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Photochemical electron transfer (ET) reaction studies (1) photooxidations of sulfides; (2) development of new ET sensitizers /Liao, Chen, January 2008 (has links)
Thesis (Ph.D.)--University of Wyoming, 2008. / Title from PDF title page (viewed on June 28, 2009). Includes bibliographical references (p. 189-202).
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Alternative research policy in troposheric ozone controlMoser, Andrew Derrick 05 1900 (has links)
No description available.
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Oxidant-induced cell death in lymphocytes : mechanisms of induction and resistance /Bergh Thorén, Fredrik, January 2007 (has links)
Diss. (sammanfattning) Göteborg : Göteborgs universitet , 2007. / Härtill 5 uppsatser.
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Biofouling control of industrial seawater cooling towersAl-Bloushi, Mohammed 11 1900 (has links)
The use of seawater in cooling towers for industrial applications has much merit in the Gulf Cooperation Council countries due to the scarcity and availability of fresh water. Seawater make-up in cooling towers is deemed the most feasible because of its unlimited supply in coastal areas. Such latent-heat removal with seawater in cooling towers is several folds more efficient than sensible heat extraction via heat exchangers. Operational challenges such as scaling, corrosion, and biofouling are a major challenge in conventional cooling towers, where the latter is also a major issue in seawater cooling towers. Biofouling can significantly hamper the efficiency of cooling towers. The most popular methods used in cooling treatment to control biofouling are disinfection by chlorination. However, the disadvantages of chlorination are formation of harmful disinfection byproducts in the presence of high organic loading and safety concerns in the storage of chlorine gas.
In this study, the research focuses on biofouling control in seawater cooling towers by investigating two different approaches. The first strategy addresses the use of alternative oxidants (i.e. ozone micro-bubbles and chlorine dioxide) in treatment of cooling towers. The second strategy investigates removing nutrients in seawater using granular activated carbon filter column and ultrafiltration to prevent the growth of microorganisms. Laboratory bench-scale tests in terms of temperature, cycle of concentration, dosage, etc. indicated that, at lower oxidant dosages (total residual oxidant (TRO) equivalent = 0.1 mg/l Cl2), chlorine dioxide had a better disinfection effect than chlorine and ozone. The performance of oxidizing biocides at pilot scale, operating at assorted conditions, showed that for the disinfectants tested, ozone could remove 95 % bioactivity of total number of bacteria and algae followed by chlorine dioxide at 85%, while conventional chlorine dosing only gave 60% reduction in bioactivities. Test results of GAC bio-filter showed that around 70 % removal of total organic carbon in the seawater feed was achieved and was effective in keeping the microbial growth to a minimum. The measured results from this study enable designers of seawater cooling towers to manage the biofouling problems when such cooling towers are extrapolated to a pilot scale.
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Etude du formaldéhyde (HCHO) en zone côtière Antarctique / Study of formaldehyde in coastal Antarctica.Pépy, Guillaume 23 November 2011 (has links)
Avec pour objectif de documenter et comprendre ses sources et puits en atmosphère de fond, nous avons réalisé un enregistrement annuel du formaldéhyde troposphérique en Antarctique, sur la base côtière de Dumont d'Urville. Des teneurs mensuelles de 50 pptv en hiver jusqu'à 200 pptv en été ont été mesurées. Au printemps, et été et à l'automne, un cycle journalier a été observé, avec un maximum l'après midi et une amplitude d'environ 40 pptv. Les artéfacts observés avec les appareils utilisés pour la mesure de HCHO (AeroLaser 4021), liés aux variations de température dans le local de mesure et pouvant induire des biais de 50 à 100 pptv, ont été éliminés en adaptant notre méthode analytique. Le formaldéhyde étant produit lors des combustions, l'influence des sources de contamination locales a été examinée en détail. Les sources de combustion par la station augmentent sporadiquement de 150 pptv au maximum les moyennes horaires. Une source locale d'émission par les sols ornithogéniques en liaison avec la présence des Manchots Adélie peut influencer jusqu'à 200 pptv les moyennes horaires en été. Au total, ces deux sources locales peuvent surestimer d'un facteur 5 au maximum l'amplitude du cycle journalier observé et impacter jusqu'à 100 pptv les moyennes mensuelles en été. Suivant ce constat, les données brutes ont été filtrées selon des critères météorologiques locaux pour éliminer toute contamination potentielle. L'étude des sources et puits en phase gaz a été réalisée à l'aide d'un modèle de photochimie développé pour les conditions de DDU. Nos résultats montrent que l'oxydation du méthane domine le budget en été (80%) du fait des fortes teneurs en radicaux HOx et en NOx en liaison avec l'impact du plateau Antarctique atteignant DDU. Le méthyl-hydroperoxyde constitue une source secondaire significative de HCHO en phase gaz (20% de l'oxydation du méthane), tandis que les faibles teneurs en hydrocarbures non-méthaniques mesurées en été nous amène à