Holothurians play an important role in carbon cycling. They dominate the abyssal oceanic megabenthos, reworking large amounts of organic matter. Holothurians require essential organic nutrients, such as carotenoids for their reproduction. Enhanced carotenoid concentration in the ovaries of echinoderms increases reproductive output and larval survival. Carotenoids cannot be synthesised de novo by holothurians, only by phytoplankton. To examine the link between diet and reproduction in deep-sea holothurians, the pigment biochemistry of holothurians, sediment and particulate organic matter from three abyssal sites as investigated. A temporal comparison at the Porcupine Abyssal Plain (PAP), NE Atlantic, has shown 1) the supply of organic material (OM) can affect the diet of holothurians, depending on their feeding adaptations and 2) holothurian reproductive biochemistry can be affected by compositional differences in the OM reaching the seafloor, although the extent of this influence appears to differ between species. Two abyssal sites around the Crozet Islands, Southern Ocean, were investigated to compare contrasting OM supply on the diet and reproductive biochemistry of holothurians. The sites are only 460 km apart, with no topographic boundary to separate them. However, they are subject to differing overlying primary productivity regimes and therefore biochemical differences can be ascribed to the composition and amount of organic matter reaching the sea floor at each site. The results showed that 1) the quantity of OM reaching the seafloor at each site differed, mirroring the overlying primary productivity regimes. This was also reflected in the diet of some holothurian species, depending on their ability to take advantage of the fresh material. 2) The reproductive biochemistry of the holothurians sampled at both sites showed quantitative differences, mirroring the supply of OM to each benthic site. The present study has shown that changes in the composition and quantity of the supply of OM to the deep-sea floor can affect holothurian diet and ovarian biochemistry. This may lead to large community changes as seen at the PAP in the NE Atlantic, which alters the reworking rate of the sediment, ultimately affecting the sequestration of carbon.

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No description available.

Little is known about the fauna that inhabits non-chemosynthetic environments associated with mid-ocean ridges. This thesis investigates a ridge and fracture zone system to assess its influence as a barrier to faunal dispersal, and as a unique bathyal habitat. It also describes the ecology of megabenthic communities inhabiting a ridge. Sites were chosen on the Mid-Atlantic Ridge in the vicinity of the Charlie-Gibbs Fracture Zone, at a target depth of 2,500 m. Four superstations were chosen north and south of the Fracture Zone, on either side of the ridge. Different productivity levels and hydrographic features were characteristic for the northern and southern sites. In order to characterise the benthic megafauna 50 ha were trawled and 32,000 m2 of seafloor were sampled with HD video footage, targeting both flat and 10 ◦ sloped habitats. Holothurians were the most abundant megafauna. In order to assess their evolutionary relationship 43 holothurian specimens were genetically studied by modelling five of their genes (16S, 18S, 28S, COI, H3) in a phylogenetic analysis. All four sites exhibited noticeably different faunal characteristics. The biomass was highest at the SE, and lowest at the NW site. Body sizes differed between sites for most taxa, that were sufficient in numbers to be compared between sites, most likely as a result of different adaptations to food supply. Differences in species richness were observed between the sampling methods, with the highest richness at the SE site in trawl samples, and highest at the NW and SW sites in the video survey. Species densities were highest at the northern sites with both methods. Differences in diversity were also observed, with trawl samples providing a higher taxonomic resolution than the video survey and showing highest diversity at the SE site and lowest at the NE site. Community composition was significantly different between sites. Variations in the composition of megabenthic assemblages were observed between flat and 10 ◦ sloped habitats, although the effect of slope appears to be site dependent. The genetic analyses revealed a close relationship between individuals from different families. The extent to which the Ridge acts as a faunal barrier was unclear as the southern sites lacked an obvious difference in community composition. Faunal differences to the north and south of the Fracture Zone, however, suggest that this feature is a barrier to dispersal. The contrasting megafaunal assemblages of the sites probably reflect a combination of environmental drivers including sediment type, phytodetrital quality, hydrography, and habitat complexity.

