Dissertations / Theses on the topic 'Speciation at equilibrium'

Speciation governs transport and toxicity of trace metals and is important to monitor in natural waters. Geochemical models that predict speciation are valuable tools for monitoring. They can be used for risk assessments and future scenarios such as termination of liming. However, there are often large uncertainties concerning the speciation of iron and aluminium in the models, due to the complicated chemistry of these metals. Both are important in governing the speciation of other metals, due to (i) their capacity to form minerals onto which metals can adsorb and (ii) their ability to compete for binding sites to natural organic matter (NOM). Aluminium is also potentially toxic and is therefore closely monitored in acidified freshwaters. In this study different phases of iron in Swedish lakes were characterised. This required a good method for preconcentrating the iron colloids. A new method was developed in this thesis that uses an anion-exchange column to isolate the iron colloids prior to characterisation with extended X-ray absorption fine structure (EXAFS) spectroscopy. Iron was present as ferrihydrite in particles but was also strongly monomerically complexed to NOM in two Swedish lakes. Based on the results an internally consistent process-based geochemical equilibrium model was presented for Swedish freshwaters. The model was validated for pH (n = 9 400) and inorganic monomeric aluminium (Ali) (n = 3 400). The model could simulate pH and Ali simultaneously, and be used for scenario modelling. In this thesis, modelling scenarios for decreases and complete termination of liming are presented for the 3 000 limed Swedish lakes. The results suggest that liming can be terminated in 30 % of the Swedish lakes and decreased in many other lakes.

QC 20120919

The theory of “punctuated equilibrium” suggests that species evolve rapidly during or immediately upon speciation, “punctuating” long periods of little or no morphological evolution. Here I confirm that body size differences within clades of birds and mammals are best explained using a model of punctuated evolution. This allows me to suggest that rates of speciation and extinction are responsible for why there are more small mammals than large, as large mammals likely speciate and go extinct at a higher rate than small mammals, and hence undergo cladogenetic change more often. Likewise, mammals appear to evolve at a higher rate than birds, because mammals, as a whole, speciate and go extinct at a higher rate than birds. Furthermore I show that mass extinctions and competition, i.e. forms of natural selection, do not seem to explain differences in body size between species on a macroevolutionary scale. Taken together, these findings not only contradict the idea that apparently different rates of evolution are due to differential selection intensities, and emphasize the importance of the speciation process in evolution, but raise the intriguing question as to what limits evolution in established species. Here I suggest that phenotypic traits, dependent on one another for development and/or function may constrain evolution by exerting stabilizing selection from within the organism, as opposed to external environmental selection, which has been the main focus of evolutionary studies thus far.
Teorin om "punkterad jämvikt" säger att arter utvecklas snabbt under och omedelbart efter artbildning, vilket "punkterar" långa perioder med lite eller ingen morfologisk föränding. I den här avhandlingen visar jag att skillnader i kroppsstorlek inom klader (grupp med gemensam förfader) hos fåglar och däggdjur förklaras bäst när man använder en modell med punkterad evolution. Detta gör i sin tur att jag kan föreslå att hastigheten var med artbildning och utdöende sker, förklarar varför det finns fler små däggdjur än stora, eftersom stora däggdjur sannolikt bildar nya arter och dör ut med en högre hastighet än små däggdjur. Likaså förefaller däggdjur i sin helhet att evolvera med en högre hastighet än fåglar, detta eftersom däggdjur bildar nya arter och dör ut med en högre hastighet än fåglar. Dessutom visar jag att massutdöenden och konkurrens (naturlig selektion) inte verkar förklara skillnader mellan arter över makroevolutionära skalor (över geologisk tid). Sammantaget motsäger dessa resultat inte bara idén om att skenbart olika hastighet på evolution främst beror på skillnader i selektionstryck utan understryker också vikten av artbildningsprocessen som en viktig faktor som styr evolutionens hastighet. Dessutom leder dessa resultat till frågan om vad som begränsar evolutionen hos redan etablerade arter. Här föreslår jag att fenotypiska karaktärsdrag som är beroende av varandra för sin funktion och utveckling kan begränsa evolutionen genom att utöva stabiliserande selektion inifrån organismen, i motsats till selektion från den omgivande miljön vilket har varit fokus för de flesta evolutionära studier hittills.

