Investigación técnica y económica sobre desinfección de aguas residuales por sistemas de oxidación

Un incremento de la demanda del agua, junto con el aumento de la contaminación, ha provocado que hoy en día la reutilización de las aguas depuradas sea necesaria, pero la reutilización de aguas debe garantizar y minimizar los posibles riesgos sanitarios y medioambientales que su práctica pueda provocar. En España estos parámetros se encuentran regulados por el RD 1620/2007 relativo al régimen jurídico de la reutilización de las aguas depuradas. Las aguas regeneradas son aguas que ya han sido sometidas a un tratamiento de depuración, y a las cuales se aplica un posterior tratamiento adicional o complementario que permita adecuar su calidad al uso al que vaya a destinarse. Siendo requeridos para los distintos reúsos procesos de desinfección, uno de los principales sistemas utilizados es el cloro, debido a su sencilla aplicación y costos bajos, sin tomar en cuenta la posible formación de compuestos organohalogenados potencialmente cancerígenos. Es por esto que surge la necesidad de aplicar distintos sistemas de oxidación objeto de estudio en esta tesis, como el dióxido de cloro estabilizado, ozono y los procesos avanzados de oxidación (Advanced Oxidation Processes, AOP), ozono/peróxido y uv/peróxido. En esta tesis se investiga los rendimientos que pueden alcanzar estos sistemas en la eliminación de los ácidos húmicos y los fenoles, siendo las principales sustancias formadoras de subproductos de la desinfección, así mismo, se considera necesario garantizar la desinfección del agua a través del estudio de tres grupos de microrganismos, los coliformes totales, e. coli y enterococos, siendo un punto importante el posible recrecimiento microbiológico debido a una desinfección escasa, por la permanencia en el agua de los compuestos antes mencionados, o por alguna fuente de alimento que pudieran encontrar en el sistema de distribución. Lo más importante será la calidad que se pueda alcanzar con estos desinfectantes, con el fin de obtener agua para los distintos reúsos que existen en la actualidad. Y así no limitar los alcances que puede tener la reutilización de las aguas residuales. Basándose en lo antes mencionado se procedió a realizar la caracterización del agua del rio Manzanares, con el fin de determinar la cantidad de ácidos húmicos disueltos y fenoles, obteniendo valores bajos, se decidió incorporar a las muestras de rio 5 mg/L de estos compuestos, con el fin de observar de que manera podrían interferir en la desinfección de esta agua. De esta forma se logran obtener resultados óptimos de los sistemas de desinfección estudiados, siendo el Ozono un oxidante eficiente en la desinfección de los microrganismos y en la eliminación de ácidos húmicos y fenoles con tiempos de contacto cortos, mostrando deficiencias al permitir el recrecimiento de los coliformes totales. Del sistema de oxidación avanzada UV/Peróxido se determino como un eficiente desinfectante para garantizar la inexistencia de rebrotes, al paso del tiempo. Así mismo se concluye que tiene buenos rendimientos en la eliminación del ácido húmico y los fenoles. An increase in water demand, coupled with increasing pollution, has caused today reuse of treated water is necessary, but must ensure water reuse and minimize potential health and environmental risks that their practice is cause. In Spain these parameters are regulated by Royal Decree 1620/2007 on the legal regime of the reuse of treated water. The reclaimed water is water that has already been subjected to a depuration treatment, which is applied as a subsequent further treatment that will bring quality to the use to which is to be delivered. As required for various reuses disinfection processes, one of the main systems used is chlorine, due to its simple implementation and low costs, without taking into account the possible formation of potentially carcinogenic halogenated organic compounds. That is why there is a need to apply different oxidation systems studied in this thesis, as stabilized chlorine dioxide, ozone and advanced oxidation processes (AOP), ozone/peroxide and UV/peroxide. This thesis investigates the rates can reach these systems in removing humic acids and phenols, the main substances forming disinfection byproducts, likewise, it is considered necessary to ensure water disinfection through the study of three groups of microorganisms, total coliform, e. coli and enterococci, the important point being a possible regrowth due to microbiological disinfection scarce, the water remaining on the aforementioned compounds, or a food source which may be found in the distribution system. The most important quality is that achievable with these disinfectants, with the water to obtain various reuses that exist today. And thus not limit the scope that can be reuse of wastewater. Based on the above we proceeded to perform characterization Manzanares river water, in order to determine the quantity of dissolved humic acids and phenols, obtaining low values, it was decided to incorporate river samples 5 mg / L of these compounds, in order to observe how they might interfere with the disinfection of the water. Thus optimum results are achieved for disinfection systems studied, being efficient ozone oxidant in the disinfection of microorganisms and the removal of humic acids and phenols with short contact times, showing gaps to allow regrowth total coliforms. Advanced oxidation system UV / peroxide were determined as an efficient disinfectant to ensure the absence of volunteers, the passage of time. Also it is concluded that has good yields in removing humic acid and phenols.

