zones, which are related to the faster dynamics of the biogeochemical soil processes caused by the effect of plants (oxidation, liberation of the exudates by the roots). Our data also show that the contribution and intensity of each process coupled to organic matter mineralization in mangrove soils may vary significantly between the distinct physiographic positions. These variations are generated by physiographic positions effects on frequency and duration of tidal flooding and grain size composition of soils. In this context, the occurrence, or dominance, of one process over the others, affects, in a significant way, pore water and solid phases chemistry.

Kvicksilver har länge varit ett populärt ämne i flertalet olika produkter på grund utav dess unika egenskaper. Detta har lett till en stor mängd av ämnet går att finna i olika produkter som förbränns i avfallsförbränning. Ämnet är dock väldigt farligt för djur och människor och därav är det av hög prioritet att utsläppen till luft minimeras. Att oxidera kvicksilver från dess elementära form Hg0 till Hg2+ anses vara av största vikt på grund utav att den senare är i högre graden enklare att rena från rökgaserna. Syftet med detta examensarbete var att se om kvicksilver förekommer i högre halt som Hg0 istället för Hg2+ i rökgaserna vid ändrade förhållanden av klor och svavel. Där den förstnämnda är olöslig i vatten och därav svårfångad i dagens reningssystem. Den kan dessutom existera i luft en längre tid och anses vara ett av de mer miljöfarliga ämnena i världen. Examensarbetet har gjorts tillsamman med Umeå Energi AB. För att nå en slutsats har en omfattande litteraturstudie gjorts om ämnet samt mätningar av kvicksilver i rökgaserna från avfallsförbränningsanläggningen Dåva 1 utanför Umeå. Mätningarna utfördes med och utan tillsats av extra svavel i form av bildäck. Analys har även utförts av innehållet i aska ifrån partikelfiltret samt överhettaren för att få en överblick huruvida dess innehåll kan ha gjort någon påverkan.  Mätningarna påvisade att svavel gjorde en påtaglig påverkan på mängden kvicksilver. Vid tillsats av svavel så gavs det indikatorer på att halten av Hg0 ökade. Den mest troliga anledningen till detta tros vara den ökade mängden SO3 som uppmättes i rökgaserna vid det tillfälle då extra svavel var tillsatt. Den ökande mängden kan sedan ha absorberats av de aktiverade kolet som tillsätts innan rökgasreningen, som annars skulle ha absorberat Hg0. Detta är inget slutgiltigt resultat och vidare undersökning är att rekommendera. En annan möjlig teori är att tillsatts av svavel ökar mängden Na2SO4 i filtret. Vilket kan leda till minskad NaCl i filtret som kanske är effektivare vid oxidation av Hg0 än HCl. Mätningarna gav även antydan om att nuvarande reningssystem fungerar bra även vid ökade halter kvicksilver i rågasen. Ökning av kvicksilver i rökgaserna som tros ha orsakats av svaveltillsatsen gav ingen ökning av kvicksilverutsläpp i luft. / For a long time, mercury has been a very popular to use in different kinds of products due to its unique properties. Which has led to a lot of different things containing mercury ends up in waste plants to be incinerated. Mercury are also considered to be one of the most dangerous substances and therefore emissions needs to be kept at minimum. Oxidizing mercury from its form Hg0 to Hg2+ is considered to be extremely important due to the later are easier to remove from the flue gas. The main objective with this thesis was to investigate if mercury would exist more in its elementary form Hg0 than its oxidized state Hg2+ in the flue gas when the ratio between sulfur and chlorine was changed. The former is insoluble in water and therefore difficult to remove from the flue gas with today’s cleaning facility’s. It is also considered one of the more dangerous substances in the world. The project was done in collaboration with Umeå Energi AB. The method that was used to explore this was measuring the mercury content of the flue gas from the waste fired boiler Dåva 1 outside Umeå. The measurement was done with and without extra sulfur added to the fuel in the form of car tires. An additional analysis was done on the ash from the fabricfilter and from the superheater to see if there was something there to give some clarity on why there would be any change in the amount of mercury. The measurement did indeed indicate that sulfur increases the amount of mercury in the flue gas. The main theory to why this has occurred was the increased amount of SO3, which could be found in the flue gas when extra sulphur was added. SO3 is then absorbed by the activated carbon that is added to the flue gas that should have absorbed Hg0 instead. However, this result is not conclusive and further studies needs to be done. Another possible theory to why this has occurred could be that the increase of sulfur could lead to more Na2SO4 in the particle filter. Which could have led to a decrease of NaCl in the filter that could perhaps be a more efficient oxidizing agent of Hg0 than HCl. Another thing that has been revealed is that the cleaning systems that is used today is capable of cleaning mercury from the flue gas even though the added sulfur caused an increase in the amount.

