Technetium environmental chemistry: Mechanisms for the surface-mediated reduction of Tc(VII)

Technetium is the lightest element whose isotopes are all radioactive. Among them, 99Tc (hereafter simply referred as technetium or Tc) is the most abundant and raises great environmental concern due to its relatively long half-life of 2.14×105 years and the high mobility of pertechnetate, Tc(VII)O4, its most stable form under aerobic conditions. The reduction from Tc(VII) to Tc(IV) is one of the most successful strategies for Tc immobilization; however, the mechanism of this redox reaction is not yet fully understood. This presents a large gap in the general knowledge of technetium chemistry and a significant obstacle for the modeling of its reactivity in contexts like a nuclear waste repository. This thesis was developed in the frame of the BMWi funded VESPA II project, and it studies the surface-mediated reduction of 99Tc(VII) using a combination of fundamental chemistry and its application for remediation and nuclear waste management. First, spectro-electrochemical methods (cyclic voltammetry, rotating disk electrode, chronoamperometry coupled with UV-vis, Raman microscopy and nuclear magnetic resonance) were employed to study the reduction mechanism of 0.5 mM KTcO4 in non-complexing media (2 M NaClO4) in the pH range from 2.0 to 10.0. It was found that the mechanism depends on the pH. At pH 2.0 it splits into two steps: Tc(VII) gains 2.1 ± 0.3 electrons and becomes Tc(V) that rapidly reduces to Tc(IV) with the transfer of further 1.3 ± 0.3 electrons. In contrast, at pH ≥ 4.0 there is a direct transfer of 3.2 ± 0.3 electrons. The complete reduction of Tc(VII) yielded a black solid that was successfully characterized by NMR and Raman microscopy as Tc(IV) regardless of the initial pH at which the reaction occurred. Unfortunately, it was not possible to observe the Tc(V) species at pH 2.0 by the spectroscopic tools used. Second, the reductive immobilization of Tc(VII) by pure pyrite and a synthetic mixture marcasite-pyrite 60:40 (synthetic FeS2, with both minerals being polymorphs) was studied by a combination of batch sorption experiments (Tc-removal was studied varying pH, contact time, ionic strength and Tc concentration) and several spectroscopies and microscopies such as Raman microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and VIII X-ray absorption spectroscopy. It was found that both pyrite and the synthetic FeS2 promote the reduction of Tc(VII) to Tc(IV). In the case of pure pyrite, the Tc-removal is complete after one day in contact at pH ≥ 5.5. The spectroscopic analysis showed at pH 6.0 an inner-sphere complex between Tc(IV) dimers and hematite formed as secondary mineral on the pyrite surface. In contrast, at pH 10.0 Tc(IV) gets incorporated into surficial magnetite by replacing Fe3+ in octahedral position, with Fe2+ providing reasonable charge compensation for Tc4+. The presence of marcasite made the process slower and less efficient since the synthetic FeS2 was capable to remove 100% Tc from solution only after seven days in contact at 6.0 < pH ≤ 9.0 while the Tc-removal at pH 10.0 was only around 80%. At pH 6.0 the formation of hematite was also observed, suggesting that the formed Tc(IV) species at the surface is the same as with pure pyrite. However, at pH 10.0 the formation of sulfate minerals evidences a change of redox active species: S2- instead of Fe2+. This, combined with the fact that in both solids the formation of TcSx species was detected by XPS at pH 10.0, shows the potential of sulfur as another reducing agent for Tc(VII). The effect of polymorphism on the Tc removal is remarkable and this work shows the relevance of more studies on the interaction of radionuclei with other mineral polymorphs. Regardless of the kinetics of the Tc removal, both pyrite and synthetic FeS2 hindered the re-oxidation of Tc(IV) when exposed to ambient atmosphere for two months. This feature makes them good candidates for the remediation of technetium from contaminated waters. Moreover, natural attenuation effects can be expected for technetium in the near and far field of nuclear waste repositories wherever iron sulfide is present. The results presented in this work contribute to a better understanding of the fundamental aqueous chemistry of technetium and confirm pyrite, a ubiquitous mineral, as a very good candidate for technetium scavenging even in the presence of marcasite. These results close important gaps in thermodynamic databases that are needed for the safety assessment, i.e. modeling of fission products