Sistema de gestión de residuos de construcción y demolición en obras de edificación residencial. Buenas prácticas en la ejecución de obra

En el sector de la edificación, las grandes constructoras comienzan a considerar aspectos medioambientales, no limitándose a lo establecido por la legislación vigente, y buscando la implementación de buenas prácticas. Si bien este hecho es una realidad para las grandes empresas constructoras, todavía falta que la gran mayoría de las empresas del sector (pequeñas y medianas) adopten ésta tendencia. En este sentido, las publicaciones y estadísticas consultadas revelan que el sector de la construcción sigue siendo el sector con menor número de Sistemas de Gestión Ambiental (SGA) certificados en comparación con otros sectores industriales, debido principalmente a las peculiaridades de su actividad. Por otra parte, el sector de la construcción genera grandes cantidades de residuos de construcción y demolición (RCD). Aunque, en los últimos años la actividad de la construcción ha disminuido, debido a la crisis económica del país, no hay que olvidar todos los problemas causados por este tipo de residuos, o mejor dicho, por su gestión. La gestión de los RCD actual está lejos de alcanzar la meta propuesta en la Directiva Marco de Residuos (DMR), la cual exige un objetivo global para el año 2020 en el que el 70% de todos los RCD generados deberán ser reciclados en los países de la UE. Pero, la realidad es que sólo el 50% de la RCD generados en la Unión Europea se recicla. Por este motivo, en los últimos años se ha producido una completa modificación del régimen jurídico aplicable a los RCD, incorporando importantes novedades a nuestro ordenamiento interno como son: la redacción de un Estudio de gestión de RCD (en fase de diseño) y un Plan de gestión de RCD (en fase de ejecución). Entre estas medidas destaca el poder conocer, con la antelación suficiente, la cantidad y el momento en que los RCD son generados, para así poder planificar la gestión más adecuada para cada categoría de RCD. Es por ello que el desarrollo de cualquier instrumento que determine la estimación de RCD así como iniciativas para su control debe ser considerado como una herramienta para dar respuestas reales en el campo de la sostenibilidad en la edificación. Por todo lo anterior, el principal objetivo de la Tesis Doctoral es mejorar la gestión actual de los RCD, a través de la elaboración e implementación en obra de un Sistema de gestión de RCD en fase de ejecución que podrá ser incluido en el Sistema de Gestión Ambiental de las empresas constructoras. Para ello, se ha identificado la actividad que más residuo genera, así como las diferentes categorías de RCD generadas durante su ejecución, a través del análisis de nueve obras de edificación de nueva planta. Posteriormente, se han determinado y evaluado, en función de su eficacia y viabilidad, veinte buenas prácticas encaminadas a reducir la generación de RCD. También, se han identificado y evaluado, en función de su coste económico, cinco alternativas de gestión para cada categoría de RCD generada. Por último, se ha desarrollado e implementado un Sistema de Gestión de RCD en una empresa de construcción real. En definitiva, el Sistema de Gestión de RCD propuesto contiene una herramienta de estimación de RCD y también proporciona una relación de buenas prácticas, según su viabilidad y eficacia, sobre los aspectos más significativos en cuanto a la gestión de RCD se refiere. El uso de este Sistema de gestión de RCD ayudará a los técnicos de la construcción en el desarrollo de los documentos "Estudio de gestión de RCD " y "Plan de gestión de RCD " - requeridos por ley -. Además, el Sistema promueve la gestión ambiental de la empresa, favoreciendo la cohesión del proceso constructivo, estableciendo responsabilidades en el ámbito de RCD y proporcionando un mayor control sobre el proceso. En conclusión, la implementación de un sistema de gestión de RCD en obra ayuda a conseguir una actividad de edificación, cuyo principal objetivo sea la generación de residuos cero. ABSTRACT