Os contaminantes lançados no ambiente decorrente das atividades humanas podem se movimentar de um compartimento ambiental para o outro e assim chegar nos corpos hídricos, onde se associam rapidamente ao material particulado e incorporam-se aos sedimentos. Desta forma, a relação água com o sedimento faz deste compartimento um dos principais alvos de preocupação e análise, dada sua importância na ciclagem de matéria e na biodisponibilidade de diversos compostos químicos para o ambiente aquático. O objetivo deste trabalho foi avaliar o comportamento geoquímico dos elementos Al, Fe, Cr, Cu, Zn, Mn, e P em sedimento superficial do reservatório Guarapiranga por meio da técnica de extração sequencial constituída de quatro etapas, seguido pela detecção em espectrometria de emissão ótica com plasma acoplado indutivamente (ICP-OES). Foram coletadas amostras de sedimento superficial em 14 (quatorze) estações estrategicamente escolhidas, de modo a conhecer a heterogeneidade do sistema e determinar a mobilidade de elementos-traço persistentes e sua distribuição espacial no compartimento sedimentar da represa. As amostras passaram por processo de secagem e foi separada a fração silte/argila. A extração sequencial foi realizada em quatro etapas, a fração 1 ácido solúvel ligada a carbonatos, a fração 2 redutível a óxidos de ferro e manganês, a fração 3 oxidável ligada a matéria orgânica e a fração 4 residual. Todo o processo foi feito em triplicata e as concentrações dos elementos foram determinadas no ICP-OES. Com base nos resultados obtidos da extração sequencial, foi possível avaliar a distribuição dos elementos nas quatro frações geoquímicas distintas bem como o fator de mobilidade individual e total desses elementos no reservatório. A soma das três primeiras frações compõe a fração considerada biodisponível enquanto que a diferença do total extraído representou a fração residual. A partir dos resultados obtidos infere-se que o reservatório do Guarapiranga apresenta dois compartimentos distintos, um mais degradado que vai do ponto GU-05 ao GU-14 que sofre os impactos da ocupação do seu entorno e um mais preservado que vai do ponto GU-01 a GU-04, com pouca influência de ocupação urbana no seu entorno. O grau de mobilidade global segue uma tendência de montante à jusante do reservatório, próxima a barragem. / The contaminants produced by human activities released in the environment may move from one environmental compartment to another and reach the water bodies, where they rapidly associate to particulate matter and are incorporated to the sediments. Thus, the relationship between water and sediment makes this compartment on of the main targets for concern and analysis, given its importance in cycling matter and in bioavailability of various chemical compounds to the water environment. The objective of this work was to study the geochemical behaviour of the elements Al, Fe, Cr, Cu, Zn, Mn and P in the surface sediments of the Guarapiranga reservoir (23°47\'S and 46°32\"W) by means of the sequential extraction technic consisting of four stages, followed by the detection in inductively coupled plasma optical emission spectroscopy (ICP-OES). Samples were collected from the superficial sediment in 14 (fourteen) stations strategically chosen, this way being able to know the heterogeneity of the system and to determinate the mobility of persistent trace elements and their spatial distribution in the sedimentary compartment of the reservoir. The samples were subjected to a drying process and then separating the silt fraction. The sequential extraction was made in four steps, fraction 1 acid soluble linked to carbonates, fraction 2 reducible to iron and manganese oxides, fraction 3 oxidable linked to organic matter and fraction 4 residual. All the process was done in triplicate and the concentration of the elements was determined by ICP-OES. Based on the results obtained by the sequential extraction, it was possible to evaluate the distribution of the elements in the four distinct geochemical fractions, as well as the individual mobility factor of those elements in the reservoir. The sum of the first three fractions composes the fraction considered bioavailable, while the difference from the total extracted represented the residual fraction. Parting from the results obtained it is inferred that the Guarapiranga reservoir has two distinct compartments, one more degraded that goes from point GU-05 to GU-14 that suffers from the impacts of the occupations in the surroundings and one more preserved that goes from point GU-01 to GU-04, with little influence from urban occupation in the surroundings. The degree of global mobility follows the tendency of up and down stream in the reservoir, next to the barrage.