évaluer la contribution de cette source initialement attendue comme importante à moins de 5% de l'oxydation de CH4. A la différence d'autres observations en Mer de Weddell, les composés halogénés semblent avoir une influence relativement limitée dans le cas de Dumont d'Urville (10% du budget total au maximum). Suivant nos estimations, l'apport continental efficace permet d'envisager une source d'émission par le manteau neigeux du plateau. Celle-ci constitue une source secondaire relativement faible en été (10%) mais domine le budget hivernal (70%). Notre exercice de modélisation sur l'échelle saisonnière et journalière souligne la nécessité d'associer les processus en phase gaz avec les flux d'émission par la neige et de dépôt afin de reproduire correctement les observations. / With the aim to investigate the production and destruction mechanisms of formaldehyde (HCHO) on a seasonal scale in the remote troposphere, HCHO was monitored over a 13-months period at Dumont d'Urville station, located near the East Coast of the Antarctic continent. Monthly means of 50 ppt in winter and up to 200 ppt in summer were measured. In spring, summer and autumn, a daily variation was detected with amplitude of ≈40 ppt and a maximum during the afternoon. The analytical instrument (Aerolaser, AL4021) deployed for the measurements, was found to be extremely sensitive to ambient temperature variations. The origin of the temperature dependence was investigated, and the deployed analytical method was adapted to eliminate this artefact. The impact of local contamination sources at the measurement site was explored in detail. Anthropogenic combustions were found to have a limited impact (maximum 150 pptv on hourly means) versus a local emission source from ornithogenic soils, induced by the omni-presence of Adelie penguins on the site in summer (maximum 200 pptv on hourly means). From november to march, these sources can introduce an overestimation by a factor 5 of the daily HCHO amplitude, while the influence on the monthly averaged budget can account up to 100 ppt. The raw dataset was thoroughly filtered using local meteorological criteria to eliminate any potential contamination. HCHO measurements were compared to simulations made with a numerical box model developed on the base of the current understanding of the photochemical sources and sinks of HCHO. During summer, methane oxidation was found to be the major source of HCHO production, likely due to enhanced levels of oxidants such as hydroxyl radical (OH) or nitrogen oxide (NO) occurring at DDU since this coastal site is under strong continental influence. Snow emissions and HCHO formation via methyl-hydroperoxyde oxidation complete the summer budget (respectively 10 to 20% of the CH4 oxidation). In contrary to what was observed for the Weddell Sea area, halogens chemistry is probably unlikely to contribute significantly at Dumont d'Urville (<10% of the CH4 oxidation). Finally, the initially attended summer source originating from non-methane hydrocarbons oxidation was found to be inefficient and to contribute only with less than 5 % of the CH4 oxidation. During winter the snowpack source was found to be preponderant (70% of CH4 oxidation) versus the gas phase chemistry sources of HCHO. Model investigations, performed on a seasonal and daily scale have shown that gas phase processes together with deposition and snow emission have to be considered to achieve a correct reconstruction of the observations.
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Water Treatment for the Removal of Iron and ManganeseIsaeva, Margarita, Montes Castro, Natasha January 2011 (has links)
The purpose of the study is to find a suitable method for removal of iron and manganese considering local economic and environmental aspects. El Salvador is situated in Central America with a coast line towards the Pacific Ocean. The country borders Guatemala and Honduras. Aguilares is a town situated in the department of San Salvador, with a population of approximately 33,000 people. Currently, the population is provided with water for about two hours per day, since it is the highest capacity of the existing wells. During these two hours many households fill a small tank with water to use for the remainder of the day. The water is not safe to use for oral consumption because of the levels of bacteria and other contamination. One of the wells, situated in the community of Florída is not in use at this date because of the high levels of Iron and Manganese in the ground water which cannot be removed with the present technique.Ground water is naturally pure from bacteria at a depth of 30 m or more, however solved metals may occur and if the levels are too high the water is unsuitable to drink. The recommended maximum levels by WHO (2008) [1] for Iron and Manganese are 2 mg/l and 0.5 mg/l respectively.Literature and field studies led to the following results; Iron and manganese can be removed by precipitation followed by separation. Precipitation is achieved by aeration, oxygenation or chemical oxidation and separation is achieved by filtration or sedimentation.The different methods all have advantages and disadvantages. However the conclusion reached in this report is that aeration and filtration should be used in the case of Florída. What equipment and construction that should be used depends on economic and resource factors as well as water requirements, which is up to the council of Aguilares to deliberate.