Abstract There are more small-bodied species of birds than those having large bodies. Generally, and relative to occurrance in any one place, small-bodied species also contain more individuals than large-bodied species. The same patterns have been documented for several groups of higher organisms for example, snakes, flowering plants and mammals, which suggests that there exists a general reason "why", which applies to other groups of species as well as to birds. This thesis attempts to identify this reason. In the first place, it is possible that most species happened to become small-bodied by chance. Simulations of neutral body-size evolution indicate however that the observed bias towards small size is stronger than that accounted for by neutral evolution. Then, the most plausible explanation for why most species are small is that small-bodied species speciate faster. However, statistical analyses accounting for historical relatedness of present-day species indicate no relation between body size and the rate of speciation. Finally, instead of little by little, the dominance of small species may have arisen suddenly, when approximately 65 million years ago (presumably) a large meteorite hit the earth, causing mass extinctions. However, analysis of body sizes and genetic differences of extant species reveals that while avian species numbers were approximately halved, the catastrophe affected small and large species equally. Thus, the reason why most species are small does not seem to be due to differential rates of speciation or extinction. Instead, the cause appears to be in the tempo and mode of evolution. It was found by analysis of extant species' body size that probably most differences in body size between species arise at the moment of speciation. Differences between small-bodied species are smaller than between large-bodied species and probably this difference also has its origin at the moment of speciation. Consequently, groups of small species stay small whereas groups of large species are more variable in body size, so that in the end most species are small
Tiivistelmä Maailman noin 10 000 lintulajin joukossa pienikokoisia lajeja on enemmän kuin suurikokoisia. Yleensä pienkokoiset lajit ovat myös yksilömääriltään suurempia kuin samalla paikalla esiintyvät suurikokoiset lajit. Koska sama ilmiö on havaittu monissa muissa suurissa eliöryhmissä (esim. nisäkkäät, käärmeet ja kukkakasvit), on ilmeistä, että on olemassa yhteinen syy, joka pätee niin linnuissa kuin muissakin eliöryhmissä. Tämän väitöskirjan tavoite on selvittää, mikä tämä yhteinen syy voisi olla. Ensinnäkin on mahdollista, että suurin osa lajeista on kehittynyt pienikokoisiksi aivan sattumalta. Ruumiin koon evoluution simulaatiot kuitenkin osoittavat, että on hyvin epätodennäköistä, että neutraali evoluutio olisi johtanut pienikokoisten lajien suuriin määrään havaitussa määrin. Toinen mahdollinen selitys ilmiölle on, että pienikokoiset lajit lajiutuvat nopeammin. Tilastolliset analyysit, jotka ottavat huomioon nykyisin elävien lajien sukulaisuussuhteet, osoittavat ettei ruumin koon ja lajiutumisen vauhdin välillä ole yhteyttä. Kolmas mahdollinen selitys pienikokoisten lajien suurelle määrällä on historiallinen. On mahdollista, että pienikokoisten lajien suhteellisen suuri määrä syntyi nopeasti noin 65 miljoonaa vuotta sitten tapahtuneen massasukupuuton seurauksena, joka fossiiliaineiston perusteella kohdistui erityisesti suurikokoisiin maaeläimiin (esimerkiksi dinosauruksiin). Vertaileva analyysi nykyään elävien lintulajien ruumiin koosta ja geneettisistä eroista osoittaa, että vaikka suuri osa lintulajeista hävisi massasukupuutossa, tämä katastrofi karsi lajeja riippumatta niiden ruumiin koosta. Näyttää siis siltä, etteivät erot lajiutumisen tai sukupuuttojen esiintymisessä selitä sitä, että suurin osa lajeista on pienikokoisia. Tämän tutkimuksen tulosten perusteella syy näyttäisi sen sijaan olevan ruumiin koon kehityksen vauhdissa ja siinä tavassa, jolla kehitys yleensä etenee. Analyysi nykyisten lajien ruumiin koosta paljasti, että suurin osa eroista lajien välillä syntyy (evolutiiviessa aikataulussa) suhteellisen nopeasti lajiutumistapahtuman yhteydessä (punktualismi) eikä vähitellen pitkien aikojen kuluessa (gradualismi), kuten yleensä oletetaan. Kehityslinjojen sisällä pienikokoisten lajien väliset erot ruumiin koossa olivat pienempiä kuin isokokoisten lajien väliset erot - ja todennäköisesti myöskin tämä ero syntyy lajiutumisen yhteydessä. Tämä johtaa evoluution kuluessa tilanteeseen, että alunperin pienikokoisista lajeista kehittyneet lajit ovat myös pienikokoisia, kun taas isokokoisten lajien kehityslinjoissa on nähtävissä huomattavasti paljon enemmän vaihtelua ruumiin koossa. Näiden seurauksena eliöstöissä suurin osa lajeista lopulta on pienikokoisia

Diabetes mellitus is one of the most threatening epidemics of modern times with rapidly increasing incidence. Vanadium and peroxovanadium compounds have been shown to exert insulin–like actions and, in contrast to insulin, are orally applicable. However, problems with side–effects and toxicity remain. The exact mechanism(s) by which these compounds act are not yet fully known. Thus, a better understanding of the aqueous chemistry of vanadates and peroxovanadates in the presence of various (bio)ligands is needed.

The present thesis summarises six papers dealing mainly with aqueous speciation in different vanadate – and peroxovanadate – ligand systems of biological and medical relevance. Altogether, five ligands have been studied, including important blood constituents (lactate, citrate and phosphate), a potential drug candidate (picolinic acid), and a dipeptide (alanyl serine) to model the interaction of (peroxo)vanadate in the active site of enzymes. Since all five ligands have been studied both with vanadates and peroxovanadates, the number of systems described in the present work is eleven, including the vanadate – citrate – lactate mixed ligand system. The pH–independent formation constants have been determined for 33 ternary vanadate – ligand, 41 quaternary peroxovanadate – ligand and two vanadate – mixed ligand species in addition to the pK_a values of all five ligands. These constants have been used to model physiological conditions, and the biomedical relevance of the different species is discussed.

The studies have been performed at 25 ºC in the physiological medium of 0.150 M Na(Cl), i.e. the ionic strength of human blood. No buffers have been used, and wide pH–ranges have usually been covered. The applied experimental techniques comprise mostly ⁵¹V NMR and potentiometry, but ³¹P, ¹³C, ¹H and ¹⁴N NMR as well as EPR and ESI–MS have also been used to gain additional information. Multimethod data have been treated by the least–squares program LAKE and modelling has been carried out by the software package WinSGW.

Whenever possible, solution structures of the species have been proposed. In addition, simple biological tests have been carried out to determine the stability of the formed peroxovanadate complexes in the presence of human catalase. A brief comparison is given of the different vanadate – ligand and peroxovanadate – ligand systems with emphasis on observed trends and general features.

Addition of alkalinity to acid mine drainage (AMD) results in the neutralisation of acidity and precipitation of dissolved metals as insoluble hydroxides. Two aspects of the current AMD treatment practice at the Stockton Mine could be enhanced. Firstly, residual water quality may be poor due to unreacted alkalinity reagents, particularly CaCO3, resulting in poor water clarity and elevated suspended solids (SS). Secondly, neutralisation to circum-neutral pH may not avoid the discharge of residual metals (Ni and Zn) due to incomplete adsorption and hydroxide precipitation. The aim of this project was to enhance the conventional neutralisation of AMD through addition of humic substances (HS) to reduce residual SS and trace metal concentrations. Humic substances are organically derived and have a high molecular weight. Functional groups on the surface of HS are capable of binding dissolved metals, forming HS-metal complexes. Incorporation of HS complexed metals into settling floc could result in increased metal removal from the dissolved phase. Modified jar testing was used to investigate the effects of HS addition before, after and during (pH 4.5) neutralisation of AMD in two treatment scenarios at the Stockton Mine; the Blackwater Treatment Plant (BTP) using NaOH and Ca(OH)2 and the Mangatini Stream-sump System (MSS) using CaCO3. Supernatant samples collected during the sedimentation period were analysed for basic water quality parameters (turbidity and suspended solids) and dissolved (< 0.45 µm) metal concentrations. The addition of HS to the BTP process before (pH 2.8) and during (pH 4.5) neutralisation resulted in HS precipitation. Precipitated HS subsequently acted as a nucleation site, triggering flocculation of precipitating metal hydroxides, resulting in low turbidity and suspended solids (SS) of less than 2 NTU and 5 mg/L, respectively. The addition of HS after neutralisation (pH 7) did not result in HS precipitation. Intermolecular bridging of HS by the divalent Ca resulted in incorporation of HS into floc when neutralised by Ca(OH)2, resulting in low turbidity and SS. However, in NaOH neutralised conditions, the monovalent Na was unable to bridge HS molecules, resulting in HS remaining dissolved and contributing to elevated turbidity and SS of up to 24.4 NTU and 18.4, respectively. The neutralisation efficiency of CaCO3 is relatively low, thus approximately 1000 mg/L CaCO3 remained unreacted in MSS scenarios, resulting in elevated turbidity and SS. When added after neutralisation, dissolved Solid Energy Humic Acid (SEHA) facilitated flocculation of residual CaCO3 SS, resulting in an up to 75% lower suspended solids than CaCO3 neutralisation alone conditions. Although the results are good, the efficiency of SEHA as a polymer compared unfavorably in a cost: benefit analysis to two commercially available polymers for the removal of residual CaCO3. Neutralisation of AMD in control samples resulted in decreased concentrations of the target metal group (Ni, Zn, Cu, Cd, and Pb) by hydroxide precipitation, co-precipitation, and adsorption. Equilibrium speciation modeling showed that the HS-metal binding affinity controlled the effectiveness of HS addition for metal removal. The low HS complexation affinity of Ni and Zn resulted in no additional metal removal by HS dosing. The removal of Cu was enhanced by over 50% for SEHA 20 during-neutralisation conditions neutralised by both NaOH and Ca(OH)2. Up to 80% lower Cd concentrations were observed for all HS dose conditions when neutralised by Ca(OH)2. Data for CaCO3 HS dosed metal removal was statistically indeterminate. The high detection limit for Pb made any HS dosed removal enhancement difficult to identify, which was unfortunate as Pb has a high HS complexation affinity (Čežı́ková, Kozler et al. 2001; Milne, Kinniburgh et al. 2003). A simple cost: benefit analysis showed that the additional removal of metals by HS dosing was less efficient than conventional neutralisation alone, on a cost basis. Overall, incorporation of HS into AMD treatment results in improved water quality for CaCO3 neutralisation and lower concentrations of metals with a high HS binding affinity, for some conditions. However, further investigation is required to improve the feasibility of HS incorporation into the AMD neutralisation process.