A contaminação dos ecossistemas aquáticos por metais-traço demanda preocupação já que estes contaminantes podem exercer efeitos tóxicos sobre a biota e aumentar os custos para tratamento da água. Em geral, tais problemas de degradação são decorrentes de uma gestão de recursos hídricos deficiente. Tendo como área de estudo a represa Paiva Casto, reservatório integrante do Sistema Cantareira, maior sistema de abastecimento público da região metropolitana de São Paulo, este trabalho teve o intuito de: investigar o histórico da contaminação por metais-traço (Cd, Cr, Cu, Ni, Pb, Zn, Mn, Al) por meio da geocronologia por 210Pb e indicar um valor de referência para estes; identificar a heterogeneidade espacial destes contaminantes; analisar a biodisponibilidade e com base na possibilidade de adequar etapas do sistema de gestão de recursos hídricos europeu, a Diretiva Quadro da Água (DQA) discutir a qualidade química dos sedimentos da represa em estudo. Foram efetuadas duas coletas em campo, destinadas à avaliação do histórico da contaminação ambiental por metais-traço e à análise da biodisponibilidade por meio da técnica de sulfetos volatilizáveis por acidificação (SVA) e metais simultaneamente extraídos (MES). O histórico da contaminação por metais-traço abrangeu um período de 100 anos e indicou que os maiores impactos na região, em relação a estes contaminantes, ocorreu em período anterior ao início de operação da represa Paiva Castro, com exceção do Cu. Para o Cu, em sedimentos superficiais, os teores excederam até três vezes e meia o VR. Este resultado é provável consequência da aplicação de sulfato de cobre para o controle de florações de algas. Os dados para os VR divergiram daqueles estabelecidos para a crosta terrestre, porém foram semelhantes aos encontrados para a bacia do Alto Tietê, com exceção dos metais Cr e Pb. A análise de (SVA/MES) indicou que os metais não estavam biodisponíveis. Dentre as áreas amostradas, a região da barragem apresentou ao longo do tempo as maiores taxas de acumulação para metais-traço em contraposição à área de captação das águas para abastecimento público. Em relação a DQA, constatou-se que existe capacidade científica para avançar na incorporação de novos instrumentos na gestão, principalmente no Estado de São Paulo, entretanto, é preciso que haja sistemas de saneamento e monitoramento adequados e especialmente decisão política e rigor na aplicação destes novos instrumentos, caso contrário a incorporação da DQA é inviável. Aplicando algumas das normas da DQA na avaliação da qualidade química dos sedimentos da represa Paiva Castro constatou-se que a qualidade geral para este manancial é boa. Apesar disto é necessário que as políticas públicas sejam de fato aplicadas contra a degradação deste importante manancial, caso contrário a boa qualidade deste reservatório estará em risco / Contamination of aquatic ecosystems by trace metals demand concern since these contaminants may cause toxic effects on biota and increase costs for water treatment. In general, such degradation problems are due to a poor water management. A study was conducted at Paiva Castro reservoir, one of the reservoirs of the Cantareira System, largest public water supply system in the metropolitan region of São Paulo, this study aimed to: investigate the history of the accumulation of trace-metals (Cd, Cr, Cu, Ni, Pb, Zn, Mn, Al), through geochronology by 210Pb; establish background values (BV); analyze spatial heterogeneity; bioavailability and based on the possibility of adjusting some instruments of the European water resources management system, the Water Framework Directive (WFD), discuss the chemical quality of Paiva Castro\'s sediments. Two collections were performed, to assess the historical environmental contamination by trace-metals and to analyze the bioavailability using the technique of sulfides volatilizable by acidification (AVS) and simultaneously extracted metals (SEM). The history of contamination by trace- metals covered a period of 100 years and indicated that the greatest impacts in the region occurred in periods prior to the reservoir operation, with the exception of Cu. For Cu, in surface sediments, the levels exceeded three times and a half the BV. This result is probable consequence of copper sulphate application for controlling algal blooms. Data