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Studies of the respiratory chain of Methylococcus capsulatus (bath)Miley, Timothy Brian. January 2000 (has links)
Thesis (Ph. D.)--West Virginia University, 2000. / Title from document title page. Document formatted into pages; contains x, 118 p. : ill. Includes abstract. Includes bibliographical references.
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Computational Investigations at the Gas-Surface Interface: Organic Surface Oxidation and Hydrolysis of Chemical Warfare Agents and SimulantsChapleski Jr, Robert Charles 25 April 2017 (has links)
Motivated by recent experiments in gas-surface chemistry, we report our results from computational investigations of heterogeneous systems relevant to atmospheric chemistry and protection against chemical weapons. To elucidate findings of ultra-high vacuum experiments that probe the oxidation of carbon-carbon double bonds on model surfaces, we used electronic structure and QM/MM methods to study the reaction of ozone with C60-fullerene and the products of nitrate addition to a vinyl-terminated self-assembled monolayer. In the first system, we followed a reaction pathway beginning with primary ozonide formation through the formation of stable products. Theoretical vibrational spectra were used to identify a ketene product in prior experimental work. Next, through the construction of a multilayer model for the initial addition product of a nitrate radical to a chain embedded within a self-assembled monolayer, we report theoretical spectra that are consistent with experimental results. We then examined the fundamentals of the hydrolysis mechanism for nerve agents by a catalyst of interest in the development of filtration materials for chemical-warfare-agent defense. By following the gas-surface reaction pathway of the nerve agent Sarin on the Lindqvist polyoxoniobate Cs8Nb6O19, we determined that the rate-limiting step is the transfer of a proton from an adsorbed water molecule to the niobate surface, concomitant with the nucleophilic addition of the nascent hydroxide to the phosphorus atom in Sarin. Our results support a general base hydrolysis mechanism, though high product-adsorption energies suggest that thermal treatment of the system is required to fully regenerate the catalyst. We report similar mechanisms for the simulants dimethyl methylphosphonate and dimethyl chlorophosphate, though the latter may serve as a better simulant in studies of this type. Finally, an investigation of Sarin hydrolysis with solvated Cs8Nb6O19 shows an increase in the rate-limiting barrier relative to the gas-surface system, revealing the role of Cs counterions in the reaction. Then, we further increased explicit solvation to model the homogeneous solution-phase reaction, finding a different mechanism in which a water molecule adds to phosphorus in the rate-limiting step and protonation of the niobate surface occurs in a subsequent barrierless step. By examining the rate-limiting barrier for protonation, we suggest that specific base hydrolysis is also likely in the homogeneous system. / Ph. D. / Phenomena that occur where gases meet the surfaces of solids or liquids find relevance in several arenas. In the lower atmosphere, reactions between oxidative gases such as ozone or nitrate on the surface of organic particulates cause these particles to grow and change, contributing to smog and harmful effects to human health. Using computational modeling, we can describe these reactions with atomic-level detail. In the first channel of research presented in this dissertation, we report results that provide insight into these environmental reactions. Then, we change our focus towards an understanding of the reactions that lead to the decontamination of chemical warfare agents on the surface of a transition metal oxide catalyst. Again with computational modeling, we follow reaction pathways as a nerve agent or less harmful simulant reacts with the surface of this material. The entire body of this work—that of atmospheric relevance and that towards an understanding of catalytic deactivation of toxic compounds—emphasizes a strong synergy with experimental efforts. Our work is motivated by a desire to understand experimental results, and the calculations we perform influence the design of future experiments.
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Oxidation status as a predictor of disease activity and response to therapy in pediatric patients with inflammatory bowel diseaseWeinbren, Nathan Leo 18 June 2019 (has links)
INTRODUCTION: Physiologic and pathophysiologic inflammation is mediated, at least in part, by the generation and release of reactive oxygen species into the local tissue milieu. The chronic inflammation observed in patients with inflammatory bowel disease (IBD) is thought to begin in the lining of the intestine and may progress to involve the entire bowel wall.In an effort to assess disease activity, clinicians rely on costly and technically invasive procedures such as colonoscopies. As such, there is currently a need for the development of less invasive and more cost-effective methods for use in the diagnosis and interval assessment of children and adults with these chronic intestinal inflammatory disorders.