Abstract This thesis is a summary of five papers, containing equilibrium and structure studies of aqueous molybdate and peroxomolybdate species. Some of the peroxomolybdate species have also been studied in terms of their dynamic and catalytic properties. The primary objective was to characterize species with potential catalytic activity, with emphasis on thebleach process of kraft pulp. For this, potentiometry, EXAFS and 17O, 31P, 1H and 95 Mo NMR have been used. The molybdate speciation in 0.300 M Na2(SO4) medium was found to differ from that in 0.600 M Na(Cl) medium, in that the uncharged monomeric molybdate species H2MoO4 was stronger in the sulphate medium, while highly charged species, such as Mo7O24 6-, became somewhat less pronounced. Diperoxomolybdate species, (MoX2)n (X = peroxo ligand, n = 1-2), dominated the peroxomolybdate systems when sufficient peroxide was available. Both sulphate and chloride coordinated to molybdenum in the presence of hydrogen peroxide and these species were more inert than diperoxomolybdate species without coordinated medium anions. Chemical exchange rates increased upon protonation. A dimeric triperoxomolydate species was the only species found that contained more than two peroxo groups per molybdenum atom. At low concentrations of hydrogen peroxide, monoperoxoheptamolybdate species, Mo7X, were found. Phosphate was found to coordinate relatively weakly to molybdate in the presence of peroxide. Species with four different nuclearities, i.e. (MoX2)nP (n = 1-4), were found. At excess of peroxide, no molybdophosphates were present. Chemical exchange rates were found to be substantially lower than in the peroxomolybdate system. The aqueous monomeric diperoxomolybdate species retain the pentagonal bipyramidal seven-coordination found in the solid state, although with increased bond lengths. Sulphate seems to coordinate to molybdenum in a monodentate fashion by replacing an oxygen atom. Chloride probably coordinates by replacing an oxygen atom as well. For the dimeric diperoxomolybdate species, a single oxygen-bridge was proposed. Conjugated carbon double bonds in the side chains of lignin model compounds were found to be hydroxylated or epoxidised by peroxomolybdate species. The addition of phosphate did not affect the type or yield of oxidation products noticeably. It was also shown that hydrogen peroxide, in the absence of molybdate, did not react to any noticeable extent with the lignin model compounds under these conditions.

La simulation des procédés est un outil de développement, de dimensionnement et d’optimisation des procédés dans les industries chimiques, pétrochimiques, pharmaceutiques, alimentaires, de l’énergie ou du traitement de gaz. Elle fournit une représentation des opérations du procédé en utilisant des modèles mathématiques pour chaque opération unitaire, s’assurant du respect des bilans de matière et d’énergie. Cependant l’utilisation de la simulation des procédés dans l’industrie peut être limitée par un manque de connaissance en thermodynamique.L’étude réalisée dans le cadre de cette thèse a pour objectif d’enrichir les modèles thermodynamiques adaptés aux solutions électrolytiques des logiciels de ProSim® avec les compétences du LaTEP dans le cadre d’applications aux géo-ressources et en profitant de la modélisation des opérations unitaires déjà présentes dans les logiciels de ProSim®.Dans un premier temps, les concepts et les définitions de base de la thermodynamique des solutions, nécessaires au développement des modèles, et notamment du cas particulier des solutions électrolytiques seront présentés, aboutissant sur l’écriture des divers équilibres permettant de décrire les solutions électrolytiques.Puis les grands principes des différents modèles thermodynamiques nécessaires à l’écriture des équilibres des solutions électrolytiques seront présentés, en mettant l’accent sur les modèles de coefficient d’activité qui sont alors spécifiques aux modèles électrolytiques prenant en compte les interactions de longue portée engendrées par la présence d’ions.Enfin, trois cas d’études de systèmes électrolytiques multiphasiques réactifs appliqués aux géo-ressources sont examinés : la géothermie profonde ; le traitement de gaz acides, issus de fumées de l'oxy-combustion d’une centrale à charbon ; la récupération du lithium
Chemical process simulation is a very useful tool to improve the development, design and optimization of processes. Then, it can help in the chemical, petrochemical, pharmaceutical, energy production, gas processing, environmental, and food industries. It provides a representation of the operations of the process using mathematical models for the different unit operations, ensuring that mass and energy balances are satisfied. However, the use of process simulation in industry is currently being limited by a lack of understanding of thermodynamics

