Desenvolvimento de um veículo para a prática de cicloturismo

Com uma Sociedade cada vez mais complexa e evolutiva, vários são os desafios a que somos postos à prova. Com isto, a população apesar das suas dependências e comodismos, tende a procurar novos meios de lazer que se envolvam com a natureza e com a prática desportiva. Deste modo, o Cicloturismo vai ao encontro destas práticas, tornando-se um mercado em evolução, cuja a aderência do número de pessoas tem vindo a crescer, sendo um tipo de turismo que acarreta resultados positivos, tais como um estilo de vida saudável, bem como a utilização de um meio de transporte de baixo custo e com uma pegada ecológica. Na mesma linha de pensamento, o presente documento aborda todo o processo de execução de um Quadriciclo. O objetivo geral do mesmo, incide em satisfazer as necessidades dos praticantes de cicloturismo e incentivar as pessoas para o uso da bicicleta como meio de transporte. Para tal, os participantes envolvidos foram utilizadores assíduos do uso da bicicleta, não só procurando-a para o lazer, mas sim para a prática do Cicloturismo. Assim, os utilizadores do veiculo projetado têm o privilégio de ter como painel de fundo das suas viagens, o coração da natureza, disfrutando do conforto e da segurança que este proporciona, e ainda como resultado das mesmas, um estilo de vida mais saudável. De forma sequencial e organizada, utilizando como base a Metodologia de Ulrich e Eppinger, são notáveis os passos que foram dados para obter o produto final. Para além dos fortes conceitos de conforto, estabilidade, engenharia e ergonomia, é primordial salientar toda a importância do Design, uma vez que influenciou a disposição do veículo de quatro rodas, do início ao fim.

Exotic dynamics in a firing rate model of neural tissue with threshold accommodation

Many of the equations describing the dynamics of neural systems are written in terms of firing rate functions, which themselves are often taken to be threshold functions of synaptic activity. Dating back to work by Hill in 1936 it has been recognized that more realistic models of neural tissue can be obtained with the introduction of state-dependent dynamic thresholds. In this paper we treat a specific phenomenological model of threshold accommodation that mimics many of the properties originally described by Hill. Importantly we explore the consequences of this dynamic threshold at the tissue level, by modifying a standard neural field model of Wilson-Cowan type. As in the case without threshold accommodation classical Mexican-Hat connectivity is shown to allow for the existence of spatially localized states (bumps) in both one and two dimensions. Importantly an analysis of bump stability in one dimension, using recent Evans function techniques, shows that bumps may undergo instabilities leading to the emergence of both breathers and traveling waves. Moreover, a similar analysis for traveling pulses leads to the conditions necessary to observe a stable traveling breather. In the regime where a bump solution does not exist direct numerical simulations show the possibility of self-replicating bumps via a form of bump splitting. Simulations in two space dimensions show analogous localized and traveling solutions to those seen in one dimension. Indeed dynamical behavior in this neural model appears reminiscent of that seen in other dissipative systems that support localized structures, and in particular those of coupled cubic complex Ginzburg-Landau equations. Further numerical explorations illustrate that the traveling pulses in this model exhibit particle like properties, similar to those of dispersive solitons observed in some three component reaction-diffusion systems. A preliminary account of this work first appeared in S Coombes and M R Owen, Bumps, breathers, and waves in a neural network with spike frequency adaptation, Physical Review Letters 94 (2005), 148102(1-4).