OBJECTIVES: The objective of this study was to first determine if ambient redox status can be reliably measured in the stool of patients with IBD. A second aim of the study was to determine if ambient stool redox status was related to underlying diagnosis, clinical disease activity, or response to therapy in patients with IBD .
METHODS: We first our ability to measure redox redox standards using three different commercially available devices. Once demonstrated, we then the process of performing sample analysis under various conditions (room tempererture, refrigerated, frozen, or spun/unspun) to determine the conditions under which we were able to achieve the most stable redox assessments. Finally, we conducted a small pilot cohort study in hospitalized pediatric patients with IBD to assess if stool redox status informed about disease activityWe collected stool samples from seven patients admitted to the inpatient gastrointestinal service at Boston Children’s Hospital during a period extending from November of 2018 to March of 2019.
RESULTS: Preliminary studies confirmed our ability to accurately measure relative redox status (RRS) using three different apparatuses. Furthermore, we were able to generate dilution curves using juices known to include oxidants, with linear regression r2 values of 0.99. In our patient population, we confirmed our ability to generate a reliable readings and consistent RRS measurements over. Frozen samples displayed less stable and higher RRS than those either refrigerated or kept at room temperature for up to 8-hours. This suggests that freeze-thaw cycles may impact adversely on the stability of oxidants and antioxidants in our samples. The RRS measurements from stool samples collected from patients who were exhibiting active symptoms of their IBD measured about -400 mV, while samples collected from hospitalized patients without IBD manifest RRS readings of about 100 mV.
CONCLUSION: This preliminary study demonstrates our ability to measure RRS in the stool of patients with and without IBD. The stability we observed in samples that were either stored at room temperature or refrigerated demonstrated that these represented optimal storage options. Additionally, measurements from homogenized stool samples appeared to be more variable when compared to the relatively smaller range from centrifuged samples. Initial studies indicated a strong difference in RRS measurements between patients with inflammatory and non-inflammatory GI disease or inactive IBD. This difference suggests that measurements of RRS could provide a quantitative real-time assessments of disease activity and response to therapy in patients with IBD.
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Estresse orgânico e atividade anti e pró-oxidante na queimadura aguda e no pós-operatório de cirurgia reparadora de seqüelas do trauma térmico / Organic stress and anti- and pro-oxidant activity in acute burns and during the postoperative period of surgery for the repair of the sequels of thermal shock.Vinha, Paula Pileggi 31 October 2008 (has links)
O estresse orgânico decorrente da queimadura é intenso e prolongado. O hipercatabolismo e o hipermetabolismo secundários alteram o sistema de pró e anti-oxidantes. Pela necessidade de reepitelização da área doadora e receptora, a cirurgia reparadora pode desencadear ou perpetuar o estresse oxidativo. Objetivos: Em pacientes vítimas de trauma térmico agudo (Grupo Queimadura) e naqueles em pós-operatório de seqüelas de queimaduras (Grupo Seqüela), comparar o estresse oxidativo e os níveis de anti e pró-oxidantes com os obtidos no pré-operatório de pacientes com seqüelas de queimaduras (Grupo Controle). Casuística e métodos: O estudo foi conduzido na Unidade de Queimados do HCFMRPUSP. O Grupo Queimadura (n=11) incluiu pacientes com 48 horas do trauma térmico agudo, SCQ 10%. Os pacientes que necessitaram de correção cirúrgica das seqüelas do trauma térmico, ocorrido 1ano (n=8), foram avaliados no pré-operatório (Grupo Controle) e após 48 horas da cirurgia (Grupo Seqüela). Todos os voluntários foram submetidos à antropometria e quantificação da ingestão alimentar. Foi realizada a avaliação laboratorial do estado nutricional, dos marcadores da atividade inflamatória e dos anti e pró-oxidantes. Resultados: Em pacientes vítimas de trauma térmico agudo, foi documentado