Marshy soil and sediment samples were collected during dry and rainy seasons within Warri, and Agbarho, 20km away as control. Levels of 16 USEPA priority Polycyclic Aromatic Hydrocarbons PAHs were determined using GC-FID. Source prediction analysis was also done. The study was in Niger Delta region, Nigeria from January to March and June to August 2012 in dry and wet seasons. Benzo(a)pyrene had highest total concentration of 3.302mg/kg and mean value of 1.651mg/kg in dry season soil samples. However, sediment samples had highest levels for total concentration of PAHs of 19.362mg/kg and mean of 4.840mg/kg for both dry and rainy seasons within Warri. PAHs concentration was higher in dry than rainy seasons for soil and sediment samples. Source prediction analysis revealed that PAHs in sediments for dry season were pyrolytic while rainy seasons were petrogenic sources. For soils, the dry season was mixed sources while the rainy season was petrogenic. / Environmental Science / M. Sc. (Environmental Science)

Polycyclic aromatic azomethine ylide (PAMY) is a versatile building block for the bottom-up construction of unprecedented nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). Here, we demonstrate the 1,3-dipolar cycloaddition between PAMY and 1,4-diphenylbut-2-yne-1,4-dione as well as the subsequent condensation reaction with hydrazine, which led to synthesis of unique N-PAHs with a phenyl-substituted pyrrolopyridazine core (PP-1 and PP-2). The molecular structures of pristine PP-1 and tert-butyl-substituted PP-2 were verified by NMR and mass spectroscopy. Moreover, the structure of PP-2 was unambiguously elucidated by X-ray single crystal analysis. The optoelectronic properties were investigated by solvent-dependent UV-Vis absorption and fluorescence emission spectroscopy as well as cyclic voltammetry. Additionally, the density functional theory (DFT) calculations exhibited a push-pull behavior for PP-1 and PP-2. Furthermore, the in situ EPR/UV-Vis-NIR spectroelectrochemistry allowed the detailed insight into the spectroscopic properties and spin distribution of radical cation species of PP-2.

This master's thesis deals with the analysis of organic substances, which are present in biochar. Biochar contains a number of organic compounds, that can be toxic and also carcinogenic to living organisms. In order for biochar to be used to improve soil quality or to be used for other applications, its safety must be declared by European or international certifications. Relevant European and international standards have been created for the determination of organic substances, that could be present in biochar. The theoretical part of the thesis was focused on selected organic substances, the process of pyrolysis and thermochemolysis, biochar characterisation and the used analytical methods. The experimental part of the thesis consisted of extraction with toluene and after that the determination of concentration of the 38 polycyclic aromatic hydrocarbons was performed. Qualitative analysis was performed by two-dimensional gas chromatography. Biochar samples were also subjected to thermochemolysis method and then they were analysed on GC-MS again. In both analytical methods, a large number of substances from groups such as PAHs, carboxylic acids, amines, substituted naphthalenes etc. was found, as well as smaller number of eg. polychlorinated biphenyls.

This diploma thesis is focused on the study of conditions of benzo[a]pyrene, one of the major contaminant of foods, photodegradation under different conditions (solvents with different polarity, light sources, presence of antioxidants). In another part of the thesis, the degradation process of benzo[a]pyrene at various concentrations was studied, in order to characterise the kinetic aspects of photoinduced degradation. The attempt to identify the products of benzo[a]pyrene photodegradation was performed involving methods of gas chromatography and high performance liquid chromatography coupled with mass detectors, as well.

Biomass pyrolysis and gasification techniques count among basic technological procedures for its use as a source of energy. As a side-effect, production of tar can be considered. Tar is a complex mixture of various organic compounds and affects negatively both the environment and the facilities where biomass is processed. Within the scope of this master thesis the analysis of tar samples from different materials was performed. As an appropriate analytical method the gas chromatography combined with flame ionization detection (GC-FID) and time-of-flight mass spectrometry (GC-TOF-MS) was chosen. The concentrations of volatile organic compounds known as BTEX, polycyclic aromatic hydrocarbons (PAH) and phenolic compounds were assessed.

Polycyclic aromatic hydrocarbons (PAHs) are recalcitrant organic pollutants, which occur widely in the environment. Some of these compounds are carcinogenic and toxic, many studies therefore focus on suitable remediation technologies. It has been shown that composting is an efficient treatment for contaminated solid matrices. Changes in several enzyme activities during co-composting of PAH-contaminated soil were studied in this thesis. The total initial concentration of analyzed PAHs in the soil was 1065 ± 86 µg·g-1 . The chosen activities represented well-known key enzymes involved in the transformation of PAHs or catechol as the central metabolite of PAH microbial degradation. At first, a method for extraction of the selected enzymes from the compost matrix was optimized. This approach was then used for the extraction of the enzymes from compost samples collected at each phase of composting. The activity of manganese peroxidase, laccase, tyrosinase and catechol-2,3-dioxygenase was detected during the cooling and the maturation phase. The only detected activity during the initial mesophilic phase was that of manganese peroxidase. The activities of catechol-1,2- dioxygenase and lignin peroxidase were not detected at all. Despite the fact that PAHs were substantially degraded, no influence of PAHs...

