Previous studies demonstrated that coplanar PCBs promote inflammation by release of pro-inflammatory cytokines like TNF, MCP-1, and VCAM-1 from endothelial cells as well as adipocytes. Also these PCBs at small doses may contribute to the development of obesity by inducing adipocyte differentiation. Obesity is a known risk factor that promotes cardiovascular disorders like atherosclerosis and AAAs. Evidence shows Ang II, a component of the RAS, leads to the formation of atherosclerosis and AAAs in both normal as well as hyperlipidemic mice. Earlier studies in our laboratory have also shown that coplanar PCB-77 promotes atherosclerotic lesion formation in ApoE-/- mice. The purpose of this study was to define the effects of PCB77 on Ang II induced vascular diseases like atherosclerosis and AAAs. Two different hyperlipidemic mouse models, which require different diets to get atherosclerosis, the ApoE deficient mice (ApoE-/-) requiring the normal mouse diet (Chow diet) and the Low Density Lipoprotein Receptor deficient mice (LDLr-/-) requiring the Western diet, were used for this study as both are susceptible to Ang II induced vascular disorders. The timing of PCB administration was also studied in LDLr-/- mice to see the profound effects of PCB77 on atherosclerosis and AAAs.

Bifenilas Policloradas (PCB) são compostos orgânicos clorados altamente tóxicos e também são considerados poluentes orgânicos persistentes. Sua alta estabilidade térmica e química é responsável pela sua difícil degradação, e quando estas substâncias são liberadas no meio ambiente, sua acumulação nos ecossistemas incorpora-se na cadeia alimentar, exibindo biomagnificação. Deve-se ressaltar a importância para o meio ambiente do tratamento de resíduos com PCB. Considerando que a Convenção de Estocolmo sobre poluentes orgânicos persistentes (POP) estabeleceu a eliminação do uso de PCB em equipamentos, por exemplo, transformadores e capacitores elétricos, até 2025. O objetivo deste trabalho foi estudar a remoção de PCB pelos processos de extração usando fluido supercrítico e a extração convencional (Soxhlet) no tratamento de materiais contaminados com PCB. Assim foi desenvolvida uma ferramenta computacional para correlacionar os dados de solubilidade de PCB em CO₂ supercrítico, usando a equação de estado de Peng-Robinson com parâmetros ajustados. O procedimento de cálculo foi inicialmente usado para uma série de compostos aromáticos (naftaleno, antraceno, fenantreno e bifenil), a fim de testar a abordagem. Os parâmetros binários para a regra de mistura quadrática clássica (vdW2) foram sistematicamente estimados, juntamente com um novo conjunto de dados de pressão de vapor, a fim de descrever a dependência da temperatura e alcançar incertezas experimentais. Finalmente, foram utilizados os parâmetros estimados para simular valores de solubilidade dos principais congêneres constituintes das misturas comerciais reais de PCB, como função das condições de operação de extração com uma solução simultânea das equações de equilíbrio para cada composto. A modelagem termodinâmica demonstrou ser viável para a análise de processos. / Polychlorinated Biphenyls (PCB) are chlorinated organic compounds which are highly toxic and are also considered persistent organic pollutants. The high thermal and chemical stability of PCB are responsible for their hard degradation, and when these substances are liberated in the environment, their accumulation in ecosystems leads to their incorporation in the food chain, exhibiting biomagnification. It should be emphasized the environmental importance for treating wastes with PCB. Considering that, Stockholm Convention on persistent organic pollutants (POP) established the elimination of the use of PCB in equipments, e.g. electrical transformers and capacitors, by 2025. The objective of this work was to study the removal of PCB by the processes of extractions using supercritical fluid and conventional (Soxhlet) extraction method in the treatment of contaminated materials with PCB. As well was the formulation of a computational tool to correlate solubility data of PCB in supercritical CO₂, using Peng-Robinson equation of state with fitted parameters. The calculation procedure was initially used for a series of aromatic compounds (naphthalene, anthracene, phenanthrene and biphenyl) in order to test the approach. The binary parameters for the classical quadratic mixing rule (vdW2) were systematically estimated, together with a new set of vapor pressure in order to describe the temperature dependence and achieve experimental uncertainties. Finally, the estimated parameters were used to simulate solubility values of the major constituent congeners of commercial and real mixtures of PCB, as function of the operational conditions of extraction by a simultaneous solution of the equilibrium equations for each compound. The thermodynamic modeling demonstrated to be feasible for process analysis and design.

