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Le soufre est un composant volatil important des magmas qui présente différents états d'oxydation en fonction des conditions d’oxydoréduction et de la phase dans laquelle il se trouve : dans le liquide silicaté, il est typiquement dissous comme S⁶⁺ et/ou S²⁻ , dans la phase gazeuse il se trouve principalement comme SO₂ (S⁴⁺ ) et H₂S (S²⁻). L’Etna, pour lequel les conditions d’oxydoréduction sont faiblement contraintes, est utilisée comme cas d’étude pour examiner le comportement du soufre dans les magmas basaltiques hydratés pendant la différenciation et le dégazage. Cette recherche combine l'étude des inclusions vitreuses avec une étude expérimentale en conditions magmatiques sur la solubilité du S dans les basaltes alcalins hydratés.Les résultats expérimentaux suggèrent l’important contrôle de la ƒO₂ sur la teneur en S dans les magmas hydratés de l’Etna, et le partage du S entre les phases fluid and liquid. Les inclusions vitreuses ont été piégées à différentes profondeurs à l'intérieur du système magmatique. Elles décrivent une tendance continue de différenciation, marquée par une cristallisation fractionnée, à partir de la composition picritique (FS) vers le basalte plus récent dégazé (2013). Le contenu en S dans le liquide de l'Etna est extrêmement variable et atteint 4150 ppm dans les inclusions vitreuses les plus primitives. Les spectres XANES Fe³⁺/ΣFe des certaines inclusions vitreuses donnent des rapports Fe³⁺/ΣFe généralement décroissants à partir du liquide le plus primitif (FS) jusqu’au plus évolué (2013). Les simulations effectué par le logiciel MELTS confirme que la diminution du rapport Fe³⁺/ΣFe est principalement due au processus de différenciation magmatique, renforcé par le dégazage du S à ƒO₂ < NNO + 1. Cette réduction du magma provoque à son tour la diminution de la solubilité du S dans les basaltes hydratés de l’Etna, et peut constituer un éventuel activateur de l’exsolution du S, à l’origine de l’important dégazage du S observé au cours des dernières décennies à l’Etna. / Sulfur is an important volatile component of magmas that presents different oxidation states, depending on the redox conditions and on the phase of occurrence: in silicate melts it is typically dissolved as S⁶⁺ and/or S²⁻ , in the gas phase it occurs principally as SO₂ (S⁴⁺ ) and H₂S (S²⁻). Mount Etna, in which magmatic redox conditions are poorly constrained, is used as a case study to investigate sulfur behavior in hydrous basaltic magmas during magma differentiation and degassing. This research integrates the study of natural olivine-hosted melt inclusions with an experimental study on S solubility in hydrous alkali basalts at magmatic conditions.Experimental results suggest the important control of ƒO₂ on the S abundance in Etnean hydrous magma and its partitioning between fluid and melt phases. Melt inclusions were entrapped at different depths inside the magmatic system (up to ~ 18 km, below crater level). They delineate a continuous differentiation trend, marked by fractional crystallization, from the picritic basalt (FS) toward the most evolved and degassed (2013) basalt. S content in Etnean melt is extremely variable and reaches 4150 ppm in the primitive melt inclusions. XANES Fe³⁺/ΣFe spectra in some glass inclusions, resulted in the generally decreasing of Fe³⁺/ΣFe ratios from the most primitive (FS) to the most evolved (2013) melts. MELTS software confirms that the Fe³⁺/ΣFe decrease is due principally to the melt differentiation process, enhanced to the S degassing at ƒO₂ < NNO+1. Magma reduction, in turn, induces the decrease of the sulfur solubility in the hydrous Etnean basalt, as well as of the sulfide saturation, and may constitute a possible enhancer of S exsolution, triggering the important S degassing observed in the last decades in Mt. Etna.

Fully-dynamic, continuous fugacity-based fate and transport models have been developed to examine all natural processes and interactions in the aquatic water systems. Within a body of surface water such as a lake or a river, a dynamic interaction among different media takes place. Chemical compounds are continuously dissolving, adsorbing into solid particles, attaching to suspended particles, resuspending, reacting, diffusing, and advecting. As the inclusion of all these interactions into a model is complex, the use of fugacity concept instead of concentration, renders the modeling task relatively easy. Fugacity, which is described as the escaping tendency of a chemical from a medium, is continuous among different phases, thus easier to follow the movement of the chemical. The first model has been developed to be used as an emergency response model by decision makers, which models the fate and transport of any contaminant in a lake. Due to uncertainties involved in the analysis, Monte Carlo simulations are performed. The fate of three representative contaminants; polychlorinated biphenyls (PCBs), atrazine, and benzene in air, water, and sediment compartments are examined. The second model developed is a continuous, dynamic river fugacity-based water quality model. In order to develop a continuous model, the hydrodynamics of the river system is solved first. Water depth and velocity at each point along the river are used in the advection-dispersion equation to determine the fate and transport of a contaminant. Interactions between different phases are also incorporated into the advection-dispersion equation which is solved numerically and coupled with a mass balance equation derived for the same contaminant in the sediments. The third model is a multispecies contaminant fate and transport model which can be used for the fate of a single contaminant and its daughter products. Trichloroethylene (TCE) and its daughter products, dichloroethylene (DCE) and vinyl chloride (VC), are used as representative of multispecies contaminants. The fate and transport of TCE and its daughter products has been analyzed first in a lake environment, and then in a river environment with the addition of a biofilm compartment where all biotransformations take place.

