The use of porous sorbents for physisorptive capture of CO2 from gas mixtures has been deemed attractive due to the low energy penalty associated with recycling of such materials. Porous organic polymers (POPs) have emerged as promising candidates with potential in the treatment of pre- and post- fuel combustion processes to separate CO2 from gas mixtures. Concurrently, significant advances have been made in establishing calculation methods that evaluate the practicality of porous sorbents for targeted gas separation applications. However, these methods rely on single gas adsorption isotherms without accounting for the dynamic gas mixtures encountered in real-life applications. To this end, the design and application of a dynamic gas mixture breakthrough apparatus to assess the CO2 separation performance of a new class of heteroatom (N and O) doped porous carbons derived from a Pyrazole precursor from flue gas mixtures is presented. Here in, two new benzimidazole linked polymers (BILPs) have been designed and synthesized. These polymers display high surface while their imidazole functionality and microporous nature resulted in high CO2 uptakes and isosteric heat of adsorption (Qst). BILP-30 displayed very good selectivity for CO2 in flue gas while BILP-31 was superior in CO­2 separation from landfill gas mixtures at 298 K and 1 bar. Additionally, a new POP incorporating a highly conjugated pyrene core into a polymer framework linked by azo-bonds is presented. Azo-Py displays a nanofibrous morphology induced by the π-π stacking of the electron rich pyrene core. Due to its high surface area and microporous nature, Azo-Py displays impressive CO2 uptakes at 298 K and 1 bar. Evaluation of the S value for CO2 separation of Azo-Py revealed competitive values for flue gas and landfill gas at 298 K and 1 bar. Finally, a highly cross-linked benzimidazole linked polymer, BILP-4, was successfully incorporated into Matrimid® polymer to form a series of new mixed matrix membranes. The surface functionality of BILP-4 was exploited to enhance the interaction with Matrimid® polymer matrix to produce robust MMMs which displayed significantly improved CO2 gas permeabilities and ideal selectivities for CO2/N2.

No description available.

Although gas and liquid chromatography have emerged as dominant separation techniques in environmental analytical chemistry, these methods do not allow for the concurrent analysis of chemically diverse groups of persistent organic pollutants (POPs). There are also a small number of compounds which are not easily amenable to either of these traditional separation techniques. The main objective of this thesis was to address these issues by demonstrating the applicability of packed column supercritical fluid chromatography (pSFC) coupled to mass spectrometry (MS) in various aspects of environmental chemistry. First, pSFC/MS analytical methods were developed for legacy POPs (PCDDs, PCDFs, and PCBs) as well as the emerging environmental contaminant Dechlorane Plus (DP), and issues relating to the ionization of target analytes when pSFC was coupled to MS were explored. Novel APPI and APCI reagents (fluorobenzene and triethylamine) were optimized and real samples (water and soil) were analyzed to demonstrate environmental applicability. The possibility of chiral and preparative scale pSFC separations was then demonstrated through the isolation and characterization of thermally labile hexabromocyclododecane (HBCDD) stereoisomers. The analytical pSFC separation of the α-, β-, and γ-HBCDD enantiomers as well as the δ and ε meso forms was shown to be superior to results obtained using a published LC method. Finally, technical mixtures of phosphorus flame retardants (RBDPP, BPA-BDPP, and DOPO; a group of related compounds which are challenging to analyze concurrently) were examined using multiple analytical techniques and pSFC was found to be the only method which facilitated the accurate determination of the components of all 3 mixtures. This thesis confirms the potential of pSFC/MS as a fast, green, and cost effective means of separating and analyzing environmental contaminants.

Human being, as an individual, is a basic element of social organization and plays different roles within different organizations such as family, school, and working setting. During the process of role-taking, individuals are influenced by three factors: personality traits, organization, and interpersonal relationship within working environment. Given that, the purpose of this study is to understand the association of personal, organizational and environmental factors and ¡§perceptions of organizational politics¡¨(POPs). 29 organizations participated in this study and , from which, 1524 valid respondents were collected and analyzed through methods of ¡§factor analysis¡¨, ¡§validity & reliability test¡¨, ¡§correlation analysis¡¨ and ¡§hierarchical regression¡¨. After applying ¡§factor analysis¡¨ of the POPs, it was categorized by three dimensions analysis: ¡§(1) behaviors of superior and subordinate; (2) go along and get ahead; (3) difference between the policies of compensation and promotion and actual practices. The results of this study in summary are: 1.Personal factor has effects on POPs with respect to all its three dimensions. 2.Organizational factor has effects on POPs with respect to all its three dimensions. 3.Environmental factor has effects on POPs with respect to all its three dimensions.

