Thesis (M.S.)--Bowling Green State University, 2009. / Document formatted into pages; contains vii, 44 p. : ill. Includes bibliographical references.

Thesis (Ph. D.)--Carleton University, 2000. / Also available in electronic format on the Internet.

Thesis (doctoral)--University of Lund, 1983. / Spine title: Transport routes of PCBs in aquatic ecosystems. Sponsoring organization: National Swedish Environmental Protection Board. Includes bibliographical references.

Thesis (Ph. D.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains xiv, 235 p. : ill. (some col.), maps. Vita. Includes abstract. Includes bibliographical references.

In the transition to a sustainable energy supply there is an increasing need to use biomass for replacement of fossil fuel. A key challenge is to utilize biomass conversion technologies in an environmentally sound manner. Important aspects are to minimize potential formation of persistent organic pollutants (POPs) such as dioxins and dioxin-like compounds. This thesis involves studies of formation characteristics of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs) in microwave-assisted pyrolysis (MAP) and torrefaction using biomass as feedstock. The research focuses are on their levels, distributions, fingerprints (homologue profiles and isomer patterns) and the underlying formation pathways. The study also included efforts to optimize methods for extracting chlorinated aromatic compounds from thermally treated biomass. The overall objective was to contribute better understanding on the formation of dioxins and dioxin-like compounds in low temperature thermal processes. The main findings include the following: Pressurized liquid extraction (PLE) is applicable for simultaneous extraction of PCDDs, PCDFs, PCNs, polychlorinated phenols and benzenes from thermally treated wood. The choice of solvent for PLE is critical, and the extraction efficiency depends on the degrees of biomass carbonization. In MAP experiments PCDDs, PCDFs and PCNs were predominantly found in pyrolysis oils, while in torrefaction experiments they were mainly retained in solid chars with minor fractions in volatiles. In both cases, highly chlorinated congeners with low volatility tended to retain on particles whereas the less chlorinated congeners tended to volatize into the gas phase. Isomer patterns of PCDDs, PCDFs and PCNs generated in MAP were more selective than those reported in combustion processes. The presence of isomers with low thermodynamic stability suggests that the pathway of POPs formation in MAP may be governed not only by thermodynamic stabilities but also by kinetic factors. Formation of PCDDs, PCDFs and PCNs depends not only on the chlorine contents in biomass but also the presence of metal catalysts and organic/metal-based preservatives. Overall, the results provide information on the formation characteristics of PCDDs, PCDFs and PCNs in MAP and torrefaction. The obtained knowledge is useful regarding management and utilization of thermally treated biomass with minimum environmental impact.

Photolysis utilises short wavelength ultraviolet radiation to excite and cleave the carbon-chlorine bond of PCBs, yielding less chlorinated PCBs and ultimately biphenyl which can serve as energy and carbon source of various bacteria. Thus integration of photolysis and biodegradation can be a feasible remediation for PCB contamination. / Polychlorinated biphenyls (PCBs) are ubiquitous environmental pollutants once used as industrial fluids (in hydraulic systems, gas turbines), dielectric fluids (capacitors, transformers), plasticizer (adhesives, textiles, sealants, copy paper), and heat exchangers due to their inertness as well as thermal and electrical insularity. However, they are found to be neurotoxic, immunosuppressive, hepatotoxic, and the USEPA classified PCBs as probable human carcinogens. Although the production of PCBs was banned by the US Congress in 1976, they persist in the environment because of their resistance. Upon entering the marine environment, PCBs will associate with particulates and ultimately with sediment due to their hydrophobic nature and thus sediment become a sink for PCBs. This exerts a threat to marine organisms and human who consume seafood. / The major sink of PCBs in the environment is marine sediment, and the presence of sediment particles as well as other sorbed chemicals may inhibit both photolysis and biodegradation. This study extracts PCBs from sediment and further purify them by various cleanups to prevent the effect of these materials on the efficiency of treatment. / Using 2,4,4'-trichlorobiphenyl (PCB 28), 2,2',5,5'-tetrachlorobiphenyl (PCB 52), 2,2',4,5,5'-pentachlorobiphenyl (PCB 101), 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153) and 2,2',3,4,4',5,5'-heptachlorobiphenyl (PCB 180) as model compounds, optimal UV intensity, reaction time, as well as reaction solvent were found to be dependent on the congeners used. While PCB 28 was highly reactive and PCB 101, PCB 153 and PCB 180 were comparatively easy to remove, PCB 52 showed high resistance towards photolysis. The photolysis of PCB mixture containing these five congeners with each of them in 1 mg/L was also being optimised. After optimisation, the reaction intermediates and products were identified by gas chromatography coupling mass spectrometry (GC-MS). Less chlorinated congeners and biphenyl were found, indicating stepwise dechlorination of PCB is the major pathway. (Abstract shortened by UMI.) / by Wong Kin Hang. / "August 2005." / Adviser: P. K. Wong. / Source: Dissertation Abstracts International, Volume: 67-01, Section: B, page: 0159. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (p. 111-140). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

No description available.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

While much is known about the toxicity of polychlorinated biphenyls (PCBs), there are tens of thousands of natural and synthetic chemicals in the environment that can activate the aryl hydrocarbon receptor (AhR) and thus cause toxicity. Since it would be difficult to conduct studies of the toxicity of each and every compound, here is presented a new model based on first-principles taking into account the basic electronic and electron trans- fer characteristics of PCBs, but can be used to predict the toxicities of other AhR-active compounds. The predictive model is based on Density Functional Theory. The model predicts that the energy gap between highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbitals is the overarching indicator of toxicity of PCBs, but not the only factor. The model explains why chlorination of both para-positions is required for maximum toxic potency. To rank potency of PCBs, the dipole moment in relation to the most chemically active chlorine-sites is critical. The theory is consistent with the accepted toxic equivalency factor (TEF) model for these molecules and is also able to improve on ranking toxic potency of PCBs with similar TEFs. This new model also includes a 13th dioxin-like PCB, PCB 74, not considered in the current TEF model developed by the World Health Organization (WHO). The model was applied to HOMO-LUMO gap mea- surements of a set of PCBs and the measurements are consistent with the model. Values of HOMO-LUMO gap can also be used to predict bio-accumulation of PCBs. The model provides an in silico method to screen a wide range of chemicals to predict their ability to act as an AhR agonist.