Currently, in the building sector, the main construction companies are considering environmental issues, not being limited to the current legislation, and seeking the implementation of good practices. While this fact is a reality for large construction companies, still the vast majority of construction companies (small and medium enterprises) need to accept this trend. In this sense, official publications and statistics reveal that the construction sector remains with the lowest number of certified Environmental Management Systems (EMS) compared to other industrial sectors, mainly due to the peculiarities of its activity. Moreover, the construction industry in Spain generates large volumes of construction and demolition waste (CDW) achieving a low recycling rate compared to other European Union countries and to the target set for 2020. Despite the complete change in the legal regime for CDW in Spain, there are still several difficulties for their application at the construction works. Among these difficulties the following can be highlighted: onsite segregation, estimating CDW generation and managing different CDW categories. Despite these difficulties, the proper CDW management must be one of the main aspects considered by construction companies in the EMS. However, at present the EMS used in construction companies consider very superficially CDW management issues. Therefore, current EMS should go a step further and include not only procedures for managing CDW globally, but also specific procedures for each CDW category, taking into account best practices for prevention, minimization and proper CDW management in order to achieve building construction works with zero waste generation. The few scientific studies analysing EMS implementation in construction enterprises focus on studying the benefits and barriers of their implementation. Despite the drawbacks found, implementing an EMS would bring benefits such as improving the corporate image in relation to the environment, ensuring compliance with the law or reducing environmental risks. Also, the international scientific community has shown great interest in defining models to estimate in advance the CDW that will be generated during the building construction or rehabilitation works. These studies analyse the overall waste generation and its different CDW categories. However, despite the many studies found on CDW quantification, analysing its evolution throughout the construction activities is a factor that must be further studied and discussed in greater depth, as results would be of great significance when planning the CDW management. According to the scientific studies analysing the implementation of good environmental practices in construction sites, it seems that, in general, the CDW collection system is done in a decentralized manner by each subcontracted company. In addition, the corporate image generated when poor practices are done may adversely affect the company's reputation and can result in loss of contracts. Finally, although there are numerous guides and manuals of good practices for CDW management, no references have been found implementing these measures in the Environmental Management System of the construction companies. From all the above, this thesis aims to provide answers to reduce the environmental impact caused by CDW generation in building construction works, in order to get a building process with zero waste generation. In this sense, is essential to generate new knowledge in order to implement a system which can carry out comprehensive management of CDW generated onsite, at the design stage until the end of its life cycle, taking into account both technical and economic criteria. Therefore, the main objective of this thesis is to define and implement a CDW management system for residential building construction works, helping construction agents not only to manage the CDW in accordance with current legislation, but also minimizing their generation on site by applying best practices, resulting in achieving the goal of zero waste in building works.