estresse orgânico caracterizado pelo aumento das proteínas de fase aguda como a PCR [8,76 (0,91 34,54) vs 0,40 (0,01 0,97)mg/dL, p=0,0004] e ferritina (254,45 ± 84,25 vs 145,10 ± 88,80ng/mL, p=0,014), além da diminuição da albumina (3,55±0,65 vs 4,16±0,26g/dL, p=0,004), da transferrina (110,67±55,13 vs 238,70±67,99mg/dL, p=0,0003), do colesterol (126,82 ± 32,19 vs 193,75 ± 51,64mg/dL, p=0,002) e triglicérides séricos (95,54 ± 36,84 vs 168,75 ± 54,83mg/dL, p=0,003), ferro [30,00 (6,00-73,00) vs 109,00 (70,00 - 252,00)µg/dL, p=0,0004] e zinco (63,55 ± 23,34 vs 92,72 ± 16,65mg/dL, p=0,014). O estresse oxidativo diminuiu os níveis séricos das vitaminas C [0,45 (0341,30) vs 0,93 (0,48 1,30)mg/dL, p=0,016], A (1,55 ± 0,87 vs 3,35 ± 0,72µmol/L, p=0,0002) e da vitamina E (9,49 ± 3,4 vs 4,96 ± 1,60µmol/g lipídeo, p=0,003). Não houve modificação nos níveis do GSH [40,37 (30,27 87,46 ) vs 49,90 (10,09 54,95)µmol/L, p= 0,48] e do MDA [1,75 (1,15 2,74) vs 1,77 (1,62 6,82nmol/g proteína), p=0,043]. O procedimento cirúrgico para correção das seqüelas de queimaduras determinou aumento da proteína C reativa [0,40 (0,01 0,97) vs 2,53 (0,56 4,70)mg/dL, p=0,01], mas não alterou os níveis de anti e pró-oxidantes, exceto a diminuição dos níveis séricos de vitamina A (3,35 ± 0,72 vs 2,52 ± 0,90µmol/L, p=0,006) Conclusões: O estresse orgânico decorrente do trauma térmico agudo diminuiu as respostas anti-oxidantes. Exceto pela queda nos níveis séricos de vitamina A, a cirurgia reparadora acarretou estresse orgânico, sem modificação na resposta anti e pró-oxidante. / Organic stress due to burns is intense and prolonged, Secondary hypercatabolism and hypermetabolism alter the pro- and anti-oxidant system. Due to the need for reepithelialization of the donor and recipient areas, reparative surgery can trigger or perpetuate the oxidative stress. Objectives: To compare the oxidative stress and the levels of anti- and pro-oxidants in patients victims of acute thermal trauma (Burn Group) and in patients during the postoperative period after surgery for burn sequels (Sequel Group) with those obtained preoperatively in patients with burn sequels (Control Group). Cases and methods: The study was conducted at the Burn Unit of HCFMRPUSP. The Burn Group (n=11) consisted of patients studied 48 hours after acute thermal trauma, SCQ 10%. The patients who required surgical correction of the sequels of thermal trauma suffered 1 year before (n=8) were assessed during the preoperative period (Control Group) and 48 hours after surgery (Sequel Group). All volunteers were submitted to anthropometry and to quantitation of food intake. Laboratory evaluation of nutritional status, of the markers of inflammatory activity and of the anti- and pro-oxidant levels was performed. Results: Organic stress was documented in the patients victims of acute thermal trauma, characterized by an increase of acute phase proteins such as C-reactive protein (CRP) [8.76 (0.91 34.54) vs 0.40 (0.01 0.97) mg/dL, p=0.0004] and ferritin (254.45 ± 84.25 vs 145.10 ± 88.80 ng/mL, p=0.014) and by a reduction of serum cholesterol (126.82 ± 32.19 vs 193.75 ± 51.64 mg/dL, p=0.002), triglycerides (95.54 ± 36.84 vs 168.75 ± 54.83 mg/dL. p=0.003), iron [30.00 (6.00 73.00) vs 109.00 (70.00 252.00) µg/dL, p=0.0004], and zinc (63.55 ± 23.34 vs 92.72 ± 16.65 mg/dL, p=0.014). Oxidative stress reduced the serum levels of vitamins C [0.45 (0341.30) vs 0.93 (0.48 1.30) mg/dL, p=0.016] and A (1.55 ± 0.87 vs 3.35 ± 0.72 µmol/L, p=0.0002), and did not modify the levels of vitamin E (9,49 ± 3,4 vs 4,96 ± 1,60µmol/g lipídeo, p=0,003)or of the anti-oxidant substance GSH [40.37 (30.27 87.46 ) vs 49.90 (10.09 54.95) µmol/L, p= 0.48, but caused a fall in MDA levels [1.04 (0.75 1.39) vs 1.26 (1.07 4.30 nmol/L), p=0.007]. The surgical procedure for the correction of burn sequels caused an increase in CRP [0.40 (0.01 0.97) vs 2.53 (0.56 4.70) mg/dL, p=0.01], but did not change the levels of anti- or pro-oxidants, except for a reduction of serum vitamin A levels (3.35 ± 0.72 vs 2.52 ± 0.90 µmol/L, p=0.006) Conclusions: The organic stress due to acute thermal stress reduced the antioxidant responses. Except for the fall in serum vitamin A levels, reparative surgery caused organic stress, with no change in the anti- or pro-oxidant response.
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