for BV were different from those found in the earth\'s crust, but similar to those found for the Alto Tietê basin, except for Cr and Pb metals. Analysis (AVS/ SEM) indicated that metals were not bioavailable. Among the sampled areas, the region of the dam, showed the highest rates of accumulation for trace- metals in contrast to the catchment area for public water supply. Regarding WFD, it was observed that there is scientific capacity to incorporate new instruments in the management, mainly in São Paulo, however, there must be adequate sanitation and monitoring systems and especially political decision and rigor in the application of these new tools, otherwise the incorporation of the WFD is unviable. Applying some of the WFD instruments in assessing the chemical quality of Paiva Castro\'s sediments, it was found that the quality of this ecosystem is good. Nevertheless, it is necessary that public policies are actually applied against the degradation of this important ecosystem; otherwise, reservoir\'s \'good quality\' will be at risk

Water chemistry in rivers is impacted by a variety of natural and anthropogenic processes including agricultural runoff, urban runoff, storm runoff, groundwater inputs, and the built environment. In this study we used trace element concentrations (including As, B, Ce, Co, Cu, Li, Mn, Rb, Sb, Sr, Tl, V, and Zn) and continuous measurements of flow rates and specific conductance to investigate dynamic processes affecting water quality in a rapidly urbanizing agricultural area typical of the western U.S. The middle Provo River, located in northern Utah, USA, was selected as the study area because it is well instrumented with water quality stations and streamflow gauges. We sampled 6 sites on the middle Provo River and 15 sites on tributaries in the watershed a minimum of 5 times between April 2014 and March 2015 to evaluate potential contributions from surface water and groundwater inputs to the Provo River. Additional water samples were collected at 13 cold, thermal, and mixed cold/thermal springs in Heber Valley during summer 2014 to evaluate regional groundwater chemistry. Samples were also collected during two storm events including high frequency sampling in a tributary and road-puddle samples to characterize potential storm runoff chemistry. Specific conductance data loggers were deployed in tributaries to monitor effects of precipitation and other runoff on the middle Provo River at 15-min intervals. See Table 1 for a summary of sampling events. Middle Provo River water chemistry is impacted by natural groundwater inputs as well as surface water tributaries. Li, B, Sr, As concentrations increased dramatically (3-10 fold) downstream of the confluence with a major tributary, Snake Creek. Snake Creek had average As concentrations of ~15 µg/L above the confluence with Provo River and accounted for roughly 20% of the flow to the middle Provo River, but increased the As concentration in Provo River ~4 fold. Thermal springs had ~20 and ~80 times higher concentrations of As and Li, respectively, relative to cold springs and was found to be a major contributor of trace elements to Snake Creek and the middle Provo River. Cl mixing calculations indicated that groundwater contributions increased downstream with up to 15% of the flow to the middle Provo River being contributed within the most downstream reach. Tributaries were found to impact the Provo River based on specific conductance fluxes in tributaries corresponding to fluxes in the river. Notably, Spring Creek, a dominantly agricultural tributary, accounts for >40% of the annual V load and >18% of the annual U, Mn, Pb, Ba, La, and Ce loads to the middle Provo River. The trace elements B, Li, As, and Sr which are found in high concentrations in groundwater, were strongly correlated with Provo River specific conductance and may indicate a potential method of predicting select trace element concentrations in the middle Provo River based on specific conductance data. Filtered puddle samples collected during a storm event had higher concentrations of Co, Cu, V, and Zn, but lower concentrations of major and select trace elements including As, Li, and Sr, relative to the middle Provo River. This study has implications for understanding water quality in complex coupled human-natural systems.

