Manmade climate change has expressed a plethora of complex effects on Earth's biogeochemical compartments. Climate change may also affect the mobilisation of natural metal sources, with potential ecological consequences beyond mountains' geographical limits; however, this question has remained largely unexplored. We investigated this by analysing a number of key climatic factors in relationship with trace metal accumulation in the sediment core of a Pyrenean lake. The sediment metal contents showed increasing accumulation trend over time, and their levels varied in step with recent climate change. The findings further revealed that a rise in the elevation of freezing level, a general increase in the frequency of drier periods, changes in the frequency of winter freezing days and a reducing snow cover since the early 1980s, together are responsible for the observed variability and augmented accumulation of trace metals. Our results provide clear evidence of increased mobilisation of natural metal sources - an overlooked effect of climate change on the environment. With further alterations in climate equilibrium predicted over the ensuing decades, it is likely that mountain catchments in metamorphic areas may become significant sources of trace metals, with potentially harmful consequences for the wider environment.

<p>Certain types of waste, e.g. bottom ash originating from municipal solid waste incineration (MSWI bottom ash) can be used as road construction materials. A potential problem is the possibility of substances leaching out of the road and spreading in the surrounding groundwater.</p><p>The aim of this master’s thesis is to conclude whether hydrogeological type settings can be employed to, based on local conditions, provide an estimate of the probable spreading of these substances in the surrounding groundwater, and whether certain types of soils can be identified as being less suitable for the localization of a MSWI bottom ash road. A hydrogeological type setting is defined as a mappable unit with similar hydrogeological properties. An advantage of this approach would be that mainly existing maps and surveys could form the basis for the assessment.</p><p>The work has been performed by placing a hypothetical road construction in different hydrogeological type settings. The expected patterns of spreading has then been evaluated using theoretical reasoning and analytical and numerical models.</p><p>The method can be used. In the report various type settings are defined. In several cases further information will be required to render possible a more exact estimate of the spreading. By locating the road on less permeable soils to reduce the local spreading of substances in groundwater, a greater proportion of the water will be drained as surface water. Thus it becomes important to take into account surface water transport aswell. In the report a procedure to estimate the maximum concentrations in groundwater at locations situated downstream the road is presented. This estimate could be used as basis for a more balanced valuation of appropriateness, e.g. by relating the estimated concentrations to background values.</p> / <p>Vissa typer av avfall, exempelvis slaggrus (sorterad bottenaska från avfallsförbränning), kan användas som vägbyggnadsmaterial. Ett potentiellt problem är möjligheten att ämnen lakas ut ur vägen och sprids i omgivande grundvatten.</p><p>Syftet med detta examensarbete är att avgöra om hydrogeologiska typmiljöer kan användas för att, utifrån omgivningens förutsättningar, ge en bild av hur den vidare spridningen av dessa ämnen i omgivande grundvatten sannolikt ser ut, och om vissa typer av mark kan pekas ut som mindre lämpade för lokalisering av en slaggrusväg. En hydrogeologisk typmiljö definieras som ett område möjligt att avgränsa med avseende på karakteristiska hydrogeologiska förhållanden. En fördel med angreppssättet skulle vara att underlagsmaterialet till bedömningen då kan utgöras av i huvudsak befintligt kartmaterial.</p><p>Studien har utförts genom att en hypotetisk vägkonstruktion placerats in i olika hydrogeologiska typmiljöer. De troliga spridningsscenarierna har sedan utvärderats genom teoretiska resonemang, samt genom användande av analytiska och numeriska modeller.</p><p>Metodiken går att använda och i rapporten definieras olika typmiljöer. I flera fall kommer platsspecifik kunskap behöva inhämtas för en närmare beskrivning av spridningsbilden. Genom placering av vägen på tätare mark för att minska lokal spridning av ämnen i grundvatten kommer en större andel av vattnet att avledas som ytvatten. Därmed blir det viktigt att även inhämta kunskap om transport med ytvatten. I rapporten presenteras också en metod för uppskattning av maximala halter i grundvatten nedströms en väg. Denna metod kan användas som underlag för en mer nyanserad värdering av lämplighet, genom att de uppskattade halterna relateras till bakgrundsvärden eller lämpliga riktvärden.</p>

