The effect of engineered nanoparticles (ENPs) mixture consisting of silver oxide, (Agg0[Silver Oxide Nanopartical], 20 nm), titanium dioxide, (TiO2[Titanium dioxide], 30-40 nm) and zinc oxide, (ZnO, 20 nm) compared with their bulk metal salts was evaluated against unspiked activated sludge (control) using 3 parallel pilot-scale treatment plants. The total concentration of the ionic species of Ag+ Ti[Silver + Titanium] and Zn(2+) in the effluent of the ENP spiked activated sludge (AS) was below limits of detection and> 99% of the spiked ENP were found in the waste activated sludge (WAS), whereas 39 – 58 % of Ag0[Silver Oxide Nanopartical], 51 – 63 % and 58 – 74 % of ZnO ion concentrations were recovered in the anaerobic digestate (AD) cake suggesting higher affinity of ENPs to WAS than to anaerobic digestate. ENPs induced a 2-fold increase of the microbial community specific oxygen uptake rate (SOUR) compared with the control and > 98 % of ammonia and 80 % of COD were removed from the AS suggesting that the heterotrophic biomass retained their ability to nitrify and degrade organic matter at the spiked ENP concentration. The floc size and cultivable microbial abundance was reduced in the ENP spiked AS with no apparent disruption of the overall AS process efficiency. However, scanning electron microscopic analysis clearly showed damage to specific microbial cells. The lipid fingerprint and 16S rRNA gene-based pyrosequencing evidenced the dominance of Proteobacteria, Firmicutes, and Bacteriodetes with a clear temporal shift in microbial community structure. The prominent nano-tolerant bacterial species identified were Acidovorax, Rhodoferax, and Comamonas whereas Methanocorpusculum and Methanosarcina were recovered in AS and were the dominant Archaea in the AD with 99 and 98 % similarities to the closest culturable relative. Their presence in the AS suggests tolerance to ENPs and oxygen-dependent respiration. V. fisheri activity was not sensitive to the ionic concentrations of the ENP or metal salt mixture in the digestate samples and illustrates the need to develop bioassay using indigenous wastewater microorganisms to detect the potential effect of ENP. Overall, unlike other xenobiotic compounds, ENPs can hasten the natural selection of microbial species in activated sludge and anaerobic digestion processes.

Abstract available in PDF copy. / Thesis (M.Sc.-Chemical Engineering)-University of Natal, 1988.

2-Benzyloxy-1-methylpyridinium trifluoromethanesulfonate (commonly referred to as benzyloxypyridinium triflate or Dudley’s salt) is a novel protecting reagent for the conversion of an alcohol functional group into a benzyl ether. This novel protecting reagent allows for protection of an alcohols, carboxylic acids, and other nucleophiles under mild conditions. The two traditional methods of forming this benzyl ether rely on either basic (Williamson ether synthesis) or acidic (coupling via trichloroacetimidate with a strong acid) conditions which may potentially decompose sensitive substrates. This research will investigate the mechanism by which benzyloxypyridinium triflate decomposes. Investigation of benzyloxypyridinium triflate will require two aspects, synthesis of various derivatives and a rate study. The synthesis of benzyloxypyridinium triflate derivatives (broadly named benzyloxypyridinium salts) will result in a series of new compounds, along with new synthetic routes to make them. Testing the derivatives to ensure they form the expected benzyl ether or ester then allows for investigation of the rate for each derivative as they form the benzyl ether. Among the various techniques that may be employed to study the mechanism, rate studies will be a significant portion of data used to draw a conclusion. Each derivative of the benzyloxypyridinium triflate is designed to affect the rate of decomposition thereby changing the rate of benzyl ether formation by either promoting or impeding the formation of a carbocation. Monitoring the rate of each derivative and comparing that rate to the rate of the benzyloxy- pyridinium triflate will give insight to a mechanistic pathway, indicating whether the pathway is more unimolecular or bimolecular. An immediate application of a known mechanism could lead to more desirable conditions for the benzyloxypyridinim triflate when forming the benzyl ether. In addition, having an understanding of the mechanism allows for the utility of arylmethylpyridinium salts to be expanded by allowing the pyridinium salt to deliver a variety of different electrophiles. The mechanism will also allow for different nucleophiles to trap the corresponding electrophile from the pyridinium salt. / No title page or introductory pages in thesis body PDF. / Department of Chemistry

