Multi-molecular markers and metals as tracers of organic matter inputs and contamination status from an Environmental Protection Area in the SW Atlantic (Laranjeiras Bay, Brazil)

The sources and concentrations of aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs), faecal and biogenic sterols, and trace metals at 10 sampling sites located in Laranjeiras Bay, a large Environmental Protection Area in the southern Atlantic region of Brazil, were determined to assess the sources of organic matter and the contamination status of estuarine sediments. Organic compounds were determined by GC-FID and GC-MS, and ICP-OES was used to evaluate trace metals. The total AHs concentration ranged from 0.28 to 8.19 mu g g(-1), and n-C-29 and n-C-31 alkanes were predominant, indicating significant inputs from higher terrestrial plants. Unresolved complex mixtures (UCM) were not detected at any site, suggesting that the study area was not significantly contaminated by fossil fuels. The total PAH concentration varied from 3.85 to 89.2 ng g(-1). The ratio between selected PAH isomers showed that combustion of biomass, coal, and petroleum is the rnain source of PAHs in the study area. The concentrations of the faecal sterols coprostanol and epicoprostanol were below the detection limits, suggesting that sewage was not a significant contributor to sedimentary organic matter. The concentrations of the trace metals (As, Cr, Cu, Ni, Pb and Zn) were low, except near sites located at the mouths of rivers that discharge into the study area and near urbanised regions (Paranagua city and the adjoining harbour). In general, the concentrations of PAHs were below the threshold effect concentrations (TEL) levels. Although the As, Cr and Ni concentrations were above the TEL levels, the study area can be considered as preserved from human activities.

Levels of selected persistent organic pollutants in blood from delivering women in seven selected areas of Sao Paulo State, Brazil

Persistent organic pollutants (POPS) present in the living environment are thought to have detrimental health effects on the population, with pregnant women and the developing foetus being at highest risk. We report on the levels of selected POPs in maternal blood of 155 delivering women residing in seven regions within the Sao Paulo State, Brazil. The following selected POPs were measured in the maternal whole blood: 12 polychlorinated biphenyls (PCBs) congeners (IUPAC Nos. 99, 101, 118, 138, 153, 156, 163, 170, 180, 183, 187, 194); dichlordiphenyltrichloroethane p,p'-DDT, diphenyldichloroethylene p,p'-DDE and other pesticides such as hexachlorocyclohexanes (alpha-HCH, beta-HCH, gamma-HCH), hexachlorobenzene (HCB), chlordane derivatives cis-chlordane, trans-chlordane. oxy-chlordane, cis-nonachlor and trans-nonachlor. Statistical comparisons between regions were performed only on compounds having concentrations above LOD in 70% of the samples. PCB118 congener was found to be highest in the industrial site (mean 4.97 ng/g lipids); PCB138 congener concentration was highest in the Urban 3 site (mean 4.27 ng/g lipids) and congener PCB153 was highest in the industrial and Urban 3 sites with mean concentration of 7.2 ng/g lipids and 5.89 ng/g lipids respectively. Large differences in levels of p,p'-DDE between regions were observed with the Urban 3 and industrial sites having the highest concentrations of 645 ng/g lipids and 417 ng/g lipids, respectively; beta-HCH was found to be highest in the Rural 1 site; the gamma-HCH in Rural 1 and industrial; the HCB in the Rural 1 and industrial sites and oxy-chlordane and t-NC in the Rural 2 sites. An association between levels of some contaminants and maternal age and parity was also found. (C) 2011 Elsevier Ltd. All rights reserved.

Optimization of anti-Trypanosoma cruzi oxadiazoles leads to identification of compounds with efficacy in infected mice