Made available in DSpace on 2016-06-02T19:02:42Z (GMT). No. of bitstreams: 1 5372.pdf: 2894679 bytes, checksum: 17d9851c1519bb9a5898a26910c5c936 (MD5) Previous issue date: 2013-08-14 / Financiadora de Estudos e Projetos / Environmental pollution has been a complex problem which generates a lot of ecological consequences. Among all chemicals produced by anthropic activity human, there isa wide range of organic compounds affecting on the environment and human health, which were grouped under the acronym POPs, Persistent Organic Pollutants. These compounds have been targeted at all conventions on the global environment. Bioremediation, phytoremediation and thermal treatment are techniques that have been tested in recent years and in many cases showed good results for decontamination matrices such as soil and water. Nanotechnology emerged in the recent years as an important tool for environmental purification and has been highly used by presenting itself as technological option for "green oxidation". Plants can also be considered as component of aggregation and transformation of organic compounds in their tissues and can also be applied in phytoremediation purposes both in vivo and in vitro models. This study developed a remediation method fully in vitro, in contrast to traditional methods in vivo. Two novel protocols were established by the development of in vitro culture: one for bamboo species Bambusa vulgaris var. vitatta and other for sunflower Helianthus annuus. L. The study of bioremediation effects of these species in vitros howed promising results for seventeen from twenty-four compounds evaluated using sunflower reaching until 87% for remediation. Moreover, it was possible to verify the nanostructured TiO2 toxicity to the studied species at different stages of development. The use of nanostructured TiO2 in the remediation of aqueous samples contaminated with POPs showed promising results in degradation of around 50% for most pollutants. This work suggests an interesting comparison of the potential of these techniques in environmental applications with respect to efficiency, practicality and toxicity especially focus in go remediation processes certainly due to its dynamic results can provide environmentally attractive and can even be used together. / A poluição ambiental é um problema capcioso com consequências ecológicas generalizadas. Entre todas as substâncias químicas produzidas, existe uma série de compostos orgânicos, de uso variado, que pelo conjunto de seus efeitos ao meio ambiente e à saúde humana, foram agrupados sob a sigla POPs, POLUENTES ORGÂNICOS PERSISTENTES, as quais têm sido alvo de discussões com diferentes ênfases em convenções mundiais sobre o meio ambiente. Técnicas como biorremediação, fitorremedição, tratamento térmico entre outras, vem sendo testadas nos últimos anos e em alguns casos demonstraram bons resultados de descontaminação das matrizes como solo e água, frente a diversos agentes poluidores. A nanotecnologia surge como uma importante ferramenta para remediação de matrizes ambientais e vem se destacando por se apresentar como uma tecnologia de oxidação verde . Plantas por sua vez também são elementos de agregação e transformação de compostos orgânicos em seus tecidos e podem também ser aplicadas em processos fitorremediativos in vivo ou como uma opção de estudo utilizando modelos in vitro. Este trabalho desenvolveu um método de remediação totalmente in vitro, em contraste aos tradicionais métodos in vivo. Para tanto, foi possível estabelecer dois protocolos inéditos para o desenvolvimento de cultura in vitro: um para espécie de bambu Bambusa vulgaris var. vitatta e outro para o girassol Helianthus annuus. L. O estudo dos efeitos biorremediativos dessasespécies mantidas in vitro apresentou resultados promissores para dezessete dos vinte e quatro compostos avaliados com o uso do girassol alcançando até 87 % de remediação. Além disso, foi possível constatar a toxicidade do TiO2 nanoestruturado para as espécies testadas, em diferentes estágios do desenvolvimento do vegetal. A utilização do TiO2 nanoestruturado na remediação de amostras aquosas contaminadas com POPs apresentou resultados promissores com degradação ao redor de 50 % para a maioria dos poluentes. Este estudo possibilitou uma comparação interessante sobre o potencial dessas técnicas em aplicações ambientais com relação à eficiência, praticidade e toxicidade especialmente focando-se nos processos de remediação que certamente devido a sua dinâmica tendem a propiciar resultados ecologicamente atraentes e que podem inclusive serem usados em conjunto.