Metodología para la remediación de instalaciones de residuos mineros procedentes de la minería metálica orientada a la reducción del riesgo ambiental y al aprovechamiento de sus residuos

Las instalaciones de residuos mineros abandonadas procedentes de la minería metálica pueden suponer un grave riesgo medioambiental y de seguridad debido a su potencial contaminante y a la posibilidad de ocasionar accidentes por su fallo estructural. Desgraciadamente, en la mayoría de los países de la Unión Europea existen un gran número de presas, balsas, pilas de lixiviación y escombreras mineras cerradas que se encuentran abandonadas y sin ningún control estructural o ambiental al haberse originado en actividades extractivas finalizadas con anterioridad a la aparición de las primeras normativas de índole ambiental aplicables. Algunas de las instalaciones de residuos mineros abandonadas pueden además contener reservas de metales apreciables al proceder sus residuos de actividades extractivas pasadas en las que se emplearon procesos metalúrgicos e hidrometalúrgicos de concentración con eficiencias de recuperación inferiores a las obtenibles con técnicas extractivas actuales. En la presente tesis doctoral se ha desarrollado una metodología de análisis que puede servir de herramienta útil para la toma de decisiones en los procesos de remediación de instalaciones de residuos mineros procedentes de la minería metálica. Dicha metodología se ha construido a partir de los resultados que se puedan obtener del análisis de riesgos ambientales de las instalaciones estudiadas, estableciendo las metodologías más apropiadas para su remediación en función de los riesgos específicos que presenten. La metodología propuesta incluye además el análisis de la posibilidad de proceder al aprovechamiento de los residuos mineros presentes en las instalaciones mediante la extracción de sus metales, para lo que se han desarrollado una serie de expresiones que pueden emplearse en el análisis de la viabilidad en términos económicos, ambientales y sostenibles de dicho aprovechamiento obtenidas sobre la base de las últimas experiencias al respecto registradas bibliográficamente y del estudio de los costes de inversión y operación que pueden suponer dichas operaciones en función de las tecnologías extractivas empleadas. Para finalizar, en la última parte de la tesis se incluye un caso práctico de aplicación de la metodología desarrollada en el que se estudian las posibilidades de remediación de tres presas mineras abandonadas procedentes de la extracción de plomo y zinc y se analiza la posibilidad de proceder al aprovechamiento de sus residuos mediante la extracción de metales de sus estériles. ABSTRACT The abandoned mining waste facilities from the metallic mining may pose environmental and safety risks due to its pollution potential as well as due to the possibility of structural collapses. Unfortunately, in most countries of the European Union there are a large number of tailing dams, tailing ponds, leaching heaps and mining waste-rock dump sites that are abandoned without any structural or environmental control. That is because they were originated in extractive activities completed prior to the appearance of the first environmental applicable regulations. Some of the abandoned mining waste facilities can also contain significant reserves of metals due to the fact that their waste comes from past mining activities when metallurgical processes and hydrometallurgical concentration were used with lower efficiency than those obtainable with present recovery mining techniques. At present thesis a method of analysis that can serve as a useful tool for decision making in the process of remediation of mining waste facilities from the metal mining has been developed. This methodology has been built from the results that may be obtained from the analysis of environmental risks at studied facilities, therefore establishing the most appropriate methodologies for its remediation based on their specific risks. The proposed methodology also includes the analysis of the possibility to beneficiate the mining residues contained on the mining waste facilities by extracting their metals. For that purpose, some expressions have been developed that can be used in the analysis of the economic viability of such extraction. Expressions are obtained on the basis of recent registered bibliographically, experiences and from the study of investment and operating costs that may suppose such extractions depending on extractive technologies used. Finally, in the last part of the thesis a case of application of the methodology proposed has been developed, in which, the possibilities for remediation of three abandoned mining dams related to the extraction of lead and zinc are studied and the possibility of beneficiate their waste by extracting metals is analyzed.

Composition, potential emissions and agricultural value of pig slurry from Spanish commercial farms

Pig slurry is a valuable fertilizer for crop production but at the same time its management may pose environmental risks. Slurry samples were collected from 77 commercial farms of four animal categories (gestating and lactating sows, nursery piglets and growing pigs) and analyzed for macronutrients, micronutrients, heavy metals and volatile fatty acids. Emissions of ammonia (NH3) and biochemical methane potential (BMP) were quantified. Slurry electrical conductivity, pH, dry matter content and ash content were also determined. Data analysis included an analysis of correlations among variables, the development of prediction models for gaseous emissions and the analysis of nutritional content of slurries for crop production. Descriptive information is provided in this work and shows a wide range of variability in all studied variables. Animal category affected some physicochemical parameters, probably as a consequence of different slurry management and use of cleaning water. Slurries from gestating sows and growing pigs tended to be more concentrated in nutrients, whereas the slurry from lactating sows and nursery piglets tended to be more diluted. Relevant relationships were found among slurry characteristics expressed in fresh basis and gas emissions. Predictive models using on-farm measurable parameters were obtained for NH3 (R2 = 0.51) and CH4

Genetic control of resistance to experimental infection with virulent Mycobacterium tuberculosis