Bioelectrochemical production of graphene oxide using bacteria as biocatalysts

2019 Summer.Includes bibliographical references.The demand for production of graphene oxide (GO), which is a precursor for large-scale production of graphene, has been increasing due to the broad array of uses of both nanomaterials. Due to the unique electrical and mechanical properties of these 2D nanomaterials, applications in composites have shown enhancements by contributing a tunable energetic band gap, high strength, and high transparency among other features. The tunable band gap of the graphene derivatives is one of the key properties of these nanomaterials. By varying the size of the energetic band gap (in eV) between the conduction and valence bands, resistance can be decreased to promote electron flow in the material lattice. A large energetic band gap (insulators) means more resistance for electron flow. Being able to control the band gap of a nanomaterial, allows for many applications in batteries, supercapacitors, and semiconductors being the most promising applications for these nanomaterials. Other applications include flexible electronics, renewable energy, drug delivery, contaminant removal, sensors, and more. Unfortunately, large-scale production of graphene using current methods is challenging due to low yield, impurities, high cost, high energy input, slow production rates and/or hazardous chemical reactants and wastes. For this study, the focus was on the bioelectrochemical production of GO (BEGO) as a novel technology for producing these nanomaterials with low energy input, inexpensive and non-hazardous reagents at standard conditions, and using microbes as biocatalysts. The BEGO process consists of a single-chamber microbial electrosynthesis cell (MES) that uses a graphite rod anode and a cathode (carbon cloth or stainless steel) to drive redox reactions. This MES can be operated at low voltage in a three-electrode (-0.8-1.4V vs. Ag/AgCl), or two-electrode system (~3.1V DC), with bacteria inoculated in a phosphate media solution. During this study, the BEGO process was investigated to advance understanding of the production process and the properties of the BEGO nanomaterial produced. To achieve this, the objectives established include: 1) developing methods for purifying and quantifying the nanomaterial during the production process in the complex aqueous-phase reactor matrix, 2) identifying key physical and chemical properties of the nanomaterial product using various spectroscopy and microscopy techniques, and 3) analyzing the microbial communities present in the reactors and in the graphite anode biofilm. To quantify the BEGO and estimate production rates, different spectrophotometric and gravimetric methods were used. Ultraviolet-visible spectroscopy (UV-Vis) at 229 nm was found to be the best method. This wavelength is specific to GO as it corresponds to the π → π * transitions of aromatic C-C bonds comprising the majority of the molecule, regardless of the oxidation state. Different centrifugation and filtration protocols were compared to purify the BEGO out of the complex matrix. For quantification methods in solution, centrifugation at 10,000 x g for 15 minutes was found to be the most effective method for removal of large particles and biological material, with BEGO remaining in solution. For material characterization, various techniques were used to identify the functional groups present and the morphology of the BEGO sheets. It was found through Fourier transform infrared spectroscopy (FT-IR) and UV-Vis, that the nanomaterial contained less carboxyl/carbonyl groups than GO produced by the traditional Hummers' method. Raman spectroscopy and thermogravimetric analysis (TGA) showed high disorder and weight loss events consistent with known GO spectra. Microscopy analysis revealed the BEGO process yields sheet sizes of a few hundred nm to 1-2 µm in lateral dimensions. Transparency and Fast Fourier transform (FFT) images indicate the BEGO consists of only single-layered to few-layered structures, which are needed for downstream applications. The microbial analysis was done on bioreactors with different inocula sources. DNA and RNA were extracted from both the bulk liquid media and the rod biofilm. At the end of the operation period, microbial communities in the bioreactors had diverged from the inoculum source. Microbial communities in the BEGO producing reactors consisted of both aerobic and anaerobic microorganisms. The most abundant genera on the rod biofilm were the unknown Comamonadaceae (10-11%), Hydrogenophaga (9-21%), Methyloversatilis (15-22%), and Pseudomonas (11-36%) all from the Proteobacteria phylum. Thus, these microbial phylotypes may play a key role in catalyzing BEGO production, enabling this novel and sustainable approach to nanomaterial synthesis