We recently showed that oxadiazoles have anti-Trypanosoma cruzi activity at micromolar concentrations. These compounds are easy to synthesize and show a number of clear and interpretable structure-activity relationships (SAR), features that make them attractive to pursue potency enhancement. We present here the structural design, synthesis, and anti-T. cruzi evaluation of new oxadiazoles denoted 5a-h and 6a-h. The design of these compounds was based on a previous model of computational docking of oxadiazoles on the T. cruzi protease cruzain. We tested the ability of these compounds to inhibit catalytic activity of cruzain, but we found no correlation between the enzyme inhibition and the antiparasitic activity of the compounds. However, we found reliable SAR data when we tested these compounds against the whole parasite. While none of these oxadiazoles showed toxicity for mammalian cells, oxadiazoles 6c (fluorine), 6d (chlorine), and 6e (bromine) reduced epimastigote proliferation and were cidal for trypomastigotes of T. cruzi Y strain. Oxadiazoles 6c and 6d have IC50 of 9.5 +/- 2.8 and 3.5 +/- 1.8 mu M for trypomastigotes, while Benznidazole, which is the currently used drug for Chagas disease treatment, showed an IC50 of 11.3 +/- 2.8 mu M. Compounds 6c and 6d impair trypomastigote development and invasion in macrophages, and also induce ultrastructural alterations in trypomastigotes. Finally, compound 6d given orally at 50 mg/kg substantially reduces the parasitemia in T. cruzi-infected BALB/c mice. Our drug design resulted in potency enhancement of oxadiazoles as anti-Chagas disease agents, and culminated with the identification of oxadiazole 6d, a trypanosomicidal compound in an animal model of infection. (C) 2012 Elsevier Ltd. All rights reserved.

Gases and volatile compounds associated with micro-organisms in blown pack spoilage of Brazilian vacuum-packed beef

This study correlated the composition of the spoilage bacterial flora with the main gaseous and volatile organic compounds (VOCs) found in the package headspace of spoiled, chilled, vacuum-packed meat. Fifteen chilled, vacuum-packed beef samples, suffering from blown pack spoilage, were studied using 16S rRNA clone sequencing. More than 50% of the bacteria were identified as lactic acid bacteria (LAB), followed by clostridia and enterobacteria. Fifty-one volatile compounds were detected in the spoiled samples. Although the major spoilage compounds were identified as alcohols and aldehydes, CO2 was identified as the major gas in the spoiled samples by headspace technique. Different species of bacteria contribute to different volatile compounds during meat spoilage. LAB played an important role in blown pack deterioration of the Brazilian beef studied.

A multiproxy assessment of organic pollution in shore sediments from the Río de la Plata Estuary, SW Atlantic

The study of organic pollution in estuaries is very relevant as they are transitional zones, which control the fluxes of water, nutrients, particles and organisms from and to the continental margins, rivers and oceans. The aims of this study are:(1) to evaluate organic pollution in coastal sediments of Montevideo, Río de la Plata Estuary by a multi-biomarker approach, (2) to identify major sources of organic pollutants through qualitative analysis using molecular indices, (3) to assess the relative contribution of different sources of hydrocarbons through quantitative source apportionment employing (PCA/MLR) as chemometric technique. Sampling surveys were carried out in July 2009, January 2010 and March 2011 in 37 stations along the middle portion of the Río de la Plata Estuary across the coast of Montevideo. In each station surface (0–2 cm depth) sediment samples were taken with a 0.05 m2 van Veen grab. The Soxhlet extracted organic compounds included aliphatic hydrocarbons (AHs) and steroids, analysed by gas chromatograph with flame ionization detector (GC-FID), linear alkylbenzenes (LABs) and polycyclic aromatic hydrocarbons (PAHs) quantified by gas chromatograph with mass spectrometer (GC/MS). All biomarkers presented the highest concentrations in the stations of Montevideo Bay indicating high levels of organic pollution. The combination of molecular indices and the chemometric technique showed that major sources of AHs and PAHs are petroleum inputs and combustion, due to oil transport and refinement, harbour activities and vehicular emissions.Major sources of LABs and steroids are urban and domestic sewage. Identification, quantification and source assignment of those organic compounds are very important to assess pollution and to give tools to help minimize the inputs into the environment