In work entitled CHANGE, I return in my memories to my home region, a town where I have lived and lived most of my life and which has been nicknamed the "Triangle of Death" for decades. This time period has had and continues to have a significant impact on my existence. In the first phase of the timeline of creating the topic of the diploma thesis, are my returns through induction and deduction. I approach my father's illness, which is not uncommon in my homeland. I connect connections leading to finding out the causes of origin and occurrence. Subsequently, I recall memories related to the stories heard from people about the factory, which was supposed to be and perhaps was the livelihood for the inhabitants of the poor eastern Slovakia, as well as the production of PCBs. I create, compile and depict images hidden in the memory of moments from my lived childhood. I depict the Chemko Strážske factory, which at that time was a kind of illusion of a happy life. I am looking for a way of acceptance and ways of reconciliation using painting techniques, through the representation of symbols and the central characters that represent it all.

No description available.

As technology advances, a need for non-metal, conductive materials has arisen for several types of applications. Lithographic techniques are helpful to develop some of these applications. Such techniques require materials that are insulating and become conductive after irradiated. Composites of polyaniline in its emeraldine base form (PANI-EB) doped with photo-acid generators (PAG) become conductive upon photo-irradiation. This increase in conductivity is due to the protonation of PANI-EB. Such materials may be utilized to fabricate conducting patterns by photo-irradiation; however, the conductivity obtained by direct irradiation of PANI-EB/PAG composites is normally quite low (<10-3 S/cm) due to aggregation of highly loaded PAG. In this work, poly(ethylene glycol) (PEG), a proton transfer polymer, was added to PANI-EB/PAG. Results showed the addition of low molecular weight (MW) (550) PEG significantly enhanced the photo-induced conductivity to a level comparable to that of PANI-salt synthesized by oxidizing aniline in the presence of an acid. High MW (8000) PEG is less effective than PEG 550, and composites of PANI-EB and N-PEG-PANI showed conductivity as high as 102 S/cm after treatment with HCl vapor. The photo-induced conductivity of the N-PEG-PANI/PANI-EB/PAG composite reached 10-2-10-1 S/cm. Polychlorinated biphenyls (PCBs) are a class of chemicals with 209 different congeners, some of which are known carcinogens, and are persistent organic pollutants in the environment. After its synthesis, it was seen as a phenomenal additive in a multitude of different applications leading to the wide spread use of PCBs and a need for a safe, effective, and inexpensive remediation technique. While it is known that magnesium can degrade PCBs, the mechanism of this reaction was not well-understood. In order for magnesium to be broadly used as a remediation tool, it is necessary to fully understand how the reaction is taking place and if the PCBs are able to be fully dechlorinated into biphenyl. This research focuses on the hydrodechlorination of PCBs with zero-valent magnesium in acidified ethanol. The degradation pathways of 2, 2', 3, 5, 5', 6- hexachlorobiphenyl were investigated to determine the identity of the daughter PCBs produced, how and if they continue to be dechlorinated into biphenyl. The proton source for this hydrodehalogenation reaction was also studied using both deuterated solvent and acid to give more detail to the mechanism of this reaction.