Obesity is a worldwide problem affecting both children and adults. Genetic, physiological, environmental, psychological, social and economic factors interact in varying degrees, influencing body weight and fat distribution and the progress of obesity. Moreover, some anthropogenic chemicals have proven to be endocrine disrupting chemicals (EDCs) with the potential to interfere with different actions of hormones in the body. EDCs may thereby disrupt homeostasis, modifying developmental, behavioral and immune functions in humans and animals, and also promoting adiposity. Because hormones generally act at low concentrations, small changes in the endocrine system may lead to extensive effects. Based on data from experimental and epidemiological studies this thesis elucidates the relationship between a large number of environmental contaminants and obesity. The experimental studies demonstrated that fructose supplementation in the drinking water resulted in unfavorable metabolic alterations such as a higher liver somatic index (LSI), an increase in plasma triglycerides and increased plasma levels of apo A-I. Fructose in combination with exposure to bisphenol A (BPA) increased liver fat content and plasma levels of apo A-I in juvenile female Fischer 344 rats. The experimental studies also showed that the retro-peritoneal fat, which in rats is a distinct fat depot easy to distinguish and dissect, correlated well with the measurements of total fat mass analyzed with MRI, and could therefore be used as a substitute for total fat mass in rats. The epidemiological studies showed that circulating levels of persistent organic pollutants (POPs) were related to fat mass measured by DXA. OCDD, HCB, TNC, DDE and the less chlorinated PCBs were positively related to fat mass, while the more highly chlorinated PCBs showed a negative association. Further, circulating levels of BPA were positively associated with levels of the hormones adiponectin and leptin, but negatively related with ghrelin, hormones which are involved in the regulation of hunger and satiety. However, serum BPA levels were not related to measures of fat mass in the elderly individuals in the PIVUS cohort. This thesis concludes that environmental contaminants such as BPA and POPs most likely are contributors, along with genetic, social and behavioral factors, to the development of obesity.

Type 2 diabetes has reached epidemic proportions in adults and youths. Persistent organic pollutants and endocrine-disrupting chemicals (EDCs), such as pesticides, dioxins, and organochlorines, are omnipresent and persist in the environment with potential for human exposure via contaminated air, waterways, soil, and human food supply. EDCs have been correlated with diabetes incidence and risks. Residential proximity to hazardous waste sites (HWS) has been correlated with increased hospital admission rates for diabetes. The study used a sample population (N = 1,724), ages ≥ 12 years from the 2005-2012 Continuous NHANES and HWS data from the National Priorities List of Superfund Sites. The ecosocial theory of disease distribution, and geocoordinates provided theoretical support. Mann-Whitney U test and binary logistic regression analysis were used to investigate the relationship between residence ≤ 1 mile compared with residence >1 mile from a HWS in NHANES surveyed counties of NJ, PA, NY, and CA on the outcome abnormal A1c ≥ 5.7% while controlling the effect of the moderators: abnormal body mass index (BMI), age, sex, and race/ethnicity on the relationship. Participants with a BMI ≥ 28.95 kg/m2 were 1.8 times and persons ≥ 58 years of age were 2.1 times more likely to have an A1c ≥ 5.7%. Also, non-Hispanic Whites residing >1 mile of a HWS had 82.1 % reduced risk of abnormal A1c compared with the same group residing ≤ 1 mile of a HWS. The results forge opportunities for future studies to consider border distance between residence and HWS. In addition, the results may promote positive social change through diabetes risks education, environmental health education, and practices and raise dialogue about social justice and the geographic distribution of hazardous waste sites.

Associée à une enquête de surveillance de la qualité de milieux aquatiques, cette étude a comme objectifs la détermination du degré et des modalités de contamination par des POPs d'origine agricole (pesticides organochlorés) et industrielle (polychlorobiphényles) des réseaux trophiques aquatiques d'une aire protégée, la Réserve de Biosphère de Camargue. Les analyses des isotopes stables du carbone et de l'azote, chez 16 espèces dominantes d'animaux aquatiques, ont confirmé le haut niveau de complexité des relations alimentaires, mais aussi leur stabilité, par des contraintes liées aux fluctuations environnementales naturelles et anthropiques. Les contaminants recherchés ont été détectés à tous les niveaux trophiques. A l'aide de la méthode isotopique, une bioamplification a été mise en évidence pour les polluants les plus persistants (dieldrine, HCB) mais aussi pour l'Α endosulfan, dont le transfert trophique dépend de l'intensité de la contamination résultant de la biodisponibilité de la substance, elle-même liée à la saison. Pour les autres composés analysés, la voie d'accumulation directe à partir de l'eau semble être la voie principale et dominante en raison, entre autres, des caractéristiques particulières (faible profondeur) de l'étang de Vaccarès. Parallèlement, des biomarqueurs ont été validés in situ en relation avec l'emplacement trophique et la structure du réseau. Les indicateurs biochimiques évalués ont montré l'incohérence du principe d'un « biomarqueur universel ».