Les chondrites à enstatite partagent un réservoir commun de l’isotope de l’oxygène avec la Terre et la Lune. Cette caractéristique soulève la question d’une possible participation de ce type de météorites à la construction de la Terre. Egalement, l’étude des chondrites à enstatite permet d’apporter de nouvelles contraintes pour comprendre plus en détail l’histoire de la différenciation de petits corps planétaires soumis à des conditions réductrices. La première étude expérimentale systématique à haute pression et haute température d’une chondrite à enstatite a ainsi été mise en oeuvre, entre 1 et 25 GPa, et entre 1200°C et 2500°C, couvrant ainsi les conditions de pression et de température du manteau supérieur terrestre. La météorite qui a été choisie pour cette étude s’appelle Indarch. Il s’agit d’une chondrite à enstatite de type EH4. A 1 GPa, l’effet de la fO2 sur les relations de phases de la météorite, ainsi que sur les coefficients de partage entre métal et silicate liquide des éléments S, Si, Cr, Mn, Ni, et Mo est étudié spécifiquement. Les phases silicatées et métalliques subissent de grands changements lorsque la fO2 varie de IW-1.5 à IW-4.5. Des monosulfures contenant les éléments (Fe, Mg, Mn, Ca, Cr) sont présents aux fO2 les plus réduites. La phase métallique de nos échantillons est toujours liquide et comprend deux phases immiscibles riches en fer : l’une pauvre en S et riche en C, et l’autre riche en S et pauvre en C. La phase riche en C est également riche en Si aux fO2 les plus réduites. Les relations de phases d’Indarch ont été déterminées entre 3 et 25 GPa, et entre 1500°C et 2500°C, nous permettant de proposer le premier diagramme de phases en pression et température pour une chondrite à enstatite. La phase métallique est toujours liquide et il s’agit d’un alliage Fe-Ni-S à ces plus hautes pressions. La formation d’un noyau planétaire à basse pression (0 à 5 GPa) sous des conditions très réductrices ne peut expliquer les appauvrissements observés de S dans les manteaux silicatés alors que plusieurs wt% de Si pourront être piégés dans le noyau. En revanche, à plus haute pression, l’incorporation de S dans le noyau sera facilitée sous des conditions plus oxydantes. Finalement, notre étude permet de proposer un modèle d’évolution d’un matériau chondritique en cours d’accrétion sous des conditions rédox variables / Enstatite chondrites share a common oxygen reservoir with Earth and Moon. This suggests that these meteorites may have participated to the building of the planet Earth. Studying enstatite chondrites will bring constraints for a better understanding of the differentiation history of planetesimals under reducing conditions. Thus, this is the first systematic study at HP-HT of an enstatite chondrite between 1 and 25 GPa, and between 1200°C et 2500°C, covering the pressure and temperature conditions of the terrestrial upper mantle. The meteorite, which was chosen for this study, is named Indarch. It is an enstatite chondrite, type EH4. At 1 GPa, the effect of the fO2 on the phase relations of the meteorite, as well as on the partitioning behavior between liquid metal and liquid of S, Si, Cr, Mn, Ni, et Mo is studied. Silicate and metallic phases undergo significant changes while the fO2 varies from IW-1.5 to IW-4.5. (Fe, Mg, Mn, Ca, Cr)-bearing monosulfides are observed at the lowest fO2’s. The me-tallic phase in our samples is always liquid and comprises of two immiscible Fe-rich phases : one S-poor and C-rich, and the other S-rich and C-poor. The C-rich phase is also rich in Si at the most reduced fO2’s. Between 3 and 25 GPa, 1500°C and 2500°C, the phase relations of Indarch have been inquired and allow us to present the first P-T phase diagram for an enstatite chondrite. The metallic phase is always liquid, and at these high pressures, it is a Fe-Ni-S alloy. The observed depletions of S in silicate mantles cannot be explained by a core formation at low pressure (0 à 5 GPa) under reducing conditions, however several wt% of Si could be trapped in the core. At higher pressure, more oxidized conditions will facilitate S incorporation in the core. Final-ly, our study proposes a model of evolution of an accreting chondritic material under variable redox conditions