Phytoremediation of mercury by terrestrial plants

Mercury (Hg) pollution is a global environmental problem. Numerous Hg-contaminated sites exist in the world and new techniques for remediation are urgently needed. Phytoremediation, use of plants to remove pollutants from the environment or to render them harmless, is considered as an environment-friendly method to remediate contaminated soil in-situ and has been applied for some other heavy metals. Whether this approach is suitable for remediation of Hg-contaminated soil is, however, an open question. The aim of this thesis was to study the fate of Hg in terrestrial plants (particularly the high biomass producing willow, Salix spp.) and thus to clarify the potential use of plants to remediate Hg-contaminated soils. Plants used for phytoremediation of Hg must tolerate Hg. A large variation (up to 30-fold difference) was detected among the six investigated clones of willow in their sensitivity to Hg as reflected in their empirical toxicity threshold (TT95b), the maximum unit toxicity (UTmax) and EC50 levels. This gives us a possibility to select Hg-tolerant willow clones to successfully grow in Hgcontaminated soils for phytoremediation. Release of Hg into air by plants is a concern when using phytoremediation in practice. No evidence was found in this study that Hg was released to the air via shoots of willow, garden pea (Pisum sativum L. cv Faenomen), spring wheat (Triticum aestivum L. cv Dragon), sugar beet (Beta vulgaris L. cv Monohill), oil-seed rape (Brassica napus L. cv Paroll) and white clover (Trifolium repens L.). Thus, we conclude that the Hg burden to the atmosphere via phytoremediation is not increased. Phytoremediation processes are based on the ability of plant roots to accumulate Hg and to translocate it to the shoots. Willow roots were shown to be able to efficiently accumulate Hg in hydroponics, however, no variation in the ability to accumulate was found among the eight willow clones using CVAAS to analyze Hg content in plants. The majority of the Hg accumulated remained in the roots and only 0.5-0.6% of the Hg accumulation was translocated to the shoots. Similar results were found for the five common cultivated plant species mentioned above. Moreover, the accumulation of Hg in willow was higher when being cultivated in methyl-Hg solution than in inorganic Hg solution, whereas the translocation of Hg to the shoots did not differ. The low bioavailability of Hg in contaminated soil is a restricting factor for the phytoextraction of Hg. A selected tolerant willow clone was used to study whether iodide addition could increase the plant-accumulation of Hg from contaminated soil. Both pot tests and field trials were carried out. Potassium iodide (KI) addition was found to mobilize Hg in contaminated soil and thus increase the bioavailability of Hg in soils. Addition of KI (0.2–1 mM) increased the Hg concentrations up to about 5, 3 and 8 times in the leaves, branches and roots, respectively. However, too high concentrations of KI were toxic to plants. As the majority of the Hg accumulated in the roots, it might be unrealistic to use willow for phytoextraction of Hg in practice, even though iodide could enhance the phytoextraction efficiency. In order to study the effect of willow on various soil fractions of Hg-contaminated soil, a 5-step sequential soil extraction method was used. Both the largest Hg-contaminated fractions, i.e. the Hg bound to residual organic matter (53%) and sulphides (43%), and the residual fraction (2.5%), were found to remain stable during cultivations of willow. The exchangeable Hg (0.1%) and the Hg bound to humic and fulvic acids (1.1%) decreased in the rhizospheric soil, whereas the plant accumulation of Hg increased with the cultivation time. The sum of the decrease of the two Hg fractions in soils was approximately equal to the amount of the Hg accumulated in plants. Consequently, plants may be suitable for phytostabilization of aged Hg-contaminated soil, in which root systems trap the bioavailable Hg and reduce the leakage of Hg from contaminated soils.

Microextraction techniques coupled to liquid chromatography with mass spectrometry for the determination of organic micropollutants in environmental water samples

[EN]Until recently, sample preparation was carried out using traditional techniques, such as liquid–liquid extraction (LLE), that use large volumes of organic solvents. Solid-phase extraction (SPE) uses much less solvent than LLE, although the volume can still be significant. These preparation methods are expensive, time-consuming and environmentally unfriendly. Recently, a great effort has been made to develop new analytical methodologies able to perform direct analyses using miniaturised equipment, thereby achieving high enrichment factors, minimising solvent consumption and reducing waste. These microextraction techniques improve the performance during sample preparation, particularly in complex water environmental samples, such as wastewaters, surface and ground waters, tap waters, sea and river waters. Liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS) and time-of-flight mass spectrometric (TOF/MS) techniques can be used when analysing a broad range of organic micropollutants. Before separating and detecting these compounds in environmental samples, the target analytes must be extracted and pre-concentrated to make them detectable. In this work, we review the most recent applications of microextraction preparation techniques in different water environmental matrices to determine organic micropollutants: solid-phase microextraction SPME, in-tube solid-phase microextraction (IT-SPME), stir bar sorptive extraction (SBSE) and liquid-phase microextraction (LPME). Several groups of compounds are considered organic micropollutants because these are being released continuously into the environment. Many of these compounds are considered emerging contaminants. These analytes are generally compounds that are not covered by the existing regulations and are now detected more frequently in different environmental compartments. Pharmaceuticals, surfactants, personal care products and other chemicals are considered micropollutants. These compounds must be monitored because, although they are detected in low concentrations, they might be harmful toward ecosystems.

