Isoprenoids are important components of conifer resin and represent an important part of constituted defence system against herbivores and pathogens. Drought is one of the most important factors that influences the tree physiology and resitance. Due to decreased turgor of resin canal cells, the water insufficiency affects the pressure of the resin and thereby the ability of trees to physically prevent pathogen or herbivore invasion by effective outpouring of the resin. In addition, drought can also change the resin composition and thus can influence the quality of volatiles emitted by the tree. The Norway spruce, Picea abies, is the predominant species of production forests in moderate climate zone. Bark beetles, Ips typographus, represent the most important pest species of spruce. In general, pioneer bark beetles use host volatiles to orient themselves toward the tree suitable for colonization and in many species host volatiles synergize bark beetle aggregation pheromones. Thus the host volatile composition could affect significantly host colonization. This diploma thesis studied the influence of drought on the production and composition of isoprenoid volatile organic compounds in 80 - 100 years old spruce trees. Using I. typographus antennae as biological detectors, we also studied which resin...

Body odour perception plays an important role in human mate choice, especially in women. It was previously proposed that women select partners whose body odour resembles that of woman's fathers. Yet, this phenomenon has only been confirmed using ethological studies based on subjective perception of body odour similarities. Therefore, the aim of my diploma thesis was to test this hypothesis instrumentally using comprehensive GC×GC-TOFMS and subsequent multidimensional analyses of body odour chemical profiles of male partners and fathers of adult women. Body odour sampling from left and right axilla of fathers and partners of 41 women (altogether 164 samples) was performed using cotton swabs, which were then frozen and extracted into hexane. Typical human volatile substances, such as hydrocarbons, carboxylic acids, esters, alcohols, aldehydes, ketones, sterols and terpenes were detected in all examined samples. Using a newly available "tile-based" chromatographic alignment algorithm, we obtained a set of 341 compounds systematically occurring in male axillary odour. The principal component analysis was used to calculate Euclidean distances for all pairs of the studied male subjects. These estimates of "chemical distances" revealed to be significantly smaller for father-partner pairs of individual...