I intend to showcase Suzan-Lori Parks's repetitious, supplemental virtuosity, which is a testament to the fluid, indeterminate condition of her concepts. I seek to demonstrate that in textualizing the quality of absence in the written dialogue, Parks's The America Play becomes uniquely deconstructive. For indeed, through the absent "presence" of an historically mythified president and a gravedigger's skewed identity, the play becomes a stage for splinters of historicized, differentiating, repeating signifiers that supplement, even as they redefine, their referential signified. Performing deconstructive thinking, Parks's textuality is accommodated by a content through which she calls attention to the structures of metaphysics in our discourse, stressing our inability to erase them, and our need to question them through continual self-reflexive thinking. I hope to show that Parks's genius is apparent in her unique mastery of language. This kind of mastery is revealed through her drama's connection to conceptual possibilities, which are hypostatize, staged through the materiality of her drama's textual configuration. In consciously imbuing her pages with representational temporal spaces akin to Derrida's différance, Parks shows how the supplemental perpetuity of metaphysical signification phenomenally attests to the conceptual, idealized absence it supplements. I speak here of idealization that underlies the structural signified, always already a supplemented absent, which carries metaphoric trappings of phenomenological substance in a form of the signifier, returning through a morphemic ideality in the assuredness of its infinite return. I read Park's intent in The America Play as inherently deconstructive because Parks dramatizes the enigma of the trace; that is, the enigma of its impossible, yet, relentless repetition. In examining the trace and its historical "genesis" through the Idea in the Kantian sense, I will show how Parks's Rep & Rev, repetitions and revision, textually performs its impossible repetition, which is always metaphysical. In self-reflexively showing the impossibility of metaphysical presences, Parks establishes a need for a persistent practice of deconstructive interrogation, questioning self-assured, metaphysical, dogmatic thinking.

Sediments from 21 Oregon lakes were analyzed for seven metals (Fe, Mn, Zn, Cu, Co, Ni, V) in three forms (exchangeable, organic+sulfides, and oxyhydroxides+ oxides+ carbonates) using a sequential fractionation procedure. The summer epilimnetic filterable concentration of an eighth (Mo) was also determined. Sedimentary diatom remains and summer phytoplankton populations of the lakes were correlated with the 22 metal parameters and with conservative water chemistry parameters, estimators of lake productivity, and watershed geology. Both the sedimentary metals and the two populations of primary producers correlated best with the ecoregions of Omernik and Gallant (1986). A number of species possessed correlations with specific trace metal extractions or ratios of those extractions. Bloom-forming Anabaenas strongly correlated with sedimentary organic and filterable epilimnetic nickel. Possible Ni limitation of this group was observed in one Cascade lake (Lava). The ratio of organic nickel to cobalt appeared to control the abundance of several sedimentary diatoms. Organic vanadium strongly correlated with a number of diatoms, particularly in the genera, Cyclotella and Fragilaria. Possible V pollution was observed in one lake (Woahink), and frustule remains of C. stelligera significantly increased with increasing total sedimentary V concentrations there. Zinc was the trace metal most frequently found to apparently limit diatom growth. Diatoms may have developed three different responses to Zn limitation; the three groups have been labelled affinity-, velocity-, and (possibly) storage- specialists following Sommer (1985). Possible Zn pollution was observed in two lakes (Oswego and Clear). Phytoplankton and sedimentary diatoms weakly correlated with sedimentary iron by comparison to Ni, V, or Zn. Few strong relationships were observed with manganese, copper, or cobalt. No statistically significant correlations were found with molybdenum, and few correlations between a conservative chemical parameter and a species of phytoplankton were found. There was poor correlation between trace metal concentrations and lake productivity, despite frequently observed correlations between individual species and particular trace metal fractions. These findings suggest that variations in absolute trace metal concentrations, and/or ratios, may be important factors for controlling species distribution, but have relatively little influence upon lake primary productivity or standing stocks.