Advances in both seabed imaging capabilities and numerical models of shelf sea dynamics means new approaches are required to study those seas which surround us. Shelf sediment transport pathways are still principally derived from bedform and sediment indicators. A wealth of newly acquired data requires novel tools for extracting meaning in order to better understand shelf sediment dynamics. A new objective and quantitative method for extracting bedform dimensions has been developed and tested against synthetic and real data. New bedform analysis results have produced the largest global bedform measurements collection and extended the analysis range by an order of magnitude. To explore sediment transport at both tidal bank (< 10 km) andmshelf (> 10 km) scales, a new well-calibrated unstructured grid model of the European shelf has been developed, and model results using uniform and observation-derived bed roughness compared. Temporal changes in shelf sediment transport over both the recent past (100 years) and during the Holocene marine transgression (last 8 ka BP)are further explored. Marine and aeolian bedforms are compared through a range of statistical analyses and are shown to share the same morphology. Variability in medium to large marine bedforms (Ashley, 1990) is greater, and due to sensitivity to relatively larger changes in flow; larger bedforms are found to be more stable. Deviations from the derived global relationships are shown, through the palaeomodelling, to be due to relict bedforms. Variable bed roughness derived from the bedform observations and grain size has produced hydrodynamic results at least as good as those obtained from uniform roughness. Modern sediment transport on the shelf is found to be more complex in areas where traditional analyses cannot capture the temporal variability. The flexible nature of the model has meant subset bank modelling has benefitted from the well calibrated shelf model, and results have highlighted the differences in sediment transport regimes on the shelf. Sediment transport evolution during the Holocene transgression is shown to have been episodic, with quiescent periods followed by rapid changes. The quantitative analysis and modelling performed here has shown it is possible to take advantage of newly acquired data: the bedform analysis has confirmed the relationship between aeolian and marine bedforms and provided a tool for use in numerical modelling. The unstructured grid shelf model flexibility has produced both individual bank transport as well as pathways across the entire shelf.

Global warming and eutrophication are driving an expansion of hypoxia in the World Ocean. This will favour organisms, such as Foraminifera (testate protists), that tolerate low-oxygen conditions and may lead to an overall decline in marine biodiversity. With this in mind, community and trophic responses of benthic Foraminifera were investigated at two contrasting sites in the upper boundary (140 m water depth; bottom-water oxygen concentrations = 2.05 mll-1 during the spring intermonsoon and 0.11 mll-1 during the SW monsoon) and the core (300 m water depth; bottom-water oxygen concentration consistently ~ 0.11 mll-1) of an intense, natural, mid-water oxygen minimum zone (OMZ) on the Pakistan Margin, NE Arabian Sea. Live macrofaunal (>300 µm fraction) Foraminifera (including softwalled species) and metazoans were examined at each site during the 2003 spring intermonsoon (April) and SW monsoon (October) seasons (4 replicate multicores/site/season, 25.5cm2 surface area, 0-5 cm depth). Wet-sorting revealed a low diversity assemblage dominated (> 60 %) by calcareous Foraminifera at both sites. A total of 36 species was recognised and diversity was not greatly affected by water depth or season. At both sites, >86 % of Foraminifera were restricted to the upper 0-1 cm layer of sediment and the Average Living Depth (ALD) decreased from the spring intermonsoon to the SW monsoon (140 m, ALD5 = 0.41 to 0.33; 300 m, ALD5 = 0.65 to 0.44). Foraminifera increased in mean abundance from 124 to 153 individuals per 10 cm2 from the spring intermonsoon to the SW monsoon at 140 m and from 86 to 122 individuals per 10 cm2 at 300 m. The calcareous species Uvigerina ex. gr. semiornata dominated communities and increased in mean abundance from 54 to 118 individuals (140 m) and from 41 to 69 individuals (300 m) per 10 cm2 following the SW monsoon. At 140 m, Foraminifera were 3.6 times more abundant than metazoans during the spring intermonsoon, rising to 13.9 times during the SW monsoon. The corresponding proportions at 300 m, where metazoans were rare, were 12.4 and 14.5. Fatty acid biomarkers suggest that foraminiferal diets vary between species. The calcareous species U. ex. gr. semiornata, Bolivina aff. dilatata and Globobulimina cf. G. pyrula selectively ingested phytodetrital material, whereas the agglutinated species, Ammodiscus aff. cretaceus, Bathysiphon sp. nov. 1, and Reophax dentaliniformis favoured bacteria. Moreover, U. ex. gr. semiornata, rapidly ingested (within two days) 13C-labelled diatoms in shipboard laboratory and in situ pulse-chase experiments at the 140-m site following the SW monsoon. This enabled the uptake and processing of organic matter (OM) to be tracked in the foraminiferal cell into individual fatty acids, using Gas Chromatography - Mass Spectrometry (selective ion scan). These results suggest that calcareous Foraminifera, in particular U. ex. gr. semiornata, play a central role in OM cycling on the sea-floor in the upper part of the Pakistan margin OMZ.