Propriedades benéficas são associadas ao consumo moderado de vinho devido à presença dos compostos fenólicos. Uma dose diária de vinho de até 200 ou 300 mL é sugerida para mulheres e homens, respectivamente. Entretanto, dentre os compostos presentes nos vinhos, podem ser encontrados compostos carbonílicos tóxicos, como o formaldeído, acroleína, acetaldeído, furfural e carbamato de etila, os quais tem sido associados a efeitos adversos à saúde humana, incluindo o câncer. O objetivo deste trabalho foi desenvolver e validar um método para a quantificação simultânea destes compostos tóxicos através da microextração em fase sólida no modo headspace associada à cromatografia gasosa acoplada à espectrometria de massas quadrupolar no modo de monitoramento de íons selecionados (HS-SPME- GC/qMS-SIM) e caracterizar o risco relacionado à exposição a estes compostos. Quatro etapas da vinificação (uva, mosto, após a fermentação alcoólica e vinho) e vinhos comercialmente disponíveis foram analisados com o uso da GC/qMS-SIM após verificar as coeluições através da cromatografia gasosa bidimensional abrangente acoplada ao detector de espectrometria de massas por tempo de voo (GC×GC- TOFMS). O acetaldeído e a acroleína derivatizados coeluíram na primeira dimensão cromatográfica com o limoneno e o hexanoato de metila, respectivamente. Em função disso, foram escolhidos como íons quantificadores na análise por GC/qMS, íons que não foram encontrados no espectro de massas dos compostos coeluídos. Os parâmetros de validação (LOD, LOQ, recuperação, repetibilidade e reprodutibilidade) mostraram que a HS-SPME-GC/qMS-SIM é adequada para quantificar simultaneamente os cinco compostos tóxicos. A acroleína foi encontrada em concentrações similares na uva e mosto, e não foi detectada após a fermentação alcoólica e no vinho. O acetaldeído foi detectado em menores concentrações no mosto e em maiores níveis após a fermentação alcoólica. A concentração de furfural foi maior nas uvas do que nas demais etapas. O carbamato de etila não foi detectado nas etapas da vinificação e nos vinhos comerciais. Os níveis de formaldeído ficaram entre os valores de LOD e LOQ em todas as etapas da vinificação e nos vinhos comerciais. Além disso, nos vinhos comercialmente disponíveis, a acroleína foi encontrada em 50% das amostras, o acetaldeído e o furfural estavam presentes em todas as amostras. O único composto cuja ingestão pode representar risco a saúde é a acroleína. Dessa forma, este estudo contribuiu para identificar os pontos críticos de controle relacionados à presença de compostos tóxicos durante a vinificação, incluindo a produção do acetaldeído durante a fermentação alcoólica e a contaminação das uvas com acroleína e furfural através do ar atmosférico. Além disso, os resultados da ocorrência destes compostos tóxicos em vinhos comercialmente disponíveis poderão contribuir para a criação de uma legislação nacional que estabeleça limites dos mesmos nesta bebida. / Beneficial properties are associated with moderate consumption of wine due to the presence of phenolic compounds. A daily intake of wine of up to 200 or 300 mL is suggested for women and men, respectively. However, toxic carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, furfural and ethyl carbamate can be found among the compounds present in wines, which have been associated with adverse effects on human health, including cancer. The objective of this work was to develop and validate a method for simultaneous quantification of these toxic compounds through headspace solid phase microextraction associated with gas chromatography with quadrupole mass spectrometric detection in selected-ion monitoring mode (HS-SPME-GC/qMS-SIM) and characterize the risk related to exposure to these compounds. Four vinification steps (grape, must, after alcoholic fermentation and wine) and commercially available wine were analyzed using GC/qMS-SIM after checking the coelutions by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS). The derivatized acetaldehyde and acrolein coeluted in the first chromatographic dimension with limonene and methyl hexanoate, respectively. Based on this, were chosen as quantifiers ions in GC/qMS analysis, ions that were not found in the mass spectra of the coeluted compounds. The validation parameters (LOD, LOQ, recovery, repeatability and reproducibility) showed that HS-SPME-GC/qMS-SIM is adequate to simultaneously quantify the five toxic compounds. Acrolein was found at similar concentrations in grape and must, and was not detected after alcoholic fermentation and in wine. Acetaldehyde was detected at lower concentrations in the must and at higher levels after alcoholic fermentation. The concentration of furfural was higher in the grapes than in the other stages. Ethyl carbamate was not detected in the vinification steps and in commercially wine. Formaldehyde levels were between the LOD and LOQ values at all stages of winemaking and commercial wines. In addition, in commercially available wines, acrolein was found in 50% of samples, acetaldehyde and furfural were present in all samples. The only compound whose intake may pose a health risk is acrolein. Thus, this study contributed to identify critical control point related to the presence of toxic compounds during winemaking, including the production of acetaldehyde during alcoholic fermentation and the contamination of grapes with acrolein and furfural through atmospheric air. In addition, the results of the occurrence of these toxic compounds in commercially available wines may contribute to the creation of national legislation that establishes limits of the same in this drink.