Résumé en français indisponible. / Mechanisms of volatile transfer from subducting slab to the melting region beneath arc volcanoes are probably the least understood process of arc magma genesis. Fluorine, which suffers minimum degassing in arc primitive melt inclusions, retains the information about the role of volatiles during magma genesis at depth. Experimentally determined solubility of F in aqueous fluid, and partition coefficients of F between fluid and minerals provide first order geochemical constraints about the volatile-transporting agent.My thesis experimentally determined F solubility in fluid and its partition coefficients among several phases. The systems are in equilibrium with hornblende and a humite group mineral (some contain melt or pyroxene) at 1 – 2 GPa, from 770 to 1047 °C, or equilibrium with hydrogrossular, pyroxene and norbergite or chondrodite at 2.5 – 3 GPa and 877 °C. The experiments were conducted with piston cylinder and cold sealing technique. The oxygen fugacity conditions were controlled by NNO buffer, while some were unbuffered. The fluids were extracted into volumetric flasks, and their compositions were determined by mass balance calculations. Moreover, the consistency was verified by HPLC for fluorine ion, and ICP-MS or ICP-AES for major cations of the quenched fluids.In 1 GPa experiments, the quench phases are so rare that the majority of the fluid compositions from direct analyses are consistent with mass balance results in their uncertainties. Moreover, my mass balance procedure takes into account all the measurements errors, which leads to large uncertainties on fluid compositions. The consistency demonstrates that most of fluorine aflter annealing in the capsule is present as fluorine ion. Futhermore, increases of the masses of starting materials, fluid proportions and analytical precisions will improve the uncertainties performances. ������������ can be represented by a single value 0.135 ± 0.036, which is independent of temperature, bulk composition and buffer conditions at 1 GPa. Df between fluid and humite group minerals is much less. Xf of hornblende and norbergite decrease from 1 to 2 GPa, while F partitionig between them doesn't change much. It indicates that F partitioning between fluid and minerals increases. Moreover, F concentrations in norbergite between NNO buffered and unbuffered experiments are significantly different. Meanwhile, Fe concentration variations of norbergite indicate that unbeffered experiments have higher oxygen fugacity than the NNO buffered ones. According to high temperature improves the free radical exchange reactions, H2O + 0.5O2 ⇄ 2OH. It indicates that both water fugacity and oxygen fugacity contribute to OH fugacity in fluid. I developed a simple model in which XF in humite group minerals are correlated to the ratio between F and OH. It is sucessfully applied to estimate the F concentration in the fluid, which co-exists with clinohumite, using Xf value.With the knowledge of my study, a new constraint can be framed on slab flux. The average F concentration in the fluid is 2700 ppm for F-rich experiments and it constrains the maximum amount of F carried by fluid in the presence of amphibole. Using partition coefficient of F to estimate F abundance in subducting slab, one can conclude that the increase of F concentration in the subarc mantle by fluid, in equilibrium with hornblende, to be less tan 5 ppm. Significant F enrichments found in arc lavas cannot be derived from aqueous fluid of subductiong slab in the presence of amphibole. Therefore, this result highlights the role either 1) slab melt, 2) fluid in equilibrium with eclogite, or perhaps 3) supercritical fluid for the element transfer from slab to mantle wedge.