Um software de modelagem de especiação geoquímica é responsável pelo cálculo da distribuição das espécies dissolvidas entre solutos e complexos aquosos, e também computar os índices de saturação para diferentes minerais. Neste trabalho nós apresentamos SHPECK, um software desenvolvido para modelar sistemas de equilíbrio geoquímico usando condições de balanço de massa baseadas no conceito da lei de fases (GARRELS; CHRIST, 1965). SHPECK gera um sistema de equações de ação de massa acopladas com restrições de equilíbrio e resolve com a utilização do método se Newton-Raphson. Nosso software aceita qualquer combinação de elementos, espécies e reações, permitindo ao usuário criar diferentes ambientes de simulação e, portanto, controlar qualquet aspecto e configuração do modelo. SHPECK contém uma interface de interação com o usuário e também um banco de dados estruturado que controla todo o gerenciamento dos dados termodinâmicos utilizados para a modelagem geoquímica. Aliado a isso, apresentamos também os conceitos básicos necessários para compreenção da modelagem geoquímica seguida por uma revisão de opções de software disponíveis para modelagem geoquímica. Para finalizar, fizemos uma validação do SHPECK através da modelagem de um sistema de reações diagenéticas observadas em um reservatório asiliclástico e realizamos um estudo comparativo dos resultados do SHPECK com outros software disponíveis. Também para validação, realizamos uma avaliação de tempo de acesso ao banco de dados e pode-se notar um aumento de performance considerável através do uso de um banco de dados relacional comparando-se aos approaches existentes.
A geochemical speciation modeling software is responsible for calculating the distribution of dissolved species between solutes and aqueous complexes, and also computes saturation indexes for different minerals. In this work we introduce SHPECK, a software program developed to model geochemical equilibrium systems using the mass-balance conditions based on the phase rule concept (GARRELS; CHRIST, 1965). SHPECK composes a system of mass-action equations coupled with equilibrium constraints and solve using Newton-Raphson method. Our software accepts any general combination of elements, species, and reactions, allowing the user to create different environments, simulations and, therefore, fully control any aspect and configuration of the model. It provides an interactive user interface as well as the support of a builtfrom- the-ground database structure that handles the management of the whole thermodynamic data used for the geochemical modeling. Also, we present the basic concepts for geochemical modeling followed by a computer science based review about the available geochemical modeling software. Finally, we validate SHPECK by modeling the diagenetic reactions observed in asiliciclastic reservoir and by performing a comparative study with other modelling software package. In addition to this, a database comparison was addressed and the results demonstrate a substantial improvement on the performance by the use of the SHPECK’s relational database comparing to the existent approaches.

Protactinium (Pa) is an actinide with chemical properties that are unique among the actinide elements. While the properties of other actinides are to a large extent understood, much of the chemistry of Pa remains a mystery. This thesis aims to illuminate new understanding of Pa chemistry through behavioral analysis using analytical techniques including liquid-liquid extraction (LL); extraction chromatography (ExC); and spectroscopic studies. Applications of radioanalytical chemistry and Pa: Through the research presented in this dissertation, we have developed a new way to separate uranium (U), thorium (Th), and Pa from complex environmental samples. The approach has been demonstrated for U-series dating of materials by alpha spectrometry. The method can be applied to geochronology, as well as to nuclear-forensic analysis of uranium-containing materials. In studies presented here, samples from a Paleolithic lake (Lake Bonneville, Utah USA) were analyzed for the radioactivity concentration of 230Th, 231Pa, 234U, 235U, and 238U by isotope dilution alpha spectrometry. Radioactivities were used to estimate of the time period of formation of the deposit from which the samples were collected. Ages were determined from the isotopics ratios; i.e., 231Pa/235U (40 ka); and 230Th/238U (39.5 ka) we found to be concordant with radiocarbon-14 dates (37 ka) obtained by collaborators at Brigham Young University. These studies inspired the development of a novel ExC resin to facilitate preparation of highly pure tracer isotope (233Pa) from a neptunium-237 (237Np) source. The material used for this development comprised 1-octanol adsorbed to a semi-porous resin material. The new approach greatly improved the yield and purity of 233Pa used for these chronometric analyses Developing an understanding of the chemistry of Pa at trace concentrations: The new-improved analytical described above led to the hypothesis that analytical separations approaches could be used to develop a more detailed understanding of Pa chemistry. Toward this goal, experiments were conducted to understand how the extraction of Pa is impacted by solution acidity [H+], anion concentration [A-; Cl-, NO3-], and extractant concentration ([2,6-dimethyl-4-heptanol, DIBC]). A full-factorial experimental design was employed to create a model that would allow for predictions in Pa behavior, as well as describe the nature of the observations. This model generated a multivariate equation that relates the distribution coefficient ([Pa] organic phase/ [Pa] aqueous phase) to each of the parameters ([H+], [A-], and [DIBC]). Further studies expanded to other alcohols (ROH) used as extractants (1-octanol, (2,6)-dimthyl-4-heptanol, and 2-ethyl-hexanol); and the results were analyzed using the slope analysis and comparative extraction studies using the model and compared to other actinide elements (Th, U, Np, americium (Am)) by both LL and ExC systems. These experiments revealed unique chemical behavior of Pa with respect to the other actinides. For example, it was found that Pa was the only actinide element to be extracted into the organic phase under acidic conditions (HCl and HNO3). Slope analysis experiments elucidated the stoichiometric identity of Pa species, with respect to the anion and extractant. Future studies will aim to identify the oxygen stoichiometry and species by X-ray absorption techniques. Investigations of the organic phase: In the final sections of this thesis, experiments are presented that are intended to determine if aggregation plays a key role in the extraction of Pa in systems containing 1-octanol and 2-ethyl-hexanol. This work is done in the absence of metal ions to control the dynamics of the organic phase, and are analyzed by tensiometry and Karl Fisher titrations with small angle X-ray scattering and molecular dynamic simulations. A key novel finding of these studies in that ROH molecules arrange in nanoscale aggregates that decrease the interfacial tension between the phases and extract a significant amount of water into the aggregates stabilized by a network of H-bonding. These studies lead to the hypothesis for future studies that Pa extraction is likely facilitated by solvation into the organic phase via ROH aggregates. The sum of the findings and observations of this dissertation provide insight into the chemical nature of Pa: (1) Novel extraction methods to obtain radiochemically pure fractions show that Pa can be efficiently extracted and separated from complex matrices to aid in chronometric analysis for geochronology or nuclear forensics; (2) Statistical modeling to develop a better understanding of the main effects of solvent extraction parameters; (3) Equilibrium analysis to improve our understanding of chemistry of Pa and how it is unique to the actinides; (4) Aggregation analysis to demonstrate a solvent centric understanding of extraction studies, these results lead to future experiments to investigate how organic phase aggregation can influence solvent extraction selectivity.

