Persistent organic pollutants (POPs) fall under a group of synthetic chemicals known for their persistence in environmental matrices such as soil and water, and are used in industrial, domestic and agricultural applications. Because of their volatility and lipophilicity, POPs can be transported far away from their point sources and bio-accumulate in food and in fatty tissues of humans and animals. In view of their toxicity and carcinogenicity some organic pollutants such as polychlorinated biphenyl (PCBs), organochlorine pesticides (OCPs) and phenolic derivatives (chlorophenol and nitrophenol) have been classified by United State Environmental Protection Agency (USEPA) and World Health Organization (WHO) as priority pollutants. The present work evaluated the distribution patterns of 19 polychlorinated biphenyls congeners, 17 organochlorine pesticides and selected phenolic derivatives (USEPA 11-priority pollutants) in the Buffalo River, in the Eastern Cape Province, South Africa between December 2015 and May 2016. The Liquid-liquid extraction technique was used for PCBs, OCPs and phenolic derivatives in the river water samples. Silica gel and florisil clean up were carried out for PCBs and OCPs samples respectively and analyzed with gas chromatography electron capture detector (GC/ECD). Phenolic compounds were derivatized and analyzed by gas chromatography mass spectrometer (GC/MS). Limits of detection (LOD), limit of quantitation (LOQ) and relative standard deviation (RSD) for the PCBs were 10 to 330 ng/L, 20 to 1,060 ng/L and 1.18 to 14.1 percent respectively. The LOD, LOQ and RSD for the OCPs were from 20 - 60 ng/L, 110 - 530 ng/L and 0.02 - 0.06 percent, while the corresponding values for the phenolic derivatives were 10 to 70 ng/L, 33 to 222 ng/L and 1.99 - 10.86 percent. In summer, the concentrations of PCBs, OCPs and phenolic derivatives ranged from <LOD to 482 ng/L, <LOD to 4,403 ng/L and <LOD to 1,546 ng/L respectively, while in autumn they were from <LOD to 2,383 ng/L, <LOD to 858 ng/L and <LOD to 713 ng/L in that order. Also, in summer, the level of occurrence of total PCB congeners detected at the various sampling sites were Buffalo River Estuary (BRE) 11 percent, Mdantsane (MSN) 16 percent, Zwelitsha (ZW) 26 percent, King William’s Town (KWT) 47 percent, Izele (IZ) 32 percent, and Maden (MD) 21 percent. The level of occurrence of total OCPs at BRE was 65 percent, at MSN 65 percent, at ZW 82 percent, at KWT 47 percent, at IZ 29 percent, and at MD 18 percent. The level of occurrence of total phenolic derivatives at BRE was 63 percent, at MSN 63 percent, at ZW 54 percent, at KWT 63 percent, at IZ 63 percent, and at MD 54 percent. In autumn, the level of occurrence of total PCBs at BRE was 68 percent, at MSN 16 percent, at ZW 42 percent, at KWT 26 percent, at IZ 47 percent, and at MD 0 percent. The level of occurrence of total OCPs at BRE was 65 percent, at MSN 53 percent, at ZW 41 percent, at KWT 35 percent, at IZ 53 percent, and at MD 18 percent. The level of occurrence of total phenolic derivatives at BRE was 63 percent, at MSN 63 percent, at ZW 54 percent, at KWT 18 percent, at IZ 18 percent, and at MD 45 percent. In summer, the levels of PCBs in all sampling sites were below WHO recommended maximum permissible levels (500 ng/L) for humans but in autumn the levels were above the recommended values in all the sites except MD. The cancer risk assessment values were above permissible 10-6 while hazard quotients were above the USEPA maximum limits of unity. OCPs levels were above the USEPA limits (100 ng/L) in all sampling locations in both seasons. The cancer risk assessment values were below permissible 10-6 but hazard quotients were above the USEPA maximum limits. Phenolic derivatives were also above the USEPA maximum permissible limit (500 ng/L) in most of the sampling locations in summer whereas during autumn the values were notably below the permissible limit at ZW, KWT, IZ and MD. The cancer risk assessment values and hazard quotients were above USEPA maximum limits of 10-6 and unity respectively. Conclusively, the results of this study reveal that the pollutants were present in the river at concentrations higher than the tolerable limit for human and wildlife and thereby may constitute a serious risk to public health. Therefore, it is recommended that proper regulation of the use of the compounds and their safe disposal be ensured to protect aquatic resources and the well-being of humans.