Propriedades benéficas são associadas ao consumo moderado de vinho devido à presença dos compostos fenólicos. Uma dose diária de vinho de até 200 ou 300 mL é sugerida para mulheres e homens, respectivamente. Entretanto, dentre os compostos presentes nos vinhos, podem ser encontrados compostos carbonílicos tóxicos, como o formaldeído, acroleína, acetaldeído, furfural e carbamato de etila, os quais tem sido associados a efeitos adversos à saúde humana, incluindo o câncer. O objetivo deste trabalho foi desenvolver e validar um método para a quantificação simultânea destes compostos tóxicos através da microextração em fase sólida no modo headspace associada à cromatografia gasosa acoplada à espectrometria de massas quadrupolar no modo de monitoramento de íons selecionados (HS-SPME- GC/qMS-SIM) e caracterizar o risco relacionado à exposição a estes compostos. Quatro etapas da vinificação (uva, mosto, após a fermentação alcoólica e vinho) e vinhos comercialmente disponíveis foram analisados com o uso da GC/qMS-SIM após verificar as coeluições através da cromatografia gasosa bidimensional abrangente acoplada ao detector de espectrometria de massas por tempo de voo (GC×GC- TOFMS). O acetaldeído e a acroleína derivatizados coeluíram na primeira dimensão cromatográfica com o limoneno e o hexanoato de metila, respectivamente. Em função disso, foram escolhidos como íons quantificadores na análise por GC/qMS, íons que não foram encontrados no espectro de massas dos compostos coeluídos. Os parâmetros de validação (LOD, LOQ, recuperação, repetibilidade e reprodutibilidade) mostraram que a HS-SPME-GC/qMS-SIM é adequada para quantificar simultaneamente os cinco compostos tóxicos. A acroleína foi encontrada em concentrações similares na uva e mosto, e não foi detectada após a fermentação alcoólica e no vinho. O acetaldeído foi detectado em menores concentrações no mosto e em maiores níveis após a fermentação alcoólica. A concentração de furfural foi maior nas uvas do que nas demais etapas. O carbamato de etila não foi detectado nas etapas da vinificação e nos vinhos comerciais. Os níveis de formaldeído ficaram entre os valores de LOD e LOQ em todas as etapas da vinificação e nos vinhos comerciais. Além disso, nos vinhos comercialmente disponíveis, a acroleína foi encontrada em 50% das amostras, o acetaldeído e o furfural estavam presentes em todas as amostras. O único composto cuja ingestão pode representar risco a saúde é a acroleína. Dessa forma, este estudo contribuiu para identificar os pontos críticos de controle relacionados à presença de compostos tóxicos durante a vinificação, incluindo a produção do acetaldeído durante a fermentação alcoólica e a contaminação das uvas com acroleína e furfural através do ar atmosférico. Além disso, os resultados da ocorrência destes compostos tóxicos em vinhos comercialmente disponíveis poderão contribuir para a criação de uma legislação nacional que estabeleça limites dos mesmos nesta bebida. / Beneficial properties are associated with moderate consumption of wine due to the presence of phenolic compounds. A daily intake of wine of up to 200 or 300 mL is suggested for women and men, respectively. However, toxic carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, furfural and ethyl carbamate can be found among the compounds present in wines, which have been associated with adverse effects on human health, including cancer. The objective of this work was to develop and validate a method for simultaneous quantification of these toxic compounds through headspace solid phase microextraction associated with gas chromatography with quadrupole mass spectrometric detection in selected-ion monitoring mode (HS-SPME-GC/qMS-SIM) and characterize the risk related to exposure to these compounds. Four vinification steps (grape, must, after alcoholic fermentation and wine) and commercially available wine were analyzed using GC/qMS-SIM after checking the coelutions by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS). The derivatized acetaldehyde and acrolein coeluted in the first chromatographic dimension with limonene and methyl hexanoate, respectively. Based on this, were chosen as quantifiers ions in GC/qMS analysis, ions that were not found in the mass spectra of the coeluted compounds. The validation parameters (LOD, LOQ, recovery, repeatability and reproducibility) showed that HS-SPME-GC/qMS-SIM is adequate to simultaneously quantify the five toxic compounds. Acrolein was found at similar concentrations in grape and must, and was not detected after alcoholic fermentation and in wine. Acetaldehyde was detected at lower concentrations in the must and at higher levels after alcoholic fermentation. The concentration of furfural was higher in the grapes than in the other stages. Ethyl carbamate was not detected in the vinification steps and in commercially wine. Formaldehyde levels were between the LOD and LOQ values at all stages of winemaking and commercial wines. In addition, in commercially available wines, acrolein was found in 50% of samples, acetaldehyde and furfural were present in all samples. The only compound whose intake may pose a health risk is acrolein. Thus, this study contributed to identify critical control point related to the presence of toxic compounds during winemaking, including the production of acetaldehyde during alcoholic fermentation and the contamination of grapes with acrolein and furfural through atmospheric air. In addition, the results of the occurrence of these toxic compounds in commercially available wines may contribute to the creation of national legislation that establishes limits of the same in this drink.

