Rozprawy doktorskie na temat „PHREEQC”

Syftet med examensarbetet har varit att studera kol i mindre vattendrag med hjälp av jämviktsmodellering i PHREEQC. Fokus har varit dynamik av löst icke organiskt kol (DIC) samt att förstå hur mycket koldioxid (CO2) som avges från mindre vattendrag och om den mängden har signifikant inverkan på den globala kolbalansen. Med hjälp av provtagen data från Krycklans avrinningsområde år 2003-2007 och 2009 har modellering av DIC och pCO2 utförts med målet att se förändring både över säsong och nedströms i ytvattensystemet. För att utvärdera modellen har tillhandahållen data över uppmätt pCO2 använts. Målet var att jämföra modellerade och tillhandahållna pCO2-värden för att se hur väl modellen kunde beskriva verkligheten och om den fungerade bättre för någon plats eller under vissa delar av året. Analysen visade att pCO2-värden för modellen följer uppmätta pCO2-värden förhållandevis bra. Avvikelserna var störst för en av provpunkterna (provpunkt 6). Modellerade pCO2-värden följde de uppmätta pCO2-värden bäst under vårfloden. Modellen och analys av data visade tydliga indikationer på en avgång av CO2 från vattendraget.
The purpose of this Master thesis has been to study carbon flux in creeks. Chemical equilibrium models were produced to this end using PHREEQC. Specifically, dissolved inorganic carbon (DIC) quantities have been studied in order to understand the discharge of carbon dioxide (CO2) from the creek headwaters and how that affects the global carbon balance. Modeling of DIC and pCO2 was conducted using data from 2003-2007 and 2009 sampled at two points in the Krycklan research catchment located in northern Sweden. Seasonal variation of DIC and pCO2 in the two sample points was studied as well as the difference of these quantities between the two points. Evaluation of the model was done in part by comparing predicted pCO2 values with actual values stemming from a previous study leading to an assessment of the validity of the model. One of the sample points showed larger discrepancies between predictedand actual values than the other. Studying the seasonal variation of discrepancies, they were at the minimum during the spring flood. Finally, the analysis showed clear indications of a net CO2 discharge from the creekstretch between the two sample points.

Le lithium est une matière première en demande croissante suite au fort développement des appareils nomades et des véhicules électriques. Ce manuscrit s’intéresse à la production de lithium à partir d’une ressource naturelle : les saumures lithinifères. Une étude bibliographique sur l’extraction du lithium présent dans les saumures a mis en avant que cette dernière requiert des quantités importantes d’énergie, d’eau et de réactifs. Cela met ainsi en évidence l’enjeu environnemental et la nécessité d’améliorer les procédés existants. A cette fin, la présente étude allie la modélisation à un travail expérimental. Le modèle sélectionné pour calculer les coefficients d’activité des éléments dissous dans les saumures est le modèle de Pitzer (1991). Un travail de paramétrisation a été effectué pour mettre au point une base de données thermodynamiques disposant des éléments nécessaires (propriétés des sels, paramètres d’interaction) à la description des systèmes électrolytiques d’intérêt. Après un travail de validation appuyé sur des données expérimentales issues de la bibliographie, cette base de données, associée au logiciel PhreeqC pour les calculs géochimiques, permet de simuler différentes transformations des saumures (dilution, évaporation, ajout de réactifs). L’outil mis en place a permis d’analyser des scenarios exploratoires de production de zabuyelite (Li2CO3) et d’effectuer une étude de sensibilité des paramètres opératoires. Des travaux expérimentaux sur des saumures modèles ont été effectués sur deux pilotes distincts : une enceinte climatique et une unité d’évaporation. Les techniques d’analyses utilisées pour suivre l’évolution de la composition de la saumure et la qualité des cristaux sont la chromatographie ionique, la DRX et l’EDX. Le modèle mis au point permet de décrire les systèmes salés complexes à l’équilibre à 25°C. Il parvient à décrire les essais dans le pilote d’évaporation du LaTEP à condition que l’on émette l’hypothèse que la zabuyelite ne précipite pas au cours du temps (sursaturation nécessaire). Il pourrait certainement être optimisé au niveau thermodynamique (spéciations, constantes de solubilité), mais également en y ajoutant une dimension cinétique et transferts liquide-vapeur