Oxidative Stress in the Local and Systemic Events of Apical Periodontitis

Oxidative stress is involved in the pathogenesis of a variety of inflammatory disorders. Apical periodontitis (AP) usually results in the formation of an osteolytic apical lesion (AL) caused by the immune response to endodontic infection. Reactive oxygen species (ROS) produced by phagocytic cells in response to bacterial challenge represent an important host defense mechanism, but disturbed redox balance results in tissue injury. This mini review focuses on the role of oxidative stress in the local and associated systemic events in chronic apical periodontitis. During endodontic infection, ligation of Toll-like receptors (TLRs) on phagocytes' surface triggers activation, phagocytosis, synthesis of ROS, activation of humoral and cellular responses, and production of inflammatory mediators, such as, cytokines and matrix metalloproteinases (MMPs). The increment in ROS perturbs the normal redox balance and shifts cells into a state of oxidative stress. ROS induce molecular damage and disturbed redox signaling, that result in the loss of bone homeostasis, increased pro-inflammatory mediators, and MMP overexpression and activation, leading to apical tissue breakdown. On the other hand, oxidative stress has been strongly involved in the pathogenesis of atherosclerosis, where a chronic inflammatory process develops in the arterial wall. Chronic AP is associated with an increased risk of cardiovascular diseases (CVD) and especially atherogenesis. The potential mechanisms linking these diseases are also discussed.Peer reviewe

Matrix Metalloproteinases as Regulators of Periodontal Inflammation

Periodontitis are infectious diseases characterized by immune-mediated destruction of periodontal supporting tissues and tooth loss. Matrix metalloproteinases (MMPs) are key proteases involved in destructive periodontal diseases. The study and interest in MMP has been fuelled by emerging evidence demonstrating the broad spectrum of molecules that can be cleaved by them and the myriad of biological processes that they can potentially regulate. The huge complexity of MMP functions within the protease web' is crucial for many physiologic and pathologic processes, including immunity, inflammation, bone resorption, and wound healing. Evidence points out that MMPs assemble in activation cascades and besides their classical extracellular matrix substrates, they cleave several signalling moleculessuch as cytokines, chemokines, and growth factors, among othersregulating their biological functions and/or bioavailability during periodontal diseases. In this review, we provide an overview of emerging evidence of MMPs as regulators of periodontal inflammation.Peer reviewe

Evaluation of long term implications of social policies: The 1967 Immigration Act as a case study (Ontario).

The purpose of this thesis was to provide an assessment of some possible implications of the 1967 Immigration Act and subsequent legislation on the distribution of occupation types for selected mother tongue groups. The Toronto and Windsor C.M.A\u27s were selected as the study area of this study and the 1981 and 1986 Censuses were selected as the study period. In order to find out the implications of the 1967 Immigration Act and subsequent legislation, the occupational statistics of the following groups were studied: English, French, German, Italian, Polish, Portuguese, Chinese, Vietnamese, Punjabi and Hindi. The occupational data was analyzed using the Index of dissimilarity and Chi square computations. The results from these tests and the review of the literature was used to make a series of conclusions on the need, of certain mother tongue groups, for Equity hiring policies.Dept. of Geography. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1994 .H467. Source: Masters Abstracts International, Volume: 33-04, page: 1122. Thesis (M.A.)--University of Windsor (Canada), 1994

IN VITRO RELEASE STUDIES OF CARBAMAZEPINE TABLETS AND BENZOYL METRONIDAZOLE SUSPENSIONS USING THE FLOW-THROUGH CELL APPARATUS AND SIMULATED GASTROINTESTINAL FLUIDS