Synthetic and mechanistic investigation of new radical processes: reaction of organic azides with group-XIII Lewis acids

Dichloroindium hydride revealed to be a valid alternative to tributyltin hydride for radical reduction of organic (alkyl, aryl, acyl, solfonyl) azides. The new approach entails mild reaction conditions and provides high yields of the corresponding amines and amides, also showing high degrees of selectivity. The system dichloroindium hydride / azides can be utilised in fivemembered ring closures of g-azidonitriles, as a new source of aminyl radicals for the attractive synthesis of interesting amidine compounds in the absence of both toxic reagents and tedious purification procedures. Allylindium dichloride seems a good substitute for dichloroindium hydride for generation of indium centred radicals under photolytic conditions, since it allows allylation of electrophilic azides (e.g. phenylsulfonyl azide) and halogen or ester δ-substituted azides, the latter through a 1,5-H transfer rearrangement mechanism. Evidences of the radical nature of the reactions mechanism were provided by ESR spectroscopy, furthermore the same technique, allowed to discover that the reaction of azides with indium trichloride and other group XIII Lewis acids, in particular gallium trichloride, gives rise to strongly coloured, persistent paramagnetic species, whose structure is consistent with the radical cation of the head-to-tail dimer of the aniline corresponding to the starting azide.

Microwave-Mediated Hetero Diels-Alder reaction: Synthesis of biologically active compounds

Heterocyclic compounds represent almost two-thirds of all the known organic compounds: they are widely distributed in nature and play a key role in a huge number of biologically important molecules including some of the most significant for human beings. A powerful tool for the synthesis of such compounds is the hetero Diels-Alder reaction (HDA), that involve a [4+2] cycloaddition reaction between heterodienes and suitable dienophiles. Among heterodienes to be used in such six-membered heterocyclic construction strategy, 3-trialkylsilyloxy-2-aza-1,3-dienes (Fig 1) has been demonstrated particularly attractive. In this thesis work, HDA reactions between 2-azadienes and carbonylic and/or olefinic dienophiles, are described. Moreover, substitution of conventional heating by the corresponding dielectric heating as been explored in the frame of Microwave-Assisted-Organic-Synthesis (MAOS) which constitutes an up-to-grade research field of great interest both from an academic and industrial point of view. Reaction of the azadiene 1 (Fig 1) will be described using as dienophiles carbonyl compounds as aldehyde and ketones. The six-membered adducts thus obtained (Scheme 1) have been elaborated to biologically active compounds like 1,3-aminols which constitutes the scaffold for a wide range of drugs (Prozac®, Duloxetine, Venlafaxine) with large applications in the treatment of severe diseases of nervous central system (NCS). Scheme 1 The reaction provides the formation of three new stereogenic centres (C-2; C-5; C-6). The diastereoselective outcome of these reactions has been deeply investigated by the use of various combination of achiral and chiral azadienes and aliphatic, aromatic or heteroaromatic aldehydes. The same approach, basically, has been used in the synthesis of piperidin-2-one scaffold substituting the carbonyl dienophile with an electron poor olefin. Scheme 2 As a matter of fact, this scaffold is present in a very large number of natural substances and, more interesting, is a required scaffold for an huge variety of biologically active compounds. Activated olefins bearing one or two sulfone groups, were choose as dienophiles both for the intrinsic characteristic flexibility of the “sulfone group” which may be easily removed or elaborated to more complex decorations of the heterocyclic ring, and for the electron poor property of this dienophiles which makes the resulting HDA reaction of the type “normal electron demand”. Synthesis of natural compounds like racemic (±)-Anabasine (alkaloid of Tobacco’s leaves) and (R)- and (S)-Conhydrine (alkaloid of Conium Maculatum’s seeds and leaves) and its congeners, are described (Fig 2).