Performing masculinity, performing the self: Rudolfo Anaya's Bless me, Ultima and Heart of Aztlan

This article explores how Bless Me, Ultima and Heart of Aztlan, the two earliest novels by acclaimed Chicano writer Rudolfo Anaya, problematise and negotiate Chicano masculinity issues. I will focus on the main characters of the novels, who, at different vital moments of their lives, question the meaning of manhood amidst important socio-economic changes and conflicting cultural traditions. Anaya reveals the complexity of being “mestizo” in American society, and exposes how hegemonic standards of masculinity are Manichean, restrictive and reliant on gender inequality. I will finally examine whether the novels challenge hegemonic gender orders, successfully negotiate non-heterosexist ideals of manhood, and ultimately contribute to the advancement of egalitarian gender relations for the Chicana/o community

Universidade Metodista Unida de Moçambique [UMUM]

Partindo dos princípios que norteiam a UMUM, não esquecendo os pontos de referência da evolução transdisciplinar da educação – partir da/para a realidade – e tendo em mente que a estrutura student oriented sustenta a organização dos cursos, problematizamos a opção pela oferta, no 1º ano da licenciatura, de um conjunto de quatro disciplinas curriculares transversais a todos os cursos. Cientes de que a educação implica a vivência da interculturalidade e a inclusão social, o alvo é identificar o papel que a língua desempenha na descoberta do ‘eu’, na sua aceitação e consolidação, para que seja viável comunicar, agir e (con)viver em sociedade; na vivência pacífica do ‘eu’ com o ‘outro’; na construção colaborativa dos saberes e dos saberes fazeres. Daí decorre que as disciplinas curriculares transversais escolhidas, para induzir e potenciar uma educação de qualidade, tenham sido o Português, enquanto língua oficial, o Inglês, enquanto língua franca, as Tecnologias da Informação e Comunicação, como mediadoras da comunicação, promotoras de redes e de comunidades de aprendizagem para a construção do conhecimento e, ainda, Diálogos, Paz e Desenvolvimento, propiciando uma emergência equilibrada do sujeito per se, na sua relação com o ‘outro’ e com o mundo – saber ser e saber conviver. Questionamos a metodologia a utilizar nestas disciplinas curriculares, respeitando as suas especificidades, sustentando as áreas científicas contempladas em cada curso, numa dinâmica inter/transdisciplinar, implicando os estudantes na realidade e na complexidade do conhecimento e, em complementaridade, desafiando os docentes para o trabalho colaborativo.

Inclusion, Participation and the Emergence of British Chinese Websites

Previous work has drawn attention to the relative absence of British Chinese voices in public culture. No one is more aware of this invisibility than British-born Chinese people themselves. Since 2000 the emergence of Internet discussion sites produced by British Chinese young people has provided an important forum for many of them to grapple with questions concerning their identities, experiences and status in Britain. In this paper we explore the ways in which Internet usage by British-born Chinese people has facilitated forms of self-expression, collective identity production and social and political action. This examination of British Chinese websites raises important questions about inclusion and exclusion, citizenship, participation and the development of a sense of belonging in Britain, issues which are usually overlooked in relation to a group which appears to be well integrated and successful in higher education.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

Prosocial behavior and self-concept of Spanish students of Compulsory Secondary Education

This study analyzed the relationship between prosocial behavior and self-concept dimensions in a sample of 2022 Spanish students (51.1% males) of Compulsory Secondary Education. The prosocial behavior was measured with the Prosocial Behavior scale of the Teenage Inventory of Social Skills (TISS) and the self-concept was measured with the Self-Description Questionnaire-II (SDQ-II). Logistic regression analyses revealed that prosocial behavior is a positive and significant statistically predictor of high scores on the following self-concept dimensions: physical ability, parent relations, same-sex relations, opposite-sex relations, verbal, school, trustworthiness, and self-esteem. Those results were found in males, females and every Compulsory Secondary education year. However, prosocial behavior is not a significant statistically predictor of high scores on physical appearance, math, and emotional stability.