M.Tech. (Chemistry) / Please refer to full text to view abstract

M. Tech. / Background: Waterborne disease contributes significantly to the total global disease burden. Populations in rural areas of South Africa depend on untreated waters for consumption and sanitation. Contamination of public water supplies by harmful bacteria such as pathogenic E. coli poses a major risk for public health. Ingestion of these pathogenic microorganisms present in the contaminated and untreated waters could cause infection, leading to systemic inflammatory responses manifested by the production of various proinflammatory cytokines. To date, there is no human system test available to detect whether water, following ingestion, would cause disease (i.e. whether the water is infectious). The current water testing methods only test for the presence of indicator organisms, such as faecal coliforms, total coliforms, and Escherichia coli. A reliable in-vitro bioassay that could assess whether the water would cause an inflammatory response was investigated in this study. Objectives: Pro-inflammatory cytokines and whole-blood have been used in similar studies to detect the inflammatory responses following exposure to specific stimulants such as dust, lipopolysaccharide (LPS), E. coli and various others. It has been reported that larger numbers of these contaminants induced higher levels of pro-inflammatory cytokine expression. This implies that the pro-inflammatory cytokine expression could be used as a marker of infection since, inflammation occurs in response to infection. Successful infection is thus necessary for inflammation to occur, and high levels of pro-inflammatory cytokine expression confirm that infection has occurred. Thus if pro-inflammatory cytokines could serve as indicators for infection, these cytokines could be used as indicators for bacterial pathogenicity of water.

M.Sc. / The prevalence of natural organic matter (NOM) in water remains a huge challenge for water treatment companies and municipalities. NOM, however, is not a stand-alone problem as it affects water quality in many ways. NOM is largely responsible for the formation of disinfection by-products (DBPs) via its interaction with disinfectants during water disinfection. It is implicated for the undesirable colour, taste and odour of water and NOM even inhibits precipitation precursors which form the backbone of drinking water treatment. There is therefore no question that NOM, which is either a precursor to or direct cause of the problems highlighted above, should be considered as one of the critical design parameters to be considered for drinking water treatment. In our laboratories, research that involves the use of cyclodextrin (CD) polyurethanes for the removal of organic pollutants from water has been extensively investigated, and the CD polyurethanes have demonstrated the ability to effectively remove the organic species from water at low (ppb) concentrations. CDs, which are cyclic oligomers consisting of glucopyranosyl units linked together through α-1,4 glycosidic linkages, behave like molecular hosts. They are capable of forming inclusion complexes with guest molecules and hence can be utilised for the removal of organic contaminants from water. Their solubility in water, however, limits their application in the removal of organic contaminants from water. This limitation is easily resolved by polymerising the CDs into water-insoluble polymers with bifunctional linkers such as hexamethylene diisocyanate (HMDI). In this study, CD polyurethanes and ion exchange resins were used for the removal of NOM and possibly its DBPs from water. This study first investigated the local NOM source to establish its type and character, hence the study involved the characterization of the bulk water samples and fractionating the NOM using ion exchange resins for further characterization. The water samples were found to consist mainly of humic substances in the form of hydrophobic NOM, with the hydrophilic basic (HpiB) fraction being the most abundant NOM fraction in all samples. Trihalomethanes (THMs) were used as a representative of DBPs in this vii study. THMs formation studies of the individual NOM fractions indicated that all six NOM fractions were found to form THMs but in varying proportions. The HpiB fraction was found to be the most reactive precursor fraction for THMs formation. The ozonation process was also independently evaluated for its ability to remove the NOM fractions from water. Ozonation was found not to be very effective at NOM removal since it only resulted in a 12% overall decrease of the NOM in the water samples. The CD polyurethanes, when used alone, were also not very effective at removing the NOM fractions from water (maximum of 33% NOM removal). On the other hand, the combination method (i.e. the use of CD polyurethanes and ozonation for NOM removal) resulted in a good capability of the CD polyurethanes at decreasing some NOM fractions in water as evidenced by a 73% and 88% decrease of the HpiB and hydrophilic acid (HpiA) fractions, respectively. The 73% reduction of the HpiB fraction demonstrates a great success of the combination approach employed herein, as this study reports this fraction as the most reactive precursor fraction for THM formation.