The goal of this research was to aid in the fight against the heroin and opioid epidemic by developing new methodology for heroin provenance determination and forensic sample comparison. Over 400 illicit heroin powder samples were analyzed using quadrupole and high-resolution inductively-coupled plasma mass spectrometry (Q-ICP-MS and HR-ICP-MS) in order to measure and identify elemental contaminants useful for associating heroin samples of common origin and differentiating heroin of different geographic origins. Additionally, 198 heroin samples were analyzed by multi-collector ICP-MS (MC-ICP-MS) to measure radiogenic strontium isotope ratios (87Sr/86Sr) with high-precision for heroin provenance determination, for the first time. Supervised discriminant analysis models were constructed to predict heroin origin using elemental composition. The model was able to correctly associate 88% of the samples to their region of origin. When 87Sr/86Sr data were combined with Q-ICP-MS elemental data, the correct association of heroin samples improved to ≥90% for all groups with an average of 93% correct classification. For forensic sample comparisons, quantitative elemental data (11 elements measured) from 120 samples, 30 from each of the four regions, were compared in order to assess the rate of discrimination (5400 total comparisons). Using a match criterion of ±3 standard deviations about the mean, only 14 of the 5400 possible comparison pairs were not discriminated resulting in a discrimination rate of 99.7%. For determining the rate of correct associations, 3 replicates of 24 duplicate samples were prepared and analyzed on separate days. Only 1 of the 24 correct pairs were not associated for a correct association rate of 95.8%. New methods for provenance determination and sample comparison are expected to be incredibly useful to intelligence agencies and law enforcement working to reduce the proliferation of heroin.

The prevalent and ongoing exposures to polychlorinated biphenyls (PCBs) demands an understanding of the threat they pose and also a means in which to mitigate their potential toxicity. This thesis set out to investigate a phenomenon associated with a specific PCB congener, 3,3',4,4',5-pentachlorobiphenyl (PCB126), for the underpinnings of its mechanism, and also its usefulness as a toxin against which to establish a mitigative strategy. The phenomenon in particular is the disruption of hepatic trace elements, specifically an increase in copper and decreases in zinc, selenium, iron, and manganese in the liver. Four questions were posed to address the overarching goals: 1) When does micronutrient disruption occur in the context of liver pathology? 2) What metal transporters or chaperones are involved? 3) Can the previously shown beneficial micronutrient, zinc, alter the disruption and improve outcome? 4) What is occurring spatially within the liver acinus where micronutrients are distributed? By answering these four questions, a fundamental understanding of this occurrence will be ascertained. A chronology of PCB126-hepatotoxicity showed onset of liver pathology at 36 hours and later alterations in micronutrients at 3 days, suggesting disruption of hepatic trace elements is likely the result of liver degeneration. In addition, a key metal transport protein, metallothionein, was induced by PCB126. Utilizing a double knockout animal model, metallothionein was shown to abrogate some toxicity but had little involvement of micronutrient perturbation. Previous investigations have suggested the unique property of zinc in rescuing/preventing hepatic damage by a variety of toxic agents. Dietary zinc had a modest effect in ameliorating PCB126 hepatotoxicity and preserving micronutrient homeostasis. This suggests that the mitigative potential of zinc supplementation on PCB126 exposure is limited. Finally, a fine spatial investigation of the liver acinus was conducted to establish the levels of trace elements from the portal triad to the central vein. In addition, novel findings of high concentrations of extracellular zinc were discovered. In all, this dissertation has shown that disruption of hepatic micronutrients caused by PCB126 are likely the result of liver degeneration by means of disturbing the spatial trace element gradients and provides appropriate context for therapeutic/preventive strategies against PCBs.

