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Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: The present study was initiated by the wine industry of South Africa to overcome the lack of available information on the flavor and aroma of South African wines. The aim was to develop new analytical methods and improve existing ones for the analysis of volatile compounds in the South African wines. Initially a new analytical method based on stir bar sorptive extraction (SBSE) in the headspace mode for the analysis of 37 pre-selected volatile compounds was developed and validated. Consequently, the method was improved by making important modifications and increasing the number of compounds analyzed to 39. This method was successfully applied to a large number of Pinotage wines of vintages 2005 and 2006. The quantitative data of these wines were subjected to chemometric analysis in order to investigate possible co- /variances. A clear distinction was observed between the two vintages, where the 2005 wines were more characterized by wood-related compounds and the 2006 wines by the fermentation compounds. The developed method was further applied to other cultivars of vintage 2005, including two white (Sauvignon Blanc and Chardonnay) and three red (Shiraz, Cabernet Sauvignon and Merlot) cultivars. In a similar fashion, the quantitative data of the six cultivars of vintage of 2005 were analysed by chemometric methods. Significant differences were observed between the two white cultivars and among the four red cultivars. It was shown that among these cultivars, the major role-players were the wood and fermentation related volatiles. A striking observation was the confirmation of the unique character of the Pinotage wines compared to the other red cultivars, mainly influenced by the high level of isoamyl acetate and low level of isoamyl alcohol, the former being categorized as a varietal compound for Pinotage expressed by a fruity (banana) odor. In addition, advanced chromatographic technology in the form of comprehensive twodimensional gas chromatography (GC × GC) coupled to time-of-flight mass spectrometry (TOFMS) was investigated for the detailed analysis of volatile compounds in young South African wines. This work focused primarily on Pinotage wines. In the first instance, solid phase micro extraction (SPME) in the headspace mode in combination with GC × GC-TOFMS was used. Due to the high resolution and large peak capacity of GC × GC, more than 200 compounds previously reported as wine components were identified. These compounds were dominated by the highly volatile and less polar compounds, mainly due to the characteristics of SPME. In an attempt to further extend these results, another selective extraction method, solid phase extraction (SPE) was used in combination with GC × GC-TOFMS analysis. Using this technique, more than 275 compounds, most of them unidentified using the previous method, were detected. These groups of compounds include volatile phenols, lactones as well as mostly aromatic esters and norisoprenoids, which can potentially influence the aroma and flavor of wine. The techniques developed as part of this study have extended our knowledge of the volatile composition of South African wines. / AFRIKAANSE OPSOMMING: Hierdie studie is geïnisieer deur die wyn industrie van Suid-Afrika om die tekort aan beskikbare inligting aangaande wyn aroma van Suid-Afrikaanse wyne te oorkom. Die doel was om nuwe analitiese metodes te ontwikkel en die huidige metodes te verbeter vir die analise van vlugtige verbindings in Suid-Afrikaanse wyne. Oorspronklik is ʼn nuwe analitiese metode ontwikkel en gevalideer gebaseer is op ‘stir bar sorptive extraction’ (SBSE) in die gas fase vir die analise van 37 vooraf geselekteerde vlugtige verbindings. Die metode is verbeter deur belangrike modifikasies aan te bring en die hoeveelheid verbindings wat analiseer word te vermeerder na 39. Hierdie metode is suksesvol aangewend op ʼn groot hoeveelheid Pinotage wyne van oesjare 2005 en 2006. Die kwantitatiewe data van hierdie wyne is onderwerp aan verskillende chemometriese analises om moontlike ko-/variasies te ondersoek. ʼn Duidelike onderskeid is opgemerk tussen die twee oesjare, waar die 2005 wyne gekarakteriseer is deur hout-verwante