Einige der Polyzyklischen Aromatischen Kohlenwasserstoffe (PAK) weisen Krebs auslösende Eigenschaften auf. Die bekannteste karzinogene PAK-Verbindung ist das Benzo[a]pyren (BaP), welches bislang als Leitsubstanz verwendet wird. Mittlerweile bestehen jedoch Zweifel, ob BaP als alleinige Leitsubstanz geeignet ist. Daher empfiehlt die EU-Kommission die Untersuchung der PAK auf die so genannten 16 EFSA-PAK auszudehnen. Zur Überprüfung der Anwendbarkeit von BaP als Leitsubstanz war es notwendig, Erkenntnisse über das Verhältnis des Gehaltes an BaP zum PAKges-Gehalt sowie die einzelnen PAK-Profile zu gewinnen. Die zu untersuchenden Lebensmittelgruppen wurden eingeschränkt auf Fleischerzeugnisse, Rauchwürzer und Räuchersalze, Räucherdärme, Gewürze, Tee und Schokolade. Nach der Entwicklung und Überprüfung von Methoden zur Bestimmung der EFSA-PAK und der anschließenden Analytik einer Anzahl repräsentativer Proben verschiedener Lebensmittelgruppen konnte mit Hilfe einer Datensammlung zu den Gehalten der 16 EFSA-PAK die Beurteilung von BaP als Leitsubstanz erfolgen. Es konnte eine Abhängigkeit der PAKges-Gehalte vom BaP-Gehalt ermittelt werden, welche sich mit zunehmender Konzentration der PAK manifestierte. Aus analytischer Sicht eignet sich BaP am besten als Leitsubstanz, da sie chromatographisch mit den heutigen Methoden leicht von anderen möglichen coeluierenden Substanzen abgetrennt werden kann und in Konzentrationen vorkommt, die zuverlässiger quantifiziert werden können.

<p>Sprovedeno istraživanje u okviru<br />disertacije obuhvata procenu distribucije<br />16 EPA primarnih policikličnih aromatičnih<br />ugljovodonika između gasovite i čvrste<br />faze u atmosferi, na selektovanim<br />lokalitetima urbanog, industrijskog i<br />ruralnog područja na teritoriji Zapadnog<br />Balkana. Rezultati eksperimentalnog<br />određivanja predstavljali su osnovu za<br />evaluaciju reprezentativnih modela<br />rasprostiranja poluisparljivih organskih<br />jedinjenja kroz povr&scaron;inski atmosferski sloj<br />i raspodele gas/suspendovane čestice,<br />čime je dat uvid u mehanizme koji<br />dominiraju atmosferskom distribucijom<br />policikličnih aromatičnih ugljovodonika.<br />Metodom dijagnostičkih odnosa<br />realizovana je kvalitativna karakterizacija<br />izvora emisije PAH u atmosferu.<br />Korekcijom postojećih empirijskih i<br />teorijskih izraza koji opisuju gas/čestičnu<br />particiju PAH, razvijen je matematički<br />model raspodele policikličnih aromatičnih<br />ugljovodonika u ambijentalnom vazduhu.</p> / <p>Gas-particle distribution of 16 EPA primary<br />polycyclic aromatic hydrocarbons in the<br />atmosphere at the selected sampling sites<br />in urban, industrial and rural area of the<br />Western Balkan countries has been<br />analyzed within the doctoral dissertation.<br />On the basis of obtained experimental<br />data, representative models of transport<br />through surface atmospheric layer and gasparticle<br />partitioning of the semivolatile<br />organic compounds have been evaluated,<br />giving the overview on mechanisms which<br />govern atmospheric distribution of<br />polycyclic aromatic hydrocarbons. Using<br />the method of diagnostic ratio, qualitative<br />characterization of emission sources of<br />PAHs in the atmosphere has been realized.<br />Through correction of actual empirical and<br />theoretical expressions, explaining gasparticle<br />partitioning of PAHs,<br />mathematical model of distribution of<br />polycyclic aromatic hydrocarbons in the<br />ambient air has been developed.</p>