Exploring coordination-driven self-assembly with autonomous chemical robots

The work presented herein focused on the automation of coordination-driven self assembly, exploring methods that allow syntheses to be followed more closely while forming new ligands, as part of the fundamental study of the digitization of chemical synthesis and discovery. Whilst the control and understanding of the principle of pre-organization and self-sorting under non-equilibrium conditions remains a key goal, a clear gap has been identified in the absence of approaches that can permit fast screening and real-time observation of the reaction process under different conditions. A firm emphasis was thus placed on the realization of an autonomous chemical robot, which can not only monitor and manipulate coordination chemistry in real-time, but can also allow the exploration of a large chemical parameter space defined by the ligand building blocks and the metal to coordinate. The self-assembly of imine ligands with copper and nickel cations has been studied in a multi-step approach using a self-built flow system capable of automatically controlling the liquid-handling and collecting data in real-time using a benchtop MS and NMR spectrometer. This study led to the identification of a transient Cu(I) species in situ which allows for the formation of dimeric and trimeric carbonato bridged Cu(II) assemblies. Furthermore, new Ni(II) complexes and more remarkably also a new binuclear Cu(I) complex, which usually requires long and laborious inert conditions, could be isolated. The study was then expanded to the autonomous optimization of the ligand synthesis by enabling feedback control on the chemical system via benchtop NMR. The synthesis of new polydentate ligands has emerged as a result of the study aiming to enhance the complexity of the chemical system to accelerate the discovery of new complexes. This type of ligand consists of 1-pyridinyl-4-imino-1,2,3-triazole units, which can coordinate with different metal salts. The studies to test for the CuAAC synthesis via microwave lead to the discovery of four new Cu complexes, one of them being a coordination polymer obtained from a solvent dependent crystallization technique. With the goal of easier integration into an automated system, copper tubing has been exploited as the chemical reactor for the synthesis of this ligand, as it efficiently enhances the rate of the triazole formation and consequently promotes the formation of the full ligand in high yields within two hours. Lastly, the digitization of coordination-driven self-assembly has been realized for the first time using an in-house autonomous chemical robot, herein named the ‘Finder’. The chemical parameter space to explore was defined by the selection of six variables, which consist of the ligand precursors necessary to form complex ligands (aldehydes, alkineamines and azides), of the metal salt solutions and of other reaction parameters – duration, temperature and reagent volumes. The platform was assembled using rounded bottom flasks, flow syringe pumps, copper tubing, as an active reactor, and in-line analytics – a pH meter probe, a UV-vis flow cell and a benchtop MS. The control over the system was then obtained with an algorithm capable of autonomously focusing the experiments on the most reactive region (by avoiding areas of low interest) of the chemical parameter space to explore. This study led to interesting observations, such as metal exchange phenomena, and also to the autonomous discovery of self assembled structures in solution and solid state – such as 1-pyridinyl-4-imino-1,2,3-triazole based Fe complexes and two helicates based on the same ligand coordination motif.

Une étude sur les déterminants biologiques, psychologiques et du travail de l'épuisement professionnel