Propriedades benéficas são associadas ao consumo moderado de vinho devido à presença dos compostos fenólicos. Uma dose diária de vinho de até 200 ou 300 mL é sugerida para mulheres e homens, respectivamente. Entretanto, dentre os compostos presentes nos vinhos, podem ser encontrados compostos carbonílicos tóxicos, como o formaldeído, acroleína, acetaldeído, furfural e carbamato de etila, os quais tem sido associados a efeitos adversos à saúde humana, incluindo o câncer. O objetivo deste trabalho foi desenvolver e validar um método para a quantificação simultânea destes compostos tóxicos através da microextração em fase sólida no modo headspace associada à cromatografia gasosa acoplada à espectrometria de massas quadrupolar no modo de monitoramento de íons selecionados (HS-SPME- GC/qMS-SIM) e caracterizar o risco relacionado à exposição a estes compostos. Quatro etapas da vinificação (uva, mosto, após a fermentação alcoólica e vinho) e vinhos comercialmente disponíveis foram analisados com o uso da GC/qMS-SIM após verificar as coeluições através da cromatografia gasosa bidimensional abrangente acoplada ao detector de espectrometria de massas por tempo de voo (GC×GC- TOFMS). O acetaldeído e a acroleína derivatizados coeluíram na primeira dimensão cromatográfica com o limoneno e o hexanoato de metila, respectivamente. Em função disso, foram escolhidos como íons quantificadores na análise por GC/qMS, íons que não foram encontrados no espectro de massas dos compostos coeluídos. Os parâmetros de validação (LOD, LOQ, recuperação, repetibilidade e reprodutibilidade) mostraram que a HS-SPME-GC/qMS-SIM é adequada para quantificar simultaneamente os cinco compostos tóxicos. A acroleína foi encontrada em concentrações similares na uva e mosto, e não foi detectada após a fermentação alcoólica e no vinho. O acetaldeído foi detectado em menores concentrações no mosto e em maiores níveis após a fermentação alcoólica. A concentração de furfural foi maior nas uvas do que nas demais etapas. O carbamato de etila não foi detectado nas etapas da vinificação e nos vinhos comerciais. Os níveis de formaldeído ficaram entre os valores de LOD e LOQ em todas as etapas da vinificação e nos vinhos comerciais. Além disso, nos vinhos comercialmente disponíveis, a acroleína foi encontrada em 50% das amostras, o acetaldeído e o furfural estavam presentes em todas as amostras. O único composto cuja ingestão pode representar risco a saúde é a acroleína. Dessa forma, este estudo contribuiu para identificar os pontos críticos de controle relacionados à presença de compostos tóxicos durante a vinificação, incluindo a produção do acetaldeído durante a fermentação alcoólica e a contaminação das uvas com acroleína e furfural através do ar atmosférico. Além disso, os resultados da ocorrência destes compostos tóxicos em vinhos comercialmente disponíveis poderão contribuir para a criação de uma legislação nacional que estabeleça limites dos mesmos nesta bebida. / Beneficial properties are associated with moderate consumption of wine due to the presence of phenolic compounds. A daily intake of wine of up to 200 or 300 mL is suggested for women and men, respectively. However, toxic carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, furfural and ethyl carbamate can be found among the compounds present in wines, which have been associated with adverse effects on human health, including cancer. The objective of this work was to develop and validate a method for simultaneous quantification of these toxic compounds through headspace solid phase microextraction associated with gas chromatography with quadrupole mass spectrometric detection in selected-ion monitoring mode (HS-SPME-GC/qMS-SIM) and characterize the risk related to exposure to these compounds. Four vinification steps (grape, must, after alcoholic fermentation and wine) and commercially available wine were analyzed using GC/qMS-SIM after checking the coelutions by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS). The derivatized acetaldehyde and acrolein coeluted in the first chromatographic dimension with limonene and methyl hexanoate, respectively. Based on this, were chosen as quantifiers ions in GC/qMS analysis, ions that were not found in the mass spectra of the coeluted compounds. The validation parameters (LOD, LOQ, recovery, repeatability and reproducibility) showed that HS-SPME-GC/qMS-SIM is adequate to simultaneously quantify the five toxic compounds. Acrolein was found at similar concentrations in grape and must, and was not detected after alcoholic fermentation and in wine. Acetaldehyde was detected at lower concentrations in the must and at higher levels after alcoholic fermentation. The concentration of furfural was higher in the grapes than in the other stages. Ethyl carbamate was not detected in the vinification steps and in commercially wine. Formaldehyde levels were between the LOD and LOQ values at all stages of winemaking and commercial wines. In addition, in commercially available wines, acrolein was found in 50% of samples, acetaldehyde and furfural were present in all samples. The only compound whose intake may pose a health risk is acrolein. Thus, this study contributed to identify critical control point related to the presence of toxic compounds during winemaking, including the production of acetaldehyde during alcoholic fermentation and the contamination of grapes with acrolein and furfural through atmospheric air. In addition, the results of the occurrence of these toxic compounds in commercially available wines may contribute to the creation of national legislation that establishes limits of the same in this drink.

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.