With the continual concern over the presence of naturally occurring and anthropogenic inorganic and trace organic contaminants in the aquatic environment there is a growing need for the implementation of innovative treatment processes for the elimination of these contaminants from natural waters and wastewater effluents. While conventional treatment methods are ineffective in the removal of emerging contaminants such as steroidal hormones and pesticides, membrane technology, including electrodialysis (ED), has been highlighted as a potential treatment option. However, the clear lack of fundamental understanding of the behaviour of contaminants in ED is a current limitation for its extensive utilisation and is a critical issue that needs to be addressed. ED processing potentialities have not been fully exploited and more research is needed to account for all the key parameters such as contaminant physicochemical properties, solution chemistry and the presence of organic matter. The purpose of this study was to elucidate the mechanisms of inorganic and trace organic contaminant removal by ED. The inorganic contaminants fluoride, nitrate and boron were selected due to their ubiquitous nature in the environment and public health concerns resulting from longterm exposure. The hydrated radius and strength of hydration shells played a significant role in ionic transport, whereby nitrate with a smaller hydrated radius was removed more effectively (94.1 %) than fluoride (68.3 %) with a larger hydrated radius. While fluoride and nitrate removal was pH independent, the pH dependent speciation of boron enhanced its removal with increasing pH. Territorial binding and/or complexation of the inorganics with organic matter enhanced removal. The removal of a range of trace inorganics (e.g. arsenic, calcium, magnesium, uranium) from a brackish groundwater from a remote Australian community was investigated. Undissociated inorganics were not transported through the membranes, whereas dissociated inorganics were due to electrostatic attraction. At acidic-neutral conditions ionic transport was the dominant removal mechanism. At neutral to alkaline conditions insoluble carbonate species precipitated and deposited as a membrane scaling layer (60 μm). This has serious implications for the long-term practical applicability of ED to treat real waters as scaling increased ED stack resistance (pH 3: 27.5 4, pH 11: 50 4) and decreased total dissolved solids removal (pH 3: 99 %, pH 11: 89.5 %). While the treatment of trace organics by other membrane processes has been widely studied, their fate in ED and interaction with ED membranes is relatively unknown. Trace contaminant-membrane interaction studies were undertaken to quantify the partitioning of trace organics; namely steroidal hormones and the pesticide endosulfan, to ED membranes by measuring membrane-water partition coefficients (log KM). The extremely high sorption capacity of the membranes was attributed to hydrogen bonding between the trace organic and membrane functional groups. Hormone sorption during ED was influenced by solution pH and organic matter. In the case of estrone, membrane sorption decreased at pH 11 (487 μg/cm3) compared to pH 7 (591 μg/cm3) due to dissociation and membrane electrostatic repulsion .At pH 11, repulsion between dissociated estrone and HA coupled with membrane electrostatic attraction resulted in increased sorption. The findings from this study highlight that the transport of trace contaminants will depend largely on the characteristics of the membranes used in the ED process as well as the physicochemical characteristics of the contaminants, their interaction with the ED membranes and the presence of other inorganic and/or organic compounds. The knowledge gained has direct applications to current problems and uncertainties in water and wastewater treatment with regards to the fate and transport of contaminants.