Cette thèse de doctorat s’intéresse à mieux comprendre, d’une part, ce qui influence la sécrétion de cortisol salivaire, et d’autre part, ce qui influence l’épuisement professionnel. Plusieurs objectifs en découlent. D’abord, elle vise à mieux cerner la contribution des conditions de l’organisation du travail (utilisation des compétences, autorité décisionnelle, demandes psychologiques, demandes physiques, horaire de travail irrégulier, nombre d’heures travaillées, soutien social des collègues, soutien social des superviseurs, insécurité d’emploi) sur la sécrétion de cortisol salivaire, ainsi que le rôle modérateur de certains traits de personnalité (extraversion, agréabilité, névrosisme, conscience, ouverture d’esprit, estime de soi, centre de contrôle) sur la relation entre les conditions de l’organisation du travail et la sécrétion de cortisol salivaire. Par ailleurs, cette thèse vise à établir la contribution des conditions de l’organisation du travail sur l’épuisement professionnel, ainsi que le rôle modérateur des traits de personnalité sur la relation entre les conditions de l’organisation du travail et l’épuisement professionnel. Finalement, cette thèse vise à vérifier si la sécrétion de cortisol salivaire joue un rôle médiateur sur la relation entre les conditions de l’organisation du travail et l’épuisement professionnel, ainsi qu’à identifier les effets de médiation modérés par les traits de personnalité sur la relation entre les conditions de l’organisation du travail et la sécrétion de cortisol salivaire. Ces objectifs sont inspirés de nombreuses limites observées dans la littérature, principalement l’intégration de déterminants à la fois biologiques, psychologiques et du travail dans la compréhension de l’épuisement professionnel. La thèse propose un modèle conceptuel qui tente de savoir comment ces différents stresseurs entraînent une dérégulation de la sécrétion de cortisol dans la salive des travailleurs. Ensuite, ce modèle conceptuel vise à voir si cette dérégulation s’associe à l’épuisement professionnel. Finalement, ce modèle conceptuel cherche à expliquer comment la personnalité peut influencer la manière dont ces variables sont reliées entre elles, c’est-à-dire de voir si la personnalité joue un rôle modérateur. Ce modèle découle de quatre théories particulières, notamment la perspective biologique de Selye (1936). Les travaux de Selye s’orientent sur l’étude de la réaction physiologique d’un organisme soumis à un stresseur. Dans ces circonstances, l’organisme est en perpétuel effort de maintien de son équilibre (homéostasie) et ne tolère que très peu de modifications à cet équilibre. En cas de modifications excessives, une réponse de stress est activée afin d’assurer l’adaptation en maintenant l’équilibre de base de l’organisme. Ensuite, le modèle conceptuel s’appuie sur le modèle de Lazarus et Folkman (1984) qui postule que la réponse de stress dépend plutôt de l’évaluation que font les individus de la situation stressante, et également sur le modèle de Pearlin (1999) qui postule que les individus exposés aux mêmes stresseurs ne sont pas nécessairement affectés de la même manière. Finalement, le modèle conceptuel de cette thèse s’appuie sur le modèle de Marchand (2004) qui postule que les réactions dépendent du décodage que font les acteurs des contraintes et ressources qui les affectent. Diverses hypothèses émergent de cette conceptualisation théorique. La première est que les conditions de l’organisation du travail contribuent directement aux variations de la sécrétion de cortisol salivaire. La deuxième est que les conditions de l’organisation du travail contribuent directement à l’épuisement professionnel. La troisième est que la sécrétion de cortisol salivaire médiatise la relation entre les conditions de l’organisation du travail et l’épuisement professionnel. La quatrième est que la relation entre les conditions de l’organisation du travail et la sécrétion de cortisol salivaire est modérée par les traits de personnalité. La cinquième est que la relation entre les conditions de l’organisation du travail, la sécrétion de cortisol salivaire et l’épuisement professionnel est modérée par les traits de personnalité. Des modèles de régression multiniveaux et des analyses de cheminement de causalité ont été effectués sur un échantillon de travailleurs canadiens provenant de l’étude SALVEO. Les résultats obtenus sont présentés sous forme de trois articles, soumis pour publication, lesquels constituent les chapitres 4 à 6 de cette thèse. Dans l’ensemble, le modèle intégrateur biopsychosocial proposé dans le cadre de cette thèse de doctorat permet de mieux saisir la complexité de l’épuisement professionnel qui trouve une explication biologique, organisationnelle et individuelle. Ce constat permet d’offrir une compréhension élargie et multiniveaux et assure l’avancement des connaissances sur une problématique préoccupante pour les organisations, la société ainsi que pour les travailleurs. Effectivement, la prise en compte des traits de personnalité et de la sécrétion du cortisol salivaire dans l’étude de l’épuisement professionnel assure une analyse intégrée et plus objective. Cette thèse conclue sur les implications de ces résultats pour la recherche, et sur les retombées qui en découlent pour les milieux de travail.