Lors d'un accident de type APRP (Accident de Perte du Réfrigérant Primaire) survenant dans réacteur nucléaire à eau pressurisé (REP), des débris sont générés et ils peuvent être partiellement transportés jusqu'aux filtres des systèmes de secours RIS-EAS des puisards situés dans le fond de l'enceinte de confinement du réacteur. Ces débris peuvent contribuer au colmatage « physique » des filtres. Un autre effet dit « effet chimique » correspond à l'apport de cations en solution de par la corrosion des débris (fibres d'isolant) et la possible corrosion de surfaces métalliques présentes dans le bâtiment réacteur. Ces cations métalliques peuvent former des précipités au sein du lit fibreux formés et accentuer le colmatage physique. En cas d'accident grave avec fusion du cœur, des charges additionnelles de débris sont à considérer comme la présence de particules formées de matériaux de structure, des barres de commande et de produits de fission et des particules de béton résultant d'un interaction corium-béton. Il a été clairement identifié dans la littérature que ces effets chimiques sont à prendre en compte pour s'assurer de la fonction recirculation sur une longue période. La question de recherche est d'être en mesure de comprendre la nature de ces effets chimiques, les paramètres les conditionnant et leurs ampleurs. Le sujet de thèse porte sur l'étude de ces effets chimiques, pour cela une approche paramétrique sera suivie en couplant plusieurs mesures chimiques et en corrélant ces mesures à une perte de charge. Les mesures chimiques en solution se feront principalement par ICP et la caractérisation des précipités potentiellement formés pourra se faire par des analyses type MEB-EDX, DRX et XPS. La boucle de filtration est à concevoir
During a LOCA accident (Loss Of Coolant Accident) occurring to a nuclear Pressurized Water Reactor (PWR), debris are generated and can be partially transported to the RIS-EAS filter in the sumps located in the bottom of the nuclear reactor containment. These debris can contribute to the « physical » clogging of the filters. Another effect called « chemical effects » corresponds to the presence of cations in solution resulting from the debris' corrosion and the possible corrosion of the metal surface present in the reactor containment vessel. In the case of a severe accident with core fuel meltdown, additional loads debris are to be considered as presence of particles formed of structural materials, control rod material, fission products and concrete particles resulting from corium-concrete interaction. To ensure the long term liquid recirculation functionality, the chemical effect have to be understood: nature of these chemical effects, conditioning parameters and potential effect on the clogging. The thesis aims at studying the chemical effects after designing a dedicated experimental loop: a parametric approach , coupled with several chemical and pressure drop measurements. Chemical speciation in solution and precipitate characterizations will/can be respectively performed by ICP and MEB-EDX, DRX and XPS techniques

The mixed metal compound, Chromated Copper Arsenate, or CCA, has been widely used as a wood preservative. The metal ions in CCA, CrO��������, Cu�����, and AsO��������, have been found in contaminated surface and subsurface soils and groundwater nearby some wood preservative facilities and nearby wood structures. Iron oxides are a ubiquitous soil-coating constituent and are believed to be a main factor in controlling the transport and fate of many metals in the soil solution. In this research, iron-oxide-coated sand (IOCS) is used as a surrogate soil to investigate the adsorption and transport behavior of the mixed metals solution, copper, chromate, and arsenate, in the subsurface environment. Copper adsorption increases with increasing pH. The presence of arsenate in the solution slightly increases, while chromate has minimal effect, on the amount of copper adsorbed. Chromate adsorption decreases with increasing pH. With arsenate present in solution, chromate adsorption is significantly suppressed over the pH range studied. In contrast, the presence of copper slightly increases chromate adsorption. Similar to chromate, arsenate adsorption decreases with increasing pH. The presence of chromate or copper does not affect the amount of arsenate adsorbed over the range of concentrations studied. Two surface complexation models, the triple layer model (TLM) and the electrostatic implicit model (EIM), were used to simulate equilibrium adsorption in both single-metal and multi-metal systems. Simulations using the specific surface complexation equilibrium constants derived from either the single-metal or the multi-metal systems with both the TLM and the EIM were successful in fitting the adsorption data in that respective single or multi-metal system. The local equilibrium assumption using batch-derived sorption isotherm parameters from the EIM failed to predict the copper and arsenate transport, while it adequately described chromate transport. The breakthrough curves of all three metals were asymmetrical and showed long-tailing behavior. This nonideal behavior is caused by nonlinear sorption and/or non-equilibrium conditions during transport. The two-site chemical non-equilibrium model, which accounts for the kinetically controlled adsorption sites, was able to fit the observed breakthrough curves for all three metals in single-metal systems. However, the model was partially successful in predicting transport in multi-metal systems.
Graduation date: 2002

