Con il primo lavoro è stato identificato un tratto fenotipico di un ceppo di L.crispatus associato alla capacità di persistere e colonizzare il colon dell’ospite e di modificarene la composizione microbica, tale L.crispatus M247 è in grado di modificare, nell’epitelio del colon, il livello di espressione dei TLR2 dei TLR4 sia in vitro che in vivo. Con il secondo studio si identifica un meccanismo antinfiammatorio, prima sconosciuto, indotto da un ceppo probiotico che coinvolge l’attivazione di PPAR-γ e fornisce una nuova visuale sui meccanismi molecolari coinvolti nel dialogo tra epitelio intestinale e microbiota simbionte. / The colonic microbiota is a major modulator of the mucosal immune system; therefore, its manipulation through supplementation with probiotics may significantly affect the host’s immune responses. Since different probiotics seem to exert various effects in vivo, we tested the relevance of the autoaggregation phenotype on the intestinal persistence of lactobacilli and their ability to modulate the host’s innate immune responses. After 14 days of diet supplementation, the aggregating strain Lactobacillus crispatus M247 but not aggregation-deficient isogenic mutant MU5 was recovered from the feces and colonic mucosa of mice. This observation was confirmed by strain-specific PCR amplification and by Lactobacillus-specific denaturing gradient gel electrophoresis analysis. Indeed, L. crispatus M247 increased Toll-like receptor 2 (TLR2) mRNA levels, while it reduced TLR4 mRNA and protein levels in the colonic mucosa, whereas MU5 was ineffective. In colonic epithelial cells (CMT-93 cells) L. crispatus M247 but not MU5 induced time-dependent extracellular signal-regulated kinase-1 (ERK1) tyrosine phosphorylation and TLR modulation, which were abolished in the presence of PD98059 (an ERK1 inhibitor). To assess the functional relevance of probiotic-induced TLR modulation, we determined the consequences of L. crispatus preexposure on TLR4 (lipopolysaccharide [LPS]) and TLR2 [Pam3Cys-Ser-(Lys)4] ligand-mediated effects in intestinal epithelial cells. Preexposure to L. crispatus M247 blunted LPS-induced interleukin-6 (IL-6) release and inhibition of CMT-93 migration over a wound edge, whereas it enhanced TLR2-mediated IL-10 up-regulation. In summary, the aggregation phenotype is required for L. crispatus persistence in the colon and for modulation of TLR2/TLR4 expression through an ERK-dependent pathway. We speculate that the aggregation phenotype in L. crispatus M247 is required to temper epithelial cell responsiveness to bacterial endotoxins, which thus affects the evolution of intestinal inflammatory processes. Accumulating evidence indicates that the peroxisome proliferator activated receptor (PPAR)- is a major player in maintaining intestinal mucosa homeostasis, but whether PPAR- is directly involved in probiotic-mediated effects and the molecular events involved in its activation are not known. Methods: We investigated the role of PPAR- in the immunomodulatory effects of Lactobacillus crispatus M247 on intestinal epithelial cells (IEC) and the role of probiotic-derived H2O2 on PPAR- activity. Results: L crispatus M247 supplementation in mice significantly increased PPAR- levels and transcriptional activity in the colonic mucosa. L crispatus M247 induced PPAR- nuclear translocation and enhanced transcriptional activity in epithelial (CMT-93) cells, as demonstrated by the increased luciferase activity of a PPAR- –responsive element, PPAR- – responsive gene up-regulation, and reduced activity of an nuclear factor- B–responsive element. Pharmacologic PPAR- inhibition or silencing by small interfering RNA cancelled the L crispatus M247–mediated effects in CMT-93 cells. Because Lactobacillus strains producing little H2O2 failed to activate PPAR- , we investigated the role of L crispatus M247– derived H2O2 in PPAR- activation. L crispatus M247 induced a transient rise in intracellular H2O2 and PPAR- transcriptional activity was cancelled by antioxidant or H2O2 scavenger. Toll-like receptor (TLR)-2 was not required for PPAR- up-regulation mediated by L crispatus M247 in mice, although the protective effects of L crispatus M247 on dextran sodium sulfate-induced colitis were less pronounced in TLR-2 / mice. Conclusions: L crispatus M247 uses H2O2 as a signal transducing molecule to induce PPAR- activation in IEC, directly modulating epithelial cell responsiveness to inflammatory stimuli.