[EN] This last few years, the trend in diesel engines has been to use different kinds of fuels to identify their influence and behaviour on the emissions and performance. Among the wide variety of fuels employed are the so called Primary Reference Fuels (PRFs), which represent the behaviour of diesel and gasoline in terms of ignition properties, as they are located at both ends of the octane rating scale and also have very different cetane numbers. One of the disadvantages of using pure gasoline or diesel-gasoline blends in diesel engines is the time needed for the mixture to ignite and to completely burn the fuel. This generally requires working with partial loads or with premixed charges. In order to isolate the fuel effects on the spray processes and to be able to study the characteristic parameters of ignition delay time, lift-off length, vapour and liquid penetration, among others; different experiments under parametric variations of diesel like conditions have been performed. The tests were performed under inert and reactive conditions in a 2-stroke optical engine and a constant-pressure flow (CPF) high-pressure high-temperature vessel using single-hole nozzles, while diverse optical techniques were being employed. To study the influence of the fuel properties, different single-component fuels were employed as well as binary blends and a six-component diesel surrogate, which was also compared to conventional diesel. Additionally, the results have been contrasted with a one-dimensional model in order to further explain the values and trends found. The results presented a strong dependency on the fuel properties for the tests performed under inert and reactive conditions. The difference in physical properties of n-decane and n-hexadecane showed an almost linear reduction of the stabilized liquid penetration down to approximately 60% under some conditions. Additionally, due to the composition of the surrogate fuel, pure n-hexadecane was demonstrated to have almost identical evaporation characteristics, hence proving itself as a good candidate for a single-component surrogate of diesel fuel. In a similar way, the chemical properties of the PRFs n-heptane and iso-octane also proved to be influential on the spray development and radiation emitted. Ignition delay values up to one order of magnitude larger where obtained for both extremes of the blend range, as well as lift-off lengths up to three times longer. The radiation emitted by the soot incandescence presented the highest variations, as some conditions showed a reduction of almost four orders of magnitude among the blend range. Moreover, some cases did not present any radiation corresponding to the soot, and increasing the sensitivity of the camera only caused the chemiluminescence of the OH* radical to be captured. On a different way, the stabilized flame length determined also by the soot radiation did not present much variation as the fuel properties or the air temperature were changed; in fact, the only noticeable differences were caused by the changes in the oxygen composition of the ambient air. In conclusion, the fuel properties proved to have a significant effect on the spray processes. Lighter fuels favoured the evaporation of the spray under a range of conditions, while fuels with lower octane numbers ignited sooner and closer to the spray tip but with more soot luminosity measured. / [ES] Estos últimos años, la tendencia en motores diesel ha sido la de emplear distintos tipos de combustibles para identificar su influencia y comportamiento sobre las emisiones y rendimiento. Dentro de la amplia variedad de combustibles empleados están los llamados combustibles de referencia (PRFs ingl. Primary Reference Fuels), los cuales representan el comportamiento del diesel y la gasolina en lo que respecta a propiedades de encendido, ya que se encuentran en ambos extremos de la escala del número de octano y también poseen números de cetano muy distintos. Una de las desventajas de utilizar gasolina pura o mezclas de diesel-gasolina en motores diesel es el tiempo que toma la mezcla en encender y quemar completamente el combustible. Esto generalmente requiere trabajar con cargas parciales o cargas premezcladas. Para poder aislar los efectos del combustibles sobre los procesos de un chorro y que sea capaz estudiar los parámetros característicos de tiempo de retraso de encendido, longitud de despegue de llama, penetración de líquido y vapor, entre otros, se han realizado distintos experimentos bajo variaciones paramétricas de condiciones de motor diesel. Los ensayos han sido realizados bajo condiciones inertes y reactivas en un motor óptico de dos tiempos y una instalación de alta presión y alta temperatura de flujo continuo a presión constante (CPF ingl. Constant-Pressure Flow) empleando toberas mono-orificio, con aplicación de diversas técnicas ópticas. Para estudiar la influencia de las propiedades de los combustibles se utilizaron distintos mono-componentes, así como mezclas binarias y un sustituto de diesel conformado por seis componentes, el cual fuel comparado con diesel convencional. Adicionalmente, los resultados han sido contrastados con un modelo unidimensional para ayudar a explicar los valores y tendencias encontrados. Los resultados presentaron una fuerte dependencia de las propiedades de los combustibles en los ensayos realizados bajo