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Thesis (DTech (Environmental Health))--Cape Peninsula University of Technology, 2011. / This study was aimed to provide baseline information about the environmental levels of selected PBDEs (BDE 28, 47, 100, 99, 154, 153, 183 & 209) and BB 153 in different matrices, including wastewater treatment plants' effluent, sludge, landfill leachate, river water and bottom sediment samples from different locations within the City of Cape Town. The monitoring of these contaminants was carried out bi-monthly over an extended period of 12 months beginning from April 2010 to March 2011. In this study, a total of 63, 168, 312, 93 and 108 samples for leachate, wastewater treatment plant (WWTP) sludge, effluent, river water and bottom sediment, respectively were collected from three landfill sites, four WWTPs and two rivers within the City of Cape Town. The aqueous matrices were extracted using a liquid-liquid extraction technique. The extraction of both sediment and sludge samples were performed using mechanical shaking and soxhlet extraction techniques, respectively. Extract obtained were further purified using multi-layer silica gel column chromatographic technique. The routine analysis of these target compounds was carried out using a gas chromatograph equipped with an electron capture detector (GC-µECD). However, the structural elucidation of these compounds was performed with a gas chromatography-time of flight-mass spectrometry (GC-TOF-MS) instrument.

A new free radical chain process for the allylation of hydrocarbons and some other substrates utilizing substituted allyl bromides (R-H + C=C-C-Br -> R-C-C=C + HBr) has been developed. Good to excellent yields were observed in all cases. Kinetic chain measurements and competition experiments were performed in order to elucidate the mechanism of the reaction. Overall, the results are consistent with a free radical chain process with bromine atom as the chain carrier. Substitution effects on the reactivity of the allyl bromides (CH2=C(Z)CH2Br) and their influence on the overall reaction rate were studied by conducting several competition experiments. The relative rate constants for addition of benzyl radical to CH2=C(Z)CH2Br are: Z=CN(180), COOEt(110), Ph(65), H(1.0). The trend of electronegativity/reactivity of these reactions was very similar to that reported for addition of benzyl radical to substituted alkenes. Other than alkyl aromatics (PhCH3, PhCH(CH3)2), other substrates (i.e., 2- propanol, phenyl cyclopropane) were also tested for this allylation reaction. The magnitude and scope of these reactions, and their synthetic utility is discussed. / Ph. D.

This thesis describes the development of a relatively novel technique for the gen- eration and subsequent trapping of cold species. Molecules in a pulsed supersonic expansion are photolysed, such that the centre-of-mass velocity vector of one of the fragments is equal in magnitude but opposed in orientation to the lab-frame velocity of the precursor molecule. This technique, known as ‘Photostop’, leaves a fraction of the fragments with a narrow velocity distribution, centered around zero velocity in the lab-frame. They can be shown to have zero velocity by changing the time between photodissociation and ionisation; fragments with a high kinetic energy will leave the ionisation volume prior to interrogation. The underlying velocity distribu- tion is uncovered by using the velocity-map imaging technique, and the temperature of the fragments can be determined. The method was originally optimised for the molecular case. Cold NO has been produced from the dissociation of NO₂ molecules, and a single rotational state has been shown to remain in the ionisation volume 10 μs after dissociation, implying a sample temperature of 1.17 K. Using the optimised experimental conditions de- rived from the velocity cancellation of NO, the atomic case is demonstrated for the dissociation of Br₂ to give zero-velocity Br fragments. The Br atoms are seen for delay times in excess of 100 μs, showing the greater applicability of the method to the atomic case. The temperature of the residual atoms is shown to be in the milliKelvin regime, as determined through detailed Monte Carlo simulation of the motion of the stopped atoms. The possibility of trapping the ultracold Br atoms in a magnetic field is explored, and a quadrupolar trap created between two per- manent bar magnets is demonstrated to confine the atoms spatially, within the ion extraction optics, for delays in excess of 1 ms. The Photostop technique is intended to be a stepping stone on the way to widening the number of chemical species available for study in the ultracold regime. The possibility of improvements to the experiment is considered, in order to increase the efficiency of the experiment such that the number density becomes high enough to be viable as a source of atoms for use in cold chemical reactive studies. The possibility of extending the method so as to be used as a tunable velocity source of atoms is also discussed.