The effects of UV pretreatment on alkaline bleaching (EOP) wastewater from a kraft pulp and paper mill were investigated prior to anaerobic digestion (AD) in an upflow anaerobic sludge blanket (UASB) reactor. The aim was to enhance the methane production, increase the reduction of total organic carbon (TOC) and determine the best UV exposure time. The exposure time of 2.6 minutes partially degraded the organic material in the EOP wastewater since it generated higher biogas and methane production than the reference period, while it also increased the reductions of solved chemical oxygen demand (CODsol) and TOCsol. The exposure time of 16 minutes, on the other hand, did not show any significant improvement regarding increased biogas and methane production nor did it increase the reduction of CODsol. However, it did increase the reduction of TOCsol, but not to the same extent as the exposure time of 2.6 minutes. The presence of unwanted microbial growth in the system during the experiment might have affected the effectiveness of the UV pretreatment more during the exposure time of 16 minutes as the amount of growth was more substantial during this period of time. Furthermore, no optimal exposure time could be determined due to lack of time.

Persistent organic pollutants (POPs) are organic compounds of anthropogenic origin that have been linked to the development of cancer, neurobehavioural impairment, and immune system biochemical alterations. These chemicals have various industrial applications as well as acting as pesticides. Dioxins and furans are some of these compounds that are unintentionally produced in combustion and industrial processes. By definition these compounds have 4 common qualities: they are highly toxic, they are resistant to environmental degradation, they are introduced into the air and water where they travel long distances, and they accumulate in fatty tissues. Photochemical degradation is a method that has been extensively researched in the last few decades. In the aqueous phase it has already been shown to be able to degrade a number of refractory organics, such as dioxins and furans. The ultimate products of this process tend to be carbon dioxide, water, and mineral anions. Air phase work has been also gaining attention in recent decades as a possible alternative to incineration methods in air pollution control. The advantages of photochemical degradation processes are that they can be initiated at low temperatures, are relatively low cost compared to incineration processes, environmentally benign, and have the potential for quick and complete degradation of organic compounds. The main aim of the research is to investigate the photochemical degradation potential of PCDD/ PCDFs in gaseous air streams as a potential air pollution control technology. In order to do this, the photodegradation reaction kinetics were determined for chlorobenzene as a suitable surrogate for PCDD/PCDFs. Three different photodegradation schemes were employed: direct photolysis, UV/O3, and UV/H2O2. In addition, ozonolysis reaction rates were also determined to evaluate the effects of on the overall photodegradation rates for the UV/O3 process. Factors such as humidity levels and temperature were investigated to determine their effects on degradation rates. Temperature and humidity were not greatly influential on the degradation rates of direct photolysis. The degradation rate of chlorobenzene at a temperature of 100°C and high humidity was noticeably reduced, but unchanged at the 10% RH and 60% RH levels for all temperatures. Ozonolysis of chlorobenzene was negligible at 30°C for all humidity levels. Ozonolysis reactions at the 60°C and 100°C levels were higher than direct photolysis rates and in the 100°C case exceeded the UV/O3 degradation rates. Ozone coupled with UV experiments proved to be the most destructive at the low temperature of 30°C and molar ratio of 10:1 ozone to chlorobenzene. There was a clear and positive relationship between the amount of ozone present in the reactor and the degradation rate. At lower ozone to chlorobenzene molar ratios the degradation rates were not much higher than those for direct photolysis of ozone. The 5:1 molar ratio saw a significant increase in degradation rates over the photolysis rates. The fastest degradation rate was achieved for the 10:1 molar ratio and high humidity, which was over 10 times the rate of direct photolysis. In addition, humidity had a noticeably significant positive effect in these reactions. The effect of temperature on the UV/ozone reaction scheme was determined for the 5:1 ozone to chlorobenzene ratio. Temperature had an interesting effect on the degradation rates at higher temperatures. As the reactor temperature increased, the degradation rates from ozonolysis and UV/O3 began to converge at 60°C, ultimately leading to the ozonolysis reaction being faster than the UV/O3. Exploratory experiments for the H2O2 scheme were performed. H2O2 had a positive influence on the degradation rate of chlorobenzene and was about 26% higher than the direct photolysis rates. However for similar conditions, the UV/O3 process had higher degradation rates as was expected from the difference in absorption values between ozone and hydrogen peroxide.