La glace polaire est sans nul doute la meilleure archive dont nous disposons en terme de paléo volcanisme. Les reconstructions du volcanisme passé se basant sur l'analyse des carottes de glace sont nombreuses. Elles alimentent notamment les modèles de forçage climatique, dans le but d'estimer l'effet refroidissant du volcanisme, dû aux interactions entre aérosols d'acide sulfuriques d'origine volcanique, et le rayonnement solaire incident. Dans ce type de reconstruction, l'un des paramètres-clés pour déterminer l'impact potentiel d'une éruption, est l'identification de son signal sur les deux calottes polaires (signal bipolaire). Cette large répartition spatiale traduit en effet un temps de résidence significatif dans la stratosphère, et donc, un impact climatique important. Les carottes de glace offrent pourtant une alternative intéressante à cette méthode : l'analyse du soufre des sulfates volcaniques révèle la présence d'anomalies isotopiques (Δ33S ≠0) dans les aérosols d'origine stratosphérique, permettant la discrimination entre éruptions de faible impact (troposphériques) et éruptions de fort impact (stratosphériques). L'étude de la signature isotopique atypique des aérosols stratosphériques permet en parallèle de contraindre les mécanismes photochimiques à l'origine de cette anomalie, qui ne sont que partiellement identifiés à ce jour. En 2010-2011, 5 carottes de névé de 100m de long ont été collectées à Dôme C, Antarctique, dans le but de reconstruire une histoire du volcanisme stratosphérique des 2500 dernières années, par la méthode isotopique. Le forage de 5 carottes identiques, à 1 m les unes des autres, nous a permis d'étudier différents aspects de la reconstruction.Premièrement, nous avons pu évaluer la variabilité du dépôt de sulfate à l'échelle locale, et donc, la représentativité statistique d'une seule carotte vis à vis d'une reconstruction volcanique. L'analyse des concentrations de sulfate révèle qu'une importante variabilité locale, associée principalement au déplacement de la neige par le vent, pouvait entraîner un enregistrement non exhaustif des évènements volcaniques (en moyenne 30% d'évènements manquants, par carotte) et une variabilité conséquente du flux archivé (jusqu'à 60%).En second lieu, le niveau de détail de nos analyses (résolution temporelle de chaque éruption) nous a permis de décrire plus précisément la signature des processus indépendants de la masse à l'œuvre dans la stratosphère. Les résultats obtenus ne permettent pas de clore le débat concernant le mécanisme photochimique à l'origine de l'anomalie, mais ils contraignent la signature stratosphérique de façon robuste, notamment en définissant les tendances isotopiques (Δ36S vs. Δ33S et Δ33S vs. δ34S). Les implications de ces contraintes sur la chimie atmosphérique actuelle sont discutées à travers l'utilisation d'un modèle simple ; nous évaluons les paramètres requis, en particulier les proportions des différentes voies d'oxydation stratosphériques (dépendantes et indépendantes de la masse), pour reproduire nos résultats.Enfin, l'analyse systématique de la composition isotopique (Δ33S) des évènements volcaniques nous a permis d'établir un historique du volcanisme stratosphérique enregistré à Dôme C au cours des 2600 dernières années. Nos résultats confirment majoritairement l'origine tropicale (stratosphérique) des évènements identifiés comme tels dans la littérature, et suggèrent le caractère stratosphérique (unipolaire) de quelques éruptions de haute latitude. Les résultats ne remettent pas en question la synchronisation des enregistrements bipolaires récemment établis, et valident l'utilisation de la méthode isotopique pour l'identification des éruptions stratosphériques dans un enregistrement glaciaire. / Polar ice has proved to be a very valuable way to access Earth's volcanism history, and a large number of volcanic reconstructions are based on ice-core analysis. Reconstructions are fed into climate forcing models in order to estimate volcanic cooling effect, resulting from the interactions between volcanic sulfuric acid aerosols and incident solar radiations. In this type of reconstruction, determining the potential impact of an eruption is a key step. It usually relies on the identification of its signal in both polar caps (bipolar signal). This wide spatial distribution indeed reflects a significant residence time in the stratosphere, and thus a sizable impact on climate. However, ice cores offer an interesting alternative to this method: the analysis of volcanic sulfates