verbindings en die 2006 wyne weer meer deur fermentasie verbindings. Die verbeterde metode is verder aangewend vir analiese van ander kultivars van oesjare 2005, wat twee wit (Sauvignon Blanc en Chardonnay) en drie rooies (Shiraz, Cabernet Sauvignon en Merlot) ingesluit het. Die kwantitatiewe data van die ses kultivars van oesjaar 2005 is op ʼn soortgelyke wyse geanaliseer deur verskillende chemometriese metodes te gebruik. Beduidende verskille is opgemerk tussen die twee wit kultivars en tussen die vier rooi kultivars. Die hoof rolspelers tussen die ses kultivars was weereens die verbindings wat ʼn hout en fermentasie aard het. Die unieke karakter van die Pinotage wyne in vergelyking met die ander rooi kultivars was opvallend. Hierdie wyn word gekarakteriseer deur hoë vlakke van isoamiel asetaat en lae vlakke van isoamiel alkohol, waar eersgenoemde gekatogiseer word as ʼn verbinding wat ʼn vrugte (piesang) geur in Pinotage uitdruk. Verder is gevorderde chromatografiese tegnologie in die vorm van ‘comprehensive two-dimentional gas chromatography’ (GC x GC) gekoppel met ‘time-of-flight mass spectroscopy’ (TOFMS) ondersoek vir die analiese van vlugtige verbindings in jong Suid-Afrikaanse wyne. Hierdie werk het hoofsaaklik op Pinotage wyne gefokus. Eerstens is ‘solid phase micro extraction’ (SPME) in die gas fase gekombineer met GC x GC-TOFMS. As gevolg van die hoë resolusie en groot piek kapasiteit van GC x GC is meer as 200 verbindings wat voorheen gerapporteer is as wyn komponente geïdentifiseer. Hierdie verbindings is gedomineer deur hoë vlugtige polêre verbindings, hoofsaaklik as gevolg van die karaktersitieke van SPME..In ʼn poging om die metode verder te verbeter is ʼn selektiewe ekstraksie metode naamlik ‘solid phase extraction’ (SPE) in kombinasie met GC x GC-TOFMS gebruik. Met hierdie tegniek is meer as 275 verbindings geïdentifiseer, waarvan die meeste nie met die vorige metode waargeneem is nie. Hierdie verbindings sluit vlugtige fenole, laktone en meestal aromatiese esters en norisoprenoïdes in, wat moontlik die reuk en smaak van wyn kan beïnvloed. Die metodes ontwikkel gedurende die studie het nuwe informasie verskaf aangaande die vlugtige komponente teenwoordig in Suid Afrikaanse wyne.

<p>This thesis is based on studies in which the suitability of various gas chromatography (GC) injection techniques was examined for the determination of polybrominated diphenyl ethers (PBDEs) and carbazoles, two groups of compounds that are thermally labile and/or have high boiling-points. For such substances, it is essential to introduce the samples into the GC system in an appropriate way to avoid degradation and other potential problems. In addition, different types of gas chromatographic column system and mass spectrometric detectors were evaluated for the determination of PBDEs.</p><p>Conventional injectors, such as splitless, on-column and programmed temperature vaporizing (PTV) injectors were evaluated and optimized for determination of PBDEs. The results show on-column injection to be the best option, providing low discrimination and high precision. The splitless injector is commonly used for “dirty” samples. However, it is not suitable for determination of the high molecular weight congeners, since it tends to discriminate against them and promote their degradation, leading to poor precision and accuracy. The PTV injector appears to be a more suitable alternative. The use of liners reduces problems associated with potential interferents such as polar compounds and lipids and compared to the hot splitless injector, it provides gentler solvent evaporation, due to its temperature programming feature, leading to low discrimination and variance.</p><p>Increasing the injection volume from the conventional 1-3 µL to >50 µL offers two main benefits. Firstly, the overall detection and quantification limits are decreased, since the entire sample extract can be injected into the GC system. Secondly, large volume injections enable hyphenation of preceding techniques such as liquid chromatography (LC), solid phase extraction and other kinds of extraction. Large-volume injections were utilized and optimized in the studies included in this thesis.