Please read the "Background" (p v) in the section 00front of this document Copyright 2002, University of Pretoria. All rights reserved. The copyright in this work vests in the University of Pretoria. No part of this work may be reproduced or transmitted in any form or by any means, without the prior written permission of the University of Pretoria. Please cite as follows: Bartie, C 2002, The life and career of the South African dramatric soprano Marita Napier, DPhil thesis, University of Pretoria, Pretoria, viewed yymmdd < http://upetd.up.ac.za/thesis/available/etd-11142007-125718 / > / Thesis (DPhil (Microbiology))--University of Pretoria, 2007. / Microbiology and Plant Pathology / unrestricted

Ph.D. (Chemistry) / In this study, carbon based electrode materials such as glassy carbon, graphene, diamond and exfoliated graphite were explored as suitable electrode materials for electrochemical detection, electrochemical and photoelectrochemical degradation of organic water pollutants. Graphene modified glassy carbon electrode sensor was developed for bisphenol A. Cyclic voltammetry was used to study the electrochemical properties of the prepared graphene- modified glassy carbon electrode using potassium ferricyanide as a redox probe. The prepared graphene- modified glassy carbon electrode exhibited more facile electron kinetics and enhanced current of about 75% when compared to the unmodified glassy carbon electrode...

No description available.

Contaminants can exist in a wide range of states in aqueous environments, especially in surface waters. They can be freely dissolved or associated with dissolved or particulate organic matter depending on their chemical and physical characteristics. The freely dissolved fraction represents the most bioavailable fraction to an organism. These freely dissolved contaminants can cross biomembranes, potentially exerting toxic effects. Passive sampling devices (PSDs) have been developed to aid in sampling many of these contaminants by having the ability to distinguish between the freely dissolved and bound fraction of a contaminant. A new PSD, the Lipid-Free Tube (LFT) sampler was developed in response to some of the shortcomings of other current PSD that sample hydrophobic organic contaminants (HOCs). The device and laboratory methods were original modeled after a widely utilized PSD, the semipermeable membrane device (SPMD), and then improved upon. The effectiveness, efficiency, and sensitivity of not only the PSD itself, but also the laboratory methods were investigated. One requirement during LFT development was to ensure LFTs could be coupled with biological analyses without deleterious results. In an embryonic zebrafish developmental toxicity assay, embryos exposed to un-fortified LFT extracts did not show significant adverse biological response as compared to controls. Also, LFT technology lends itself to easy application in monitoring pesticides at remote sampling sites. LFTs were utilized during a series of training exchanges between Oregon State University and the Centre de Recherches en Ecotoxicologie pour le Sahel (CERES)/LOCUSTOX laboratory in Dakar, Senegal that sought to build "in country" analytical capacity. Application of LFTs as biological surrogates for predicting potential human health risk endpoints, such as those in a public health assessment was also investigated. LFT mass and accumulated contaminant masses were used directly, representing the amount of contaminants an organism would be exposed to through partitioning assuming steady state without metabolism. These exposure concentrations allow for calculating potential health risks in a human health risk model. LFT prove to be a robust tool not only for assessing bioavailable water concentrations of HOCs, but also potentially providing many insights into the toxicological significance of aquatic contaminants and mixtures. / Graduation date: 2010

Call number: LD2668 .T4 1984 K55 / Master of Science

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy