A thesis submitted to the Faculty of Science, University of the Witwatersrand in fulfilment of the requirements for the degree of Doctor of Philosophy. November 2016. / This research was directed towards the environmental monitoring and assessment of the most used non-steroidal anti-inflammatory drugs (NSAIDs) which are naproxen, ibuprofen and diclofenac. The work involved the development and application of sensitive techniques for the quantification of naproxen, ibuprofen and diclofenac in the South African aquatic environment. Based on this information, a multi-templates molecularly imprinted polymer (MIP) was synthesized and applied alongside the commercial available sorbent (Oasis MAX) in the solid-phase extraction (SPE) of target compounds from water samples. The extracted compounds were then quantified using high performance liquid chromatography (HPLC). MIP was synthesized by applying a bulk polymerization approach at 70 ͦ C where all target compounds were used as multi-templates. Other reagents used in synthesis were 2-vinyl pyridine, 1,1’-azobis-(cyclohexanecarbonitrile), ethylene glycol dimethacrylate and toluene as functional monomer, initiator, cross-linker and porogenic solvent, respectively. Synthesis of a non-imprinted polymer (NIP) under similar reaction conditions as MIP was carried out with the omission of templates. Techniques employed in characterization of MIP and NIP were Fourier transform infrared spectroscopy (FTIR), Brunauer, Emmett and Teller (BET) method, CHNS analyzer, zeta potential, cross-polarization/magic angle spinning nuclear magnetic resonance spectroscopy, thermogravimetric analysis, differential scanning calorimetry and x-ray diffraction. Monomer-template interactions were investigated using molecular dynamics. The performance of the MIP was evaluated based on its ability to selectively extract target compounds in organic (acetonitrile, acetone, chloroform and toluene) and aqueous media. The extraction capacity of the MIP in organic solvents for naproxen, ibuprofen and diclofenac increased from high polarity to low polarity solvents. In a low polarity solvent (toluene), the extraction capacity achieved for naproxen, ibuprofen and diclofenac were 14.4, 11.0 and 14.0 mg/g, respectively. In this case, the selectivity of the MIP where gemfibrozil was employed as the competing species was evident. Selectivity of the MIP collapsed during the adsorption of naproxen, ibuprofen and diclofenac from water using gemfibrozil and fenoprofen as competitors. This resulted in high extraction efficiencies for target compounds and competitors, however, both gemfibrozil and fenoprofen were easily desorbed from the MIP using weak organic solvent due to lack of molecular recognition. During the binding sites characterization, the best fit of pseudo-second-order implied a chemisorption of all target compounds onto MIP sorbent. The data also fitted well in Langmuir isotherm which meant that the adsorption of target pharmaceuticals occurred on the homogeneous binding sites of the MIP. Optimized adsorption conditions in water such as MIP amount of 50 mg, extraction time of 10 min, sample pH of 2.5 and sample volume of 10 mL were applied for the selective adsorption of naproxen, ibuprofen and diclofenac in contaminated wastewater and river water. In WWTP influent, naproxen recovery was 38%, whereas ibuprofen and diclofenac were 69% and 87%, respectively. MIP was further used as a selective adsorbent in solid-phase extraction (SPE) of three drugs from environmental samples. The selectivity of the MIP in environmental samples was compared to that of the commercially available Oasis MAX sorbent. The application of molecularly imprinted solid-phase extraction (MISPE) reduced matrix effects and improved the sensitivity of the analytical method. In this case, the detection limits for naproxen, ibuprofen and diclofenac were 0.2, 1 and 0.6 μg/L, respectively. When deionized water was spiked with 5 and 50 μg/L of target compounds, recoveries greater than 80% were obtained. Thereafter, the developed MISPE was applied for selected acidic drugs from environmental samples. Environmental samples were collected from urban (Durban) and semi-urban/rural areas (Ladysmith) of KwaZulu-Natal Province in South Africa. The most abundant compound in the environment was ibuprofen. In river water samples from Durban, the maximum concentrations found for naproxen, ibuprofen and diclofenac were 6.8, 19 and 9.7 μg/L, respectively. The maximum amounts found for the same drugs in Ladysmith river samples were generally lower with naproxen, ibuprofen and diclofenac detected at 2.8, 6.7 and 2.6 μg/L, respectively. The same trend was observed in wastewater. Further work on the monitoring of acidic compounds in wastewater was conducted using Oasis MAX as the SPE sorbent prior to HPLC analysis. All target compounds were detected in Kingsburg and Umbilo WWTPs located in Durban surroundings. The influent and effluent concentrations detected were in the ranges of 6.4 to 69 μg/L and 0.6 to 4.2 μg/L, respectively. Further to this, the removal efficiency of the target compounds during the WWTP process in Kingsburg and Umbilo was in the range of 69 to 97%. The extent of pollution in the environment was further assessed by the monitoring of ketoprofen and triclosan in wastewater and river water using SPE with Oasis HLB sorbent and HPLC. Traces of both compounds ranging from 1.2 to 9.0 μg/L were detected in wastewater. The maximum concentrations found in river water were 2.0 and 0.9 μg/L for ketprofen and triclosan, respectively. Overall, the analytical methods implemented in this work were highly accurate, precise and sensitive. The synthesized MIP was highly selective and its application in environmental studies led to the development of a less expensive analytical method. This work also gives the overview of the extent of water pollution caused by acidic pharmaceuticals in various water matrices. / MT2017