condiciones inertes y reactivas. La diferencia entre las propiedades físicas del n-decano y n-hexadecano mostraron una reducción casi lineal sobre la longitud líquida estabilizada hasta aproximadamente un 60% bajo ciertas condiciones. Adicionalmente, debido a la composición del combustible de sustitución, el n-hexadecano puro demostró tener características de evaporación prácticamente idénticas, probándose a sí mismo como un buen candidato para ser un sustituto mono-componente del diesel convencional. De una manera similar, las propiedades químicas de los PRFs n-heptano e iso-octano también probaron tener influencia sobre el desarrollo del chorro y radiación emitida. Se obtuvieron valores de tiempo de retraso con diferencias de hasta un orden de magnitud entre ambos extremos del rango de las mezclas, así como longitudes de despegue de llama hasta tres veces más largas. La radiación emitida por la incandescencia del hollín presentó las variaciones más altas, ya que algunas condiciones mostraron reducciones de hasta cuatro órdenes de magnitud dentro del rango de mezclas. Es más, algunos casos no presentaron radiación correspondiente al hollín, e incrementar la sensibilidad de la cámara solo ocasionó que la quimioluminiscencia del radical OH* sea detectada. Por otro lado, la longitud estabilizada de llama calculada mediante la radiación del hollín no presentó mucha variación respecto a las propiedades del combustible o la temperatura del aire. De hecho, la única diferencia apreciable fue causada por los cambios en la composición del oxígeno del aire ambiente. En conclusión, las propiedades de los combustibles demostraron tener un efecto significativo en los procesos de un chorro diesel. Los combustibles más ligeros favorecieron la evaporación del chorro en un rango de condiciones, mientras que combustibles con números de octano más bajos encendieron más pronto y cerca de la tobera pero con mayor luminosidad del hollín medida. / [CA] En aquests últims anys, la tendència en motors Diesel ha estat la d'emprar diferents tipus de combustibles per a identificar la seva influència i comportament sobre les emissions i rendiment. Dintre de l'àmplia varietat de combustibles emprats estan els anomenats combustibles de referència (PRFs angl. Primary Reference Fuels), els quals representen el comportament del dièsel i la gasolina pel que fa a propietats d'encesa, ja que es troben en ambdós extrems de l'escala del nombre d'octà i també posseeixen nombres de cetà molt diferents. Un dels desavantatges d'utilitzar benzina pura o barreges de Diesel-benzina en motors Diesel és el temps que pren la barreja a encendre i cremar completament el combustible. Això generalment requereix treballar amb càrregues parcials o càrregues premesclades. Per a poder aïllar els efectes del combustibles sobre els processos d'un doll i que sigui capaç estudiar els paràmetres característics de de temps de retard d'encesa, longitud d'enlairament de flama, penetració de líquid i vapor, entre altres, s'han estudiat diferents experiments sota variacions paramètriques de condicions de motor Diesel. Els assajos han estat realitzats sota condicions inertes i reactives en un motor de dos temps i una instal·lació d'alta pressió i alta temperatura de flux continu a pressió constant (CPF angl. Constant-Pressure Flow) emprant toberes mono-orifici, amb aplicació de diverses tècniques òptiques. Per a estudiar la influència de les propietats dels combustibles, van ser utilitzats distints mono-components, així com barreges binàries i un substitut de Diesel conformat per sis components, el qual fuel comparat amb Diesel convencional. Addicionalment, els resultats han estat contrastats amb un model unidimensional per a ajudar a explicar els valors i tendències trobats. Els resultats van presentar una forta dependència de les propietats dels combustibles en els assajos realitzats sota condicions inertes i reactives. La diferència entre les propietats físiques del n-decà i n-hexadecà van mostrar una reducció gairebé lineal sobre la longitud líquida estabilitzada fins a aproximadament un 60% sota certes condicions. Addicionalment, degut a la composició del combustible de substitució, el n-hexadecà pur va demostrar ser tindre característiques d'evaporació pràcticament idèntiques a aquell, demostrant ser un bon candidat per a ser un substitut mono-component del dièsel convencional. D'una manera similar, les propietats químiques dels PRFs n-heptà i iso-octà també provaren tindre influència sobre el desenvolupament del doll i la radiació emesa. Es van obtenir valors de temps de retard amb diferències de fins a un ordre de magnitud entre ambdós extrems del rang de les barreges, així com longituds d'enlairament de flama fins a tres vegades més llargues. La radiació emesa per la incandescència del sutge va presentar les variacions més grans, ja que algunes condicions van mostrar reduccions de fins a quatre ordres de magnitud dintre del rang de barreges. Encara més, alguns casos no van presentar radiació corresponent al sutge, i incrementar la sensibilitat de la càmera solament va ocasionar que la quimioluminiscència del radical OH* sigui detectada. D'altra banda, la longitud estabilitzada de flama calculada mitjançant la radiació del sutge no va presentar molta variació respecte a les propietats del combustible o la temperatura del aire. De fet, la única diferència apreciable va ser causada pels canvis en la composició del oxigen de l'aire ambient. En conclusió, les propietats dels combustibles van demostrar tenir un efecte significatiu en els processos d'un doll dièsel. Els combustibles més lleugers van afavorir l'evaporació del doll en un rang de condicions, mentres que els combustibles amb nombre d'octà més baixos van prendre més aviat i prop de la tovera però amb més lluminositat del sutge mesurat. / Vera-Tudela Fajardo, WM. (2015). An experimental study of the effects of fuel properties on diesel spray processes using blends of single-component fuels [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/58865