The issue of granite petrogenesis plays a key role in our overall understanding of the growth and differentiation of continents, as well as in our ability to unravel the tectonic histories of orogenic belts. Granites are ubiquitous magmatic products found in almost all tectonic settings: oceanic and continental rifts (i.e., plagiogranites - extreme basalt differentiates), active continental margins (e.g,. the granitic batholiths of central and southern Andes), continent-continent collision zones (e.g., the orogenic batholiths of the Himalayas, Western Anatolia), post-collisional settings (e.g., the Variscan provinces of Europe), complex within-plates settings (e.g., Limmo massif, Afar, Ethiopia). Furthermore, granitoids are characterized by considerable petrological and geochemical heterogeneity, as they can form from a vast array of sources: sediments (e.g., pelites, arkoses, psammites), metamorphic rocks (e.g., (mica)schists, gneisses, etc.), and igneous rocks (e.g. andesites, dacites, tonalites, etc.). Aside from fertile sources (i.e., protoliths), granite petrogenesis is dependent upon two critical parameters: temperature (to promote melting of the protoliths) and water availability - either as freely available aqueous solutions/vapors (e.g., water input in subduction zones); or water released via dehydration melting of hydrous minerals (e.g., micas, amphiboles). The presence of water in protoliths depresses the melting temperature of mineral components and provides the environment for redistribution of chemical components. Understanding the origins of granitic rocks presents unique challenges, given that in many of the tectonic settings where granites are encountered, it is clear that their modes of formation can involve a spectrum of igneous and metamorphic processes that are not readily accessible for examination, either through the study of modern environments or via analogy to "classical" localities. The petrogenesis and emplacement of granites in post-collisional tectonic settings is one of the thornier challenges, as these rocks appear to be derived via thermal and magmatic processes within highly deformed and compositionally diverse continental crust for which we lack a clear understanding. A number of unconventional and difficult-to-test mechanisms have been posited to drive crustal heating, melting, and subsequent pluton post-collisional emplacement. Although large volumes of granitic magmas have been emplaced in post-collisional settings, the complexities of the processes active in such settings make it challenging to put forward testable models that effectively combine available geochemical, petrologic, and geophysical data. Models for granite genesis away from plate margins (by means of crustal thickening, thermal blanketing, and internal heating from radioactive decay of 40K, 230Th, 235U, and 238U; delamination of the crustal lithosphere and juxtaposition of hot mantle melts at the base of the crust; underplating of mantle melts; or slab brake-off and upwelling of mantle melts) have been successfully applied in comparatively young orogenic regions, such as the Himalayas, the Carpathians, and Turkey. These models have proven challenging to employ in older orogenic belts, given their sometimes intricate tectonic and metamorphic histories, and the loss of pertinent evidence due to the effects of post-emplacement tectonic reworking, and often extensive alteration and erosion. A series of ancient but fresh, age-correlative granitic plutons are exposed in Alpine nappes on the flanks of the Carpathians Mountains in southwestern Romania. These granites, all mapped as intruding the Neoproterozoic basement of the Danubian tectonic terrane, were emplaced during the post-collisional stages of two world-scale orogenies: an older, Pan-African event (~600 Ma) and a younger, Variscan event (~330- 280 Ma). My dissertation is focused on the study of late Variscan post-collisional plutons and associated sub-volcanic dykes, as they are tremendous tools for understanding and quantifying the mantle-crust interaction in post-collisional environments and the overall evolution of the continental crust during the Variscan orogeny. Originally believed to be Proterozoic in age, zircon U/Pb dating showed that the plutons are much younger (Chapter 1 - Post-collisional Late Variscan magmatism in the Danubian domain (South Carpathians, Romania) documented by zircon U/Pb LA-ICP-MS) and correspond to the latest stages of the Variscan orogeny, as recorded elsewhere in the European Variscan provinces. The granitic plutons are relatively small and are generally concordant with the structures preserved by the country rocks. The extraordinary petrological and geochemical heterogeneities, even at pluton scale (Chapter 2 - Petrology and geochemistry of the Late Variscan post-collisional Furătura granitic pluton South. Carpathian Mts. (Romania)) argue against unique protoliths and simple evolutionary processes (e.g., closed-system fractional crystallization; anatexis). Trace elemental data for the Furătura pluton shows that the melts were formed in equilibrium with a garnet-amphibole restite, under pressure-temperature conditions deeper than the plagioclase stability field, implying that the melting took place at depths in excess of 40 km in the continental crust. Stable and radiogenic isotope data suggest that a protolith was of (possibly enriched) mantle affinities, and that the melts were subsequently contaminated in various degrees by deep crustal lithologies. In