Lead (Pb), a trace metal notorious for its impacts on human health, has achieved worldwide environmental dispersal resulting from centuries of use by human society. The toxicity of Pb is governed largely by its mineral form, which is in turn controlled by pH, localized reactivity and soil processes that differ according to soil type, location and Pb source. Given the context of these localized dependencies, or site specificity, efforts to predict Pb toxicity and refine sustainable remediation techniques are most useful when Pb behavior is constrained and predicted within environments with homogeneous conditions, such as a single soil. I evaluated and predicted the behavior of Pb, a typical anthropogenic contaminant, within a single soil using bioaccessibility testing and predictive geospatial modeling to assess potential impacts and refine sustainable remediation methods. To test the hypothesis that Pb speciation is influenced by competitive sorption processes in soils, I investigated changes in mobility and speciation of Pb upon addition of amendments at multiple scales using flow-through column experiments, soil characterization and synchrotron-based x-ray techniques. Kriging and cokriging maps provided a successful estimation of background and total Pb, the latter incorporating housing age as a secondary variable to increase model accuracy, though efforts to automate detection of background Pb were complicated by approximation of building extents, and overall heterogeneity of soil Pb concentration gives high error. Acute Pb heterogeneity is observed at the scale of a single site among near-structure samples. At the city-scale, determination of bioaccessibility revealed that bioaccessible and total Pb are well-correlated, to the extent that bioaccessibility may be predicted for the soil underlying Burlington, VT; this information, combined with predictive blood lead level modeling and the CDC's recent establishment of 5 μg kg-1 as a threshold for blood lead toxicity, enabled the establishment of a site-specific revised soil Pb limit of 360 mg kg-1, lower than the EPA's general soil Pb threshold of 400 mg kg-1. Characterization of leached and unleached soil using scanning electron microscope energy dispersive spectroscopy (SEM-EDS) and microfocused x-ray techniques provided a first look at Pb paint species using synchrotron technologies. Pb was present within paint chips as hydrocerussite, but appeared to weather to anglesite over time. Pb also seemed to act as cation bridge, attracting clay minerals electrostatically and becoming incorporated into heterogeneous soil aggregates. Accessory paint elements are identified in soil and within paint chips and may further complicate these systems. Column experiments, at acidic pH, yielded little evidence of Pb mobility change in response to modification of competitive sorbents. Kinetics of Pb release were driven by pH, with Pb solubilizing at pH of ˜4.9 as column soil acidifies. This work provides evidence for changes in Pb speciation over time in urban soils impacted by Pb paint, and presents a framework for predictive risk analysis at a local site using experimental and modeling tools. Multiscale observations and analytical results can be used in future efforts to model and refine sustainable remediation solutions within a site-specific context.

A adsorção de metais em solos tem sido estudada no escopo da geotecnia ambiental principalmente para prever formação de plumas, estudar viabilidade de técnicas de remediação e projetar revestimentos impermeabilizantes em sistemas de disposição de resíduos, entre outros. A consideração da adsorção como um fenômeno imediato e reversível é geralmente aceitável nessas aplicações, porém tem-se verificado que para solos tropicais o estudo da cinética pode melhorar as retroanálises de dados de campo e as interpretações de resultados experimentais. Este trabalho apresenta aspectos teóricos da cinética de adsorção, incluindo fatores que afetam a cinética de adsorção, modelos para determinar os mecanismos que controlam a cinética de adsorção e modelos de cinética de adsorção. A adsorção e a cinética de adsorção de cádmio e chumbo em um Latossolo roxo foram investigadas por meio de ensaios de adsorção tipo Batch. As concentrações iniciais nas soluções variaram de 2 mg/L até 2000 mg/L. OS tempos de contatos variaram de 5 minutos até 6 meses. Também foram realizados ensaios de extração e digestão química. A seguir, foram aplicados modelos para determinar os mecanismos que controlam a cinética de adsorção e também foram ajustados modelos de cinética de adsorção aos dados experimentais. Os resultados mostram que a adsorção pode ser representada por dois distintos comportamentos: curto prazo, até cerca de 8 horas, e longo prazo, para tempos superiores. A adsorção não específica aumenta com o aumento da concentração do contaminante na fase sólida no caso do cádmio, enquanto para o chumbo esta relação não ficou clara. Os modelos de cinética de adsorção testados representam apenas o comportamento de curto prazo e o ajuste desses modelos aos dados experimentais, mesmo para a adsorção de curto prazo, varia consideravelmente em função do método matemático utilizado. Finalmente, concluiu-se que a cinética de adsorção é bem representada por uma função tipo potência com expoente negativo. / Metal adsorption in soils has been studied in the scope of environmental geotechnics mainly to predict migration of contaminant plumes, to study feasibility of remediation techniques, and to design waste disposal sites. The consideration of adsorption as an immediate and reversible phenomenon is generally accepted in those applications; however, the study of adsorption kinetics in tropical soils may improve back-calculation of field data and interpretation of experimental results. This study presents theoretical aspects of adsorption kinetics, including factors that affect adsorption kinetics, models to determine mechanisms that control adsorption kinetics and adsorption kinetics models. Adsorption and adsorption kinetics of cadmium and lead in a Brazilian lateritic red clay were investigated by means of Batch adsorption tests on. Initial solutions concentrations varied from 2 mg/L to 2000 mg/L. Contact times varied from 5 minutes to 6 months. Chemical extraction and digestion tests were also performed. Models were then applied to experimental data to determine the mechanisms that control adsorption kinetics and adsorption kinetics models were also fitted to experimental data. The results show that adsorption can be represented by two different behaviors: a short time behavior, until circa 8 hours, and a long time behavior, for longer times. For cadmium, the importance of non specific adsorption increases as the contaminant concentration in the solid phase increases, while this relation is not clear for lead. The investigated adsorption kinetics models can only represent the short time behavior, and fitting of these models, even for short-time adsorption, depends considerably on the utilized mathematical method. Finally, adsorption kinetics can be well represented by a power function with negative exponent.