Over 2 billion people are estimated to be infected with virulent Mycobacterium tuberculosis, yet fewer than 10% progress to clinical tuberculosis within their lifetime. Twin studies and variations in the outcome of tuberculosis infection after exposure to similar environmental risks suggest genetic heterogeneity among individuals in their susceptibility to disease. In a mouse model of tuberculosis, we have established that resistance and susceptibility to virulent M. tuberculosis is a complex genetic trait. A new locus with a major effect on tuberculosis susceptibility, designated sst1 (susceptibility to tuberculosis 1), was mapped to a 9-centimorgan (cM) interval on mouse chromosome 1. It is located 10–19 cM distal to a previously identified gene, Nramp1, that controls the innate resistance of mice to the attenuated bacillus Calmette–Guérin vaccine strain. The phenotypic expression of the newly identified locus is distinct from that of Nramp1 in that sst1 controls progression of tuberculosis infection in a lung-specific manner. Mice segregating at the sst1 locus exhibit marked differences in the growth rates of virulent tubercle bacilli in the lungs. Lung lesions in congenic sst1-susceptible mice are characterized by extensive necrosis and unrestricted extracellular multiplication of virulent mycobacteria, whereas sst1-resistant mice develop interstitial granulomas and effectively control multiplication of the bacilli. The resistant allele of sst1, although powerful in controlling infection, is not sufficient to confer full protection against virulent M. tuberculosis, indicating that other genes located outside of the sst1 locus are likely also to be important for controlling tuberculosis infection.

Fate of biological control introductions: monitoring an Australian fungal pathogen of grasshoppers in North America.

In North America there are two generally recognized pathotypes (pathotypes 1 and 2) of the fungus Entomophaga grylli which show host-preferential infection of grasshopper subfamilies. Pathotype 3, discovered in Australia, has a broader grasshopper host range and was considered to be a good biocontrol agent. Between 1989 and 1991 pathotype 3 was introduced at two field sites in North Dakota. Since resting spores are morphologically indistinguishable among pathotypes, we used pathotype-specific DNA probes to confirm pathotype identification in E. grylli-infected grasshoppers collected at the release sites in 1992, 1993, and 1994. In 1992, up to 23% of E. grylli-infected grasshoppers of the subfamilies Melanoplinae, Oedipodinae, and Gomphocerinae were infected by pathotype 3, with no infections > 1 km from the release sites. In 1993, pathotype 3 infections declined to 1.7%. In 1994 grasshopper populations were low and no pathotype 3 infections were found. The frequency of pathotype 3 infection has declined to levels where its long-term survival in North America is questionable. Analyses of biocontrol releases are critical to evaluating the environmental risks associated with these ecological manipulations, and molecular probes are powerful tools for monitoring biocontrol releases.

Efeitos dos agrotóxicos Kraft®36EC e Score®250EC (e seus princípios ativos) em ecossistemas aquáticos: análises comparativas e ecossistêmicas

Com o advento da agricultura ampliou-se a produção alimentar e os bens de consumo, no entanto, os riscos ambientais também foram maximizados em função da adoção de técnicas produtivas baseadas no uso intensivo de insumos agrícolas. Esta problemática é mundial, embora mais evidenciada nos países em desenvolvimento e que tem, na produção agrícola, a base de sua economia. O Brasil enquadra-se nesta situação e desde 2009 é considerado o maior consumidor de agrotóxicos do mundo, criando um cenário de risco ambiental e de saúde humana. Os efeitos ambientais, base deste estudo, estão relacionados não somente à perda de espécies não-alvo, uma vez que os agrotóxicos não são seletivos, mas também as alterações em nível ecossistêmico, a qual se relaciona com as perdas das funções e dos serviços gerados pelos sistemas naturais. Adiciona-se a esta complexidade, a forma de ação de cada agrotóxico, a distribuição dos mesmos nos diferentes compartimentos (ar, solo e água), o período de permanência de cada um, as relações sinérgicas decorrentes das interações entre diferentes produtos, a formação de subprodutos no processo de degradação, entre outros fatores, como as diferenças existentes entre o ingrediente ativo e a formulação comercial, na qual existem os chamados ingredientes inertes em sua composição, os quais podem ser muito mais tóxicos para espécies e ecossistemas. Considerando esta abordagem, a presente pesquisa foi desenvolvida com base na realidade de um local de referência, o município de Bom Repouso (MG/BR), no qual a intensificação da produção de morango e batata tem trazido uma série de riscos sociais e ambientais. Semelhante a outras regiões produtivas do país, o uso de agrotóxicos é recorrente, amplo e irrestrito, com destaque para as formulações comerciais Kraft®36EC e Score®250EC, as quais, juntamente com seus respectivos ingredientes ativos (abamectina e difenoconazol), foram avaliadas por meio de testes de toxicidade com espécies de diferentes níveis tróficos representativas de um ecossistema aquático, gerando informações que foram avaliadas em nível de espécie e de ecossistema, simulando o cenário de aplicação dos produtos no local de referência. Os resultados obtidos permitiram concluir sobre as diferenças de sensibilidade das espécies e quais seriam as mais indicadas para se avaliar os efeitos tóxicos de ambos os agrotóxicos; os efeitos diferenciados entre a formulação comercial e os ingredientes ativos; bem como as respostas em termos de espécies e de ecossistemas, demonstrando a necessidade de que ambas as análises sejam consideradas na avaliação de risco ecológico.