Application of comprehensive gas chromatography (GCxGC) to measurements of volatile organic species in ambient air

The focus of this thesis was the in-situ application of the new analytical technique "GCxGC" in both the marine and continental boundary layer, as well as in the free troposphere. Biogenic and anthropogenic VOCs were analysed and used to characterise local chemistry at the individual measurement sites. The first part of the thesis work was the characterisation of a new set of columns that was to be used later in the field. To simplify the identification, a time-of-flight mass spectrometer (TOF-MS) detector was coupled to the GCxGC. In the field the TOF-MS was substituted by a more robust and tractable flame ionisation detector (FID), which is more suitable for quantitative measurements. During the process, a variety of volatile organic compounds could be assigned to different environmental sources, e.g. plankton sources, eucalyptus forest or urban centers. In-situ measurements of biogenic and anthropogenic VOCs were conducted at the Meteorological Observatory Hohenpeissenberg (MOHP), Germany, applying a thermodesorption-GCxGC-FID system. The measured VOCs were compared to GC-MS measurements routinely conducted at the MOHP as well as to PTR-MS measurements. Furthermore, a compressed ambient air standard was measured from three different gas chromatographic instruments and the results were compared. With few exceptions, the in-situ, as well as the standard measurements, revealed good agreement between the individual instruments. Diurnal cycles were observed, with differing patterns for the biogenic and the anthropogenic compounds. The variability-lifetime relationship of compounds with atmospheric lifetimes from a few hours to a few days in presence of O3 and OH was examined. It revealed a weak but significant influence of chemistry on these short-lived VOCs at the site. The relationship was also used to estimate the average OH radical concentration during the campaign, which was compared to in-situ OH measurements (1.7 x 10^6 molecules/cm^3, 0.071 ppt) for the first time. The OH concentration ranging from 3.5 to 6.5 x 10^5 molecules/cm^3 (0.015 to 0.027 ppt) obtained with this method represents an approximation of the average OH concentration influencing the discussed VOCs from emission to measurement. Based on these findings, the average concentration of the nighttime NO3 radicals was estimated using the same approach and found to range from 2.2 to 5.0 x 10^8 molecules/cm^3 (9.2 to 21.0 ppt). During the MINATROC field campaign, in-situ ambient air measurements with the GCxGC-FID were conducted at Tenerife, Spain. Although the station is mainly situated in the free troposphere, local influences of anthropogenic and biogenic VOCs were observed. Due to a strong dust event originating from Western Africa it was possible to compare the mixing ratios during normal and elevated dust loading in the atmosphere. The mixing ratios during the dust event were found to be lower. However, this could not be attributed to heterogeneous reactions as there was a change in the wind direction from northwesterly to southeasterly during the dust event.

Simulating short lived carbonaceous compounds with an atmospheric chemistry general circulation model

Ein neu entwickeltes globales Atmosphärenchemie- und Zirkulationsmodell (ECHAM5/MESSy1) wurde verwendet um die Chemie und den Transport von Ozonvorläufersubstanzen zu untersuchen, mit dem Schwerpunkt auf Nichtmethankohlenwasserstoffen. Zu diesem Zweck wurde das Modell durch den Vergleich der Ergebnisse mit Messungen verschiedenen Ursprungs umfangreich evaluiert. Die Analyse zeigt, daß das Modell die Verteilung von Ozon realistisch vorhersagt, und zwar sowohl die Menge als auch den Jahresgang. An der Tropopause gibt das Modell den Austausch zwischen Stratosphäre und Troposphäre ohne vorgeschriebene Flüsse oder Konzentrationen richtig wieder. Das Modell simuliert die Ozonvorläufersubstanzen mit verschiedener Qualität im Vergleich zu den Messungen. Obwohl die Alkane vom Modell gut wiedergeben werden, ergibt sich einige Abweichungen für die Alkene. Von den oxidierten Substanzen wird Formaldehyd (HCHO) richtig wiedergegeben, während die Korrelationen zwischen Beobachtungen und Modellergebnissen für Methanol (CH3OH) und Aceton (CH3COCH3) weitaus schlechter ausfallen. Um die Qualität des Modells im Bezug auf oxidierte Substanzen zu verbessern, wurden einige Sensitivitätsstudien durchgeführt. Diese Substanzen werden durch Emissionen/Deposition von/in den Ozean beeinflußt, und die Kenntnis über den Gasaustausch mit dem Ozean ist mit großen Unsicherheiten behaftet. Um die Ergebnisse des Modells ECHAM5/MESSy1 zu verbessern wurde das neue Submodell AIRSEA entwickelt und in die MESSy-Struktur integriert. Dieses Submodell berücksichtigt den Gasaustausch zwischen Ozean und Atmosphäre einschließlich der oxidierten Substanzen. AIRSEA, welches Informationen über die Flüssigphasenkonzentration des Gases im Oberflächenwasser des Ozeans benötigt wurde ausgiebig getestet. Die Anwendung des neuen Submodells verbessert geringfügig die Modellergebnisse für Aceton und Methanol, obwohl die Verwendung einer vorgeschriebenen Flüssigphasenkonzentration stark den Erfolg der Methode einschränkt, da Meßergebnisse nicht in ausreichendem Maße zu Verfügung stehen. Diese Arbeit vermittelt neue Einsichten über organische Substanzen. Sie stellt die Wichtigkeit der Kopplung zwischen Ozean und Atmosphäre für die Budgets vieler Gase heraus.