Lithium is a critical element regarding to the development of portable devices and electric vehicles. This manuscript is dedicated to lithium production from natural lithium bearing brines. A bibliographic review shows that lithium production consumes lots of water, energy and reactive. It underlines environmental issues and the necessity to improve existing processes. In order to achieve this, modeling and experimental work are associated for this study. The Pitzer model (Pitzer, 1991) is used to calculate the activity coefficients of dissolved aqueous species in brines. After parametrization (salt properties, interaction parameters) and validation with experimental data from literature, a database was optimized to allow the description of key electrolytic systems. Associated with phreeQC software, it is possible to simulate transformations of the brine (such as dilution, evaporation, reactions). It can be used as a predictive tool to explore zabuyelite (Li2CO3) production and study the sensibility of the operative parameters (temperature, pH, pCO2). Experimental work on model-brines was done on two separate pilots: a climatic chamber and a crystallization unit. The evolution of the brine composition and quality of crystals produced was monitored by ionic chromatography, XRD and EDX. The model designed in this study can describe the equilibrium of complex brines at 25°C. It can also describe the experiment in the crystallization unit if a hypothesis of supersaturation (Li2CO3) is used. It could be improved thermodynamically with more speciation and solubility constants, and also with kinetics and liquid-vapor transfers

Dans le cadre du projet Cigeo (centre industriel pour le dépôt géologique de déchets radioactifs), le comportement diffusif des radionucléides dans les matériaux cimentaires est un sujet d’étude de l’Andra. Après la fermeture du site d’entreposage de déchets radioactifs, les radionucléides se retrouveront à terme en solution sous forme d’ions. Ils seront alors susceptibles de migrer vers la roche argileuse entourant le site d’entreposage et ses ouvrages en béton seront la première barrière qu'ils rencontreront lors de leur diffusion. Lorsque l'eau provenant de la roche se trouvera en contact avec les ouvrages, cela entrainera une décalcification et une dégradation progressive du matériau cimentaire. De nombreux travaux de recherche traitent de la diffusion d’espèces ioniques dans les matériaux cimentaires. Il existe cependant très peu d'études comparatives sur la diffusion de traceurs différemment chargés dans les matériaux cimentaires à différents états de dégradation, et notamment sur le matériau qui est à l'étude par l'Andra (à base de CEM V). Cette thèse a donc pour objectif d’étudier la diffusion de différentes espèces anioniques, cationiques et neutres dans un matériau cimentaire à base de CEM V à différents états de dégradation. Dans cette optique, un protocole expérimental optimisé a été mis au point et une étude numérique sur un logiciel de transport réactif multi-espèces a été menée. Des essais de diffusion sur des pâtes de ciment à base de ciment CEM I ont d'abord été réalisés afin de calibrer la procédure. Les essais principalement réalisés sont des essais de diffusion accélérée sous champ électrique, appelés aussi essais de migration. Des essais complémentaires de diffusion naturelle, tels que les essais de lixiviation et d’immersion, permettent de valider et de compléter les résultats des essais de migration. On utilise le logiciel PhreeqC (v3.3.12 Ampère prenant en compte l'application d'un champ électrique lors de la diffusion). Il permet de comparer les comportements diffusifs des traceurs utilisés à l’aide d’un facteur unique, appelé facteur de formation F(i) = D(E,i) / D(L,i) qui représente le chemin accessible à la diffusion de l'espèce i. Ce facteur prend en compte la topologie de la microstructure (porosité, tortuosité…) et les phénomènes électro-capillaires d’adsorption. Afin d'affiner notre modèle numérique, nous nous appuyons sur les courbes d’évolution du courant électrique et des concentrations (traceurs et espèces secondaires). L'étude comparative a été réalisée sur des pâtes de ciment puis du béton à base de CEM V. Les pâtes ont été conservées à différents états de dégradation : sain (la solution porale du matériau est riche en alcalins), lixivié (le matériau s’appauvrit en