Riesgos medioambientales en los espacios informativos: análisis cualitativo de la televisión española

Dada la influencia fundamental de los medios de comunicación en la difusión de amenazas y riesgos, nuestro objetivo es analizar el discurso mediático en torno a un riesgo en particular: el medioambiental. A partir de una muestra de 84 programas informativos emitidos en las tres cadenas de televisión españolas con mayores índices de audiencia a nivel nacional, se ha localizado y analizado un total de 138 noticias, todas ellas relativas al medio ambiente y la naturaleza. La información recogida ha sido codificada y clasificada de acuerdo a cuatro temáticas: causas, consecuencias, soluciones y referencias a problemas medioambientales. En términos generales, las noticias tienden a centrarse en eventos concretos y a mostrar preferencia por contenidos emocionales, de entretenimiento o anecdóticos, frente a explicaciones en torno a soluciones, consecuencias y, sobre todo, causas de los problemas medioambientales.

Analysis of the Brominated Dioxin and Furan Emission Congener Pattern from Different Sources

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) have been studied for several decades and are well-known as unintentionally generated persistent organic pollutants (POPs), which pose serious health and environmental risks on a global scale1. Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/F) have similar properties and effects to PCDD/F, as they are structural analogs with all the chlorine atoms substituted by bromine atoms. PBDD/F have been found in various matrices such as air, sediments, marine products, and human adipose samples.

Landfill Leachate Toxicity to Oncorhynchus mykiss (Rainbow Trout) at the Merrick Landfill

At the Merrick Landfill, located outside of North Bay (Ontario, CA), an investigation into the potential for an environmental impact to the Little Sturgeon River as a result of landfill leachate discharge was undertaken using toxicity testing using 96 hour acute lethality on Oncorhynchus mykiss (Rainbow Trout). Landfill leachate may present a risk to receiving environments as it is comprised of an array of chemicals including organics, ammonia, and metals. Testing was conducted in three phases, firstly testing was completed on site throughout an existing natural attenuation zone where the presence of several groundwater seeps down gradient of the site had been identified to determine the effectiveness of the existing leachate control features at reducing the environmental risks. These tests indicated that the existing capture strategies were largely effective at reducing toxicity risks to the receiving environment. Testing was also completed on two pilot-scale hybrid-passive treatment systems to determine their effectiveness for leachate treatment. Summer performance of a constructed gravel wetland system was also shown to be effective at reducing the toxicity of the landfill leachate at the site. Lastly in order to support evaluation of leachate treatment requirements, a toxicity identification evaluation (TIE) was performed to determine the principle cause of toxicity within the leachate. Based on water chemistry analyses of samples collected at various locations at the site, the TIE identified ammonia toxicity as the primary source of toxicity in the leachate, with a secondary focus on metal toxicity.

Characterization and Degradation of Fatty Acid Methyl Esters and Biodiesel in Artificial Seawater Under UV Exposure Using Raman Spectroscopy

Thesis (Master's)--University of Washington, 2016-06

Flood risk analysis of the White Oak Creek watershed in Oak Ridge, Tennessee using MIKE SHE and MIKE 11 software

The purpose of this study was to determine the flooding potential of contaminated areas within the White Oak Creek watershed in the Oak Ridge Reservation in Tennessee. The watershed was analyzed with an integrated surface and subsurface numerical model based on MIKE SHE/MIKE 11 software. The model was calibrated and validated using five decades of historical data. A series of simulations were conducted to determine the watershed response to 25 year, 100 year and 500 year precipitation forecasts; flooding maps were generated for those events. Predicted flood events were compared to Log Pearson III flood flow frequency values for validation. This investigation also provides an improved understanding of the water fluxes between the surface and subsurface subdomains as they affect flood frequencies. In sum, this study presents crucial information to further assess the environmental risks of potential mobilization of contaminants of concern during extreme precipitation events.