Mitochondria are key generators of cellular ATP, vital to complex life. Historically, mitochondrial generation of reactive oxygen species (ROS) was considered to be an unregulated process, produced by dysfunctional mitochondria. More recently, mitochondrial ROS generated by complex I, particularly by the process of reverse electron transfer (RET), has emerged as a potentially biologically relevant signal that is tightly-regulated and dependent on mitochondrial status. ROS production by RET is reported to play a role in the innate immune response and lifespan extension in fruit flies. One way in which mitochondrial ROS may behave as a signal is by altering the activity of AMP-activated protein kinase (AMPK), a key metabolic sensor and regulator of cell metabolism, which is activated when cellular ATP levels decrease during energy demand. Mitochondria can signal to AMPK via the magnitude of the cellular ATP/AMP and ATP/ADP ratios, which alter in response to mitochondrial function. Our view is mitochondria may also signal to AMPK via ROS. Important studies have helped to clarify the role of exogenous or cytosolic ROS in AMPK regulation. However, the effects of mitochondrial ROS on AMPK activity, specifically that generated by complex I, remain unclear and is the main focus of this thesis. I characterized the effects of exogenous H2O2 on cellular AMPK activity, ATP/ADP ratios and cellular redox state in a cell model. I then compounded this with selective mitochondria generated ROS by the mitochondria-targeted redox-cycler, MitoParaquat (MPQ). AMPK activity appeared to correlate with decreasing cell ATP/ADP ratios, indicating that both sources of ROS primarily activate AMPK in an AMP/ADP-dependent mechanism. In parallel, I developed an approach for analyzing the redox state of candidate proteins, an important step in determining if a protein is directly regulated by ROS. I also initiated development of a cell model for studying the downstream effects of mitochondrial ROS production by RET, by expressing alternative respiratory enzymes in a mammalian cell line.

Made available in DSpace on 2016-06-02T19:55:30Z (GMT). No. of bitstreams: 1 DoutRF.pdf: 2859796 bytes, checksum: 5d0499b766cb39300c0cdcb26a074d32 (MD5) Previous issue date: 2003-08-14 / Universidade Federal de Sao Carlos / The titanium incorporation in the MFI structure generated a new material, called TS-1, which showed highly active in oxidation reactions of organic compounds. A very important aspect in this titanium-silicate is that it can be used as catalytic for the oxidation in liquid phase with H2O2 as oxidant. However, the TS-1 possesses small pore diameter, which limits its application to molecules with kinetic diameter less than 5,5Å. This limitation has stimulated several investigators to study the incorporation of titanium into molecular sieves with larger pore diameter. This work has as purpose the incorporation of titanium into the structure MOR; verify the influence of the increase of the Si/Al ratio, the titanium content and source in the physical-chemical properties of this material; and finally verify the influence in the catalytic selectivity and activity in the oxidation of ciclo-hexeno with H2O2 as oxidant. The maximum Si/Al ratio in the samples of Ti-MOR prepared was of 10.5. The samples synthesized with TEOT as Ti source presented higher titanium contents in the solid that the samples synthesized with H2TiF6. The morphology of all the samples was in the form of needles. The IR spectra present a band at 960 cm-1, which was related to framework defects and not to Ti incorporation, as stated by other authors. The samples synthesized with H2TiF6 presented greater amount of pentacoordinated Ti atoms in the framework and a superior specify activity, compared to the samples synthesized with TEOT. Compared to TS-1, Ti-MOR presented higher activity in cyclohexene oxidation, however they are less selective to the epoxide. / A incorporação de titânio na estrutura MFI gerou um novo material, a TS-1, que se mostrou bastante ativo nas reações de oxidação de compostos orgânicos e despertou um grande interesse. Um aspecto muito importante no uso de Titano-silicatos como catalisador para a oxidação de substratos orgânicos, tais como olefinas e parafinas, lineares e cíclicas, em fase líquida, é que o agente oxidante empregado, o H2O2, libera a água como subproduto de reação. No