Structure-Property Relationships and Charge Transport Modeling of Organic Molecular Materials

From the perspective of a new-generation opto-electronic technology based on organic semiconductors, a major objective is to achieve a deep and detailed knowledge of the structure-property relationships, in order to optimize the electronic, optical, and charge transport properties by tuning the chemical-physical characteristics of the compounds. The purpose of this dissertation is to contribute to such understanding, through suitable theoretical and computational studies. Precisely, the structural, electronic, optical, and charge transport characteristics of several promising organic materials recently synthesized are investigated by means of an integrated approach encompassing quantum-chemical calculations, molecular dynamics and kinetic Monte Carlo simulations. Particular care is addressed to the rationalization of optical and charge transport properties in terms of both intra- and intermolecular features. Moreover, a considerable part of this project involves the development of a home-made set of procedures and parts of software code required to assist the modeling of charge transport properties in the framework of the non-adiabatic hopping mechanism applied to organic crystalline materials. As a first part of my investigations, I mainly discuss the optical, electronic, and structural properties of several core-extended rylene derivatives, which can be regarded to as model compounds for graphene nanoribbons. Two families have been studied, consisting in bay-linked perylene bisimide oligomers and N-annulated rylenes. Beside rylene derivatives, my studies also concerned electronic and spectroscopic properties of tetracene diimides, quinoidal oligothiophenes, and oxygen doped picene. As an example of device application, I studied the structural characteristics governing the efficiency of resistive molecular memories based on a derivative of benzoquinone. Finally, as a second part of my investigations, I concentrate on the charge transport properties of perylene bisimides derivatives. Precisely, a comprehensive study of the structural and thermal effects on the charge transport of several core-twisted chlorinated and fluoro-alkylated perylene bisimide n-type semiconductors is presented.

Perfluorinated compounds in environmental matrices of Lake Victoria Gulf

ABSTRACT One of the major ecological challenges on Lake Victoria resources is the existence of “hot spots”, caused by human waste, urban runoff, and industrial effluents. The lake is tending towards eutrophication which is attributed to the increasing human population in its watershed. A report of the levels of perfluorooctane sulfonate and perfluorooctanoic acid in environmental matrices of Lake Victoria is presented, and the management implication of perfluorinated compounds and similar potential organic pollutants examined. Two widely consumed and economically important fish species namely Lates niloticus (Nile perch) and Oreochromis niloticus (Nile tilapia) were obtained from Winam gulf of Lake Victoria, Kenya, and analysed for perfluorooctane sulfonate and perfluorooctanoic acid in muscles and liver using liquid chromatography coupled with mass spectroscopy. Variability in the concentrations of perfluorooctanoic acid or perfluorooctane sulfonate in river waters (range perfluorooctanoic acid 0.4 – 96.4 ng/L and perfluorooctane sulfonate < 0.4 – 13.2 ng/L) was higher than for Lake waters (range perfluorooctanoic acid 0.4 – 11.7 ng/L and perfluorooctane sulfonate < 0.4 – 2.5 ng/L respectively). Significant correlations were tested between perfluorinated compounds levels in sediments, fish and water. Wastewater treatment plants and other anthropogenic sources have been identified as significant sources or pathways for the introduction of perfluoroalkyl compounds into Lake Victoria ecosystem. In this study, elevated concentrations of perfluorooctanoic acid and perfluorooctane sulfonate was found in two wastewater treatment plants (WWTPs) in Kisumu, City of Kenya. An alternative analytical method to liquid chromatography/ mass spectroscopy for analysis of perfluorocarboxylic acids in abiotic and biotic matrices where high concentrations are expected is also presented. Derivatisation of the acid group to form a suitable alkyl ester provided a suitable compound for mass spectroscopy detection coupled to gas chromatography instrumental analysis. The acid is esterified by an alkyl halide i.e benzyl bromide as the alkylating agent for Perfluorocarboxylic acids quantification. The study also involved degradability measurements of emerging perfluorinated surfactants substitutes. The stability of the substitutes of perfluorinated surfactants was tested by employing advanced oxidation processes, followed by conventional tests, among them an automated method based on the manometric respirometry test and standardized fix bed bioreactor [FBBR] on perfluorobutane sulfonate (PFBS), a fluoroethylene polymer, fluorosurfactant (Zonyl), two fluoraliphaticesters (NOVEC ™ FC4430 and NOVEC ™ FC4432) and 10-(trifluoromethoxy) decane-sulfonate. Most of these emmerging surfactants are well-established in the market and have been used in several applications as alternatives to PFOS and PFOA based surfactants. The results of this study can be used as pioneer information for further studies on the sources, behaviour and fate of PFOA and PFOS and other related compounds in both abiotic and biota compartments of Lake Victoria and other lakes. Further an overview in degradation of emerging perfluorinated compounds substitutes is presented. Contribution in method development especially for acid group based fluorosurfactants is presented. The data obtained in this study can particularly be considered when formulating policies and management measures for preservation and sustainability of Lake Victoria resources.