Development and psychometric evaluation of the basic electrocardiogram interpretation self-efficacy scale

Purpose: Research suggests that nurses and nursing students lack competence in basic electrocardiogram (ECG) interpretation. Self-efficacy is considered to be paramount in the development of one's competence. The aim of this study was to develop and psychometrically evaluate a scale to assess self-efficacy of nursing students in basic ECG interpretation. Materials and methods: Observational cross-sectional study with a convenience sample of 293 nursing students. The basic ECG interpretation self-efficacy scale (ECG-SES) was developed and psychometrically tested in terms of reliability (internal consistency and temporal stability) and validity (content, criterion and construct). The ECG-SES’ internal consistency was explored by calculating the Cronbach's alpha coefficient (α); its temporal stability was investigated by calculating the Pearson correlation coefficient (r) between the participants’ results on a test–retest separated by a 4-week interval. The content validity index of the items (I-CVI) and the scale (S-CVI) was calculated based on the reviews of a panel of 16 experts. Criterion validity was explored by correlating the participants’ results on the ECG-SES with their results on the New General Self-Efficacy Scale (NGSE). 1 Construct validity was investigated by performing Principal Component Analysis (PCA) and known-group analysis. Results: The excellent reliability of the ECG-SES was evidenced by its internal consistency (α = 0.98) and its temporal stability at the 4-week re-test (r = 0.81; p < 0.01). The ECG-SES’ content validity was also excellent (all items’ I-CVI = 0.94–1; S-CVI = 0.99). A strong, significant correlation between the NGSE and the ECG-SES (r = 0.70; p < 0.01) showed its criterion validity. Corroborating the ECG-SES’ construct validity, PCA revealed that all its items loaded on a single factor that explained 74.6% of the total variance found. Furthermore, known-groups analysis showed the ECG-SES’ ability to detect expected differences in self-efficacy between groups with different training experiences (p < 0.01). Conclusion: The ECG-SES showed excellent psychometric properties for measuring the self-efficacy of nursing students in basic ECG interpretation.

Porous self-protonating spiropyran-based NIPAAm gels with improved reswelling kinetics

The final publication is available at Springer via http://dx.doi.org/[10.1007/s10853-015-9458-2]

REAL TIME FUZZY CONTROLLER FOR QUADROTOR STABILITY CONTROL

In this report, we develop an intelligent adaptive neuro-fuzzy controller by using adaptive neuro fuzzy inference system (ANFIS) techniques. We begin by starting with a standard proportional-derivative (PD) controller and use the PD controller data to train the ANFIS system to develop a fuzzy controller. We then propose and validate a method to implement this control strategy on commercial off-the-shelf (COTS) hardware. An analysis is made into the choice of filters for attitude estimation. These choices are limited by the complexity of the filter and the computing ability and memory constraints of the micro-controller. Simplified Kalman filters are found to be good at estimation of attitude given the above constraints. Using model based design techniques, the models are implemented on an embedded system. This enables the deployment of fuzzy controllers on enthusiast-grade controllers. We evaluate the feasibility of the proposed control strategy in a model-in-the-loop simulation. We then propose a rapid prototyping strategy, allowing us to deploy these control algorithms on a system consisting of a combination of an ARM-based microcontroller and two Arduino-based controllers. We then use a combination of the code generation capabilities within MATLAB/Simulink in combination with multiple open-source projects in order to deploy code to an ARM CortexM4 based controller board. We also evaluate this strategy on an ARM-A8 based board, and a much less powerful Arduino based flight controller. We conclude by proving the feasibility of fuzzy controllers on Commercial-off the shelf (COTS) hardware, we also point out the limitations in the current hardware and make suggestions for hardware that we think would be better suited for memory heavy controllers.