En la present tesi doctoral s’han estudiat diversos mètodes per a l’eliminació de contaminants orgànics persistents en olis de peix amb finalitat alimentària. S’han posat al punt les metodologies d’anàlisi necessàries per a la correcta determinació d’aquests compostos en la matriu d’estudi. S’han avaluat amb detall les etapes de purificació de la mostra, fraccionament dels analits i anàlisi instrumental. El mètode ha estat validat amb resultats satisfactoris, i s’ha comprovat el seu bon funcionament a través de la participació en diversos exercicis d’intercalibtage, així com la realització de diversos estudis amb mostres reals d’oli de peix. S’ha estudiat l’eliminació dels contaminants orgànics persistents a través d’adsorbents sòlids amb base silícica i carbonàcia. Les condicions experimentals han estat estudiades més a fons mitjançant dissenys d’experiències, per acabar optimitzant el mètode d’adsorció amb un disseny d’evolució. Els millors resultats s’han obtingut amb el carbó actiu, que mostra una elevada eficàcia en l’eliminació de PCDD/Fs, d-l PCBs i HCB. S’ha estudiat l’eliminació dels contaminants orgànics persistents mitjançant tècniques de degradació fotoquímiques. Inicialment s’ha fotodegradat cada família de contaminants per separat, per poder estudiar més a fons les condicions necessàries per la seva eliminació, així com els seus mecanismes i productes de degradació. Posteriorment s’ha estudiat la fotodegradació simultània dels analits d’interès en oli de peix. Aquesta tècnica s’ha mostrat efectiva en l’eliminació de DDT, PBDEs, HCB i PCBs similars a dioxines. Paral•lelament als estudis d’eliminació mitjançant adsorbents sòlids i tècniques fotoquímiques, s’ha comprovat la qualitat dels olis de peix abans i després del tractament. El procés d’adsorció en sòlids no afecta significativament a la qualitat de l’oli, mentre que les tècniques fotoquímiques degraden una part dels àcids grassos insaturats. S’ha estudiat l’eliminació de contaminants orgànics persistents en oli de peix mitjançant la combinació de les dues tècniques estudiades anteriorment, amb una primera etapa de degradació fotoquímica i una segona etapa d’adsorció. S’han comparat els resultats finals d’eliminació que s’obtenen amb cada un dels mètodes desenvolupats (adsorció, fotodegradació i combinat). L’adsorció en carbó actiu és el procés més adequat per l’eliminació de COPs en oli de peix. S’ha realitzat un estudi dels nivells diastereomèrics i enantiomèrics d’un contaminant emergent -l’hexabromociclododecà (HBCD)- en oli de peix. S’ha avaluat la seva eliminació de la matriu d’estudi mitjançant adsorbents amb base carbonàcia i degradació fotoquímica, sent principalment eliminat per aquesta segona via. / En la presente tesis doctoral se han estudiado diversos métodos para la eliminación de contaminantes orgánicos persistentes en aceites de pescado con finalidad alimentaria. Se han desarrollado los métodos de análisis necesarios para la correcta determinación de estos compuestos en la matriz de estudio. Se han evaluado con detalle las etapas de purificación de la muestra, fraccionamiento de los analitos y análisis instrumental. El método ha sido validado con resultados satisfactorios, y se ha comprobado su buen funcionamiento mediante ejercicios de intercalibraje, así como la realización de diversos estudios con muestras reales de aceite de pescado. Se ha estudiado la eliminación de los contaminantes persistentes mediante adsorbentes sólidos con base silícica y carbonacea. Las condiciones experimentales han estado estudiadas en profundidad mediante diseños de experiencias y de evolución. Los mejores resultados se han obtenido con carbón activo, que demuestra una elevada eficacia en la eliminación de PCDD/Fs, dl-PCBs y HCB. Se ha estudiado la eliminación de los contaminantes orgánicos persistentes mediante técnicas de degradación fotoquímica. Inicialmente se ha fotodegradado cada familia de contaminantes por separado, para poder estudiar más a fondo las condiciones necesarias para su eliminación. Posteriormente se ha estudiado la degradación simultánea de los analitos de interés en aceite de pescado. Esta técnica se ha mostrado efectiva en la eliminación de DDT, PBDEs, HCB y PCBs similares a dioxinas. Paralelamente a los estudios de eliminación mediante adsorbentes sólidos y técnicas fotoquímicas, se ha comprobado la calidad de los aceites de pescado antes y después del tratamiento. El proceso de adsorción en sólidos no afecta significativamente a la calidad del aceite, mientras que las