A contaminação das águas subterrâneas e recursos hídricos superficiais nas últimas décadas representam uma ameaça para a saúde pública. No Brasil, as águas subterrâneas desempenham importante papel no abastecimento público e privado, suprindo as mais variadas necessidades de água em diversas cidades e comunidades. Com a finalidade de garantir a qualidade da água consumida, o ser humano vem desenvolvendo desde a década de 70 diversas técnicas analíticas para monitorar a presença de contaminantes. No entanto, algumas dessas técnicas podem gerar resíduos piores ao meio ambiente do que as já existentes. Desta maneira a partir da década de 90, surge uma nova tendência na forma como conduzir as análises químicas, com o intuito de reduzir o impacto ambiental. No presente trabalho, foi explorada uma técnica de extração que atende tais objetivos, denominada como microextração líquido-líquido dispersivo DLLME, desenvolvida por M.Rezaee e colaboradores. Onde foram validados os hidrocarbonetos policíclicos aromáticos, atingindo limites entre 0,04 a 1,56 μgL-1, também foram analisadas amostras de águas subterrâneas coletadas aleatoriamente, em 4 postos de gasolina localizados na cidade de São Paulo. / Contaminations of groundwater and surface water resources in recent decades represent a threat to public health. In Brazil, groundwater plays an important role in public and private provision, meeting the diverse needs of water in various cities and communities. In order to ensure the quality of water consumed, the human being has been developing since the 70`s analytical techniques to monitor the presence of contaminants. However, some of these techniques can generate worst waste to the environment than the existing ones. Thus from the 90\'s, a new trend in how to conduct chemical analysis, aiming to reduce the environmental impact arises. In the present study, we explored a technique for extraction that meets these goals, termed as dispersive liquid-liquid microextraction - DLLME, developed by M.Rezaee and collaborators. Where polycyclic aromatic hydrocarbons have been validated, reaching limits between 0.040 to 1.558 μgL-1, also groundwater samples randomly collected from four gas stations located in the city of São Paulo analyzed.

Part 1: The emergence of environmentally friendly commercial products and their impact on fire debris analysis. Environmentally friendly products (i.e. green products) are environmentally preferable choices relative to comparable commercial products. They are readily available to the public, often highly flammable, and can be used by criminals as accelerants to facilitate the start and/or spread of fire. It is critical for analysts to have an understanding of their composition and chromatographic characteristics. Green products include paint thinners, solvents, removers, and cleaning and surface preparation products. As the composition of commercial products continually change over time, the fire debris community needs to be aware of the variety of environmentally friendly ignitable liquids that could be encountered during casework. Traditionally, when fire debris analysts have been trained, they are taught that most of the ignitable liquid residues they will encounter in casework are petroleum-based products. With the increasing emergence of non-petroleum based green products in the consumer marketplace, such products may be encountered more often than ever before in fire debris evidence submitted to forensic laboratories. Analysts should become familiar with the chromatographic features of these products as neat liquids as well as when present in fire debris samples. The purpose of this study is to introduce fire debris analysts to the prevalence of green products and increase knowledge regarding a variety of green product compositions and the characteristics they exhibit when analyzed as neat liquids and in "mock" fire debris samples. Several green products were analyzed as neat liquid samples and subsequently extracted from fire debris samples using typical fire debris extraction and analysis techniques in order to familiarize fire debris analysts with the chromatographic and mass spectral features of these products. General information about different types of green commercial products, their chromatographic and mass spectral characteristics, and their interpretation will be summarized. Analytical methods were developed for the analysis of environmentally friendly products and included considerations of gas chromatography oven temperature and ramp rate, hold times, and flow rate, as well as the scan rate and range of the mass spectrometer. Analyses involving common substrates were performed, including spiking green products onto various substrates with subsequent analysis and comparison of burned and unburned samples. Part 2: Application of fast GC/MS analysis for the identification of ignitable liquids in fire debris samples. Fire debris samples that contain ignitable liquid residues undergo a two-step process of extraction, most commonly