Ce travail s'inscrit dans le cadre d'un projet soutenu par la Région wallonne et a été réalisé en collaboration entre les unités de Chimie Organique et Médicinale (CHOM), de Chimie Structurale et des Mécanismes Réactionnels (CSTR), et de Chimie et Physique des Hauts Polymères (POLY). Il concerne la modification des propriétés du polypropylène (PP) isotactique par mise en œuvre réactive, et plus particulièrement le contrôle de sa cristallinité par l'action d'un composé bromé (N-bromosuccinimide) en présence d'un initiateur de radicaux libres à haute température (entre 180 et 260°C). L'objectif principal de cette étude est de parvenir à identifier et à contrôler les modifications induites au sein des produits, ce qui implique une compréhension fine des mécanismes chimiques intervenant lors de la mise en œuvre réactive du PP. Ces connaissances permettraient en outre de substituer la N-bromosuccinimide (qui génère des sous-produits toxiques et polluants) par un autre additif en vue d'une meilleure valorisation du procédé et des produits. La stratégie repose sur une double approche, basée d'une part sur une étude des divers paramètres qui influencent la réaction sur polymère, et d'autre part sur la synthèse d'un composé modèle du PP : le 2,4,6,8,10-pentaméthylundécane (PMU). Par extrusion réactive du polymère, nous avons obtenu des PP à cristallinité contrôlée (PPCC ; de semi-cristallin à amorphe), dont certains présentent un caractère élastomère marqué. Des études effectuées principalement par analyse thermique et par résonance magnétique nucléaire ont permis de corréler ces propriétés macroscopiques à une microstructure à stéréoblocs isotactiques/atactiques (épimérisation des carbones tertiaires du PP), combinée à la présence de branchements longs (recombinaison de macroradicaux). Par ailleurs, nous avons mis en évidence les différents paramètres susceptibles d'influencer la réaction d'épimérisation du PP. Bien que les informations découlant de ces études nous aient permis de proposer les principaux mécanismes qui entrent en jeu lors de la réaction, seule une étude sur composé modèle peut néanmoins donner accès aux méthodes d'analyses nécessaires à la confirmation de ces mécanismes. Nous avons par conséquent entrepris la synthèse d'un oligomère de propylène pour permettre cette étude sur composé modèle. La synthèse du PMU telle que rapportée dans la littérature s'est avérée plus difficile que prévu, principalement du fait d'un manque de reproductibilité au niveau de l'étape clé. Nous avons donc établi une voie de synthèse originale permettant l'obtention du PMU (mélange de stéréoisomères) avec un rendement global de 45% sur 7 étapes (à l'échelle de plusieurs grammes de produit). En outre, cette voie nous a donné accès au 6-hydroxyméthyl-2,4,8,10-tétraméthylundécane et au 6-p-toluènesulfonyloxyméthyl-2,4,8,10-tétraméthylundécane, pour lesquels des techniques chromatographiques ont permi une séparation des diastéréoisomères. La transposition de ces expériences à plus grande échelle permettra d'envisager l'obtention du (4R,6s,8S)-PMU, en vue de futures études mécanistiques relatives à l'épimérisation du PP de configuration initialement isotactique. / This work is part of a project supported by the Walloon Region, and it was performed in collaboration between the Chimie Organique et Médicinale (CHOM), Chimie Structurale et des Mécanismes Réactionnels (CSTR), and Chimie et Physique des Hauts Polymères (POLY) laboratories. Its object is the modification of the isotactic polypropylene (PP) properties by reactive processing, and more especially the control of PP crystallinity by means of a brominated additive (N-bromosuccinimide) in presence of a free radical initiator at high temperatures (between 180 and 260°C). The main objective of this study is to identify and to control the modifications induced in the products, which implies a fine understanding of the chemical mechanisms occuring during the PP reactive processing. This knowledge would allow us, subsequently, to substitute another additive for the N-bromosuccinimide (which yields toxic and polluting by-products), in order to achieve a better applicability of both the process and the products. The strategy relies on a double approach : on one side, on a study of the various parameters affecting the reaction on the polymer, and on the other side on the synthesis of a model compound of PP : 2,4,6,8,10-pentamethylundecane (PMU). By means of reactive extrusion of the polymer, we obtained controlled crystallinity PP's (from semi-crystalline to amorphous), including some with an elastomeric behaviour. Studies carried out mainly by thermal analysis and nuclear magnetic resonance allowed us to correlate these macroscopic properties to an isotactic/atactic stereoblock microstructure (epimerization of the PP tertiary carbons), combined with the presence of long chain branchings (recombination of macroradicals). Moreover, we highlighted the various parameters that are able to influence the yield of the epimerization reaction. Even if the informations arising from these studies allowed us to propose the main mechanisms involved in the PP