comparison, other post-collisional Variscan plutons from the Danubian domain (Chapter 4 - The role of the continental crust and lithospheric mantle in Variscan post-collisional magmatism - insights from Muntele Mic, Ogradena, Cherbelezu, Sfârdinu, and Culmea Cernei plutons (Romanian Southern Carpathians)) have trace elemental compositions that suggest they were formed at different levels in the crust, under P-T conditions corresponding to both garnet-amphibole and plagioclase stability fields. Some of the plutons lack mantle geochemical signatures and their isotopic compositions are indicative of substantial involvement of both lower- and upper-crustal rocks in their formation and subsequent evolution. On the other hand, plutons emplaced during the same time interval and most likely in close geographical proximity have trace elemental and isotopic compositions indicating strong input from previously enriched mantle components which experienced various degrees of assimilation fractionation-crystallization and/or assimilation of continental crust material during their evolution. This variability in both protoliths and processes responsible for the formation of the granites, coupled with the presence of mantle signatures in late-orogenic post-collisional melts are strong evidence to support delamination as means of providing both the mantle-derived input and energy required for generation of granitoids in the crust. The pronounced variation in petrological and chemical compositions of synchronous plutons suggests that delamination in the Danubian domain was not a single, large scale event that affected the entire crust, but rather a collection of disparate, spatially and chronologically limited event, that affected the Variscan crust during the latest stages of the orogeny. This hypothesis is further tested on a series of sub-volcanic dykes (the Motru Dyke Swarm) crosscutting the entire Danubian basement (Chapter 3 - Post-collisional magmatism associated with Variscan orogeny in the Danubian Domain (Romanian Southern Carpathians): the Motru Dyke Swarm). Initially, the emplacement age of these dykes was assumed as "pre-Silurian" but our mapping has showed that they intrude components of the Danubian domain that shared a documented common history not earlier than the Carboniferous. Furthermore, the dykes are in intrusive relationship with two of the Danubian Variscan plutons, thus arguing for an early Permian emplacement age. Geochemical data show extraordinary heterogeneities in the dykes' composition and record both mantle and crust involvement in their formation. The dykes were emplaced at much shallower depths in the crust, as compared with the granitic plutons. Still, their isotopic compositions clearly indicate that they sampled both lower- and upper-crustal compositions during their evolution. This means that after the crustal thickening episodes that define continent-continent collisions, during the latest stages of the Variscan orogeny, the crust became progressively thinner, as a way to compensate for its metastable state. Thinning of the crust is greatly favored by delamination of the lithosphere. A delamination event, which usually postdates the cessation of continental collision or prolonged crustal shortening, involves the geologically rapid foundering of negatively buoyant lithosphere comprised of mantle and (potentially) lower crust into underlying hotter and less dense asthenosphere. Such a process will remove the lithospheric mantle (and potentially segments of the lower crust) along pre-existing lineaments or mechanical flaws, and juxtapose hot upwelling asthenosphere against the base of the crust, leading to partial melting. Field, petrological, and geochemical data presented in my dissertation document pronounced variations in the overall composition of synchronous plutons and dykes, and further suggest that delamination in the Danubian domain was an active process. This bears great importance in our understanding of the evolution of the crust and argues that mantle-crust interactions are responsible for the generation of continental crust even in the latest stages of an orogen.

No description available.

An investigation of heavy metal concentrations in sediments from Coxs River catchment, a tributary of the Hawkesbury-Nepean River system, has been undertaken. A number of digestion methods were assessed for the determination of Pb, Cu, Cd, Zn, Ni, Mn, Fe, Co and Cr in reference materials by flame AAS. The method that produced the best recovery is reverse aqua regia, HNO3-HC1 with ultrasonification followed by heating on a hotplate. Based on analysis of sediments from 133 sites, background concentrations were established. Elevated heavy metal concentrations were recorded in some samples. The three most polluted areas were investigated for heavy metal associations and distributions. Metal bioavailability was assessed from sediment samples by using selective extraction techniques. The association of heavy metals with different solid phases was assessed by a sequential extraction technique involving a series of extraction reagents. Pd, Cu, Fe and Cr were mainly associated with Fe/Mn oxides and organic matter plus sulphide phases. While Cd, Zn, Ni and Co which behave similarly were extracted from each step, the largest percentages of these metals were found in Fe/Mn oxides and organic matter phases. Mn was different to other metals, in that it predominantly associated with the ion exchangeable form. / Master of Science (Hons)