As leveduras Dekkera/Brettanomyces estão envolvidas na deterioração de vinhos após o término das fermentações alcoólicas e maloláticas, tendo se apresentado como agente contaminante de processos contínuos de produção de etanol industrial. São caracterizadas pela morfologia celular típica (células alongadas e ogivais), alta produção de ácido e crescimento lento, porém de difícil identificação. Embora muitos trabalhos já tenham sido publicados acerca do seu papel na fermentação do vinho, pouco se conhece sobre o seu comportamento no processo de fermentação para produção de álcool combustível. Desta forma, este trabalho objetivou selecionar, identificar e caracterizar linhagens de Dekkera e Brettanomyces isoladas de processos fermentativos, através de testes de taxonomia clássica, moleculares (PCR e sequenciamento) e de biotipagem através do sistema killer, visando a avaliação de fermentações mistas de Saccharomyces cerevisiae e Dekkera bruxellensis, a última em níveis de contaminação variando de 101 a 103 células/mL, em meio de caldo de cana, em processo de fermentação em batelada com reciclo celular (14 ciclos de 12 horas) para produção de etanol. Os testes morfológicos e fisiológicos/bioquímicos de oito linhagens selecionadas pela alta produtividade de ácido a partir da glicose e morfologia celular característica, apontaram os gêneros Dekkera ou Brettanomyces, sem possibilidade de identificação em nível de espécie devido à ambigüidade dos resultados dos testes fisiológicos. O sequenciamento da região ITS (Internal transcribed spacer) do DNA ribossomal confirmou somente três linhagens como Dekkera bruxellensis, sendo as demais predominantemente pertencentes à espécie Pichia guillermondii. O tamanho da região ITS, incluindo o gene 5,8S, variou de 400 500 pb entre as três linhagens. A utilização do sistema killer como método de biotipagem para leveduras Dekkera mostrou-se inviável devido ao fenótipo predominantemente neutro apresentado pelas linhagens. Somente a levedura killer CCA510 (Kluyveromyces marxianus) apresentou atividade inibitória contra as três linhagens de D. bruxellensis. Os ensaios fermentativos realizados com a linhagem de D. bruxellensis (CCA059) em fermentações puras e mistas com S. cerevisiae (CCA193, PE-02), mostraram que a levedura contaminante foi capaz de crescer em meio de caldo de cana, independentemente do tamanho do seu inóculo inicial (101 a 103 células/mL), impactando negativamente a fermentação etanólica, causando a diminuição da viabilidade de S. cerevisiae, diminuindo o pH do meio, decréscimo na produção de etanol e eficiência fermentativa, possivelmente devido à produção de ácido acético a partir do ART do meio de fermentação. Extrapolando-se os resultados obtidos em escala de laboratório para a escala industrial de uma destilaria de médio porte, a contaminação por Dekkera bruxellensis acarretaria uma perda de 6 milhões a 15 milhões de litros de álcool na safra, que deixariam de ser produzidos, dependendo do nível de contaminação. / Dekkera/Brettanomyces yeasts are found to be either contaminants in wine after completion of alcoholic and malolactic fermentations and in continuous fermentations for fuel alcohol production. They are characterized by typical cell morphology (elongated and ogival cells), high acid production and slow growth, however not easily identified. Although their role in wine fermentations is well-defined, a little is known about their behavior during fermentation for ethanol production. This work aimed the screening, identification and characterization of Dekkera and Brettanomyces strains isolated from fermentative