via passive adsorption elution (PAE) onto an activated carbon strip, and instrumental analysis by gas chromatography/mass spectrometry. Upon completion of PAE, adsorbed compounds are eluted from the adsorbent with a suitable solvent and analyzed using (GC/MS) for the potential identification of ignitable liquid residues. A thorough evaluation of the literature revealed the average run time for gas chromatography of fire debris samples that contain hydrocarbon or petroleum based ignitable liquids to be 30 minutes. Additionally, a blank sample is run before an evidentiary sample to ensure solvent purity and to ensure any chromatographic carry over has not occurred between subsequent injections. The average run time, along with case volume, extraction times and case reviews contributes significantly to the backlog of samples to be analyzed in most crime laboratories around the country. Fast-GC/MS would significantly reduce analysis time, lower operating costs and would use less consumables. Based on a process known as pattern recognition, an initial goal of a fire debris analyst is to identify a pattern that is consistent with an ignitable liquid class. The standard method followed by most fire debris analysts use or base standard operating procedures (SOPs) on the American Society of Testing and Materials (ASTM) E1618, which defines the classes of commercial ignitable liquids based on chemical composition and boiling point range (or volatility). This study was conducted to optimize current methods of ignitable liquid detection and to optimize fast-GC/MS conditions for the identification of ignitable liquids in fire debris samples. Additionally, this study was conducted to determine if fast-GC/MS can reduce chromatographic separation times without sacrificing peak resolution and subsequently allow for ignitable liquid discrimination. Method development included considerations of flow rate, initial GC oven temperature, ramp rate, and mid and end temperature hold times. Fast-GC/MS conditions were tested on neat ignitable liquids from all nine ASTM E1618 classes. Optimizing fast-GC/MS method parameters led to an increase in sample throughput in comparison to traditional GC/MS methods. As a result, the GC/MS identification of ignitable liquids and their residues was performed in a quarter of the amount of time when compared to traditional methods.

A reconnaissance survey of the 1000 Km\(^2\) of Masirah Island, Oman, has revealed a fully-developed ophiolite complex which is believed to represent a fragment of Cretaceous ocean crust and upper mantle generated at a constructive plate margin. The complex consists of mantle serpentinites, plutonic rocks ranging from dunite to trondhjemite, a sheeted dyke complex and pillow lava-sediment sequences, all of which have been chemically and petrographically analysed. Several belts of serpentinite occur within the ophiolite associated with major fault-lines. The serpentinites are clearly derived from depleted harzburgitic mantle and their field relations suggest that some were emplaced in the oceanic environment. The chemistry of the plutonic rocks suggests that they are products of dominantly open-system fractional crystallisation of tholeiitic liquid(s), possibly in several discrete magma chambers. Modelling of trace and RE elements suggests that moderate degrees of mantle peridotite melting were involved in production of the magma chamber parental liquid(s). At a higher crustal level sheeted dyke-massive gabbro relationships are interpreted in a model of roof underplating, which causes a decreasing frequency of dyke injection. Metamorphism of the sheeted dykes and lavas is interpreted as sub-sea floor in origin and its effect on whole-rock chemistry is assessed. The dykes and lavas have a chemistry largely typical of present-day ocean tholeiites and the relative contributions of the processes of partial melting and fractional crystallisation to that chemistry are evaluated. Two localised volcanic groups were identified, which appear to have enriched chemistries compatible with origin at off -axis oceanic islands. A major tectonic zone cross-cuts the ophiolite units and has features reminiscent of the modern oceanic transform faults. The importance of this structure, both in the oceanic environment and during the process of ophiolite emplacement, is assessed. Intrusive into the ophiolite is a granite whose trace and RE element chemistry is alien to the oceanic environment and suggests melting of continental crust Finally, a synthesized model of the former constructive margin is produced and an attempt is made to define the type of spreading centre represented. Comparison of the Masirah Ophiolite with the Semail Ophiolite of the Oman Mountains suggests that their former correlation may be ill founded. An assessment of late Mesozoic -early Tertiary plate motions indicates an origin during Cretaceous sea-floor spreading of an early Indian Ocean. Several features may indicate a slow-spreading, much-faulted, constructive margin.