DIFFUSE-INTERFACE FIELD APPROACH TO MODELING SELF-ASSEMBLY OF HETEROGENEOUS COLLOIDAL SYSTEMS AND RELATED DIPOLE-DIPOLE INTERACTION PHENOMENA

Colloid self-assembly under external control is a new route to fabrication of advanced materials with novel microstructures and appealing functionalities. The kinetic processes of colloidal self-assembly have attracted great interests also because they are similar to many atomic level kinetic processes of materials. In the past decades, rapid technological progresses have been achieved on producing shape-anisotropic, patchy, core-shell structured particles and particles with electric/magnetic charges/dipoles, which greatly enriched the self-assembled structures. Multi-phase carrier liquids offer new route to controlling colloidal self-assembly. Therefore, heterogeneity is the essential characteristics of colloid system, while so far there still lacks a model that is able to efficiently incorporate these possible heterogeneities. This thesis is mainly devoted to development of a model and computational study on the complex colloid system through a diffuse-interface field approach (DIFA), recently developed by Wang et al. This meso-scale model is able to describe arbitrary particle shape and arbitrary charge/dipole distribution on the surface or body of particles. Within the framework of DIFA, a Gibbs-Duhem-type formula is introduced to treat Laplace pressure in multi-liquid-phase colloidal system and it obeys Young-Laplace equation. The model is thus capable to quantitatively study important capillarity related phenomena. Extensive computer simulations are performed to study the fundamental behavior of heterogeneous colloidal system. The role of Laplace pressure is revealed in determining the mechanical equilibrium of shape-anisotropic particles at fluid interfaces. In particular, it is found that the Laplace pressure plays a critical role in maintaining the stability of capillary bridges between close particles, which sheds light on a novel route to in situ firming compact but fragile colloidal microstructures via capillary bridges. Simulation results also show that competition between like-charge repulsion, dipole-dipole interaction and Brownian motion dictates the degree of aggregation of heterogeneously charged particles. Assembly and alignment of particles with magnetic dipoles under external field is studied. Finally, extended studies on the role of dipole-dipole interaction are performed for ferromagnetic and ferroelectric domain phenomena. The results reveal that the internal field generated by dipoles competes with external field to determine the dipole-domain evolution in ferroic materials.

Effect of pH and temperature on the carbonate promoted dissolution of sodium meta-autunite

Release of uranium from Na-autunite, an artificial mineral created as a result of polyphosphate injection in the subsurface at the DOE Hanford Site, takes place during slow dissolution of the mineral structure. Stability information of the uranyl-phosphate phases is limited to conditions involving pH, temperature, and a few aqueous organic materials. The carbonate ion, which creates very strong complexes with uranium, is the predominant ion in the groundwater composition. The polyphosphate technology with the formation of autunite was identified as the most feasible remediation strategy to sequester uranium in contaminated groundwater and soil in situ. The objectives of the experimental work were (i) to quantify the effect of bicarbonate on the stability of synthetic sodium meta-autunite created as a result of uranium stabilization through polyphosphate injection, (ii) calculate the kinetic rate law parameters of the uranium release from Na-autunite during dissolution, and (iii) to compare the process parameters with those obtained for natural calcium meta-autunite. Experiments were conducted using SPTF apparatus, which consists of syringe pumps for controlling flow rate, Teflon reactors and a heating/cooling system. 0.25 grams of synthetic Na-autunite was placed in the reactor and buffer solutions with varying bicarbonate concentrations (0.0005 to 0.003 M) at different pH (6 - 11) were pumped through the reactors. Experiments were conducted at four different temperatures in the range of 5 - 60oC. It was concluded that the rate of release of uranium from synthetic Na-autunite is directly correlated to the bicarbonate concentration. The rate of release of uranium increased from 1.90 x 10-12 at pH 6 to 2.64 x 10-10 (mol m-2 s-1) at pH 11 at 23oC over the bicarbonate concentration range tested. The activation energy values were invariant with the change in the bicarbonate concentration; however, pH is shown to influence the activation energy values. Uranyl hydroxides and uranyl carbonates complexes helped accelerate the dissolution of autunite mineral.

Emergence and fate of siloxanes in waste streams: Release mechanisms, partitioning and persistence in three environmental compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. ^ The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. ^ Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.^