Motivation: The health effects of platinum on the human body are a great concern. It affects the respiratory system as well as the skin. The demands for platinum have seemingly increased over the last few years due to its use in automobile exhaust gas catalysts. Thus there will be an increase in the production and processing of platinum and therefore a greater possibility of exposure to platinum compounds. This is why it is of great importance to evaluate the surface sampling methods, to ensure that they are effective for platinum use. Objectives: 1) To evaluate and compare a few different surface sampling methods for removal of platinum salts from contaminated surfaces in order to determine which one of these methods has the best retention and recovery efficiency. 2) To use the most effective method to monitor surface contamination on porous and non–porous surfaces in a platinum refinery. Methods: Two types of filters (mixed cellulose ester and polyvinyl chloride) and GhostwipesTM were evaluated and compared in this study. Platinum solution (hexachloroplatinic acid) concentrations of 50, 150 and 300 ug Pt/ml solution were used. The retention efficiency of the different sampling mediums was tested by releasing 1 ml of each concentration directly onto the sampling medium. Efficiencies were tested on a non–porous (glass) and porous surface (semi–face bricks). This was done to see how the collection efficiency of the medium will differ on these two surfaces. A total of three wipes were used per surface, however were analyzed individually. All the samples were analyzed using the Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP–AES) analytical method by an accredited laboratory. Results: The results obtained indicated the retention and recovery efficiencies of the three sampling mediums at the three platinum concentrations of 50, 150 and 300 ug Pt/ml solutions. The retention efficiency of the GhostwipesTM was 93.2% at 50 ug Pt/ml solution, 95.3% at 150 ug Pt/ml solution and 93.6% at 300 ug Pt/ml solution, whilst the mixed cellulose ester (MCE) filters and polyvinyl chloride (PVC) filters were lower than 30% at all three concentrations. The overall recovery efficiencies of all three concentrations of the GhostwipesTM and MCE filter were the highest: the GhostwipesTM with levels of 73.9 %, 84.4% and 63.5% and the MCE filters with levels of 71.4%, 84.4% and 80.2%, whilst the PVC filters did not achieve levels above 60%. The wipe materials were also evaluated in terms of the ASTM E1792 standard requirements for wipe materials. Conclusion: GhostwipesTM were found to be the most suitable sampling medium based on retention and recovery efficiencies. The GhostwipesTM also complies with all the requirements listed in the ASTM E1792 standard for wipe materials, which makes it the most suitable wipe sampling material. The MCE and PVC filters however do not comply with all the ASTM E1792 requirements. / Thesis (M.Sc. (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2011.