</p><p>With a loop-type injector/interface large sample volumes can be injected on-column providing low risk of discrimination against compounds with low volatility. This injector was used for the determination of PBDEs in air and as an interface for the determination of carbazoles by LC-GC. Peak distortion is a frequently encountered problem associated with this type of injector that was addressed and solved during the work underlying this thesis.</p><p>The PTV can be used as a large volume injector, in so-called solvent vent mode. This technique was evaluated for the determination of PBDEs and as an interface for coupling dynamic sonication-assisted solvent extraction online to GC. The results show that careful optimization of the injection parameters is required, but also that the PTV is robust and yields reproducible results.</p><p>PBDEs are commonly detected using mass spectrometry in electron capture negative ionization (ECNI) mode, monitoring bromine ions (m/z 79 and 81). The mass spectrometric properties of the fully brominated diphenyl ether, BDE-209, have been investigated. A high molecular weight fragment at m/z 486/488 enables the use of 13C-labeled BDE-209 as an internal surrogate standard.</p>

This thesis is based on studies in which the suitability of various gas chromatography (GC) injection techniques was examined for the determination of polybrominated diphenyl ethers (PBDEs) and carbazoles, two groups of compounds that are thermally labile and/or have high boiling-points. For such substances, it is essential to introduce the samples into the GC system in an appropriate way to avoid degradation and other potential problems. In addition, different types of gas chromatographic column system and mass spectrometric detectors were evaluated for the determination of PBDEs. Conventional injectors, such as splitless, on-column and programmed temperature vaporizing (PTV) injectors were evaluated and optimized for determination of PBDEs. The results show on-column injection to be the best option, providing low discrimination and high precision. The splitless injector is commonly used for “dirty” samples. However, it is not suitable for determination of the high molecular weight congeners, since it tends to discriminate against them and promote their degradation, leading to poor precision and accuracy. The PTV injector appears to be a more suitable alternative. The use of liners reduces problems associated with potential interferents such as polar compounds and lipids and compared to the hot splitless injector, it provides gentler solvent evaporation, due to its temperature programming feature, leading to low discrimination and variance. Increasing the injection volume from the conventional 1-3 µL to &gt;50 µL offers two main benefits. Firstly, the overall detection and quantification limits are decreased, since the entire sample extract can be injected into the GC system. Secondly, large volume injections enable hyphenation of preceding techniques such as liquid chromatography (LC), solid phase extraction and other kinds of extraction. Large-volume injections were utilized and optimized in the studies included in this thesis. With a loop-type injector/interface large sample volumes can be injected on-column providing low risk of discrimination against compounds with low volatility. This injector was used for the determination of PBDEs in air and as an interface for the determination of carbazoles by LC-GC. Peak distortion is a frequently encountered problem associated with this type of injector that was addressed and solved during the work underlying this thesis. The PTV can be used as a large volume injector, in so-called solvent vent mode. This technique was evaluated for the determination of PBDEs and as an interface for coupling dynamic sonication-assisted solvent extraction online to GC. The results show that careful optimization of the injection parameters is required, but also that the PTV is robust and yields reproducible results. PBDEs are commonly detected using mass spectrometry in electron capture negative ionization (ECNI) mode, monitoring bromine ions (m/z 79 and 81). The mass spectrometric properties of the fully brominated diphenyl ether, BDE-209, have been investigated. A high molecular weight fragment at m/z 486/488 enables the use of 13C-labeled BDE-209 as an internal surrogate standard.