The geology, petrology and geochemistry of Catface porphyry Cu (Mo-Au) deposit, located on the west coast of Vancouver Island are examined in detail. Detailed core logging and sampling was carried out to characterize the geometry and identity of different intrusive phases and alteration styles prevalent during the emplacement and formation of the deposit, as well as their geochemical affinity. Early- and late-stage potassic alteration is identified, as well as main-stage sodic-calcic and calcic-sodic alteration. Four distinct Paleogene intrusive phases vary from quartz diorite to granodiorite in composition. The rocks are broadly calc-alkaline, weakly peraluminous to moderately metaluminous, and have typical arc geochemical affinity. The timing of emplacement and mineralization is constrained by U-Pb and Re-Os geochronology at 40.4-41.4 Ma and 40.9 ±0.2 Ma, respectively. All four Paleogene Catface intrusive phases were emplaced close in time with a direct temporal correlation to mineralization. The chalcopyrite- and pyrite-bearing miarolitic cavities in the Halo Porphyry intrusive, combined with U-Pb and Re-Os dates suggest this intrusive phase is the most likely source of mineralizing fluids. The intrusions were emplaced at depths of less four kilometers in the crust, as evidenced by the presence of miarolitic cavities and confirmed through amphibole-plagioclase thermobarometry, which record conditions of 615–700 °C and <200 MPa. The lack of primary anhydrite and hematite, and the presence of pyrrhotite in the ore system indicate a reduced magmatic-hydrothermal event. The SO3 contents in apatites are <450 ppm, indicative of a degassed and/or sulphate-free (reduced) magma. The assemblage K-feldspar-quartz-biotite-ilmenite yields oxygen fugacities (fO2) which are 0.5 to 3.0 log units below the quartz-fayalite-magnetite (QFM) buffer at an assumed pressure of 300 MPa; orders of magnitude more reduced than typical porphyry deposits. Parental magmas to the Catface deposit were either derived from intrinsically-reduced mantle, or more typical oxidized arc magma that was subsequently reduced during ascent and emplacement. Further isotopic work is required to determine which process contributed to the reduction of these magmas in an arc setting. Nevertheless, recognition of reduced porphyry-related magmatism on west-central Vancouver Island is of similar age to that of North Fork (~36.8-38.9 Ma) deposit in Washington suggesting a consanguinity of reduced magmatism with the Paleogene Cascade arc. / Graduate

Polyzyklische aromatische Kohlenwasserstoffe (PAK) sind eine Klasse krebserregender Schadstoffe. Aufgrund ihres weit verbreiteten Vorkommens und der toxischen Risiken für die menschliche Gesundheit und das Ökosystem ist es unerlässlich, durch systematische Forschung wirksame Minderungsstrategien auf verschiedenen Ebenen zu etablieren. In dieser Dissertation wurden Quellenzuordnung, Multimedia-Schicksal, Schlüsselemis-sionssektoren und globale gesundheitliche Auswirkungen von PAK-Belastungen unter-sucht. Diese Forschung wurde durchgeführt, um Daten zur Verfügung zu stellen, die po-tenzielle Minderungsstrategien unterstützen, um PAK-Verschmutzungen und damit ver-bundene gesundheitliche Auswirkungen auf regionaler, nationaler und globaler Ebene zu reduzieren. Zunächst wurde die Quellenzuordnung von Langzeit-PAH in acht Flüssen untersucht. Diese Studie untersuchte systematisch die zeitlichen und saisonalen Trends, die peri-odische Oszillation, die Quellenzuordnung und die Risikobewertung von PAKs für die menschliche Gesundheit in acht Flüssen, die eine quellenorientierte PAK-Minderung in der Region unterstützen können. Zweitens ist das Multimedia-Schicksal von PAKs entscheidend für eine bessere Umwelt-politik. Diese Studie bewertete systematisch die räumlich-zeitliche Verteilung, die Quellenzuordnung, den multimedialen Transport und den Verbleib von PAK, die an Schwebstaub (SPM) in Rhein und Elbe adsorbiert sind, was die Stadtplanung unterstützen kann, um PAK in den Regionen zu lindern. Drittens wurden in dieser Studie die wichtigsten Emissionssektoren von PAK bestimmt, indem die langfristigen verkörperten und ermöglichten PAK-Emissionen in verschiedenen Sektoren abgeschätzt und die Beiträge sozioökonomischer Determinanten quantifiziert wurden. Die Ergebnisse können wirksame Strategien zur Verringerung der PAK-Emissionen in verschiedenen Sektoren aus der Perspektive des Endverbrauchs und des primären Inputverhaltens auf nationaler Ebene unterstützen. Schließlich wurden in dieser Studie die globalen Triebkräfte der gesundheitlichen Auswir-kungen von PAH untersucht, indem ein integrierender Rahmen angewendet wurde, der das globale PAH-Emissionsinventar, das