reveals a mass independent fractionation of sulfur (S-MIF) in the aerosols formed in the stratosphere, allowing us to discriminate between low climatic impact (tropospheric) and high climatic impact eruptions (stratospheric). Studying the unusual isotopic signature of stratospheric aerosols simultaneously allows for constraining photochemical mechanisms responsible for this anomaly (Δ33S≠ 0), which are currently only partially identified. In 2010-2011, 5 100m-cores were drilled at Dome C, Antarctica in order to reconstruct a history of stratospheric volcanic over the past 2500 years, by the isotopic method. Drilling 5 replicate cores, 1 m apart, allowed us to study various aspects of the reconstruction.Firstly, we were able to assess the sulfate deposition variability on a local scale, and therefore the statistical representativeness of a single core in a volcanic reconstruction. Sulfate concentration analysis of the 5 cores reveals that local scale variability, essentially attributed to snow drift and surface roughness at Dome C, can lead to a non-exhaustive record of volcanic events if a single core is used; on average 30% of the volcanic events are missing per core, and the uncertainty on the volcanic flux (up to 60%) is substantial.Secondly, our detailed analysis (temporal resolution of each eruption) has allowed us to more accurately describe the stratospheric S-MIF signature. Implications on current atmospheric chemistry are evaluated through the set of trends obtained in our samples. We used a simple model implemented with fractionation factors available in the literature to account for the isotopic pattern observed on volcanic sulfate deposition. Through this tool, we evaluated the respective proportions of the different mechanisms assumed to take part in the oxidation process (mass dependent vs. mass independent processes, self-shielding vs. spectral isotopic effect) needed to reproduce natural data, in the current state of experimental knowledge.Finally, the systematic analysis of the isotopic composition (Δ33S) in volcanic events has allowed us to establish a history of the stratospheric volcanism recorded in Dome C in the last 2600 years. Through the isotopic method, in most cases we confirmed the tropical origin of volcanic events as reported in the literature. Discrepancies hinted at high latitude stratospheric events, but the synchronization between North and South Pole records recently established is not questioned. The results also validate the use of the isotopic method to identify stratospheric eruptions in a glacial record.

abstract: The Toledo Core Based Statistical Area (CBSA) presents an interesting case study for the new sulfur dioxide (SO2) one hour standard. Since no SO2 monitor within 75 miles to estimate the attainment status of the area, American Meteorological Society/Environmental Protection Agency Regulatory Model (AERMOD) was used in this study to predict potential problems associated with the newly revised standard. The Toledo CBSA is home to two oil refineries, a glass making industry, several coal fired lime kilns, and a sulfuric acid regeneration plant, The CBSA 3 has coal fired power plants within a 30 mile radius of its center. Additionally, Toledo is a major Great Lakes shipping port visited by both lake and ocean going vessels. As a transportation hub, the area is also traversed by several rail lines which feed four rail switching yards. Impacts of older generation freighters, or "steamers", utilizing high sulfur "Bunker C" fuel oil in the area is also an issue. With the unique challenges presented by an SO2 one hour standard, this study attempted to estimate potential problem areas in advance of any monitoring data being gathered. Based on the publicly available data as inputs, it appears that a significant risk of non-attainment may exist in the Toledo CBSA. However, future on-the-books controls and currently proposed regulatory actions appear to drive the risk below significance by 2015. Any designation as non-attainment should be self-correcting and without need for controls other than those used in these models. The outcomes of this screening study are intended for use as a basis for assessments for other mid-sized, industrial areas without SO2 monitors. The results may also be utilized by industries and planning groups within the Toledo CBSA to address potential issues in advance of monitoring system deployment to lower the risk of attaining long term or perpetual non-attainment status. / Dissertation/Thesis / M.S. Technology 2011