Objective: To characterize the in vitro release of carbamazepine tablets and benzoyl metronidazole suspensions using the flow-through cell apparatus and simulated gastrointestinal fluids.Methods: Tegretol® tablets, Flagyl® suspension, and generic formulations of each were tested. Release studies were performed using an automated flow-through cell apparatus. Simulated gastric fluid (with and without pepsin) and simulated intestinal fluid (without pancreatin) at 16 ml/min and fasted state simulated intestinal fluid at 8 ml/min, all at 37.0±0.5 °C, were used as dissolution media. The quantity of dissolved carbamazepine and benzoyl metronidazole was determined at 5-min intervals until 60 min at 285 and 278 nm, respectively. Percentage dissolved at 60 min, mean dissolution time, dissolution efficiency values, and t10%, t25%, t50% and t63.2% were calculated. Mean values for all parameters were compared between the reference and generic formulations using Studentʼs t-test. Dissolution data were fitted to different kinetic models.Results: Simulated gastric fluid without pepsin showed no discriminative capability for carbamazepine tablets. Significant differences were observed between the reference and generic formulations for almost all parameters (*P&lt;0.05). In some cases, the logistic model best described the in vitro release of both drugs.Conclusion: Using an apparatus and media that best simulates the gastrointestinal environment, we identified differences in the rate and extent of dissolution of both drugs that could help to optimise the design of interchangeable formulations. Based on the physicochemical characteristics of carbamazepine and benzoyl metronidazole and the conditions in which the formulations were tested, these differences could be of clinical relevance.Â

Optimizacion del sistema logistico de distribucion de producto terminado y granel de la empresa Viawines S.A

196 p.El presente estudio exhibe la optimización del sistema de distribución para producto terminado y producto granel de la empresa VIA WINES S.A., la cual permite evaluar la conveniencia de establecer un centro de consolidación de carga para este último producto. La optimización consiste en establecer modelos de transporte acorde con la situación actual de la empresa, de manera de establecer rutas óptimas para la distribución de productos entre bodegas y despacho hacia puerto. El producto terminado en este momento está siendo despachado desde la bodega “Las Chilcas”, única bodega con factibilidad de despacho para este producto, ya que es la única que cuenta con línea de embotellado y etiquetado. Para producto a granel, los despachados son efectuados de diferentes bodegas hacia puerto, lo que incluye situaciones de traslado interno entre bodegas y, posteriormente, su llevada a puerto (transbordo). Es así como se observan traslados internos de vino a granel “circulares” que desde el punto de vista logístico, no agregan valor. Prácticamente, la mitad de lo trasladado se lleva hacia el sur, alejándose del punto final de despacho (puerto) y la otra mitad hacia el norte, acercándose al destino final (puerto). Hoy en día, los costos involucrados en estas operaciones representan el 80 % de los costos totales de transporte, por lo cual se hace necesario optimizar las rutas involucradas, en conjunto con establecer propuestas de mejoras de la logística actual de la empresa. Para ello, se realizan actividades de reconocimiento y formalización del actual proceso de distribución usado por la empresa, además de realizar un detallado análisis de los flujos de carga y de los costos involucrados para las diferentes rutas en cuestión. Los datos son analizados mensualmente desde Junio hasta Noviembre del presente año. Posteriormente se realiza la aplicación mensualmente del modelo de transporte con transbordo mediante la utilización del software Industrial LINGO, en donde se obtienen diagramas con detalles de las rutas óptimas a seguir por la empresa, es decir, la cantidad de litros a transportar, empresa transportista designada y ahorro estimativos de costos mensuales. Finalmente, se presentan propuestas de mejoramiento de la situación logística actual, evaluando la factibilidad económica de la creación de un centro de consolidación de carga para producto granel. Los resultados de esta evaluación son satisfactorios obteniendo una TIR del orden de 40%

Microbial diversity in hummock and hollow soils of three wetlands on the Qinghai-Tibetan plateau revealed by 16S rRNA pyrosequencing