by Wong Kin-hang. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 99-127). / Text in English; abstracts in English and Chinese. / by Wong Kin-hang. / Acknowledgements --- p.i / Abstracts --- p.ii / Contents --- p.vi / List of Figures --- p.ix / List of Tables --- p.x / Abbreviations --- p.xi / Chemical Equations --- p.xii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Poly chlorinated biphenyls --- p.1 / Chapter 1.1.1 --- Characteristics of polychlorinated biphenyls (PCBs) --- p.1 / Chapter 1.1.2 --- Use of polychlorinated biphenyls --- p.3 / Chapter 1.1.3 --- World-wide production of polychlorinated biphenyls --- p.7 / Chapter 1.1.4 --- Polychlorinated biphenyls in the environment --- p.8 / Chapter 1.1.5 --- Toxicity of polychlorinated biphenyls --- p.12 / Chapter I. --- Mechanism --- p.12 / Chapter II. --- Toxicity towards plant and animals --- p.13 / Chapter III. --- Toxicity towards human --- p.14 / Chapter IV. --- Enzymatic induction by PCBs --- p.14 / Chapter V. --- Carcinogenicity of PCBs --- p.18 / Chapter 1.2 --- Treatments of pollutant --- p.19 / Chapter 1.2.1 --- Physical treatment --- p.19 / Chapter 1.2.2 --- Chemical treatment --- p.20 / Chapter 1.2.3 --- Biological treatment --- p.22 / Chapter 1.2.4 --- Photocatalytic oxidation (PCO) --- p.25 / Chapter Chapter 2 --- Objectives --- p.35 / Chapter Chapter 3 --- Materials and methods --- p.36 / Chapter 3.1 --- Chemical reagents --- p.36 / Chapter 3.2 --- Photocatalytic oxidation reactor --- p.36 / Chapter 3.3 --- Separation and determination of eight PCB congeners --- p.39 / Chapter 3.4 --- Determination of tetra-CB concentration --- p.40 / Chapter 3.5 --- Determination of PCO intermediates and products --- p.41 / Chapter 3.6 --- Optimisation of reaction conditions for UV-PCO in batch system --- p.44 / Chapter 3.6.1 --- Control experiments and effect of initial titanium dioxide concentration --- p.44 / Chapter 3.6.2 --- Effect of initial hydrogen dioxide concentration and UV intensity --- p.44 / Chapter 3.6.3 --- Effect of initial titanium dioxide concentration and initial pH --- p.45 / Chapter 3.7 --- Estimation of tetra-CB degradation pathway by photocatalytic oxidation --- p.45 / Chapter 3.8 --- Evaluation for the toxicity of hydrogen peroxide and toxicity change of tetra-CB during PCO by Microtox® test --- p.45 / Chapter 3.9 --- Determination of H202 concentration after PCO --- p.47 / Chapter Chapter 4 --- Results --- p.50 / Chapter 4.1 --- Separation and determination of eight PCB congeners --- p.50 / Chapter 4.2 --- Photocatalytic oxidation of mono-CB --- p.50 / Chapter 4.3 --- Determination of tetra-CB --- p.55 / Chapter 4.4 --- Optimisation of reaction conditions for UV-PCO in batch system --- p.56 / Chapter 4.4.1 --- Control experiments and effects of initial titanium dioxide concentration --- p.56 / Chapter 4.4.2 --- Effect of initial hydrogen peroxide concentration and UV intensity --- p.56 / Chapter 4.4.3 --- Effect of initial titanium dioxide concentration and initial pH --- p.60 / Chapter 4.5 --- Estimation of tetra-CB degradation pathway by photocatalytic oxidation --- p.71 / Chapter 4.6 --- Evaluation for the toxicity of hydrogen peroxide and toxicity change of tetra-CB by Microtox® test --- p.72 / Chapter 4.7 --- Determination of H202 concentration after PCO --- p.72 / Chapter Chapter 5 --- Discussion --- p.89 / Chapter 5.1 --- Separation and determination of eight PCB congeners --- p.89 / Chapter 5.2 --- Photocatalytic oxidation of mono-CB --- p.89 / Chapter 5.3 --- Determination of tetra-CB --- p.90 / Chapter 5.4 --- Optimisation of reaction conditions for UV-PCO in batch system --- p.90 / Chapter 5.4.1 --- Control experiments and effects of initial titanium dioxide concentration --- p.91 / Chapter 5.4.2 --- Effect of initial hydrogen peroxide concentration and UV intensity --- p.91 / Chapter 5.4.3 --- Effect of initial titanium dioxide concentration and initial pH --- p.93 / Chapter 5.5 --- Estimation of tetra-CB degradation pathway by photocatalytic oxidation --- p.95 / Chapter 5.6 --- Evaluation for the toxicity of hydrogen peroxide and toxicity change of tetra-CB by Microtox® test --- p.96 / Chapter 5.7 --- Determination of H202 concentration after PCO --- p.97 / Chapter Chapter 6 --- Conclusions --- p.98 / Chapter Chapter 7 --- References --- p.99