For centuries chemists have sought to improve humankind’s quality of life and address many of society’s most pressing needs through the development of chemical processes and synthesis of new compounds, often with phenomenal results. Unfortunately, there also are many examples where these chemicals have had unintended, detrimental consequences that are not apparent until years or decades after their initial use. There are numerous halogenated molecules in this category that are globally dispersed, resistant to natural degradation processes, bioaccumulative, and toxic to living organisms. Chemicals such as these are classified as persistent organic pollutants (POPs), and due to their negative environmental and health effects, they require safe, effective, and inexpensive means of remediation. This research focuses on the development and optimization of a reaction matrix capable of reductively dehalogenating several POPs. Initial experiments determined that powdered magnesium and 1% V/V acetic acid in absolute ethanol was the most effective system for degrading polychlorinated biphenyl (PCB), an extraordinarily recalcitrant environmental contaminant. Further studies showed that this matrix also was capable of degrading polychlorinated dibenzo-p-dioxins (PCDDs), polybrominated diphenyl ethers (PBDEs), and four organochlorine pesticides (OCPs); dieldrin, heptachlor, heptachlor epoxide, and chlordane. During this phase of testing, field samples contaminated with chlordane were washed with ethanol and this ethanol/chlordane solution was degraded using the same reaction matrix, thereby demonstrating this technology’s potential for “real-world” remediation projects. Finally, a set of experiments designed to provide some insight into the mechanism of dechlorination seems to indicate that two distinct processes are necessary for degradation to occur. First, the passivated iv outer layer of the magnesium must be removed in order to expose the zero-valent magnesium core. Next, an electron is transferred from the magnesium to the target molecule, causing the cleavage of the halide bond and the subsequent abstraction of either a hydrogen or proton from a solvent molecule. It is anticipated that an understanding of these fundamental chemical processes will allow this system to be tailored to a wide range of complex environmental media

No description available.

No description available.

This thesis describes the creation of RECOVERY-RD, a numerical model capable of representing the biotransformation processes associated with Polychlorinated Biphenyl (PCB) compounds in contaminated sediments for a variety of aquatic environments, including rivers and marine systems. RECOVERY-RD is intended as a screening tool for evaluating the impact of engineered sediment caps on contaminant remediation. The two key components that provided the framework for RECOVERY-RD are RECOVERY, a model for contaminant transport in stratified sediment, and SEAM3D, a numerical transport model for contaminated groundwater systems. The predictions made by RECOVERY-RD are verified using a series of test cases organized to test each phase of the modification process individually. The results show that the processes simulated by RECOVERY-RD are reasonably represented when compared to alternative calculation methods that have been previously verified. A hypothetical application of the initial version of the model provides evidence of the usefulness as a screening-level tool for the assessment of remedial efficacy. / Master of Science

Polychlorinated Biphenyls (PCBs) are persistent organic pollutants known for their toxicological effects. Though industrial production of legacy PCBs was banned in 1977, they can still be measured in nearly all environmental matrices. The Chicago Sanitary and Ship Canal (CSSC) is lined with industry and the receiving waters to the Stickney Water Reclamation Plant, the World's largest waste water treatment plant and was therefore speculated to be a potential source of PCBs to the Greater Chicago Area. Surficial sediment samples were acquired along a 45 km stretch of the CSSC, from Kedzie Ave. to Lockport. PCBs in the bulk sediment were extracted using accelerated solvent extraction while PCBs in the porewater were extracted using solid phase micro extraction. The PCBs were identified and quantified using a variation on EPA method 1668C. A total of 176 individual and coeluting PCBs were identified and quantified in this study. The sum of PCB concentrations in the bulk sediment was found to range from 70 to 4970 ng/g dry wt. The sum of PCB concentrations in the freely dissolved sediment-porewater was found to range from 2 to 366 ng/L. The bulk and porewater concentrations were used to estimate an average mass flow rate of PCBs through the CSSC of 368 kg/y. The large mass flow rate of PCBs passing through the CSSC and the fact that the CSSC connects Lake Michigan to the Mississippi River suggest that continued monitoring of PCB concentrations are necessary to better understand the transport and fate of PCBs in and out of the Great Chicago Area.