Motivation: The health effects of platinum on the human body are a great concern. It affects the respiratory system as well as the skin. The demands for platinum have seemingly increased over the last few years due to its use in automobile exhaust gas catalysts. Thus there will be an increase in the production and processing of platinum and therefore a greater possibility of exposure to platinum compounds. This is why it is of great importance to evaluate the surface sampling methods, to ensure that they are effective for platinum use. Objectives: 1) To evaluate and compare a few different surface sampling methods for removal of platinum salts from contaminated surfaces in order to determine which one of these methods has the best retention and recovery efficiency. 2) To use the most effective method to monitor surface contamination on porous and non–porous surfaces in a platinum refinery. Methods: Two types of filters (mixed cellulose ester and polyvinyl chloride) and GhostwipesTM were evaluated and compared in this study. Platinum solution (hexachloroplatinic acid) concentrations of 50, 150 and 300 ug Pt/ml solution were used. The retention efficiency of the different sampling mediums was tested by releasing 1 ml of each concentration directly onto the sampling medium. Efficiencies were tested on a non–porous (glass) and porous surface (semi–face bricks). This was done to see how the collection efficiency of the medium will differ on these two surfaces. A total of three wipes were used per surface, however were analyzed individually. All the samples were analyzed using the Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP–AES) analytical method by an accredited laboratory. Results: The results obtained indicated the retention and recovery efficiencies of the three sampling mediums at the three platinum concentrations of 50, 150 and 300 ug Pt/ml solutions. The retention efficiency of the GhostwipesTM was 93.2% at 50 ug Pt/ml solution, 95.3% at 150 ug Pt/ml solution and 93.6% at 300 ug Pt/ml solution, whilst the mixed cellulose ester (MCE) filters and polyvinyl chloride (PVC) filters were lower than 30% at all three concentrations. The overall recovery efficiencies of all three concentrations of the GhostwipesTM and MCE filter were the highest: the GhostwipesTM with levels of 73.9 %, 84.4% and 63.5% and the MCE filters with levels of 71.4%, 84.4% and 80.2%, whilst the PVC filters did not achieve levels above 60%. The wipe materials were also evaluated in terms of the ASTM E1792 standard requirements for wipe materials. Conclusion: GhostwipesTM were found to be the most suitable sampling medium based on retention and recovery efficiencies. The GhostwipesTM also complies with all the requirements listed in the ASTM E1792 standard for wipe materials, which makes it the most suitable wipe sampling material. The MCE and PVC filters however do not comply with all the ASTM E1792 requirements. / Thesis (M.Sc. (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2011.