modification, only a mechanistic study carried out on a model compound would give us access to the characterization methods required for the confirmation of these mechanisms. We undertook, subsequently, the synthesis of a propene oligomer. The PMU synthesis, as stated in the litterature, revealed itself more difficult than initially foreseen, mainly due to a lack of reproducibility concerning the key step. Therefore we established a new synthesis pathway for the PMU (as a mixture of stereoisomers) with a global yield of 45% over 7 steps (multigram scale). Moreover, this pathway gave us access to 6-hydroxymethyl-2,4,8,10-tetramethylundecane and 6-p-toluenesulfonyloxymethyl-2,4,8,10-tetramethylundecane, for which chromatographic techniques allowed a separation of the diastereoisomers. The transposition of these experiments on a larger scale would allow us to obtain the (4R,6s,8S)-PMU for future mechanistic studies relative to the epimerization reaction of initially isotactic PP.

Brominated organic compounds (BOCs) of both natural and anthropogenic origin are abundant in the environment. Most compounds are either clearly natural or clearly anthropogenic but some are of either mixed or uncertain origin. This thesis aims to identify some naturally produced BOCs and to develop a method for analysis of the bromine isotopic composition in BOCs found in the environment. Polybrominated dibenzo-p-dioxins (PBDDs) in the Baltic Sea are believed to be of natural origin although their source is unknown. Since marine sponges are major producers of brominated natural products in tropical waters, BOCs were quantified in a sponge (Ephydatia fluviatilis) from the Baltic Sea (Paper I). The results showed that the sponge does not seem to be a major producer of PBDDs in the Baltic Sea. In this study, mixed brominated/chlorinated dibenzo-p-dioxins were however discovered for the first time in a background environment without an apparent anthropogenic source. The use of nuclear magnetic resonance spectroscopy (NMR) is unusual in analytical environmental chemistry due to its sample requirements. Preparative capillary gas chromatography was used to isolate a sufficient amount of an unidentified BOC from northern bottlenose whale (Hyperoodon ampullatus) blubber (Paper II) to enable NMR analysis for identification of the compound. The bromine isotopic composition of BOCs may give information on the origin and environmental fate of these compounds. The first steps in this process are the development of a method to determine the bromine isotope ratio in environmentally relevant BOCs (Paper III) and measuring the bromine isotope ratio of several standard substances to establish an anthropogenic endpoint (Paper IV). / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

This dissertation attempts to extend the classes of halogen-containing systems which may be studied using solid-state nuclear magnetic resonance (SSNMR). As line shape broadening due to the quadrupolar interaction (QI) scales inversely with the applied field, high-field magnet technology is indispensable for this research. Combining advanced radiofrequency pulse sequences with high-field wideline data acquisition allowed for the collection of very broad SSNMR signals of all quadrupolar halogen nuclei (i.e., 35/37Cl, 79/81Br and 127I) within a reasonable amount of experimental time. The initial systems for study were of the MX2 variety (M = Mg, Ca, Sr, Ba; X = Cl, Br, I). In total, 9 anhydrous compounds were tested. The effects of hydrate formation were tested on 7 additional compounds. Systematic trends in the observed δiso values (and to a lesser extent, Ω and CQ) were found to be diagnostic of the extent of hydration in these materials. Resolving power was successfully tested using SrBr2, which possesses 4 magnetically unique sites. The composition of CaBr2•xH2O was convincingly determined using SSNMR data and the hydration trends noted above. The sensitivity of the QI to the local bonding environment (e.g., bond distance changes of less than 0.05 Å) was used to refine (when coupled with gauge-including projector augmented-wave density functional theory (GIPAW DFT) quantum chemical computations) the structure of MgBr2, and was used to correct prior NMR data for CaCl2 (earlier accounts had been performed upon a CaCl2 hydrate). During NMR data analysis of certain iodine-containing materials, it was found that standard fitting software (which uses perturbation theory) could not reproduce the observations. Proper analysis required the use of exact simulation software and allowed for the observation of high-order quadrupole-induced effects (HOQIE). This motivated further studies using rhenium-185/187 nuclei, where it was expected that HOQIE would be more dramatic. The observed rhenium SSNMR spectra possessed additional fine structure that had never been observed before experimentally, nor would be expected from currently-available perturbation theory analysis software. Lastly, preliminary results are shown where 127I SSNMR is used to study important supramolecular systems, and the composition of the popular synthetic reagent ‘GaI’ is elucidated.