processes, through classical taxonomic tests, molecular analysis (PCR and DNA sequencing) and biotyping by killer system. Following fermentation essays were carried out to evaluate mixed fermentations of Saccharomyces cerevisiae and Dekkera bruxellensis, the last one in contamination levels varying from 101 to 103 cells/mL, in sugar cane medium, using batch fermentation process with cell recycle (fourteen 12-hour cycles) for fuel ethanol production. Morphological and physiological/biochemical tests involving eight strains selected for their high acid production from glucose and typical cell morphology, pointed out to the genera Dekkera or Brettanomyces, without possibility of species identification due to the variability and ambiguity of physiological tests. DNA sequencing of the ITS (Internal transcribed spacer) region belonging to ribosomal DNA confirmed only three strains as Dekkera bruxellensis, the others were predominantly Pichia guilliermondii. The ITS region, including the 5,8S gene, varied from 400 to 500 bp among the three strains. The use of killer system as a biotyping method for Dekkera strains might not be applied because the strains were predominantly neutral to killer toxins. Only the killer strain CCA510 (Kluyveromyces marxianus) showed to have inhibitory activity against the strains of D. bruxellensis. The fermentative essays using a strain of D. bruxellensis (CCA059) in mixed and pure fermentations with S. cerevisiae (CCA193, PE-02), have shown that the contaminant yeast was able to grown in sugar cane juice, regardless of the initial inoculum size ((101 to 103 cells/mL), impairing the bioethanol fermentation, causing diminished S. cerevisiae viability, pH decrease, lower ethanol production and fermentative efficiency, mainly due to the acetic acid production from reducing sugar present in fermentation medium. Extrapolation of the results obtained in laboratory scale to industrial scale in a medium-sized distillery, have revealed that contamination by Dekkera bruxellensis would result in a alcohol loss of 6 millions to 15 millions of liters, which would not be produced, depending on the contamination level.

Mistura compactada de materiais inconsolidados das formações Serra Geral e Botucatu foram percoladas por soluções com diversas concentrações de K+, Cl- e Cu++, em testes de coluna, para a avaliar a potencialidade da sua utilização como liner. Na modelagem dos resultados adotaram-se resoluções analíticas e semi-analíticas (programa POLLUTE v6). Estudo complementar sobre o comportamento eletroquímico destes solos foi realizado pelos ensaios de titulação potenciométrica, capacidade de tamponamento, pH em água e KCI, CTC e análise mineralógica por difração de Raios-X e térmica diferencial. Os resultados mostraram uma forte influência das características da carga elétrica superficial do solo no comportamento competitivo dos íons. / A compacted mixture of soils from Serra Geral and Botucatu formations were percolated by chemical solutions with several concentrations of K+, Cu++ e Cl-, in column tests, in order to assess the potential of this mixture as a liner-building material. In the modeling procedures for the results, analytical and semi-analytical solutions (POLLUTE v.6 software) were used. Additional studies about the electrochemical behavior of these soils were performed, using potenciometric titration, soil buffer capacity, pH in water and KCI and mineralogical assessment by X-Ray Diffraction and differential thermal analysis. The results showed a very strong influence of the soil superficial charge in the competitive ion behavior.