In der vorliegenden Arbeit wurde die elektronische Struktur verschiedener undotierter und mit Alkalimetallen beziehungsweise 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethan (F 4 TCNQ) dotierter, polyzyklischer aromatischer Kohlenwasserstoffe (PAK) untersucht. Diese Untersuchungen waren motiviert durch verschiedene Veröffentlichungen in denen supraleitendes Verhalten an unterschiedlichen alkalimetalldotierten PAK beschrieben wurde. Erste Studien erfolgten an undotiertem 1,2:8,9-Dibenzopentacen (DBP) und Pentacen unter Nutzung von Photoelektronenspektroskopie (PES), Elektronenenergieverlustspektroskopie (EELS) und Dichtefunktionaltheorie (DFT). Die spektroskopischen Methoden zeigten für beide Materialien eine große Ähnlichkeit der elektronischen Zustände, vor allem im niederenergetischen Bereich, welche durch die theoretischen Ergebnisse bestätigt wurde. Die elektronische Ähnlichkeit beider Materialien ist im starken Gegensatz zu dem in der Literatur bei Dotierung beobachteten Verhalten, bei dem Pentacen zum Mott-Isolator wird, während DBP Supraleitung zeigt. Weitere Untersuchungen erfolgten an Picen und Coronen. Bandstrukturrechnungen zeigten, dass Picen vermutlich ein stark korreliertes Elektronensystem besitzt. Neben dem mit PES ermittelten Ionisationspotential und der Austrittsarbeit waren auch die mit EELS gemessenen optischen Bandlücken der beiden Materialien sehr ähnlich. Unterschiede zeigten sich hingegen vor allem in der Dichte der gemessenen Zustände von Picen und Coronen am Ferminiveau. Bei der Untersuchung der elektronischen Eigenschaften von mit Kalium-dotierten Picen und Coronen wurde trotz der erfolgreichen Dotierung in keinem der untersuchten Filme eine Zustandsdichte am Ferminiveau beobachtet somit wurde auch keiner der untersuchten Filme metallisch. Dasselbe Verhalten konnte auch für Natrium-dotierte Filme beobachtet werden. Eine Diskussion dieses Ergebnisses, welches im Gegensatz zu der von anderen Gruppen in dotierten Molekülen beobachteten Supraleitung steht, erfolgte im Hinblick auf die Bildung unterschiedlich dotierter Phasen, Elektron-Phonon-Kopplung, der Formierung von Bi-Polaronen und Korrelationseffekten. Für ein weitergehendes Verständnis der dotierungsinduzierten elektronischen Eigenschaften in den untersuchten Molekülen wurden diese nicht nur mit Alkalimetallen, sondern teilweise auch mit elektronenziehenden Molekülen wie F 4 TCNQ interkaliert. Dabei entstanden Kristalle verschiedener Ladungstransfersalze. Eine ausführliche Charakterisierung erfolgte für Picen/F 4 TCNQ-Kristalle, welche im Rahmen dieser Arbeit zum ersten Mal hergestellt und untersucht wurden. Dabei wurde zunächst deren Kristallstruktur mit Röntgendiffraktometrie (XRD) bestimmt. Eine Abschätzung der Größe des Ladungstransfers innerhalb der Molekülpaare aus Picen/ F 4 TCNQ erfolgte über Infrarot- und Bindungslängendaten, die auf diese Weise gefunden Werte wurden zusätzlich durch DFT-Rechnungen untermauert. Transportmessungen zeigten außerdem, dass die hergestellten Kristalle entlang ihrer Hauptwachstumsrichtung Isolatoren sind. Die Untersuchung der elektronischen Eigenschaften wurde mit EELS und PES an Picen/ F 4 TCNQ -Dünnfilmen durchgeführt, welche durch die Verdampfung der Einkristalle hergestellt wurden. Die Molekülpaare zeigen einen Ladungstransfer, der neue elektronische Anregungen im Niederenergiebereich der mit EELS gemessenen Verlustfunktion hervorruft. Im weiteren Verlauf der Arbeit erfolgte eine Diskussion bezüglich des Charakters und der Lokalisierung dieser neuen Anregungen. Bei den PES-Messungen zeigte sich der Ladungstransfer durch energetische Verschiebungen in den gemessen Rumpfniveauspektren sowie durch im Vergleich zu den reinen Materialien deutlich veränderte Ionisationspotentiale. Trotz des erfolgreichen Ladungstransfers und der damit verbundenen Füllung von unbesetzten Zuständen mit Elektronen in F 4 TCNQ wurde jedoch in den Valenzbandspektren keine Emission am Ferminiveau beobachtet. DFT-Rechnungen ermöglichten schließlich Aussagen über den Charakter des Ladunstransfers und die daraus resultierende, fehlende Zustandsdichte am Ferminiveau.

A field study was conducted for two years in three semi-arid regions of Syria in order to define, under field conditions, the wheat (Triticum aestivum L.) yield response function to irrigation water salinity and to study the process of soil salt accumulation. The three regions experience similar climatic conditions (semi-arid Mediterranean climate) but have different soil textures, varying from sandy loam to clay. The study involved 74 farms all of which had been irrigating for more than 3 years prior to this study, with well water of different salinity values (0.44 to 14.1 dS/m). All of these farms operated with similar cultural practices. / Results indicate that the wheat yield response function to irrigation water salinity differs between the three regions. The irrigation water threshold salinity value beyond which wheat yield started to decline, was found to be 6.5 dS/m, 3.5 dS/m and 1.2 dS/m in the Khabur low plains; Aleppo south plains and Shedadeh area respectively. Wheat was more salt tolerant to irrigation water salinity in sandy loam soils than clay loam soils. The three threshold values obtained in this study are different from the "universal" value of 4 dS/m which is proposed in current literature. The "universal" value was obtained from artificially salinized field plots seeded under non-saline conditions. / In addition, it was found that salt accumulation in the soil profile increases as soil clay content increases. / The results demonstrate the necessity of establishing regional water quality criteria when planning the use of saline water sources for irrigation in semi-arid regions.

No description available.