The wetlands of the Qinghai-Tibetan Plateau are believed to play an important role in global nutrient cycling, but the composition and diversity of microorganisms in this ecosystem are poorly characterized. An understanding of the effects of geography and microtopography on microbial populations will provide clues to the underlying mechanisms that structure microbial communities. In this study, we used pyrosequencing-based analysis of 16S rRNA gene sequences to assess and compare the composition of soil microbial communities present in hummock and hollow soils from three wetlands (Dangxiong, Hongyuan and Maduo) on the Qinghai-Tibetan Plateau, the world’s highest plateau. A total of 36 bacterial phyla were detected. Proteobacteria (34.5% average relative abundance), Actinobacteria (17.3%) and Bacteroidetes (11%) had the highest relative abundances across all sites. Chloroflexi, Acidobacteria, Verrucomicrobia, Firmicutes, and Planctomycetes were also relatively abundant (1–10%). In addition, archaeal sequences belonging to Euryarchaea, Crenarchaea and Thaumarchaea were detected. Alphaproteobacteria sequences, especially of the order Rhodospirillales, were significantly more abundant in Maduo than Hongyuan and Dangxiong wetlands. Compared with Hongyuan soils, Dangxiong and Maduo had significantly higher relative abundances of Gammaproteobacteria sequences (mainly order Xanthomonadales). Hongyuan wetland had a relatively high abundance of methanogens (mainly genera Methanobacterium, Methanosarcina and Methanosaeta) and methanotrophs (mainly Methylocystis) compared with the other two wetlands. Principal coordinate analysis (PCoA) indicated that the microbial community structure differed between locations and microtopographies and canonical correspondence analysis indicated an association between microbial community structure and soil properties or geography. These insights into the microbial community structure and the main controlling factors in wetlands of the Qinghai-Tibetan Plateau provide a valuable background for further studies on biogeochemical processes in this distinct ecosystem

Estudios biológicos sobre los parasitoides, Mastrus ridens Horstman y Ascogaster quadridentata Wesmael, para evaluar su potencial como agentes de control biológico de Cydia pomonella (L.) plaga clave del manzano

Tesis para obtener el grado de Doctora en el área de Ciencias Biológicas, de la Universidad de Buenos Aires, en 2015La carpocapsa (Cydia pomonella) es una de las plagas clave del cultivo de pomáceas en todo el mundo. En la Argentina, si bien actualmente se están implementando medidas de control de bajo impacto ambiental, como la técnica de confusión sexual, la principal forma de control continúa siendo el empleo de productos químicos. El objetivo general de esta tesis fue estudiar aspectos básicos de la biología de Mastrus ridens y Ascogaster quadridentata a los efectos de evaluar su potencial como agentes de control de Cydia pomonella en nuestro país. Los principales aportes de este trabajo son: -Disponibilidad de un sistema de cría a nivel experimental para M. ridens y A. quadridentata en condiciones de laboratorio. -Conocimiento de los principales atributos biológicos y poblacionales de A. quadridentata sobre C. pomonella. -Estudio de la fecundidad y preferencia de M. ridens sobre dos especies de lepidópteros plaga presentes en nuestro país (C. pomonella- Grapholita molesta). -Determinación de la selectividad de los principales insecticidas utilizados en la producción de pomáceas para M. ridens. -Colonización y evaluación del establecimiento de M. ridens y A. quadridentata en el Alto Valle de Rio Negro. Los estudios realizados proporcionaron información y herramientas para impulsar el empleo de estos parasitoides a través del desarrollo de una estrategia de control biológico clásico de C. pomonella.The codling moth is a key pest of apple crops. In Argentina, pest management strategies mainly relay on chemical control, although recently the technique of sexual confusion has been implemented with success. The aim of this thesis was to study the potential of the parasitoids, Mastrus ridens and Ascogaster quadridentata as biological control agents of Cydia pomonella in our country. The most important contributions from this thesis are: -Better understanding of rearing methodologies for M. ridens y A. quadridentata in the laboratory. -Knowledge of the reproductive biology and population parameters of A. quadridentata in C. pomonella. -Knowledge of the biology and host preference by M. ridens for C. pomonella and G. molesta. -Determination of the side effect of some pesticides use in apple crops on M. ridens. -Colonization and evaluation of establishment of M. ridens y A. quadridentata in the field. These results provided useful information to enhance the use of the parasitoids in classical biological control strategies against C. pomonella in Argentina.Instituto de Microbiología y Zoología AgrícolaFil: Hernandez, Carmen Marcela. Instituto Nacional de Tecnología Agropecuaria (INTA). Instituto de Microbiología y Zoología Agrícola; Argentin