um die Umwelt erweiterte multiregionale Input-Output-Modell, das GEOS-Chem-Chemikalientransportmodell und das lebenslange Lung-enkrebsrisiko verknüpfte Bewertung und Analyse der Strukturzerlegung. Die Ergebnisse können politische Entscheidungen zur Optimierung von Minderungsstrategien aus verschiedenen Perspektiven unterstützen, um PAK-Emissionen und gesundheitliche Aus-wirkungen weltweit effektiv zu reduzieren. / Polycyclic aromatic hydrocarbons (PAHs) are a class of carcinogenic pollutants. Due to their widespread occurrence and toxic risks to human health and ecosystem, it is essen-tial to establish effective mitigation strategies at different scales through systematic re-search. In this dissertation, source apportionment, multimedia fate, key emission sectors and global health impacts of PAH pollutions have been investigated. This research was conducted to provide data to assist potential mitigation strategies to reduce PAH pollu-tions and related health impacts at regional, national, and global scales. Firstly, the source apportionment of long-term PAHs in eight rivers were investigated. This study systematically investigated the temporal and seasonal trends, periodic oscilla-tion, source apportionment, and human health risk assessment of PAHs in eight rivers, which can assist source-oriented PAH mitigation in the region. Secondly, the multimedia fate of PAHs is critical for achieving better environmental poli-cies. This study systematically evaluated the spatiotemporal distribution, source appor-tionment, multimedia transport and fate of PAHs adsorbed on suspended particulate matter (SPM) in Rhine and Elbe Rivers, which can assist urban planning to alleviate PAHs in the regions. Thirdly, the key emission sectors of PAHs were determined in this study through estimat-ing the long-term embodied and enabled PAH emissions in various sectors and quantify-ing the contributions of socioeconomic determinants. The results can assist effective strategies for mitigating PAH emissions in different sectors from the perspectives of final consumption and primary input behaviors at a national scale. Finally, the global driving forces of PAH health impacts were investigated in this study through applying an integrating framework, linking global PAH emission inventory, envi-ronmentally extended multi-regional input-output model, GEOS-Chem chemical transport model, lifetime lung cancer risk assessment, and structure decomposition analysis. The results can assist policy decisions to optimize mitigation strategies from different per-spectives for effectively reducing PAH emissions and health impacts in the world.

In the studies underlying this thesis, various source tracing techniques were applied to environmental samples from the Baltic region. Comprehensive sampling and analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in surface sediments in Swedish coastal and offshore areas resulted in a unique data set for this region. Nearly 150 samples of surface sediments were analyzed for all tetra- to octa-chlorinated PCDD/Fs. The levels showed large spatial variability with hotspots in several coastal regions. Neither Sweden nor the EU has introduced guideline values for PCDD/Fs in sediment, but comparisons to available guidelines and quality standards from other countries indicate that large areas of primarily coastal sediments may constitute a risk to marine organisms. Multivariate pattern analysis techniques and receptor models, such as Principal Component Analysis (PCA) and Positive Matrix Factorization (PMF), were used to trace sources. These analyses suggested that three to six source types can explain most of the observed pattern variations found in the sediment samples. Atmospheric deposition was suggested as the most important source to offshore areas, thus confirming earlier estimates. However, spatial differences indicated a larger fraction of local/regional atmospheric sources, characterized by PCDFs, in the south. This was indicated by the identification of several patterns of atmospheric origin. In coastal areas, the influence of direct emission sources was larger, and among these, chlorophenol used for wood preservation and emissions from pulp/paper production and other wood related industry appeared to be most important. The historic emissions connected to processes involving chemical reactions with chlorine (e.g. pulp bleaching) were found to be of less importance except at some coastal sites. The analysis of PCDD/Fs in Baltic herring also revealed spatial variations in the levels and pollution patterns along the coast. The geographical match against areas with elevated sediment levels indicated that transfer from sediments via water to organisms was one possible explanation. Fugacity, a concept used to predict the net transport direction between environmental matrices, was used to explore the gas exchange of hexachlorocyclohexanes (HCHs) and polychlorinated biphenyls (PCBs) between air and water. These estimates suggested that, in the Kattegat Sea, the gaseous exchange of HCHs primarily resulted in net deposition while PCBs were net volatilized under certain environmental conditions. The study also indicated that, while the air concentrations of both PCBs and γ-HCH are mostly dependent upon the origin of the air mass, the fluctuations in α-HCH were primarily influenced by seasonal changes.