entanto a TS-1 possui microporos de tamanho médio, o que dificulta a difusão de moléculas com diâmetro cinético maiores que 5,5Å. Estes fatos levaram pesquisadores a estudar a incorporação de titânio em peneiras moleculares com estruturas que possuam diâmetro de microporos maiores. Este trabalho tem como objetivo a incorporação de titânio na rede da zeólita MOR; verificar a influência do aumento da razão Si/Al, do teor e da fonte de titânio nas propriedades físico-químicas da Ti-MOR e estudar a atividade catalítica na reação de oxidação do ciclo-hexeno utilizando H2O2 como oxidante. Os resultados mostram que a razão Si/Al máxima na Ti-MOR obtida nessas condições é de 10,5. As amostras sintetizadas com TEOT apresentaram maior teor de titânio no sólido do que as amostras sintetizadas com H2TiF6. A morfologia de todas as amostras é de agulhas. Os espectros no infravermelho apresentam a banda a 960 cm-1 que está relacionada com defeitos na estrutura zeolítica. As amostras sintetizadas com H2TiF6 apresentaram maior quantidade de espécies de Ti pentacoordenado. As amostras sintetizadas com H2TiF6 apresentaram uma maior atividade especifica do que as sintetizadas com TEOT. Ao comparar com a TS-1, as amostras de Ti-MOR apresentaram maior atividade, porém se mostraram menos seletivas à formação de epóxidos.

Submitted by Marlene Santos (marlene.bc.ufg@gmail.com) on 2018-07-13T19:29:17Z No. of bitstreams: 2 Dissertação - Maria Carolina de Almeida - 2017.pdf: 6786764 bytes, checksum: 4574a29178a9cb373e63d3280e95024e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-07-17T13:38:02Z (GMT) No. of bitstreams: 2 Dissertação - Maria Carolina de Almeida - 2017.pdf: 6786764 bytes, checksum: 4574a29178a9cb373e63d3280e95024e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-07-17T13:38:02Z (GMT). No. of bitstreams: 2 Dissertação - Maria Carolina de Almeida - 2017.pdf: 6786764 bytes, checksum: 4574a29178a9cb373e63d3280e95024e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-05-05 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / The objective of this work was to compare the efficiency of conventional treatments such as activated carbon (AC) Adsorption and the advanced oxidation process (AOP), UV-C/H2O2, for degradation of diethyl phthalete (DEP) and coupling UV-C/H2O2/AC in laboratory effluent, ultrapure water and faucet water doped with DEP and laboratory effluent with multicomponents (DEP and phenol). The chemical characterization (Boehm method, pHPZC, IRTF, elemental analysis) and physical (volume of micropores and mesopores, mean micropore width by the Dubini-Radushkevich method were used as a predecessor to the kinetic adsorption study, Surface area and microporous specific volume by the alpha method, microporous and total surface, BET surface area by BET method, cumulative mesopore distribution and pore volume, cumulative area and surface area and pore size by BJH method) of AC. The factorial design with eleven tests and three independent variables (AC mass, temperature and pH) was applied, resulting in response surfaces for adsorption capacity, DEP elimination rate and equilibrium time without significant difference between the studied variables. Mathematical modeling of adsorption kinetics using the pseudo-first, pseudo-second order and intraparticle models was performed and the pseudo-second order model was fitted to the experimental kinetic adsorption data. It was followed by the study of the adsorption isotherms for the lower, intermediate and longer equilibrium experimental conditions. It was performed the mathematical modeling of the adsorption isotherms using the Langmuir and Freundlinch models, and adjusted to the Freundlinch model to the experimental data of the adsorption isotherms with higher determination coefficients (R2), confirming the predominant chemorandomization adsorption phenomenon. The treatment of AOP UV-C/H2O2 was then applied alone. The factorial design with eleven tests and three independent variables (H2O2 concentration, temperature and pH) was applied, resulting in surfaces of responses to DEP elimination rate with significant difference between the variables studied for pH, positive effect of H2O2 concentration (p < 0.5). The mathematical modeling of the kinetics of AOP using the first order models was carried out, and the kinetic experimental data of the photodegradation with high coefficients of determination (R2> 0.9) were fitted to the model. The degradation kinetics of DEP by AOP coupling and AC, UV-C/H2O2/AC were followed. The factorial design with eleven tests and three independent variables (H2O2 concentration, temperature and pH) and with 0.4 g of AC, resulting in surfaces of responses to elimination rate of DEP with significant difference between the variables studied for pH, positive effect of H2O2 concentration (p <0.5). The mass of AC was determined in 0.4 g for all eleven tests, because it was the mass applied at the highest rates of elimination of DEP by kinetics of Adsorption, which was confirmed by repeatability at the central points of the factorial design (C9, C10 and C11). The catalytic activity of the carbons for the Adsorption process in the presence of tertbutanol was high, however, after the determination of the kinetic parameters, the contribution was higher for photooxidation of DEP by the action of the AOP (homogeneous system). / O objetivo desse trabalho foi comparar a eficiência de tratamentos convencionais como a adsorção com carvão ativado (CA) e o processo oxidativo avançado (POA), UV-C/H2O2, para degradação de dietil ftlato (DEP) e a acoplagem UV-C/H2O2/CA em efluente de laboratório, água ultrapura e água de torneira dopados com DEP e efluente de laboratório com multicomponentes (DEP e fenol). De modo predecessor ao estudo cinético da adsorção, aplicado isoladamente, realizou-se a caracterização química (método de Boehm, pHPZC, IRTF, análise elementar) e física (volume de microporos e mesoporos, largura média de microporos pelo método de Dubini-Radushkevich, superfície exterior e volume específico microporoso pelo método alfa, superfície microporosa e total, área de superfície de BET pelo método de BET, distribuição dos mesoporos cumulativo e volume do poro, área cumulativa e área superficial e tamanho do poro pelo método BJH) do CA. O delineamento fatorial com onze ensaios e três variáveis independentes (massa de CA, temperatura e pH) foi aplicado, resultando em superfícies de respostas para capacidade de adsorção, taxa de eliminação de DEP e tempo de equilibrio sem diferença significativa entre as variáveis estudadas. Foi realizada a modelagem matemática das cinéticas de adsorção utilizando os modelos de pseudo-primeira, pseudosegunda ordem e intrapartícula, e ajustou-se ao modelo de pseudo-segunda ordem aos dados experimentais cinéticos de adsorção. Seguiu-se com o estudo das isotermas de adsorção paras as condições experimentais de menor, intermediário e de maior tempo de equilíbrio. Foi realizada a modelagem matemática das isotermas de adsorção utilizando os modelos de Langmuir e Freundlinch, e ajustou-se ao modelo de Freundlinch aos dados experimentais das isotermas de adsorção com maior coeficientes de determinação (R2), confirmando o fenômeno de adsorção predominante quimiosorção. Seguiu-se a aplicação do tratamento de POA UVC/ H2O2, isoladamente. O delineamento fatorial com onze ensaios e três variáveis independentes (concentração de H2O2, temperatura e pH) foi aplicado, resultando em superfícies de respostas para taxa de eliminação de DEP com diferença significativa entre as variáveis estudadas para o pH, e efeito positivo da concentração de H2O2 (p<0,5). Foi realizada a modelagem matemática das cinéticas de POA utilizando os modelos de primeira ordem, e ajustaram-se ao modelo os dados experimentais cinéticos da fotodegradação com elevados coeficientes de determinação (R2>0,9). Seguiu-se para o estudo das cinética de degradação de DEP pela acoplagem POA e CA, UV-C/H2O2/CA. O delineamento fatorial com onze ensaios e três variáveis independentes (concentração de H2O2, temperatura e pH) e com 0,4 g de CA, resultando em superfícies de respostas para taxa de eliminação de DEP com diferença significativa entre as variáveis estudadas para o pH, efeito positivo da concentração de H2O2 (p<0,5). A massa de CA foi determinada em 0,4 g para todos os onze ensaios, porque foi a massa aplicada nas maiores taxas de eliminação de DEP pelas cinéticas de adsorção, que se confirmou, pela repetitibilidade, nos pontos centrais do delineamento fatorial (C9, C10 e C11). A atividade catalítica dos carvões para o processo de adsorção em presença de tércio butanol foi elevada, contudo a contribuição, após a determinação das constantes cinéticas, revelou-se maior para foto-oxidaçao de DEP pela ação do POA (sistema homogêneo).