In order to meet increasing indium demands, (bio)hydrometallurgical winning of low-grade sources will likely be required. The goal of this work in the scope of the Biohydrometallurgical Centre Freiberg, was to use geochemical modelling to improve indium leaching and extraction efficiency. Indium stability constants and chemical conditions of process relevant solutions were required. Electrochemical methods were used to determine the stability constants of indium complexes with nitrate, chloride, sulfate, and hydroxide ions, as well as with electrowinning additives. High pressure liquid chromatography techniques were adapted to quantify polysulfides (Sx2–) and metal ions in leaching and extraction solutions. This cumulative information was used in geochemical modelling. Predominance, Pourbaix, and speciation diagrams were produced to describe and explain the behaviour of multiple components in various process relevant solutions.
Um den steigenden Bedarf an Indium zu decken, ist eine (bio-)hydrometallurgische Gewinnung von ‚low-grade sources‘ erforderlich. Ziel dieser Arbeit im Rahmen des Biohydrometallurgischen Zentrums Freiberg war es, durch geochemische Modellierung die Indium-Laugungs- und Extraktionseffizienz zu verbessern. Dazu wurden Indium-Stabilitätskonstanten und chemische Bedingungen prozessrelevanter Lösungen benötigt. Mit elektrochemischen Methoden wurden die Stabilitätskonstanten von Indiumkomplexen mit Nitrat-, Chlorid-, Sulfat- und Hydroxidionen sowie mit Elektrogewinnungsadditiven bestimmt. Hochdruck-Flüssigkeitschromatographieverfahren wurden zur Quantifizierung von Polysulfiden (Sx2–) und Metallionen in Laugungs- und Extraktionslösungen angepasst. Alle experimentell bestimmten Parameter wurden in der geochemischen Modellierung verwendet. Prädominanz-, Pourbaix- und Speziationsdiagramme wurden erstellt, um das Verhalten mehrerer Komponenten in verschiedenen prozessrelevanten Lösungen zu beschreiben und zu erklären.