Bioconjugation and synthetic approach towards enantioenriched gem-difluoromethylene compounds through carbenium ions

Bioconjugation of peptides and asymmetric synthesis of gem-difluoromethylene compounds are areas of the modern organic chemistry for which mild and selective methods continue to be developed. This thesis reports new methodologies for these two areas based on the use of stabilized carbenium ions. The reaction that makes the bioconjugation of peptides possible takes place via the direct nucleophilic substitution of alcohols and is driven by the spontaneous formation of stabilized carbenium ions in water. By reacting with the thiol group of cysteine in very mild conditions and with a high selectivity, these carbenium ions allow the site-specific ligation of polypeptides containing cysteine and their covalent derivatization with functionalized probes. The ligation of the indole ring of tryptophan, an emerging target in bioconjugation, is also shown and takes place in the same conditions. The second area investigated is the challenging access to optically active gem-difluoromethylene compounds. We describe a methodology relying on the synthesis of enantioenriched 1,3-benzodithioles intermediates that are shown to be precursors of the corresponding gem-difluoromethylene analogues by oxidative desulfurization-fluorination. This synthesis takes advantage of the highly enantioselective organocatalytic α-alkylation of aldehydes with the benzodithiolylium ion and of the wide possibilities of synthetic transformations offered by the 1,3-benzodithiole group. This approach allows the asymmetric access to complex gem-difluoromethylene compounds through a late-stage fluorination step, thus avoiding the use of fluorinated building blocks.

Kinetic modeling and experiments on gas uptake and chemical transformation of organic aerosol in the atmosphere