A busca por uma política nacional dos biocombustíveis como tutela do direito fundamental ao meio ambiente : acautelamento e avaliação de riscos

The work is to demonstrate the scope of modern-day major regulatory provisions and the policies implemented to adoption of biofuels in the national energy matrix. The adoption of biofuels as an alternative to fossil fuels, is based on the realization of the fundamental right to an ecologically balanced environment mitigating hazards and environmental hazards arising from a postmodern society. However, the change in the Brazilian energy matrix observe the precepts of certain environmental principles to essentially environmental preservation The proposed Environmental rule of law is founded on the realization of the right (duty) key to an ecologically balanced environment for sustainable development. Thus, it is up to the State, in addition to considering the dangers and risks fruits of government decisions, present the possible instruments to mitigate the irreversible environmental damage to the environment. The management of environmental risks present in the ideals of an Environmental rule of law, plays an important role in the preservation and economic development, using, therefore, of acautelatórios legal instruments, such as environmental licensing and the ecological-economic zoning, measures adopted in the light of the principles of precaution and preservation. The adoption of research in the environmental field, improvement and development of environmental technology, building a system to observe ecological changes, imposition of environmental policy objectives to be achieved in the medium and long term and systematization of organizations plan a protection policy environmental, are essential measures to control possible environmental risks and damage guided by the aforementioned environmental principles. Thus, it will be used the inductive method of approach, starting from the analysis of the new perspective of Environmental rule of law and the implementation of biofuels in the context of a post-modern society, marked by uncertainty and the risk of damage, from the study of the principles of caution, maintaining and cautionary measures in mitigating the hazards and potential risks.

Effects of Natural Organic Matter on the Dissolution Kinetics and Bioavailability of Metal Oxide Nanoparticles

The rapid development of nanotechnology and wider applications of engineered nanomaterials (ENMs) in the last few decades have generated concerns regarding their environmental and health risks. After release into the environment, ENMs undergo aggregation, transformation, and, for metal-based nanomaterials, dissolution processes, which together determine their fate, bioavailability and toxicity to living organisms in the ecosystems. The rates of these processes are dependent on nanomaterial characteristics as well as complex environmental factors, including natural organic matter (NOM). As a ubiquitous component of aquatic systems, NOM plays a key role in the aggregation, dissolution and transformation of metal-based nanomaterials and colloids in aquatic environments.

The goal of this dissertation work is to investigate how NOM fractions with different chemical and molecular properties affect the dissolution kinetics of metal oxide ENMs, such as zinc oxide (ZnO) and copper oxide (CuO) nanoparticles (NPs), and consequently their bioavailability to aquatic vertebrate, with Gulf killifish (Fundulus grandis) embryos as model organisms.

ZnO NPs are known to dissolve at relatively fast rates, and the rate of dissolution is influenced by water chemistry, including the presence of Zn-chelating ligands. A challenge, however, remains in quantifying the dissolution of ZnO NPs, particularly for time scales that are short enough to determine rates. This dissertation assessed the application of anodic stripping voltammetry (ASV) with a hanging mercury drop electrode to directly measure the concentration of dissolved Zn in ZnO NP suspensions, without separation of the ZnO NPs from the aqueous phase. Dissolved zinc concentration measured by ASV ([Zn]ASV) was compared with that measured by inductively coupled plasma mass spectrometry (ICP-MS) after ultracentrifugation ([Zn]ICP-MS), for four types of ZnO NPs with different coatings and primary particle diameters. For small ZnO NPs (4-5 nm), [Zn]ASV was 20% higher than [Zn]ICP-MS, suggesting that these small NPs contributed to the voltammetric measurement. For larger ZnO NPs (approximately 20 nm), [Zn]ASV was (79±19)% of [Zn]ICP-MS, despite the high concentrations of ZnO NPs in suspension, suggesting that ASV can be used to accurately measure the dissolution kinetics of ZnO NPs of this primary particle size.