Im Rahmen der Arbeit wurde eine Methode für die Quantifizierung von freiem 17β-Estradiol, Estron sowie der hydroxylierten und methylierten Metabolite im Brustgewebe entwickelt. Aufgrund der geringen Probengehalte erforderte dies eine gezielte Isolierung der Analyte aus der Probenmatrix sowie eine effektive Aufreinigung und Aufkonzentrierung, so dass eine Extraktion mit anschließender Festphasenextraktion durchgeführt wurde. Zudem wurde eine empfindliche Mess-Methode etabliert, welche auf Grundlage einer multi-reaction-monitoring-Methode, mittels Gaschromatographie und gekoppelten Triple-Quadrupol-Massenspektrometer, entwickelt wurde. Die Anwendbarkeit der Aufarbeitungs- und Mess-Methode wurde überprüft, indem diese auf 30 Realproben übertragen wurde. Dabei sind die ermittelten Gehalte mit den publizierten Daten der Gewebekonzentrationen von 17β-Estradiol, Estron und deren Metaboliten verglichen und Korrelationen mit ausgewählten Brustkrebs-begünstigenden Risikofaktoren betrachtet worden. Um ein quantitatives Metabolitenprofil von 17β-Estradiol, Estron und deren Metaboliten im Gewebe zu erstellen, wurden mit Hilfe einer multi-reaction-monitoring-Methode für alle Metabolite ein spezifischer Quanti- und Qualifier-Übergang etabliert. Durch die Optimierung der Ionisierungs- und Kollisionsenergien sowie der Initial-, Transferline- und Ionenquell-Temperatur beziehungsweise der dwell-time wurden Methoden- und Geräte-bedingte Empfindlichkeitsverluste so weit wie möglich reduziert, so dass maximale Signalintensitäten aller Quantifier-Übergänge gewährleistet waren. Zur gezielten Isolation sowie Aufreinigung und Anreicherung der Analyten,... ...so dass trotz der geringen Anzahl analysierter Gewebe-spenden der Einfluss des Body-Mass-Index und die Einnahme oraler Kontrazeptiva auf die Gehalte von 17β-Estradiol in der prämenopausalen Frau deutlich wurden. Die entwickelte Mess-Methode ermöglicht den routinemäßigen Einsatz für die Quantifizierung von freiem 17β-Estradiol, Estron und deren Methyl-Catecholen in humanem Brustgewebe. Beim Vergleich der berechneten Nachweisgrenzen von Catechol-Estrogenen mit Literaturangaben wurde herausgestellt, dass empfindlichere flüssigchromatographische Methoden als Methode der Wahl bei deren Analytik heranzuziehen sind. Die Übertragung der in Standardlösungen durchgeführten Versuche zur enzymatischen Hydrolyse von Glucuronid-und Sulfat-Konjugaten auf Gewebematrix stellt für weiterführende Arbeiten den entscheidenden Ansatzpunkt dar, um ein quantitatives Metabolitenprofil von freiem und gebundenem 17β-Estradiol, Estron und den Metaboliten in Brustgewebe erstellen zu können. / The aim of the present work was to develop a method for the quantification of free estradiol, estrone, catechol estrogens and methylation products in breast tissue. Due to trace amounts in the samples it was necessary to isolate the analytes from the sample matrix, purify and concentrate them prior to tissue extraction and solid phase extraction. Additionally, a sensitive method of measurement based on multi reaction monitoring using gas chromatography and triple quadrupole mass spectrometry was developed. The applicability of the sample preparation and measurement method was tested in 30 tissue samples by comparing the measured levels with published data concerning concentrations of estradiol, estrone and their metabolites in breast tissue. Also it was necessary to find possible correlations between the analytes concentrations and selected risk factors for breast cancer. In order to develop a quantitative profile of estradiol, estrone and metabolites in tissue, qualifier and quantifier transitions were established using the multi reaction monitoring mode. By optimising the ionisation and collision energy, the initial, transferline and ion source temperatures and the dwell-time, it was possible to reduce the loss of sensitivity caused by both method and equipment and maximize the signal intensity of all quantifier transitions. For the isolation, purification and concentration of the analytes... ...have some influence on the levels of estradiol in premenopausal women. The developed measurement method enabled a routine usage for the quantification of free estradiol, estrone and methylcatechols in human breast tissue. The comparison between the calculated detection levels of catechol estrogens and the published data led to the conclusion that liquid chromatographic methods are more sensitive. The transference of these methods and experiments conducted, such as for the enzymatic hydrolysis of glucuronide- and sulfate-conjugates on tissue matrix in standard solution, seem to offer a starting point for future research projects. Especially, for the purpose of establishing a quantitative metabolite profile of free and conjugated estradiol, estrone and their metabolites.