This dissertation attempts to extend the classes of halogen-containing systems which may be studied using solid-state nuclear magnetic resonance (SSNMR). As line shape broadening due to the quadrupolar interaction (QI) scales inversely with the applied field, high-field magnet technology is indispensable for this research. Combining advanced radiofrequency pulse sequences with high-field wideline data acquisition allowed for the collection of very broad SSNMR signals of all quadrupolar halogen nuclei (i.e., 35/37Cl, 79/81Br and 127I) within a reasonable amount of experimental time. The initial systems for study were of the MX2 variety (M = Mg, Ca, Sr, Ba; X = Cl, Br, I). In total, 9 anhydrous compounds were tested. The effects of hydrate formation were tested on 7 additional compounds. Systematic trends in the observed δiso values (and to a lesser extent, Ω and CQ) were found to be diagnostic of the extent of hydration in these materials. Resolving power was successfully tested using SrBr2, which possesses 4 magnetically unique sites. The composition of CaBr2•xH2O was convincingly determined using SSNMR data and the hydration trends noted above. The sensitivity of the QI to the local bonding environment (e.g., bond distance changes of less than 0.05 Å) was used to refine (when coupled with gauge-including projector augmented-wave density functional theory (GIPAW DFT) quantum chemical computations) the structure of MgBr2, and was used to correct prior NMR data for CaCl2 (earlier accounts had been performed upon a CaCl2 hydrate). During NMR data analysis of certain iodine-containing materials, it was found that standard fitting software (which uses perturbation theory) could not reproduce the observations. Proper analysis required the use of exact simulation software and allowed for the observation of high-order quadrupole-induced effects (HOQIE). This motivated further studies using rhenium-185/187 nuclei, where it was expected that HOQIE would be more dramatic. The observed rhenium SSNMR spectra possessed additional fine structure that had never been observed before experimentally, nor would be expected from currently-available perturbation theory analysis software. Lastly, preliminary results are shown where 127I SSNMR is used to study important supramolecular systems, and the composition of the popular synthetic reagent ‘GaI’ is elucidated.