Lactic acid recovery from dilute fermentation broths is a growing requirement due to the increasing demand for pure lactic acid. Reactive extraction is proposed as an alternative to conventional methods of recovery, since the selectivity of separation is remarkably enhanced in reactive extraction. The aim of this study is to perform the equilibrium studies for the recovery of lactic acid from its synthetic aqueous solutions (not from real fermentation broths) by reactive extraction and investigate the effects of various parameters such as initial lactic acid concentration in the aqueous phase (0.25 - 1.3 M), initial pH of the aqueous phase (2 &ndash / 6), organic phase extractant concentration (0.1 &ndash / 0.5 M), type of the extractant (chloride, hydrogensulphate and hydroxide salts of tri-n-octylmethylammonium) and the type of diluent (oleyl alcohol or octanol). The results of the experiments showed that the degrees of extraction decreased with increasing use of diluent with the extractant and increasing initial lactic acid concentration of the aqueous phase. Highest degrees of extraction were achieved for undiluted extractants. The performance of the diluents were investigated by performing extraction experiments with solutions of TOMAC in oleyl alcohol or octanol at different pH values and it was observed that octanol had a higher solvating power than oleyl alcohol especially at lower aqueous phase pH values. Higher extraction efficiencies were obtained for TOMAC dissolved in octanol rather than oleyl alcohol. Initial aqueous pH of 6 was identified as the optimum pH for the extraction, also due to its being equal the average fermentation pH for the extractions with Lactobacillus species. Among the different salts of tri-n-octylmethylammonium, hydroxide salt exhibited the highest degrees of extraction (83% with undiluted TOMA(OH) and 78% with 0.5 M TOMA(OH) in octanol for the extraction of 0.316 M lactic acid solutions). The present work is the first step in the design of an industrial reactive extraction process that is going to attempt forward and backward extraction of lactic acid simultaneously in a hollow fiber membrane module that is going to be attached to the lactic acid fermentor to achieve continuous product recovery. The equilibrium data obtained from this study can be combined with the kinetic studies as the next step of designing a separation module.

Quaternary ammonium compounds (QACs) are ubiquitous contaminants found worldwide in both engineered and natural systems. QACs are toxic to aquatic organisms and cause co-selection for antibiotic resistance, thus providing a reservoir of antibiotic-resistant bacteria, as well as antibiotic resistance genes in QAC-polluted environments. The objectives of the research presented here were to: a) systematically assess the fate and toxicity of QACs using quantitative structure-activity relationships (QSAR); b) evaluate the biotransformation potential of QACs under aerobic, anoxic and anaerobic conditions; and c) assess the potential toxicity of QACs biotransformation products. Nine QACs, belonging to three homologous groups -- monoalkonium, dialkonium and benzalkonium chlorides -- were the target QACs. The QACs critical micelle concentration (CMC) was determined. Then, the CMC was used as a descriptor to derive relationships between QAC structure and partitioning to biosolids as well as acute Microtox® toxicity. QACs with low CMCs had a relatively high adsorption affinity for biosolids and a lower toxicity than QACs with higher CMCs, which suggests that QACs that are more mobile and more (bio)available are more toxic. The biotransformation potential of benzalkonium chlorides (BAC) -- the most commonly used QACs found in engineered and natural biological systems -- under aerobic, methanogenic, nitrate reducing, and fermentative conditions was evaluated using bioenergetics and batch bioassays. The aerobic BAC biotransformation involved sequential dealkylation and debenzylation steps resulting in the formation of benzyl dimethyl amine, and dimethyl amine, respectively. The bacterial community involved in the aerobic BAC degradation was mainly composed of species belonging to the Pseudomonas genus. All QACs tested were recalcitrant under methanogenic conditions and inhibited methanogenesis at and above 25 mg QAC/L. Under nitrate reducing and fermentative conditions, BAC was transformed to alkyldimethyl amines via an abiotic reaction known as modified Hofmann degradation and a biotic reaction known as fumarate addition, respectively. Both reactions are based on a mechanism known as nucleophilic substitution. The discovery of BAC transformation by the above mentioned two reactions is the first ever report to document QAC transformation under anoxic/anaerobic conditions and delineate the transformation pathway.