Nowadays, there is an increasing awareness on the importance of biomass waste as a renewable source of energy, materials and chemicals. In this context, the European project MOBILE FLIP aims at developing and demonstrating mobile conversion processes suitable with variousunderexploited agro- and forest based biomass resources in order to produce energy carriers, materials and chemicals. One of these processes is torrefaction, which consists in a mild thermal treatment, occurring typically between 200 and 300°C during a few tens of minutes in a defaultoxygen atmosphere. The solid product obtained has thermal and processing properties closer to coal, and thus is suitable as fuel for combustion or gasification. During torrefaction, condensable coproducts are released, that may also be source of “green” chemicals. It is therefore crucial to characterize them to optimize the torrefaction process and design industrial units. Up to now, only few works have been focused on characterizing and modelling both solid and condensable species during torrefaction versus operating conditions and feedstock type. Furthermore, these studies typically include a reduced number of biomasses. Cellulose, hemicellulose and lignin,which constitute biomass macromolecular composition, are determining properties to predict biomass behaviour during torrefaction. However, torrefaction tests on these constituents are rare and always based on commercial compounds, which were proved as little representative of the native biomass. The objective of this study is to analyse the influence of biomass characteristics, mainly represented by the macromolecular composition in cellulose, hemicellulose and lignin, on the global behaviour of biomass in torrefaction, both in terms of solid mass loss and of productionprofiles of the volatile species released, in function of the operating conditions.14 biomasses from the main biomass families (deciduouswood, coniferous wood, agricultural byproductsand herbaceous crops) were selected for this study. An optimized extraction procedure was proposed to recover cellulose, hemicellulose and lignin fractions from 5 reference biomasses. Experiments were performed on a thermogravimetric analyzer coupled to a gas chromatography mass spectrometer device through a heated storage loop system (TGA-GC/MS). Solid degradation kinetics and volatile release profiles were followed during torrefaction experiments combining non-isothermal (200 to 300°C at 3°C/min) and isothermal (300°C, 30 min) conditions, ensuring the chemical regime thanks to the appropriate operating conditions. The results obtained with the raw materials demonstrated that biomass macromolecular composition is a main factor influencing biomass behavior in torrefaction. Consequently, the heterogeneity of the resource results in a diverse behavior in torrefaction, particularly in the case of agricultural biomasses. The results with the extracted components evidenced their very different behavior compared to thecommercial compounds, particularly in the case of cellulose. This suggests that a limitation could be induced by the common use in literature of commercial components for torrefaction modelling. The impact on the characterization of macromolecular components was also shown to be prevailing in their behavior in torrefaction, especially in the case of hemicellulose sugar composition and cellulose crystallinity. Furthermore, differences in release kinetics of volatile species during torrefaction were observed, even for volatiles belonging to the same chemical family (acids, furans, ketones). Derived from these results, a torrefaction model based on the additive contribution of extracted cellulose, hemicelluloses and lignin to the global behavior of biomass in torrefaction was proposed, and this for the 5 representative biomasses.