There are 209 PCB congeners, 136 of which have been found in technical PCB mixtures and hence may be found in the environment as a result of either intentional or unintentional release. The identification and quantification of the congeners are difficult due to analytical bias from coeluting PCBs and other persistent organic pollutants. Among the 209 possible PCB congeners, 19 tri- and tetra-ortho chlorinated congeners exist in stable atropisomeric conformations. The racemization barrier were determined for twelve of the nineteen atropisomers and was found to be between 176-185 kJ × mol-1 and ca. 250 kJ × mol-1 for tri- and tetra-ortho PCB, respectively. Further, a buttressing effect of 6.4 kJ × mol-1 was observed for congeners with vicinal ortho-meta chlorines. Comprehensive two-dimensional gas chromatography (GC×GC) was used to analyze the atropisomers and other PCBs. A Longitudinally Modulated Cryogenic System (LMCS) was used with liquid CO2 as cryogen. The LMCS was optimized for semi-volatile organic substances, primarily PCBs. The trap temperature was shown to be an important factor for the trapping and desorption efficiency, as was the thermal mass of the column used in the modulator region. A number of column sets were tested and the separation efficiency, congener resolution and analysis time was evaluated. Good separation of non- and mono-ortho PCBs and “bulk” PCBs (in a technical PCB) was obtained within 8 min using a smectic liquid crystal column (LC50) as the first and a nonpolar column as the second dimension column. Using a second column, an efficient nonpolar (DB-XLB) column, which separates many PCB congeners, were combined with a polar (cyanopropyl) or shape selective (LC50) second dimension column. As a maximum, 181 of the 209 congeners and 126 of the 136 Aroclor PCBs were resolved. The seven frequently measured PCBs (PCBs 28, 52, 101, 118, 138, 153 and 180) and all WHO-PCBs were separated from all other Aroclor PCBs. Chiral PCBs are released into the environment as racemic mixtures. However, organisms have been shown to enantiomerically enrich many of the atropisomers, suggesting that enantioselective biotransformations occur. Non-racemic PCB enrichment has also been seen in mammalians including humans, which is of particular concern because of the potential health risk. An analytical procedure were therefore developed and used to determine the levels of atropisomeric PCBs, planar-PCBs (WHO-PCBs) and total PCBs in seals with different health status. GC×GC was used to separate the target PCBs from other PCBs and potential interferences. A chiral column (permethylated â-cyclodextrin) was used in combination with a polar or shape selective column and enantiomeric fractions (EFs) were determined for five atropisomeric PCBs, i.e. CBs 91, 95, 132, 149 and 174. Some atropisomers had EF that deviated largely from racemic. The deviation was larger in liver than blubber, indicating enantioselective metabolism. However, there was no selective passage of the studied atropisomeric PCBs across placenta and no selective blood-brain barrier. Similarly, no correlation between EFs and health status was observed, although there was a correlation between total PCBs and health status.

Die elektrokinetische Bodensanierung nutzt Transporteffekte aus, die entstehen, wenn ein elektrisches Feld an einen Bodenkörper angelegt wird. Die Sanierungsmethode versagt bei immobilen Schadstoffen. Allerdings scheint unter bestimmten Bedingungen ein im Boden induzierter Abbau der Schadstoffe möglich. Dafür müssen so genannte &amp;quot;Mikroleiter&amp;quot; und Redox-Systeme im Boden vorhanden sein. Hierzu werden theoretische Modelle vorgestellt. An einem konkreten Beispiel (mit aliphatischen Chlorkohlenwasserstoffen kontaminierter Boden) wurde getestet, ob direkt im Boden ein Abbau der Schadstoffe mit der Technik der elektrochemischen Bodensanierung erzielt werden kann. Die Analyse der CKW wurde per GC-MS durchgeführt. Theoretisch ist ein reduktiver Abbau oder eine Dechlorierung durch Eliminierungsreaktionen möglich. Die Ergebnisse der Laborversuche (Einwaage 100-3.000 g) erbrachten unter Einhaltung bestimmter Faktoren einen erfolgreichen Abbau der CKW. Bei ständiger Bewässerung des Bodens und einer Feldstärke von mindestens 600 V/m konnte ein Abbau festgestellt werden. Die Erhöhung des Chlorid-Gehaltes im Abwasser zeigt die erfolgreiche Abbaureaktion an. Potentielle Abbauprodukte mit weniger Chlor-Atomen im Molekülaufbau konnten nachgewiesen werden. Diese Stoffe lassen sich mit den ursprünglichen Kontaminationssubstanzen verknüpfen. Da eine Migration der Schadstoffe im elektrischen Feld nicht beobachtet wurde, wird eine im Boden induzierte Abbaureaktion angenommen. In Bodenzonen mit hohem pH-Wert (Eliminierung) und in Kathodennähe (Reduktion) waren die stärksten Abbauraten zu verzeichnen. Bei Versuchen ohne ständige Bewässerung war der CKW-Abbau schwach. Die Widerstände stiegen stark an. Ein Versuch in einem Container (Einwaage Boden: ca. 2 t) erbrachte nur einen punktuellen Abbau der CKW. Die Struktur des Originalbodens verhinderte den Aufbau eines homogenen elektrischen Feldes. In einem Fassversuch (Einwaage Boden: ca. 33 kg) wurden die Versuchsbedingungen modifiziert. Anlagerungen an allen Elektroden verhinderten eine ausreichend hohe effektive Feldstärke im Bodenkörper. Sanierungseffekte fanden nur lokal begrenzt statt. Im Vergleich von Labor zu Großversuchen zeigte sich, dass die eingetragene Ladungsmenge eine entscheidende Rolle spielt.

The submitted thesis deals with determination of selected pesticides in water samples by gas chromatography. The target pesticides belong to the group of organophosphates (chlorpyrifos, diazinon, parathion, dimethoate, phosmet) and carbamates (carbofuran, aldicarb, methiocarb, pirimicarb, and propamocarb). In the theoretical part, the division of pesticides is stated, and their properties are described, as well as their fate in the environment and their negative effects. Then, the possibilities of analytical determination based on gas chromatography are characterized. The experimental part describes the treatment of the samples and their subsequent analysis. Solid phase extraction was chosen as the extraction technique. Two kinds of cartridges were optimized (Oasis HLB and Supelclean ENVI-18) in combination with various elution reagents. The most suitable combination was then used for processing of real samples of waste-water, which was taken from WWTP in Brno Modřice. For the final determination of the target compounds by gas chromatography, two types of detectors were used: mass spectrometer and an electron capture detector.

Die elektrokinetische Bodensanierung nutzt Transporteffekte aus, die entstehen, wenn ein elektrisches Feld an einen Bodenkörper angelegt wird. Die Sanierungsmethode versagt bei immobilen Schadstoffen. Allerdings scheint unter bestimmten Bedingungen ein im Boden induzierter Abbau der Schadstoffe möglich. Dafür müssen so genannte &amp;quot;Mikroleiter&amp;quot; und Redox-Systeme im Boden vorhanden sein. Hierzu werden theoretische Modelle vorgestellt. An einem konkreten Beispiel (mit aliphatischen Chlorkohlenwasserstoffen kontaminierter Boden) wurde getestet, ob direkt im Boden ein Abbau der Schadstoffe mit der Technik der elektrochemischen Bodensanierung erzielt werden kann. Die Analyse der CKW wurde per GC-MS durchgeführt. Theoretisch ist ein reduktiver Abbau oder eine Dechlorierung durch Eliminierungsreaktionen möglich. Die Ergebnisse der Laborversuche (Einwaage 100-3.000 g) erbrachten unter Einhaltung bestimmter Faktoren einen erfolgreichen Abbau der CKW. Bei ständiger Bewässerung des Bodens und einer Feldstärke von mindestens 600 V/m konnte ein Abbau festgestellt werden. Die Erhöhung des Chlorid-Gehaltes im Abwasser zeigt die erfolgreiche Abbaureaktion an. Potentielle Abbauprodukte mit weniger Chlor-Atomen im Molekülaufbau konnten nachgewiesen werden. Diese Stoffe lassen sich mit den ursprünglichen Kontaminationssubstanzen verknüpfen. Da eine Migration der Schadstoffe im elektrischen Feld nicht beobachtet wurde, wird eine im Boden induzierte Abbaureaktion angenommen. In Bodenzonen mit hohem pH-Wert (Eliminierung) und in Kathodennähe (Reduktion) waren die stärksten Abbauraten zu verzeichnen. Bei Versuchen ohne ständige Bewässerung war der CKW-Abbau schwach. Die Widerstände stiegen stark an. Ein Versuch in einem Container (Einwaage Boden: ca. 2 t) erbrachte nur einen punktuellen Abbau der CKW. Die Struktur des Originalbodens verhinderte den Aufbau eines homogenen elektrischen Feldes. In einem Fassversuch (Einwaage Boden: ca. 33 kg) wurden die Versuchsbedingungen modifiziert. Anlagerungen an allen Elektroden verhinderten eine ausreichend hohe effektive Feldstärke im Bodenkörper. Sanierungseffekte fanden nur lokal begrenzt statt. Im Vergleich von Labor zu Großversuchen zeigte sich, dass die eingetragene Ladungsmenge eine entscheidende Rolle spielt.

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