Using the ASV technique to directly measure dissolved zinc concentration, we examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg-C L-1) for Suwannee River humic acid (SRHA), Suwannee River fulvic acid and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. NOM isolates with higher SUVA were also more effective at enhancing the colloidal stability of the NPs; however, the NOM-promoted dissolution was likely due to enhanced interactions between surface metal ions and NOM rather than smaller aggregate size.

Based on the above results, we designed experiments to quantitatively link the dissolution kinetics and bioavailability of CuO NPs to Gulf killifish embryos under the influence of NOM. The CuO NPs dissolved to varying degrees and at different rates in diluted 5‰ artificial seawater buffered to different pH (6.3-7.5), with or without selected NOM isolates at various concentrations (0.1-10 mg-C L-1). NOM isolates with higher SUVA and aromatic carbon content (such as SRHA) were more effective at promoting the dissolution of CuO NPs, as with ZnO NPs, especially at higher NOM concentrations. On the other hand, the presence of NOM decreased the bioavailability of dissolved Cu ions, with the uptake rate constant negatively correlated to dissolved organic carbon concentration ([DOC]) multiplied by SUVA, a combined parameter indicative of aromatic carbon concentration in the media. When the embryos were exposed to CuO NP suspension, changes in their Cu content were due to the uptake of both dissolved Cu ions and nanoparticulate CuO. The uptake rate constant of nanoparticulate CuO was also negatively correlated to [DOC]×SUVA, in a fashion roughly proportional to changes in dissolved Cu uptake rate constant. Thus, the ratio of uptake rate constants from dissolved Cu and nanoparticulate CuO (ranging from 12 to 22, on average 17±4) were insensitive to NOM type or concentration. Instead, the relative contributions of these two Cu forms were largely determined by the percentage of CuO NP that was dissolved.

Overall, this dissertation elucidated the important role that dissolved NOM plays in affecting the environmental fate and bioavailability of soluble metal-based nanomaterials. This dissertation work identified aromatic carbon content and its indicator SUVA as key NOM properties that influence the dissolution, aggregation and biouptake kinetics of metal oxide NPs and highlighted dissolution rate as a useful functional assay for assessing the relative contributions of dissolved and nanoparticulate forms to metal bioavailability. Findings of this dissertation work will be helpful for predicting the environmental risks of engineered nanomaterials.

Maternal-Fetal Attachment and Health Behaviors among Women with HIV/AIDS

Background: Mothers with HIV often face personal and environmental risks for poor maternal health behaviors and infant neglect, even when HIV transmission to the infant was prevented. Maternal-fetal attachment (MFA), the pre-birth relationship of a woman with her fetus, may be the precursor to maternal caregiving. Using the strengths perspective in social work, which embeds MFA within a socio-ecological conceptual framework, it is hypothesized that high levels of maternal-fetal attachment may protect mothers and infants against poor maternal health behaviors. Objective: To assess whether MFA together with history of substance use, living marital status, planned pregnancy status, and timing of HIV diagnosis predict three desirable maternal health behaviors (pregnancy care, adherence to prenatal antiretroviral therapy–ART, and infant’s screening clinic care) among pregnant women with HIV/AIDS. Method: Prospective observation and hypothesis-testing multivariate analyses. Over 17 consecutive months, all eligible English- or Spanish-speaking pregnant women with HIV ( n = 110) were approached in the principal obstetric and screening clinics in Miami-Dade County, Florida at 24 weeks’ gestation; 82 agreed to enroll. During three data collection periods from enrollment until 16 weeks after childbirth (range: 16 to 32 weeks), participants reported on socio-demographic and predictor variables, MFA, and pregnancy care. Measures of adherence to ART and infant care were extracted from medical records. Findings: Sociodemographic, pregnancy, and HIV disease characteristics in this sample suggest changes in the makeup of HIV-infected pregnant women parallel to the evolution of the HIV epidemic in the USA over the past two decades. The MFA model predicted maternal health behaviors for pregnancy care (R2 = .37), with MFA, marital living status, and planned pregnancy status independently contributing ( = .50, = .28, = .23, respectively). It did not predict adherence to ART medication or infant care. Relevance: These findings provide the first focused evidence of the protective role of MFA against poor maternal health behaviors among pregnant women with HIV, in the presence of adverse life circumstances. Social desirability biases in some self-report measures may limit the findings. Suggestions are made for orienting future inquiry on maternal health behaviors during childbirth toward relationship and protection.