La formation des noyaux planétaires métalliques est un évènement majeur pour l’évolution des propriétés physico-chimiques des planètes telluriques telles que nous les connaissons aujourd’hui. En effet, l’abondance des éléments sidérophiles (i.e. qui ont des affinités chimiques avec les phases métalliques) dans les manteaux planétaires s’explique par les conditions dans lesquelles se sont séparées les phases métalliques et silicatées. Au premier rang de ces conditions se trouvent la pression, la température et la fugacité d’oxygène. La distribution des éléments dans le noyau et le manteau ne peut en effet s’expliquer que pour un équilibre obtenu dans un océan magmatique profond, donc à haute pression et haute température ; et dans des conditions d’oxydo-réduction variables, dont l’évolution la plus probable est de passer d’un état réduit à un état oxydé. Un autre paramètre important est la présence ou non d’eau dans l’océan magmatique primitif. En effet, nous disposons de plus en plus d’arguments permettant d’expliquer l’arrivée des éléments volatils, notamment l’eau, pendant l’accrétion, à partir de briques élémentaires qui contiennent ces éléments. Si l’eau est présente tout au long de l’accrétion, et donc pendant la ségrégation du noyau, elle peut donc avoir un effet sur ce dernier phénomène. Dans cette hypothèse, nous avons mené des expériences de haute pression et haute température permettant de modéliser expérimentalement la formation du noyau en condition hydratée. Ces expériences nous ont permis de montrer que la présence d’eau a un effet sur l’évolution de l’état d’oxydation des manteaux planétaires. Cette évolution oxydo-réductive nous a permis de contraindre des modèles d’accrétion basés sur un mélange de chondrites EH et CI, qui confirment des modèles construits à partir de données isotopiques. Ces modèles nous ont permis de contraindre les concentrations primitives maximum en eau probables sur Terre (1,2-1,8 % pds.) et sur Mars (2,5-3,5 % pds.). D’autre part, nos avons mis en évidence le caractère lithophile (i.e. qui a des affinités chimiques avec les phases silicatées) de l’hydrogène à haute pression, a contrario de plusieurs études précédentes. De ce fait, la différence entre les concentrations initiales élevées en eau que nous obtenons dans nos modèles d’accrétion et les concentrations en eau estimées sur Terre et sur Mars actuellement (2000 ppm et 200 ppm, respectivement) ne peut pas être expliquée par un réservoir d’hydrogène dans le noyau. Enfin, pour améliorer les modèles de formation du noyau, nous avons mis en évidence, par des modèles numériques, l’effet important de la viscosité de l’océan magmatique sur le taux d’équilibre entre noyaux et manteaux des planètes telluriques. Cela nous mène à ré-évaluer les modèles de formation des planètes telluriques basés sur des résultats expérimentaux à l’équilibre, notamment l’extension maximale de l’océan magmatique. L’évolution de la viscosité de l’océan magmatique a donc un impact important sur la composition finale des noyaux planétaires (par exemple les teneurs en soufre, oxygène ou silicium des noyaux terrestres et martiens). / The formation of the metallic planetary cores is a major event regarding to the evolution of physical and chemical properties of the telluric planets as we know it today. Indeed, the siderophile elements (i.e. which has affinities with metallic phases) abundances in planetary mantles is explained by the conditions of core-mantle segregation. Among these conditions, pressure, temperature and oxygen fugacity are the main ones controlling distribution of the elements between mantle and core. This distribution can only be explained by an equilibrium between metal and silicate obtained in a deep magma ocean, which implies high pressure and high temperature of equilibrium. Moreover, the oxygen fugacity must have varied during core-mantle segregation, in a reduced-to-oxidized path most probably. Another important parameter is whether or not water is present in the primordial magma ocean. Indeed, we now have more and more lines of evidences showing that the volatile elements, especially water, arrived during accretion and therefore during the core-mantle segregation, which means that water can have an effect on the latter phenomenon. Considering this hypothesis, we performed several high pressure-high temperature experiments which allowed us to model the formation of the core under hydrous conditions. These experiments demonstrated that water has a significant effect on the redox state evolution of planetary mantles. We use this redox evolution to constrain models of planetary accretions, based on a mix of EH and CI chondrites, showing a good agreement with models based on isotopic data. The output of these models is the maximum initial concentration in water on the Earth (1.2 -1.8 %wt) and on Mars (2.5-3.5 %wt). Furthermore, these experiments showed a lithophile behavior (i.e. which has affinities with silicated phases) of hydrogen at high pressures, contrary to previous studies. Therefore, the difference between high initial concentrations in water yielded by our accretion models and the estimated actual concentrations on the Earth and Mars (2000 ppm and 200 ppm, respectively) cannot be explained by a hydrogen reservoir in the core. Finally, to improve the models of core-mantle segregation, we showed by numerical simulations the important effect of the magma ocean viscosity on the equilibrium between planetary mantles and cores. it lead us to reevaluate the models of accretion based on experimental data, especially the maximum extent of magma oceans. The evolution of the magma ocean viscosity has therefore significant implications on the final composition of planetary cores (for instance on the sulfur, oxygen and silicon content of the Earth’s and Mars’ core).