La métabolomique permet une étude à large échelle du profil métabolique d'un individu, représentatif de son état physiologique. La comparaison de ces profils conduit à l'identification de métabolites caractéristiques d'une condition donnée. La métabolomique présente un potentiel considérable pour le diagnostic, mais également pour la compréhension des mécanismes associés aux maladies et l'identification de cibles thérapeutiques. Cependant, ces dernières applications nécessitent d'inclure ces métabolites caractéristiques dans un contexte plus large, décrivant l'ensemble des connaissances relatives au métabolisme, afin de formuler des hypothèses sur les mécanismes impliqués. Cette mise en contexte peut être réalisée à l'aide des réseaux métaboliques, qui modélisent l'ensemble des transformations biochimiques opérables par un organisme. L'une des limites de cette approche est que la métabolomique ne permet pas à ce jour de mesurer l'ensemble des métabolites, et ainsi d'offrir une vue complète du métabolome. De plus, dans le contexte plus spécifique de la santé humaine, la métabolomique est usuellement appliquée à des échantillons provenant de biofluides plutôt que des tissus, ce qui n'offre pas une observation directe des mécanismes physiologiques eux-mêmes, mais plutôt de leur résultante. Les travaux présentés dans cette thèse proposent une méthode pour pallier ces limitations, en suggérant des métabolites pertinents pouvant aider à la reconstruction de scénarios mécanistiques. Cette méthode est inspirée des systèmes de recommandations utilisés dans le cadre d'activités en ligne, notamment la suggestion d'individus d'intérêt sur les réseaux sociaux numériques. La méthode a été appliquée à la signature métabolique de patients atteints d'encéphalopathie hépatique. Elle a permis de mettre en avant des métabolites pertinents dont le lien avec la maladie est appuyé par la littérature scientifique, et a conduit à une meilleure compréhension des mécanismes sous-jacents et à la proposition de scénarios alternatifs. Elle a également orienté l'analyse approfondie des données brutes de métabolomique et enrichie par ce biais la signature de la maladie initialement obtenue. La caractérisation des modèles et des données ainsi que les développements techniques nécessaires à la création de la méthode ont également conduit à la définition d'un cadre méthodologique générique pour l'analyse topologique des réseaux métaboliques. / Metabolomics allows large-scale studies of the metabolic profile of an individual, which is representative of its physiological state. Metabolic markers characterising a given condition can be obtained through the comparison of those profiles. Therefore, metabolomics reveals a great potential for the diagnosis as well as the comprehension of mechanisms behind metabolic dysregulations, and to a certain extent the identification of therapeutic targets. However, in order to raise new hypotheses, those applications need to put metabolomics results in the light of global metabolism knowledge. This contextualisation of the results can rely on metabolic networks, which gather all biochemical transformations that can be performed by an organism. The major bottleneck preventing this interpretation stems from the fact that, currently, no single metabolomic approach allows monitoring all metabolites, thus leading to a partial representation of the metabolome. Furthermore, in the context of human health related experiments, metabolomics is usually performed on bio-fluid samples. Consequently, those approaches focus on the footprints left by impacted mechanisms rather than the mechanisms themselves. This thesis proposes a new approach to overcome those limitations, through the suggestion of relevant metabolites, which could fill the gaps in a metabolomics signature. This method is inspired by recommender systems used for several on-line activities, and more specifically the recommendation of users to follow on social networks. This approach has been used for the interpretation of the metabolic signature of the hepatic encephalopathy. It allows highlighting some relevant metabolites, closely related to the disease according to the literature, and led to a better comprehension of the impaired mechanisms and as a result the proposition of new hypothetical scenario. It also improved and enriched the original signature by guiding deeper investigation of the raw data, leading to the addition of missed compounds. Models and data characterisation, alongside technical developments presented in this thesis, can also offer generic frameworks and guidelines for metabolic networks topological analysis.