This diploma thesis is focused on the problem of volatile aroma active compounds in chocolate, directly connected with the formation of chocolate aroma. Organoleptic properties of chocolate (aroma and taste) are the most important for evaluating by consumers. In this work four types of plain chocolate: Figaro Sweet Passion 70 % cacao, Figaro plain chocolate, Figaro for cooking and KAUMY chocolate glaze were tested. SPME method (fiber CAR/PDMS 85µm) in conjunction with gas chromatography was chosen for their analysis. Solid phase micro-extraction (SPME) is simple, sensitive, reproducible, rapid and low-cost method for evaluation of key odorant compounds found in cocoa and chocolate products. Using SPME-GC method total 56 aromatic compounds: 14 acids, 9 aldehydes, 8 ketones, 17 alcohols, 7 esters and 1 nitrogen compound were identified and quantified. Taste and aroma are the most important for evaluating of chocolate by consumer. Taste and aroma should be aromatic, pleasant and after used raw material. The single organoleptic properties (appearance, colour, taste, aroma and texture) were observed by sensory analysis using scale and also aroma and taste profiles of samples were created. The assessors were students and staffs faculty of chemistry BUT. The high content of alcohols (methanol, ethanol, propanol, butan-2,3-diol) and fatty acids was found in all types of chocolate , these compounds are probably important components of chocolate aroma. Some detected aromatic compounds doesn´t contribute positively to typical chocolate aroma. Unpleasant odour of these compounds often influences total flavour of chocolate, which was also proved by sensory evaluating.

It is common practice to add oxygenates, such as ethers or alcohols, to gasoline in areas suffering from ozone or smog problems in order to reduce pollution. The most commonly used oxygenates are ethanol (EtOH) and methyl tert-butyl ether (MTBE). However, MTBE is now forbidden by the environmental protection agency (EPA) because of the possibility of ground water contamination. The current trend is to use EtOH, therefore this work focuses on the analysis and quantification of EtOH in gasoline by solid phase microextraction (SPME). The major problem in quantifying EtOH in gasoline is the coelution of hydrocarbons with EtOH. There have been several approaches to solve this problem; among the chromatographic ones, three major types have been proposed: (1) the first one uses a detector selective for oxygen containing compounds; (2) the second one uses two or more columns; (3) and the third one uses an extraction step prior to GC analysis. In this work an extraction step with water is used prior to a solid phase microextraction (SPME) sample preparation coupled to a gas chromatographic (GC) analysis. Solid phase microextraction is a recent technique, invented by Pawliszyn in 1989, and available commercially since 1994. A fiber is used to extract small amounts (ppm, ppb, ppt) of analytes from a solution, usually water. The fiber is beneficial in concentrating analytes. Most work using SPME has been done with hydrophobic (non polar) analytes, extracted using a polydimethylsiloxane (PDMS; non polar) coating on a fused silica fiber. Since very little work has been done with polar analytes, the novel approach of this work is the extraction of EtOH. Since EtOH is the analyte of interest, a polar fiber, carboxen/polydimethyl siloxane (Car/PDMS) is used. Two methods are used for quantification of EtOH in gasoline: the method of a standard calibration curve, and the method of standard addition. They are both successful in quantifying the amount of EtOH in gasoline. The relative errors, with the method of standard addition, vary from 5.3% to 14%, while the ones with the method of calibration curve vary from 1.6% to 7.2%. Moreover, some extraction time studies for both direct and headspace sampling are performed. Direct sampling shows the presence of an equilibrium condition for the carboxen/PDMS fiber, for which no extraction theory is available. Conversely, headspace sampling shows no equilibrium state; after a sampling time of one hour, the amount of EtOH extracted decreases with sampling time. This is probably due to displacement of EtOH by other compounds in the fiber. / Master of Science

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...

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.