<p>The two additive brominated flame retardants, tetrabromoethylcyclohexane (TBECH) and hexabromocyclododecane (HBCD) are used to prevent fire to start and spread. They are simply mixed with material and are most likely to leach out in the environment, because of non-covalently binding to the material. TBECH can exist as four pairs of enantiomers, α-, β-, γ- and δ-TBECH. The technical HBCD can exist as three pairs of enantiomers, α-, β- and γ-HBCD and two meso forms δ- and ε-HBCD. None of these compounds are produced in Sweden, but they are imported to industries. TBECH has been found in Beluga blubber and can accumulate in zebrafish. HBCD has been found in water environments and can be toxic to and bioaccumulate in water-living animals.</p><p>In this study, a method was developed for separation and detection of α-, β-, γ- and δ-TBECH on HRGC/HRMS. All TBECH-isomers could be separated with the developed method. How much of the TBECH isomers that were recovered after applying existing extraction and clean-up procedures, normally applied for clean-up and extraction of PCBs and PCDD/Fs, was evaluated. Low recovered amounts (6.8-35.5 %) of TBECH-isomers added in known amounts to three different whale samples indicate severe evaporation losses and possibly photolytic degradation. None of the four enantiomers were detected in the three whale samples. For HBCD analysis, both the chromatography and MS/MS parameters were optimised for δ- and ε- HBCD yielding good chromatography and sensitivity. However, due to technical difficulties during the time-period of this project, no whale samples could be analysed for HBCD on UPLC/MS/MS. </p>

Analytical instrumentation for quantitative in vivo stable isotope metabolic studies has included gas chromatography-mass spectrometry (GC-MS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Limitations of existing MS techniques include excessive parent ion fragmentation, time-consuming sample preparation, and complex instrument operating parameters. In this thesis, procedures for set up and implementation of four GC-MS techniques are described. The first three replicate existing GC-MS single quadrupole methods on an ion trap, and are electron ionization (EI), external methane positive chemical ionization (PCI), and methane negative chemical ionization (NCI). The fourth method is a novel GC-MS mass-selected ion trap internal isobutane positive chemical ionization technique. Four groups of rats were administered isotopic linoleic acid, and liver tissue was collected for labelled linoleic and n-6 polyunsaturated fatty acids (PUFA) metabolites analyses. Qualitative utility of EI was confirmed, and its quantitative limitations exposed. Labelled 18:2n-6 and n-6 PUFA metabolites were detected using external methane PCI, though limited due to significant fragmentation. Methane NCI also detected labelled 18:2n-6, as well as minimizing fragmentation. However, time-consuming sample preparation and non-linear responses were major limitations. Internal isobutane PCI was useful in detecting isotopic 18:2n-6 and n-6 PUFA metabolites. Fragmentation was reduced compared to EI and external methane PCI. Limitations include fragmentation of HUFAs such as EPA and DHA. The novel internal isobutane PCI is more sensitive than external methane PCI and NCI, produces highly linear responses, is simpler and less expensive to operate than C-IRMS, offers reliable instrument operation, and sample preparation time is minimal. Regular quantitative analyses of HUFAs such as EPA and DHA may require further refinements such as using lower energy reagents than isobutane, including acetonitrile and ammonia.

Syftet med detta examensarbete var att utveckla en GC-metod för analys av etylenglykoler i förorenade vattenprover, exempelvis industriavloppsvatten. Detta skulle åstadkommas med en GC-FID och MMI (Multimode Inlet), samt helst utan provupparbetning. Ett annat av målen var att kunna kvantifiera inom området 1 ppm till 100 ppm, och att metoden skulle vara tillräckligt stabil för att kunna ackreditera den.Ett flertal kolonner testades, där en HP-5 med dimensionerna 30 m*0,53 mm*0,88 μm från Agilent var den som gav bäst resultat. Även två olika liners provades, dels en med glasull och dels en 2 mm dimpled liner, där dimpled linern gav bäst resultat, och minst ”carry-over” mellan analyserna. Bland de parametrar som gav störst effekt utmärker sig trycket i injektorn, och tiderna som de olika flödena är igång. För fullständiga inställningar, se bilaga 2.En metod redo för ackreditering hann ej tas fram, det finns ett flertal parametrar som bör undersökas för en effektivare och stabilare analys. Men metoden som är framtagen är redo för omfattande repeterbarhetstest. / The purpose of this bachelor’s thesis was to develop a GC method for analysis of ethylene glycols in polluted water samples, for example industrial sewage water. This was meant to be accomplished with a GC FID and MMI (Multimode Inlet), preferably without sample preparation. One of the goals was to be able to quantify between 1 ppm and 100 ppm, and that the method was stable enough for accreditation.A number of columns were tested, from where a HP-5 with the dimensions 30 m*0,53 mm*0,88 μm from Agilent gave the best results. Also, two different liners were tested, one with glass wool and one 2 mm dimpled liner, where the dimpled liner gave the best results and the least carry-over between samples. Amongst the parameters which gave the biggest effect, the inlet pressure and the different flow times stands out. For a full set of settings, see Bilaga 2.A method ready for accreditation was not developed due to short of time. There are still a number of parameters which should be investigated for a more efficient and stabile analysis. But the method developed is ready for extensive repeatability tests.