técnicas fotoquímicas degradan una parte de los ácidos grasos insaturados. Se ha estudiado la eliminación de contaminantes orgánicos persistentes en aceites de pescado mediante la combinación de las dos técnicas estudiadas anteriormente, con una primera etapa de degradación fotoquímica y una segunda etapa de adsorción. Se han comparado los resultados finales de eliminación que se obtienen con cada uno de los métodos desarrollados. La adsorción en carbón activo es el proceso más adecuado para la eliminación de COPs en aceite de pescado. Se ha realizado un estudio de los niveles diastereoisoméricos y enantioméricos de un contaminante emergente –HBCD- en aceite de pescado. Se ha evaluado su capacidad de eliminación de la matriz de estudio mediante adsorbentes con base carbonacia y degradación fotoquímica, siendo principalmente eliminado por la segunda vía. / During the present doctoral thesis several methods for the elimination of persistent organic pollutants from fish oil have been studied. Analytical methodologies for the determination of these compounds in fish oil have been developed. Sample purification, fractionation of the analytes and instrumental determination steps have been deeply studied. The method has been validated with satisfactory results, and its performance has been verified through its participation in several intercalibration exercises and studies with real fish oil samples. Elimination of persistent organic pollutants with silicon and carbon-based adsorbents has been studied. The experimental conditions have been studied in depth with an experimental design, to finally optimize the adsorption method using an evolutionary design. Best results have been obtained with the active carbon, showing high efficiency of the removal of PCDD/Fs, dioxin-like PCBs and HCB. Elimination of persistent organic pollutants with photochemical degradation techniques has been studied. Initially, each family of pollutants has been photodegraded separately, to determine its degradation conditions, as well as degradation mechanisms and by-products. Later, simultaneous photodegradation of the analytes has been studied in fish oil. This technique has shown high efficiency on the degradation of DDT, PBDEs, HCB and dioxin-like PCBs. The quality of the oils before and after the treatments with solid adsorbents and photochemical degradation has also been studied. The adsorption process does not significantly affect the quality of the oils, while photochemical techniques can degrade the unsaturated fatty acids. Elimination of persistent organic pollutants in fish oil combining adsorption in solids and photochemical degradation has been studied. Results obtained with each of the developed methodologies (adsorption, photodegradation and combined method) were compared. Adsorption in active carbon is the most suitable process for COPs elimination in fish oil. Finally, diastereoisomeric and enantiomeric levels of an emerging pollutant –hexabromocyclododecane (HBCD)- in fish oil have been studied. Its elimination has been evaluated with carbon-based adsorbents and photochemical degradation, being mainly eliminated with the photodegradation techniques.

The purpose of this paper is to discuss and find the coincidental consequences of the organizational politics perception model by clustering organizational politics perception groups. This investigation uses the model proposed by Ferris et al. (1989) to study the relationships between the perceptions of organizational politics, organizational influences, work environment influences, personal influences, and study the relationships between the perceptions of organizational politics, job satisfaction, job stress, organizational commitment, work performance, job involvement, organization citizenship behavior, and exit intention. The sample consisted of 2559 employee selected from 36 organizations covering 9 industrial sectors in Taiwan. The data was analyzed by applying statistical methods, including factor, reliability, correlation, regression and multiple linear regression analysis. The different groups of perception of organizational politics were found to have been involved in the relationship between organizational influences and some personal influences. Also the different groups of perception of organizational politics were involved in the relationships between perceptions of organizational politics and employee¡¦s work performance, job involvement, job stress, organization citizenship, job satisfaction, and organizational commitment.