Orientador: Rogério Falleiros Carvalho / Resumo: O nitrogênio (N), elemento essencial ao crescimento e desenvolvimento vegetal, é absorvido principalmente como nitrato (NO3-). Esse elemento pode controlar a arquitetura de raízes e dessa forma favorecer a absorção de nutrientes pelas plantas. Para isso, tem sido mostrado que esses eventos estão relacionados ao controle hormonal, especialmente as auxinas, pois esse hormônio controla o crescimento das raízes de modo dependente de NO3-. Entretanto, esses mecanismos são complexos, pois dependem de várias moléculas, especialmente peróxido de hidrogênio (H2O2), o qual parece atuar nas sinalizações das auxinas em situações estressoras nas plantas, a exemplo da deficiência de N. Entretanto, a forma como auxinas e H2O2 interagem nas raízes sob deficiência de N foi pouco explorado. Assim, objetivou-se verificar se as auxinas dependem de H2O2 nas respostas das raízes de tomateiro à deficiência de NO3-. Para isso, plantas de da cultivar Micro-Tom de tomateiro foram cultivadas em hidroponia sob suficiência e deficiência de NO3-, ambas com presença e ou ausência de inibidor de transporte de auxinas, o (ácido 2,3,5-triiodo-benzóico- TIBA) e inibidor do acúmulo de H2O2 (Catalase). O delineamento experimental foi inteiramente casualizado, disposto em fatorial 2x4, com três repetições. Foi analisado comprimento e biomassa seca da parte aérea e biomassa seca, comprimento, área e volume das raízes. Além disso, foi quantificado conteúdo de MDA e H2O2. A deficiência de NO3- diminuiu o crescimento... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Nitrogen (N) is essential for plant growth and development, and is mainly absorbed as nitrate (NO3-). It also controls root architecture, improving plant nutritional status. These characteristics are related to hormonal control, especially by auxins. Auxins control root growth via NO3-dependent cell expansion, but these mechanisms are complex and depend on several molecules. Hydrogen peroxide (H2O2) appears to act on these auxins signalling in plant stress situations. However, how auxins and H2O2 interact in roots under N deficiency has not been well explored. Therefore, this study aimed to verify if auxins depend on H2O2 for responses of tomato roots to N deficiency. Micro-Tom plants were grown in hydroponic systems under sufficiency and deficiency of NO3-, both with and without auxin transport inhibitor, 2,3,5-triiodo-benzoic acid (TIBA), and the inhibitor of H2O2 accumulation (Catalase) in plants. The experiment was carried out in a completely randomized design in a factorial scheme (2x4) with three replications. Shoot length and dry biomass, as well as root dry biomass, length, area and volume were analysed. In addition, MDA and H2O2 content were also quantified. NO3- deficiency reduced shoot growth and, interestingly, promoted higher root growth. Furthermore, TIBA inhibited root growth under both NO3- conditions and the presence of catalase in NO3-deficiency resulted in lower root growth. These results show that auxins depend on H2O2 for tomato root responses to N defici... (Complete abstract click electronic access below) / Mestre

NR 20140805

Oxidative dissolution of std. UO2 and UO2 doped with Cr2O3 and Al2O3, i.e. ADOPT, induced by H2O2 and γ radiation has been the main focus in this licentiate thesis. The catalytic decomposition of H2O2 on oxides like Gd2O3, HfO2, CeO2, Fe2O3 and CuO were also investigated. A kinetic study was performed by determining first and second order rate constants together with Arrhenius parameters for the decomposition of H2O2. The reactivity of H2O2 towards the oxides mentioned was observed to differ significantly despite their similarities. In the mechanistic study, the yields and dynamics of the formation of the intermediate hydroxyl radical from the decomposition of H2O2 was determined for the oxides and found to differ considerably. A turnover point could be found for most of oxides studied, i.e. an increase in the rate of hydroxyl radical scavenging after a specific amount of consumed H2O2. The reactivity of the std. UO2 and ADOPT towards H2O2 was similar to what was observed for other UO2-based materials in previous studies. The oxidative dissolution in radiation experiments showed a slight but