Vi har i denna rapport jämfört produktionsmetoder vid byggande av gång- och cykeltunnel under järnväg. de metoder vi har jämfört är lansering och platsgjutning. Projektet som vi har studerat är byggandet av en gong- och cykeltunnel under järnväg vid Mjölby station. Vid detta projekt lanseras halva tunneln in och halva platsgjuts. Det vi har jämfört är dels de geotekniska aspekterna, där vi främst har tittat på vikten av förundersökningar, jordegenskapens inverkan, spontning och grundvattnets inverkan. Vi har också tittat på produktionstekniska aspekter, då främst storleken av arbetsområdet och arbetsmiljön. Vi har även betraktat ekonomi och produktionstid i de båda metoderna. Vi har i denna rapport främst använt oss av muntliga källor som gett sina synpunkter på hur tunneln ska eller bör utformas. Vi har sedan sammanställt alla synpunkter och åsikter och skaffat oss en egen uppfattning om de båda metoderna och när de bör användas. Det vi kommit fram till när vi har jämfört dessa båda metoder är att lansering har många fördelar vad gäller arbetsmiljö, tid och ekonomi. vid enklare tunnelprojekt är denna metod att föredra om förutsättningar finns. platsgjutning har dock de fördelar att den kan användas vid de flesta tunnelbyggnationer och att tågtrafiken kan flyta på utan längre störningar. Vid stora projekt som det i Mjölby anser vi att en kombination av metoderna är den allra bästa lösningen.

Analytical instrumentation for quantitative in vivo stable isotope metabolic studies has included gas chromatography-mass spectrometry (GC-MS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Limitations of existing MS techniques include excessive parent ion fragmentation, time-consuming sample preparation, and complex instrument operating parameters. In this thesis, procedures for set up and implementation of four GC-MS techniques are described. The first three replicate existing GC-MS single quadrupole methods on an ion trap, and are electron ionization (EI), external methane positive chemical ionization (PCI), and methane negative chemical ionization (NCI). The fourth method is a novel GC-MS mass-selected ion trap internal isobutane positive chemical ionization technique. Four groups of rats were administered isotopic linoleic acid, and liver tissue was collected for labelled linoleic and n-6 polyunsaturated fatty acids (PUFA) metabolites analyses. Qualitative utility of EI was confirmed, and its quantitative limitations exposed. Labelled 18:2n-6 and n-6 PUFA metabolites were detected using external methane PCI, though limited due to significant fragmentation. Methane NCI also detected labelled 18:2n-6, as well as minimizing fragmentation. However, time-consuming sample preparation and non-linear responses were major limitations. Internal isobutane PCI was useful in detecting isotopic 18:2n-6 and n-6 PUFA metabolites. Fragmentation was reduced compared to EI and external methane PCI. Limitations include fragmentation of HUFAs such as EPA and DHA. The novel internal isobutane PCI is more sensitive than external methane PCI and NCI, produces highly linear responses, is simpler and less expensive to operate than C-IRMS, offers reliable instrument operation, and sample preparation time is minimal. Regular quantitative analyses of HUFAs such as EPA and DHA may require further refinements such as using lower energy reagents than isobutane, including acetonitrile and ammonia.