Per- and polyfluoroalkyl substances (PFASs) are a group of man-made organic chemicals that have been commercially used since the 1950s in many consumer products, including impregnated textiles, impregnated paper, nonstick products (e.g., Teflon), cleaning agents, and in firefighting foams. However, PFASs have in recent years received increasing public attention due to their persistence, bioaccumulative potential, and potentially toxic effects on humans and animals. Firefighting training sites have been identified as one of the most important sources for the spread of PFASs in the environment, due to the use of PFAS-containing firefighting foam of type AFFFs (aqueous film forming foams). This has resulted in contamination of both drinking water and groundwater in several municipalities in Sweden. At the former fire station in Åkersberga, AFFFs were handled and used during the fire-training exercises. WSP Environmental Sweden has performed a preliminary investigation on site and elevated levels of PFASs in both soil and groundwater were observed. Since the property is located next to a railroad track, there is a concern that PFASs will spread through the railroad track towards the nearby Åkers canal. The aim of this master’s thesis has therefore been to map the transport of PFASs in groundwater from this former fire station. A groundwater flow model was first constructed in the software program Visual MODFLOW. The groundwater model was then used as a basis for the construction of a transport model with MODPATH and MT3DMS. The transport of four PFAS homologues was modeled; perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), 6:2 Fluorotelomer sulfonate (6:2 FTS), and perfluoropentanoic acid (PFPeA). The result of the groundwater modelling showed that groundwater from the property flows towards the southwest and then further towards Åkers canal. The approximated velocity of a water molecule varied between 270 m/year and 400 m/year. The transport modelling showed that all four PFAS homologues traveled towards Åkers canal via the railroad track and that the short-chain PFAS homologues (6:2 FTS and PFPeA) traveled longer and faster than the long-chain PFAS homologues (PFOS and PFOA). The approximated velocity of the contaminant plume for the concentration 4.5 ·10−5 mg/L was 0.6 m/year for PFOS, 3 m/year for PFOA, 8 m/year for 6:2 FTS, and 16 m/year for PFPeA. / Per- och polyfluorerade alkylsubstanser (PFAS) är en grupp av konstgjorda organiska kemikalier som sedan 1950-talet har kommersiellt använts i många konsumentprodukter, inklusive impregnerade textilier, impregnerat papper, nonstick-produkter (t.ex. Teflon), rengöringsmedel och brandsläckningsskum. PFAS har dock under senare år fått ökad allmän uppmärksamhet på grund av deras persistens, bioackumuleringspotential och potentiella toxiska effekter på människor och djur. Brandövningsplatser har identifierats som en av de största källorna för spridningen av PFAS i miljön, på grund av användningen av PFAS-innehållande brandsläckningsskum av typen AFFF (aqueous film forming foams). Detta har resulterat i förorening av både dricksvatten och grundvatten i flera kommuner i Sverige. På den tidigare brandstationen i Åkersberga har hantering och användning av AFFF ägt rum under släckningsövningarna. WSP Environmental Sverige har utfört förundersökning på plats och förhöjda halter PFAS i både jord och grundvatten observerades. Då fastigheten gränsar mot en banvall, finns det en oro att PFAS ska sprida via banvallen mot den närliggande Åkers kanalen. Syftet med detta examensarbete har därför varit att kartlägga transporten av PFAS i grundvatten från denna tidigare brandstation. En grundvattenflödesmodell konstruerades först i programvaran Visual MODFLOW. Grundvattenmodellen användes sedan som grund för konstruktionen av en transportmodell med MODPATH och MT3DMS. Transporten av fyra PFAS-homologer modellerades; perfluoroktansulfonat (PFOS), perfluorooktansyra (PFOA), 6:2 fluortelomersulfonat (6: 2 FTS) och perfluorpentansyra (PFPeA). Resultatet av grundvattenmodelleringen visade att grundvatten från fastigheten strömmar mot sydväst och sedan vidare mot Åkers kanal. Den approximerade hastigheten hos en vattenmolekyl varierade mellan 270 m/år och 400 m/år. Transportmodelleringen visade att alla fyra PFAS-homologerna spred mot Åkers kanal via banvallen och att de kortkedjiga PFAS-homologerna (6:2 FTS och PFPeA) spred längre och snabbare än de långkedjiga PFAS-homologerna (PFOS och PFOA). Ungefärlig hastighet av föroreningsplymen för koncentration 4.5 ·10−5 mg/L var 0,6 m/år för PFOS, 3 m/år för PFOA, 8 m/år för 6: 2 FTS och 16 m/år för PFPeA.