Marine Inseln beherbergen einen großen Teil der biologischen Vielfalt unseres Planeten und weisen gleichzeitig einen hohen Anteil endemischer Arten auf. Inselbiota sind allerdings zudem besonders anfällig für anthropogene Einflüsse wie den globalen Klimawandel, Habitatverlust und invasive Arten. Für ihren Erhalt ist es daher wichtig, die ökologischen Prozesse auf Inseln detailliert zu verstehen. Aufgrund ihrer definierten Größe und isolierten Lage eignen sich Inseln als Modellsysteme in der ökologischen und evolutionären Forschung. Der Großteil der bisherigen Inselstudien hat sich allerdings mit kleinräumigen Mustern befasst, so dass standardisierte globale Daten zu den biogeographischen Eigenschaften und eine makroökologische Synthese ihrer Biota bislang fehlen. In dieser Arbeit stelle ich eine physische und bioklimatische Charakterisierung der Inseln der Welt vor und behandle die Frage, wie abiotische Inseleigenschaften die Diversität von Inselfloren beeinflussen. Ich bearbeite zwei Hauptaspekte dieser Fragestellung: Zuerst konzentriere ich mich auf historische und heutige Klimabedingungen und physische Inseleigenschaften als Triebfedern von Pflanzendiversitätsmustern auf Inseln. Hierbei setze ich einen Schwerpunkt auf die räumliche Anordnung von Inseln und Struktur von Archipelen. Als Zweites behandle ich taxon-spezifische Unterschiede in der Antwort von Diversitätsmustern auf abiotische Faktoren. Hierzu stelle ich eine globale Datenbank mit historischen und heutigen Klimabedingungen und physischen Eigenschaften, wie Fläche, Isolation und Geologie, von 17883 Inseln größer als 1 km² vor. Mit Hilfe von Ordinations- und Klassifikationsverfahren charakterisiere und klassifiziere ich die Inseln in einem multidimensionalen Umweltraum. Außerdem entwickele ich einen Satz von ökologisch relevanten Maßen zur Beschreibung von Isolation von Inseln und ihrer räumlichen Anordnung in Archipelen, darunter Maße zu Trittstein-Inseln, Wind- und Meeresströmungen, klimatischer Ähnlichkeit, Distanzen zwischen Inseln und umgebender Landfläche. Diese Maße berücksichtigen verschiedene Aspekte von Isolation, welche Immigration, Artbildung und Aussterben auf Inseln sowie Austausch zwischen Inseln beeinflussen. Um abiotische Bedingungen mit biotischen Eigenschaften von Inselfloren in Verbindung zu bringen, nutze ich eine für diese Arbeit erstellte Datenbank aus 1295 Insel-Artenlisten, die insgesamt ca. 45000 heimische Gefäßpflanzenarten umfassen. Dies ist der umfassendste und erste globale Datensatz für Pflanzen auf Inseln, der Artidentitäten anstatt lediglich Artenzahlen beinhaltet. Die globale Insel-Charakterisierung bestätigt quantitativ, dass sich Inseln in bioklimatischen und physischen Eigenschaften vom Festland unterscheiden. Inseln sind im Durchschnitt signifikant kühler, feuchter und weniger saisonal geprägt als das Festland. Die weiteren Ergebnisse zeigen, dass eine sorgfältige Beschreibung der räumlich-physischen Eigenschaften von Inseln und Archipelen nötig ist, um die Diversitätsmuster ihrer Biota zu verstehen. Isolation ist nach Inselfläche der zweitwichtigste Einflussfaktor für den Gefäßpflanzenartenreichtum auf Inseln. Von den verglichenen Isolationsmaßen eignet sich der Anteil an umgebender Landfläche am besten zur Erklärung der Artenzahlen. Außerdem erhöht sich durch die Berücksichtigung von Trittsteininseln, großen Inseln als Quell-Landflächen und klimatischer Ähnlichkeit der Quell-Landflächen die Vorhersagekraft der Modelle. Isolation spielt eine geringere Rolle auf großen Inseln, wo in situ Diversifizierung den negativen Effekt von Isolation auf Immigration ausgleicht. Die räumliche Struktur innerhalb von Archipelen ist von besonderer Bedeutung für β-Diversität, d.h. für den Unterschied in der Artenzusammensetzung der Inseln. Außerdem beeinflusst sie indirekt, durch den Effekt auf die β-Diversität, auch die γ-Diversität, d.h. die Diversität des gesamten Archipels. Die Ergebnisse heben die enorme Bedeutung der relativen räumlichen Position von Inseln zueinander für Diversitätsmuster auf Inseln hervor und zeigen die Notwendigkeit für Inselforschung und Naturschutz, Inseln im Kontext ihres Archipels zu betrachten. Die Ergebnisse für Farne auf südostasiatischen Inseln zeigen, dass die Bedeutung von physischen Inseleigenschaften für Diversität kontinuierlich mit der Größe der betrachteten Untersuchungsfläche von der Insel- bis zur Plotebene abnimmt, wohingegen der Einfluss von lokalen Umweltbedingungen zunimmt. Lokale Artgemeinschaften sind häufig gesättigt, wodurch die Anzahl an Arten, die aus dem regionalen Artenbestand einwandern können, limitiert wird. Um Vorhersagen über lokalen Artenreichtum zu machen, ist es daher wichtig, die Skalenabhängigkeit der Effekte des regionalen Artenbestandes zu berücksichtigen. Großgruppen von Pflanzen unterscheiden sich in ihrer Ausbreitungsfähigkeit, ihrem Genfluss, Artbildungsraten und Anpassungen an das Klima. Dementsprechend zeigen die vergleichenden Analysen zwischen taxonomischen Pflanzengruppen deutliche Unterschiede in der Reaktion von Artenreichtum und phylogenetischen Diversitätsmustern auf abiotische Faktoren. Die Arten-Fläche-Beziehung, d.h. die Zunahme von Artendiversität mit zunehmender Fläche, variiert zwischen den Pflanzengruppen. Die Steigung der Arten-Fläche-Beziehung ist für Spermatophyten größer als für Pteridophyten und Bryophyten, wohingegen der y-Achsenabschnitt kleiner ist. Unter der Annahme, dass Merkmale und klimatische Anpassungen innerhalb von taxonomischen Gruppen phylogenetisch konserviert sind, führen die Filterwirkung von Ausbreitungsbarrieren und Umwelteigenschaften sowie in situ Artbildung zu Gemeinschaften eng verwandter Arten (phylogenetic clustering). Die Ergebnisse zeigen, dass physische und bioklimatische Inseleigenschaften, die mit der Filterwirkung und Artbildung in Verbindung stehen, die phylogenetische Struktur von Inselgemeinschaften beeinflussen. Die Stärke und Richtung der Zusammenhänge variieren zwischen taxonomischen Gruppen. Abiotische Faktoren erklären mehr Variation in phylogenetischer Diversität für alle Angiospermen und Palmen als für Farne, was auf Grund höherer Ausbreitungsfähigkeit und größerer Verbreitungsgebiete von Farnen den Erwartungen entspricht. Die abiotische Charakterisierung und Klassifizierung der weltweiten Inseln und die zugehörigen Daten ermöglichen eine integrativere Berücksichtigung von Inseln in der makroökologischen Forschung. In dieser Arbeit präsentiere ich die ersten Vorhersagen globaler Pflanzenartenvielfalt auf Inseln und die ersten Analysen zu unterschiedlichen Diversitätskomponenten (α, β, γ und phylogenetische Diversität) von Inselsystemen und ihren abiotischen Einflussfaktoren auf globalem Maßstab. Ich zeige, dass Zusammenhänge zwischen Umweltfaktoren und Artenzahl sowie phylogenetischen Eigenschaften von Inselgemeinschaften zwischen unterschiedlichen taxonomischen Gruppen in Abhängigkeit ihrer vorwiegenden Ausbreitungs- und Artbildungseigenschaften variieren können. Dies ist eine neue Sichtweise in der makroökologischen Inselforschung, die Rückschlüsse auf die Mechanismen hinter Diversitätsmustern von Pflanzen auf Inseln erlaubt. Ein detailliertes Verständnis davon, wie Diversität unterschiedlicher Pflanzengruppen durch Immigration und Diversifizierung auf Inseln entsteht, dürfte auch das Verständnis globaler Diversitätsmuster im Allgemeinen verbessern.