significant difference. This was attributed to a difference in exposed surface area instead of an effect of doping. The difference in oxidative dissolution yield was too small to be significant which supports the previous conclusion. Leaching experiments using spent nuclear fuel were also performed on the two types of fuel showing the same behavior as the unirradiated pellets, i.e., a slightly lower 238U release from ADOPT. The difference was attributed to difference in exposed surface area. The release of fission products with low UO2 solubility displayed a higher release from ADOPT which was attributed to a difference in matrix solubility. Cs was released to a larger extent from std. UO2. This is attributed to the larger grain size of ADOPT, extending the diffusion distance. The release of lanthanides and actinides was slightly higher for the conventional UO2, nevertheless the difference was relatively small. / <p>QC 20140527</p>

The kinetics for radiation induced dissolution of spent nuclear fuel is a key issue in the safety assessment of a future deep repository. Spent nuclear fuel mainly consists of UO2 and therefore the release of radionuclides (fission products and actinides) is assumed to be governed by the oxidation and subsequent dissolution of the UO2 matrix. The process is influenced by the dose rate in the surrounding groundwater (a function of fuel age and burn up) and on the groundwater composition. In this licentiate thesis the effects of HCO3- (a strong complexing agent for UO22+) and ionic strength on the kinetics of UO2 oxidation and dissolution of oxidized UO2 have been studied experimentally. The experiments were performed using aqueous UO2 particle suspensions where the oxidant concentration was monitored as a function of reaction time. These reaction systems frequently display first order kinetics. Second order rate constants were obtained by varying the solid UO2 surface area to solution volume ratio and plotting the resulting pseudo first order rate constants against the surface area to solution volume ratio. The oxidants used were H2O2 (the most important oxidant under deep repository conditions), MnO4- and IrCl62-. The kinetics was studied as a function of HCO3- concentration and ionic strength (using NaCl and Na2SO4 as electrolytes). The rate constant for the reaction between H2O2 and UO2 was found to increase linearly with the HCO3- concentration in the range 0-1 mM. Above 1 mM the rate constant is independent of the HCO3- concentration. The HCO3- concentration independent rate constant is interpreted as being the true rate constant for oxidation of UO2 by H2O2 [(4.4 ± 0.3) x 10-6 m min-1] while the HCO3- concentration dependent rate constant is used to estimate the rate constant for HCO3- facilitated dissolution of UO22+ (oxidized UO2) [(8.8 ± 0.5) x 10-3 m min-1]. From experiments performed in suspensions free from HCO3- the rate constant for dissolution of UO22+ was also determined [(7 ± 1) x 10-8 mol m-2 s-1]. These rate constants are of significant importance for simulation of spent nuclear fuel dissolution. The rate constant for the oxidation of UO2 by H2O2 (the HCO3- concentration independent rate constant) was found to be independent of ionic strength. However, the rate constant for dissolution of oxidized UO2 displayed ionic strength dependence, namely it increases with increasing ionic strength. The HCO3- concentration and ionic strength dependence for the anionic oxidants is more complex since also the electron transfer process is expected to be ionic strength dependent. Furthermore, the kinetics for the anionic oxidants is more pH sensitive. For both MnO4- and IrCl62- the rate constant for the reaction with UO2 was found to be diffusion controlled at higher HCO3- concentrations (~0.2 M). Both oxidants also displayed ionic strength dependence even though the HCO3- independent reaction could not be studied exclusively. Based on changes in reaction order from first to zeroth order kinetics (which occurs when the UO2 surface is completely oxidized) in HCO3- deficient systems the oxidation site density of the UO2 powder was determined. H2O2 and IrCl62- were used in these experiments giving similar results [(2.1 ± 0.1) x 10-4 and (2.7 ± 0.5) x 10-4 mol m-2, respectively]. / QC 20101116