Os contaminantes emergentes são considerados compostos onipresentes em águas, portanto investigar a degradação e comportamento dessas substâncias torna-se necessária, pois é reportado que estes compostos causam efeitos adversos em seres vivos. O composto 2-(tiocianometiltio) benzotiazol (TCMTB), considerado um contaminante emergente, é amplamente empregado na indústria do couro como biocida com a finalidade de inibir o desenvolvimento de microrganismos na pele. Sendo assim, o objetivo do presente trabalho foi estudar a degradação do contaminante emergente TCMTB, por meio das técnicas de fotólise direta com radiação UV, radiação solar e oxidação com ozônio. Experimentos de fotólise direta do TCMTB, em soluções aquosas com diferentes concentrações, em efluente do processo de remolho e efluente simulado do remolho, foram conduzidos em reator com lâmpada de vapor de mercúrio (250 W). O teste de hidrólise foi realizado protegido da luz, a temperatura ambiente com diferentes concentrações do TCMTB para observar o comportamento do contaminante na ausência de luz. O maior coeficiente de absorção molar foi medido e identificado em 220 e 280 nm como 20489 e 11317 M-1 cm-1, respectivamente, para pH 5,0. Os resultados experimentais da fotodegradação mostraram que TCMTB foi rapidamente degradado por fotólise direta em soluções aquosas em 30 min de tratamento fotolítico. Os resultados do estudo do pH, demonstraram que pH interfere no processo fotoquímico, uma vez que em condições alcalinas o composto é mais estável e a taxa de fotodegradação diminui. Os ensaios com o efluente do processo de remolho mostraram que a degradação do TCMTB tem comportamento semelhante às soluções aquosas. O efluente simulado do remolho mostrou que uma alta concentração do contaminante leva a um maior tempo de irradiação de luz para a degradação. A aplicação de luz natural evidenciou degradação mais lenta, mas ainda assim, foi possível observar degradação de até 96% para a concentração de 6 mg L-1 em 420 min. A utilização do oxidante ozônio como tratamento, alcançou 40% de remoção do contaminante em 30 min, assinalando a alta estabilidade do composto. Portanto, este trabalho aponta o potencial do uso de fotólise direta (luz v artificial), ou radiação solar (luz natural) para a degradação de contaminantes emergentes como o 2 (tiocianometiltio) benzotiazol (TCMTB). / Emerging contaminants are considered omnipresent compounds in water, thus investigate the degradation and behavior of these substances becomes necessary as it is reported that these compounds cause adverse effects on living beings. The 2- (thiocyanomethylthio) benzothiazole compound (TCMTB), considered an emerging contaminant, is widely used in the leather industry as a microbicide for the purpose of inhibiting the development of microorganisms in the skin and leather. In this context, the purpose of the present work was to study the degradation of the emerging contaminant TCMTB by direct photolysis with UV radiation, solar radiation and ozone. Experiments of direct photolysis of the TCMTB in aqueous solutions with different concentrations, in the effluent from the soaking process were conducted in a reactor with mercury vapor lamp (250 W). The hydrolysis test was performed protected from light at room temperature with different concentrations of TCMTB to observe the behavior of the contaminant in the absence of light. The highest molar absorption coefficient was measured and identified at 220 and 280 nm as 20489 and 11317 M-1 cm -1, respectively, at pH 5.0. The experimental results of photodegradation showed that TCMTB was rapidly degraded by direct photolysis in aqueous solutions in 30 min of photolytic treatment. The results of the pH study showed that pH interfered in the photochemical process, since under alkaline conditions the compound is more stable and the photodegradation rate decreases. Assays of the direct photolysis in effluent from the soaking process have shown that TCMTB degradation behaves similarly to aqueous solutions. The direct photolysis of the the simulated effluent from the soaking showed that a high concentration of the contaminant leads to a longer time of light irradiation for degradation. The application of natural light evidenced slower degradation, however, it was possible to observe degradation of up to 96% for the 6 mg L-1 concentration with 420 min. The use of the ozone oxidant as a treatment, achieved 40% removal of the contaminant for 30 min of treatment, indicating the high stability of the compound. Therefore, this work highlights the potential of the use of direct photolysis (artificial light), or solar radiation (natural light) for the vii degradation of emerging contaminants such as 2 (thiocyanomethylthio) benzothiazole (TCMTB).