Aerosolpartikel beeinflussen das Klima durch Streuung und Absorption von Strahlung sowie als Nukleations-Kerne für Wolkentröpfchen und Eiskristalle. Darüber hinaus haben Aerosole einen starken Einfluss auf die Luftverschmutzung und die öffentliche Gesundheit. Gas-Partikel-Wechselwirkunge sind wichtige Prozesse, weil sie die physikalischen und chemischen Eigenschaften von Aerosolen wie Toxizität, Reaktivität, Hygroskopizität und optische Eigenschaften beeinflussen. Durch einen Mangel an experimentellen Daten und universellen Modellformalismen sind jedoch die Mechanismen und die Kinetik der Gasaufnahme und der chemischen Transformation organischer Aerosolpartikel unzureichend erfasst. Sowohl die chemische Transformation als auch die negativen gesundheitlichen Auswirkungen von toxischen und allergenen Aerosolpartikeln, wie Ruß, polyzyklische aromatische Kohlenwasserstoffe (PAK) und Proteine, sind bislang nicht gut verstanden.rn Kinetische Fluss-Modelle für Aerosoloberflächen- und Partikelbulk-Chemie wurden auf Basis des Pöschl-Rudich-Ammann-Formalismus für Gas-Partikel-Wechselwirkungen entwickelt. Zunächst wurde das kinetische Doppelschicht-Oberflächenmodell K2-SURF entwickelt, welches den Abbau von PAK auf Aerosolpartikeln in Gegenwart von Ozon, Stickstoffdioxid, Wasserdampf, Hydroxyl- und Nitrat-Radikalen beschreibt. Kompetitive Adsorption und chemische Transformation der Oberfläche führen zu einer stark nicht-linearen Abhängigkeit der Ozon-Aufnahme bezüglich Gaszusammensetzung. Unter atmosphärischen Bedingungen reicht die chemische Lebensdauer von PAK von wenigen Minuten auf Ruß, über mehrere Stunden auf organischen und anorganischen Feststoffen bis hin zu Tagen auf flüssigen Partikeln. rn Anschließend wurde das kinetische Mehrschichtenmodell KM-SUB entwickelt um die chemische Transformation organischer Aerosolpartikel zu beschreiben. KM-SUB ist in der Lage, Transportprozesse und chemische Reaktionen an der Oberfläche und im Bulk von Aerosol-partikeln explizit aufzulösen. Es erforder im Gegensatz zu früheren Modellen keine vereinfachenden Annahmen über stationäre Zustände und radiale Durchmischung. In Kombination mit Literaturdaten und neuen experimentellen Ergebnissen wurde KM-SUB eingesetzt, um die Effekte von Grenzflächen- und Bulk-Transportprozessen auf die Ozonolyse und Nitrierung von Protein-Makromolekülen, Ölsäure, und verwandten organischen Ver¬bin-dungen aufzuklären. Die in dieser Studie entwickelten kinetischen Modelle sollen als Basis für die Entwicklung eines detaillierten Mechanismus für Aerosolchemie dienen sowie für das Herleiten von vereinfachten, jedoch realistischen Parametrisierungen für großskalige globale Atmosphären- und Klima-Modelle. rn Die in dieser Studie durchgeführten Experimente und Modellrechnungen liefern Beweise für die Bildung langlebiger reaktiver Sauerstoff-Intermediate (ROI) in der heterogenen Reaktion von Ozon mit Aerosolpartikeln. Die chemische Lebensdauer dieser Zwischenformen beträgt mehr als 100 s, deutlich länger als die Oberflächen-Verweilzeit von molekularem O3 (~10-9 s). Die ROIs erklären scheinbare Diskrepanzen zwischen früheren quantenmechanischen Berechnungen und kinetischen Experimenten. Sie spielen eine Schlüsselrolle in der chemischen Transformation sowie in den negativen Gesundheitseffekten von toxischen und allergenen Feinstaubkomponenten, wie Ruß, PAK und Proteine. ROIs sind vermutlich auch an der Zersetzung von Ozon auf mineralischem Staub und an der Bildung sowie am Wachstum von sekundären organischen Aerosolen beteiligt. Darüber hinaus bilden ROIs eine Verbindung zwischen atmosphärischen und biosphärischen Mehrphasenprozessen (chemische und biologische Alterung).rn Organische Verbindungen können als amorpher Feststoff oder in einem halbfesten Zustand vorliegen, der die Geschwindigkeit von heterogenen Reaktionenen und Mehrphasenprozessen in Aerosolen beeinflusst. Strömungsrohr-Experimente zeigen, dass die Ozonaufnahme und die oxidative Alterung von amorphen Proteinen durch Bulk-Diffusion kinetisch limitiert sind. Die reaktive Gasaufnahme zeigt eine deutliche Zunahme mit zunehmender Luftfeuchte, was durch eine Verringerung der Viskosität zu erklären ist, bedingt durch einen Phasenübergang der amorphen organischen Matrix von einem glasartigen zu einem halbfesten Zustand (feuchtigkeitsinduzierter Phasenübergang). Die chemische Lebensdauer reaktiver Verbindungen in organischen Partikeln kann von Sekunden bis zu Tagen ansteigen, da die Diffusionsrate in der halbfesten Phase bei niedriger Temperatur oder geringer Luftfeuchte um Größenordnungen absinken kann. Die Ergebnisse dieser Studie zeigen wie halbfeste Phasen die Auswirkung organischeer Aerosole auf Luftqualität, Gesundheit und Klima beeinflussen können. rn