Geotextildukar används idag som tillfällig kontroll av sedimentgrumling vid vattenarbeten. Syftet med examensarbetet är att ge ökad kunskap kring olika geotextildukars genomsläpplighet med avseende på suspenderat material, PAH (Polycykliska aromatiska kolväten) och kvicksilver vid suspension av sediment från Karlbergskanalen. Detta har gjorts genom en laboration. Resultaten visar att det inom några minuter bildas en filterkaka på de tre undersökta dukarna. Dukarna blir täta då de utsätts för finpartikulärt suspenderat sediment med koncentrationen 57 g/l hämtat från Karlbergskanalen. Under de 2,5 timmar långa försöken har dukarnas permeabilitet kraftigt reducerats. Under laborationen var PAHtot och mängden PAH i den filtrerade fraktionen störst vid turbiditetsmaximum. Den filtrerade fraktionen PAH följde turbiditeten och reducerades med 21 % samtidigt som turbiditeten reducerades med 24 % under försöket. Även den totala kvicksilvermängden var störst vid turbiditetsmaximum, resultaten är dock inte statistiskt säkerställda. Under laborationen gav en högre halt suspenderat material en lägre andel PAH i den filtrerade fraktionen, troligtvis beroende på re-adsorption. För att utvärdera hur stor andel av PAH, kvicksilver, kadmium och koppar som befinner sig i den filtrerade fasen har det genomförts försök där sediment och vatten skakats 3x10 timmar. Av den totala PAH koncentrationen var 0,07 % i den lösta fasen. Endast en låg andel av koppar, kadmium och kvicksilver återfanns i den lösta fasen (&lt; 1 %). Trots den låga andelen i den filtrerade fraktionen skulle motsvarande haltökningar i Karlbergskanalen innebära halter långt över aktuella gränsvärden[1]i dukbassängen. Innan filterkakan bildats sker ingen reduktion av turbiditeten för två av de tre undersökta dukarna. Geotextilskärmarna förhindrar således ingen spridning av miljögifter utan bildningen av en filterkaka. Om filterkakan bildas och består i fält går inte att fastställa utifrån laborationen. [1]MKN MAC för löst Hg och Cd, Naturvårdsverkets föreslagna GV för löst Cu MKN MAC för den totala PAH koncentrationen / Geotextiles are used as temporary sediment controls in water during construction work. The aim of this project is to give background information to a cost effective control program and to increase the knowledge about geotextiles and their permeability for suspended sediment, PAH and Hg for a site specific sediment. Laboratory studies have been conducted in order to evaluate three geotextiles with regard to their ability to separate suspended sediment, PAH and Hg. The results show that a filter cake is formed. The textiles became clogged within a time period of 15 minutes and no sediment passed the textiles after this. A sediment concentration of 57 g/l was used. The separation of suspended particulate matter is 28-78 % and the textile with the greatest reduction capacity was the thinnest one. The separation of PAHtot was 79 %, meanwhile the average separation of suspended sediments was 78 %. The geotextile did not reduce the dissolved fraction of PAH. This fraction was larger on the outside suggesting that the concentration of suspended material was too low to re-adsorb the dissolved PAH. The turbidity decreased with 24 % during the experiment due to sedimentation, the dissolved fraction of PAH was reduced with 21 % during the same time period. The amount of Hgtot was largest at turbidity maximum. Laboratory experiments where sediment was shaken 3x10 hours with distilled water have also been conducted in order to evaluate the amounts of PAH, Hg, Cu and Cd that partition in the dissolved phase. 0, 07 % of the total amount of PAH was found in the filtered phase and only small fractions of Cu, Cd and Hg (&lt; 1 %). Despite the small percentage in the filtered fractions the corresponding increase in Karlbergskanalen would result in concentrations well above maximum allowed concentrations[1]in the geotextile encircled area. There is no reduction of the turbidity before the filter cake is formed. It is not possible to draw any conclusions about the formation of a filter cake in field and if a formed filter cake would be broken by hydraulic forces or not. [1]MKN MAC for dissolved Hg and Cd, Swedish Environmental Protection Agency’s suggested limit value for dissolved Cu, MKN MAC for the total PAH concentration

Mass spectrometry (MS) has become a widely used technique for the characterization of a wide range of substances in diverse fields. The selection of appropriate ionization techniques, source parameters, charge carriers based on the analyte’s polarity is essential in MS as only the ions are detected. When using a soft ionization technique, single stage-MS at best provides only chemical composition; thus, tandem MS is needed to determine structural information and dissociation pathways. This dissertation focuses on the characterization of various small molecules and ions using different ionization techniques, charge carriers, and collision-induced dissociation (CID). In Chapter II, commercially available ionic liquid (IL) cations, specifically imidazolium-based IL cations with different side-chain chemistries, were characterized by CID-MS. The imidazolium-based IL cations have diverse dissociations pathways depending on the nature of the side chain (aliphatic or aromatic) or the functional groups (allyl, vinyl, alcohol, methoxy, nitro) present on the side chain. Additionally, it was observed that some IL cations undergo thermal degradation under normal operating temperatures of electrospray ~275 °C. A variety of experimental and complementary computational chemistry results are presented. In Chapter III, cis-3-hydroxyproline (c3hPro) and cis-4-hydroxyproline (c4hPro) isomers were differentiated upon lithiation using CID-MS. The CID-MS of [c4hPro+Li]+ produces three primary fragmentation pathways, namely the neutral losses of H2O, CO, and CO2; whereas CID-MS of [c3hPro+Li]+ produces only loss of CO2 in this same region. These observations may have analytical utility, and in this work, the experimental observations were explored with thermodynamic and transition state calculations to better understand the processes. In Chapter IV, the accurate mass of synthetic monomers including PAH perfluorocycloalkene monomers and their precursors were measured and reported with a publication-quality mass accuracy using atmospheric pressure chemical ionization (APCI)-MS. Additionally, the effect of solution flow rate, ionization mode, source parameters (such as vaporization temperature, dry gas temperature and dry gas flow rate, nebulizer gas pressure), acidification, and different solvent systems on APCI-MS signal intensity were studied.