本研究聚焦2009年到2013年，中國廣州的一場圍繞垃圾處理展開的社會運動。運動最初是當地居民動員起來反對市政府垃圾焚燒項目的鄰避抗爭。勝利後，運動領袖成立了一個環保組織，和政府從對抗走向合作，力圖推动焚燒技術以外的替代性垃圾治理方案。不過，儘管政府和環保者致力於解決垃圾，垃圾問題在消費社會中始終無法消除。本研究試圖理解後社會主義中國的綠色治理和環保行動之間的對抗與合作。 / 首先，我分析當代中國高速城市化和消費社會急速發展所帶來的垃圾危機。然后，我檢視圍繞垃圾焚燒技術的主要爭議，並描繪廣州居民是如何針對政府計劃中的垃圾焚燒項目做出抗爭的。我指出，他們結合地方性知識和科學話語，將自己建構為"常民專家"，對全球性的焚燒科技的"地方適用性"作出成功挑战。接下來，我提供一個民族誌，追溯抗議成功后運動的歷史軌跡。我注意到，通過成立一個環保組織"EC"，反焚運動走向合法化、組織化和制度化，抗爭被體制吸納，轉變為參與協助國家環境治理的運動。最後，我描繪EC與广州政府聯手推動的垃圾分類運動。指出，國家在此運動中的尷尬身份、以利潤為導向的回收市場影響、理想化的垃圾分類知識與普通民眾的知識存在斷裂，都使得推動垃圾分類異常艱難。 / 通過展示運動變遷與國家治理轉型相互交織的辯證关系，本研究挑戰了國家與社會的二元對立，指出在國家在治理轉型過程中不斷收編反抗的行動和話語，而於此同時反焚者又在不斷生產新的另類知識做出挑戰。此外，本研究還貢獻於對廢棄物的理解，將廢棄物視為是一個動態的範疇，國家、市場、科學技術、普通消費者、環保行動者等多個行動者共同生產、競爭、建構其意義。還有，本研究對於科技知識的普遍性的探討，對科學技術研究領域做出了貢獻。 / This is a study on social movements that focused on waste treatment in Guangzhou, China from 2009-2013. The campaign began as a NIMBY (Not-In-My-Backyard) movement that mobilized community residents to protest against municipal government's proposed incineration projects. After its success, the movement leaders changed their dissident role to form an environmental protection NGO, collaborating with the state to explore alternative waste treatment solutions other than incineration. However, despite of the politicians and activists' attempt to eliminate waste, waste continues to exist in tandem of our consumption spree. I endeavor to understand the contradiction as well as collusion between green governance and environmental activisms in post-socialist China. / Firstly, I analyze the garbage crisis caused by the rapid urbanization and the dramatic growth of consumer society in contemporary China. Then I examine a few major technological controversies of waste incineration and depict how the activists protest against the pro-incineration government. I argue that through deploying local knowledge, the activists, as "lay experts", successfully challenged the "local appropriateness" of the global technology of incineration. Next, I provide an in-depth ethnography of the transformation of this campaign after its initial success. I notice that by taking the form of an environmental NGO called "EC", the campaign was legitimized, institutionalized and incorporated into the state’s governance framework. The environmental activism became an aid to the state’s green governmentality. Lastly, I take a detailed look at the waste classification campaign jointly launched by Guangzhou government and EC. I point out that the ambiguous role of the state in this campaign, the profit-oriented recycling market together with the idealist knowledge/practice systems of this project make this campaign extremely difficult. / My research challenges the state-society dichotomy by showing that the trajectory of the campaign is dialectically entangled with the transformation of the state’s governance. The state constantly incorporates the resistance and alternative discourses produced in the movement, whereas the activists keep on producing alternative knowledge to challenge the state. Moreover, this study deepens the understanding of waste by considering waste as a flexible category in which various actors such as state, market, technosicence, consumers as well as the environmental activists are producing, competing and reconstructing its meaning. Also, my discussions of the universal knowledge of science contribute to the field of science and technology studies. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / 張劼穎. / Parallel title from added title page. / Thesis (Ph.D.) Chinese University of Hong Kong, 2015. / Includes bibliographical references (leaves 220-236). / Abstracts also in English. / Zhang Jieying.

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Hexachlorobenzene (HCB) is a pollutant, and there is an urgent need to degrade it. Two methods of degrading HCB to ethers are nucleophilic substitution and electroreduction, chosen for their viability and safety. The kinetics of substitution of HCB by potassium hydroxide and methanol were examined. The substitution of HCB by methoxide produced 1,2,3,5-tetrachloro-4.6-dimethoxybenzene (1,2,3,5-TCDMB) as the major substitution product, and side reactions produced extra chloride due to other substitution products. Thus, the proposed reaction mechanism is complicated due to the formation of ethers and phenols due to consecutive and parallel reactions. The substitution products of HCB were uncatalytically and catalytically electroreduced. Products with increasingly more methoxy substituents had lower electron affinities and increasing positive free energies. Catalysed electroreduction was more effective than uncatalysed electroreduction in dechlorinating the HCB substitution products to aromatic ethers. The most effective organic catalysts were those that possessed the lowest electron affinity as reflected in the reduction potential. A combination of nucleophilic substitution and electroreduction of HCB and its substitution products produced mono-, di- and trimethoxide chloroaromatic ethers and phenols. These products, particularly the ethers, may have future applications as fragrance ingredients / Doctor of Philosophy (PhD)