Numerous glacial advances over the past 2 million years have covered the entire Canadian and Fennoscandian Shield outcrop. During glacial advance and retreat, permafrost is expected to form in front of the glacier. The question of how permafrost and freezing impact the formation and evolution of brines in natural systems may be vital to understanding the chemistry of groundwater in crystalline rocks. Investigations of groundwater conditions beneath thick permafrost can provide valuable information that can be applied to assessing safety of deep, underground nuclear waste repositories and understanding analogues to potential life-bearing zones on Mars. However, very little scientific investigation of cryogenic processes and hydrogeology deep within crystalline systems has been published. The purpose of this research is to evaluate the impacts of thick permafrost (>300m) formation on groundwater chemical and flow system evolution in the crystalline rock environment over geologic timescales. A field investigation was conducted at the Lupin Mine in Nunavut, Canada, to characterize the physical and hydrogeochemical conditions within and beneath a thick permafrost layer. Taliks, or unfrozen channels within the permafrost, are found beneath large lakes in the field area, and provide potential hydraulic connections through the permafrost. Rock matrix waters are dilute and do not appear to affect groundwater salinity. Permafrost waters are Na-Cl and Na-Cl-SO4 type, and have been contaminated with chloride and nitrate by mining activities. Sulfide oxidation in the permafrost may be naturally occurring or is enhanced by mining activities. Basal permafrost waters (550 to 570 mbgs) are variably affected by mining. The less contaminated basal waters have medium sulfate concentrations and are Ca-Na dominated. This is similar to deeper, uncontaminated subpermafrost waters, which are Ca-Na-Cl or Na-Ca-Cl type with a wide range of salinities (2.6 to 40 g•L-1). The lower salinity subpermafrost waters are attributed to dissociation of methane hydrate and drawdown of dilute talik waters by the hydraulic gradient created by mine dewatering. This investigation was unable to determine the influence of talik waters to the subpermafrost zone in undisturbed conditions. Pressures are also highly variable, and do not correlate with salinity. Fracture infillings are scarce and calcite δ18O and δ13C values have a large range. Microthermometry indicates a large range in salinities and homogenization temperatures as well, indicative of a boiling system. In situ freezing of fluids and methane hydrate formation may have concentrated the remaining fluids. Field activities at the Lupin mine also provided an opportunity to study the nature of gases within crystalline rocks in a permafrost environment. Gases were generally methane-dominated (64 to 87), with methane δ13C and δ2H values varying between -56 and -42‰ VPDB and -349 to -181 ‰ VSMOW, respectively. The gases sampled within the Lupin mine have unique ranges of chemical and isotopic compositions compared with other Canadian and Fennoscandian Shield gases. The gases may be of thermogenic origin, mixed with some bacteriogenic gas. The generally low δ2H-CH4 ratios are somewhat problematic to this interpretation, but the geologic history of the site, a metaturbidite sequence, supports a thermogenic gas origin. The presence of gas hydrate in the rock surrounding Lupin was inferred, based on temperature measurements and hydrostatic pressures. Evidence also suggests fractures near the mine have been depressurized, likely due to mine de-watering, resulting in dissipation of methane hydrate near the mine. Modeling results indicate methane hydrates were stable throughout the Quaternary glacial-interglacial cycles, potentially limiting subglacial recharge. The effects of deep permafrost formation and dissipation during the Pleistocene glacial/interglacial cycle to deep groundwaters in the Canadian Shield were also investigated by compiling data from thirty-nine sites at twenty-four locations across the Canadian Shield. Impacts due to glacial meltwater recharge and surficial cryogenic concentration of fluids, which had been previously considered by others, and in situ freeze-out effects due to ice and/or methane hydrate formation were considered. At some Canadian Shield sites, there are indications that fresh, brackish, and saline groundwaters have been affected by one of these processes, but the data were not sufficient to differentiate between mixed, intruded glacial meltwaters, or residual waters resulting from either permafrost or methane hydrate formation. Physical and geochemical data do not support the cryogenic formation of Canadian Shield brines from seawater in glacial marginal troughs. The origin and evolution of Canadian and Fennoscandian Shield brines was explored with a survey of chlorine and bromine stable isotope ratios. The δ37Cl and δ81Br isotopic ratios varied between -0.78 ‰ and 1.52 ‰ (SMOC) and 0.01 ‰ and 1.52 ‰ (SMOB), respectively. Variability of chlorine and bromine isotope ratios decreases with increasing depth. Fennoscandian Shield groundwaters tend to be more enriched than Canadian Shield groundwaters for both 37Cl and 81Br. Other sources and processes which may affect δ37Cl and δ81Br composition are also explored. Primary processes such as magmatic and/or hydrothermal activity are thought to be responsible for the isotopic composition of the most concentrated fluids at each site. Positive correlations between δ81Br, and δ37Cl with δ2H-CH4 and δ13C-CH4 were noted. At this time the cause of the relationship is unclear, and may be a result of changing redox, pH, temperature, and/or pressure conditions during hydrothermal, metamorphic, or volcanogenic processes. The data suggest solute sources and fluid evolution at individual sites would be better constrained utilizing a multi-tracer investigation of δ37Cl, δ81Br, and 87Sr/86Sr ratios comparing fluids, rocks, and fracture filling minerals (including fluid inclusions).