The risks associated with a soil contaminated by polycyclic aromatic hydrocarbons (PAHs) are generally assessed by measuring individual PAHs in the soil and correlating the obtained amounts to known adverse biological effects of the PAHs. The validity of such a risk estimation is dependent on the presence of additional compounds, the availability of the compounds (including the PAHs), and the methods used to correlate the measured chemical data and biological effects. In the work underlying this thesis the availability, chemical composition and biological effects of PAHs in samples of soils from PAH-contaminated environments were examined. It can be concluded from the results presented in the included papers that the PAHs in the studied soils from industrial sites were not generally physically trapped in soil material, indicating that the availability of the PAHs was not restricted in this sense. However, the bioavailable fraction of the PAHs, as assessed by bioassays with the earthworm Eisenia Fetida, could not be assessed by a number of abiotic techniques (including: solid phase micro extraction, SPME; use of semi-permeable membrane devices, SPMDs; leaching with various solvent mixtures, leaching using additives, and sequential leaching) and it seems to be difficult to find a chemical method that can accurately assess the bioavailability of PAHs. Furthermore, it was shown that PAH-polluted samples may be extensively chemically characterized by GC-TOFMS using peak deconvolution, and over 900 components can be resolved in a single run. The chemical characterization also revealed that samples that appeared to be similar in terms of their PAH composition were heterogeneous in terms of their overall composition. Finally, single compounds from this large set of compounds, which correlated with different biological effects, could be identified using the multivariate technique partial least squares projections to latent structures (PLS). This indicates that PLS may provide a valid alternative to Effect Directed Analysis (EDA), an established method for finding single compounds that correlate to the toxicity of environmental samples. Thus, the instrumentation and data evaluation tools used in this thesis are clearly capable of providing a broad chemical characterization as well as linking the obtained chemical data to results from bioassays. However, the link between the chemical analyses and the biological tests could be improved as as an organic solvent that solubilised virtually all of the contaminants was used during the chemical analysis while the biological tests were performed in an aqueous solution with limited solubility for a number of compounds. Consequently the compounds probably have a different impact in the biological tests than their relative abundance in profiles obtained by standard chemical analyses suggests. The availability and bioavailability of contaminants in soil also has to be studied further, and such future studies should focus on the molecular interactions between the contaminants and different compartments of the soil. By doing so, detailed knowledge could be obtained which could be applied to a number of different contaminants and soil types. Such studies would generate the data needed for molecular-based modelling of availability and bioavailability, which would be a big step forward compared to current risk assessment practices.

No description available.

The Ceratitis capitata is a very important agricultural pest, whose reproduction behaviour is controled by chemical signals. Males initiate mating by creating leks, where they release sexual pheromones to attract females. The main goal of this diploma thesis was to determine the influence of host plants on the composition of male sex-pheromones C. capitata and to compare emanations of wild males with those originating from laboratory population. We studied the chemical composition of volatiles, released by calling males C. capitata from laboratory and two wild populations, using two-dimensional gas chromatography with time-of-flight mass spectrometric detection (GC×GC-TOFMS), gas chromatography with electroantennographic and flame ionization detection (GC-EAD-FID). All data were statistically analyzed by multivariate data analyses. Significant differences were observed in the quantitative and qualitative composition of the chemical emanations among males from the three populations. The GC-EAD-FID analyses revealed fourteen antenally active compounds with a possible behavioral function. Isomenthone, geraniol, bornyl acetate, geranyl acetone and ethyl octanoate were newly identified antenally active compounds of C. capitata male sex pheromone. Statistical analyses indicated that males and females of...

Fungus Gloeophyllum trabeum (Agaricomytes: Gloeophyllates) is a brown rot wood-decay fungus which produces a vast spectrum of volatile secondary metabolites. Scientific publications state, that one of the metabolites produced by G. trabeum, can be the substance (3Z,6Z,8E)-dodecatrien-1-ol. This chemical substance is also the main component of trail-following pheromone of Rhinotermitidae termite family. In this diploma thesis, I was trying to verify whether various species of G. trabeum are in fact capable of producing the substance (3Z,6Z,8E)-dodecatrien-1-ol. I was also focusing on the effects of saccharides, present in nutrient solutions, on quantitative and qualitative change in composition of volatile secondary metabolites produced by G. trabeum. The saccharides I used for my research were - maltose, fructose, sucrose, xylose, and mannose. The analysis was made by using comprehensive two-dimensional gas chromatography separation technique with time-of-flight mass spectrometric detection (GC×GC-TOFMS). During my research I discovered that one of obtained species of G. trabeum can produce substance (3Z,6Z,8E)-dodecatrien-1-ol, but only under specific conditions. It is produced when cultivating on Petri dishes on agar - cellulose growth media. The measurement was further validated by...