alcalins au contact d'une solution d'eau pure) et dégradé à pH 12,5 (une solution calcaire remplace la solution porale du matériau sans modifier sa microstructure). Il a alors été observé que les espèces ioniques ne diffusaient pas de la même manière suivant leur charge et l’état de dégradation du matériau (donc de la composition de sa solution porale). Cette observation a été confirmée par les essais de diffusion sur du béton, un matériau de microstructure plus complexe. Sur un type de matériau donné, le facteur de formation F(i) varie d'une espèce à l'autre alors que la géométrie macroscopique du matériau est la même. Cela semble donc faire apparaitre des phénomènes microscopiques qui pourraient influencer la diffusion de l'espèce i et qui dépendent de l’espèce étudiée et de la composition de la solution porale du matériau
Radionuclides diffusive behavior in cement materials is one of the topics studied by Andra for the Cigeo project (industrial center for geological disposal of radioactive waste). After the site closure, radionuclides will be released in solution by the end as ionic species. Therefore, it has high potential to migrate to the argillaceous rock surrounding the disposal site and its concrete vaults will be the first barriers against radionuclides diffusion. When water coming from the argillaceous rock is in contact with concrete vaults, it will lead to a decalcification and a progressive degradation of the cement materials. Numerous research works deal with diffusion of ionic species in cement materials. However, there are very few comparative studies about diffusion of tracer differently charged in cement material untainted and at different degraded states, particularly on the material studied by Andra on its Cigeo project (based on CEM V cement). The aim of this thesis is to study ionic diffusion of different anionic, cationic and neutral species in a cement material based on CEM V at different degradation states. In this purpose, an optimized experimental protocol has been developed and a numerical multi-species reactive transport software study has been lead. Firstly, diffusion tests on CEM I cement paste have been carried out in order to calibrate the procedure. Main tests are electrical field applied accelerated diffusion, also named migration tests. Complementary tests of natural diffusion, like in-diffusion or out-diffusion tests, allow us to validate and round off migration test results. We use PhreeqC software (v3.3.12 Ampère taking into account the application of an electrical field during the diffusion). It permits us to compare diffusive behavior of the studied tracers thanks to a unique factor, named formation factor F(i) = D(E,i) / D(L,i), which represents the accessible way for a ionic species i diffusion. This factor takes into account the microstructure topology (porosity, tortuosity…) and electro-capillarity adsorption phenomenon. In order to improve the numerical model, we use electrical current and concentrations (tracer and secondary species) evolution curves. Comparative study has been conducted on cement pastes and concrete based on CEM V. Pastes were stored at different degradation states : untainted (material pore solution full of alkaline), leached (material depleted in alkaline on contact with pure water) and degraded at pH 12.5 (a calcium solution replace the pore solution without modifying microstructure). We notice that ionic species do not diffuse the same way depending on their charge and the material state (it is therefore a function of the pore solution). These observations had been corroborated by diffusion tests on concrete, a material whose microstructure is more complex. On a given material, the formation factor F(i) changes with the studied ionic species, whereas the macroscopic geometry of the material is the same. It seems to emphasize that microscopic phenomenon influence the species diffusion that depends on the species studied, as well as the pore solution composition of the material

L'arsenic est un metalloïde toxique et cancérigène. Ubiquiste dans la pedosphere, il est très sensibleaux fluctuations des conditions redox du sol, ce qui influe significativement sa toxicité et mobilité. Nousétudions le cycle biogéochimique global de l'arsenic, en tenant compte de l'usage croissant des ressources, etpassons en revue l'importance respective de l'arsenic geogénique et anthropogénique dans l'environnement.La contamination à l'arsenic est souvent diffuse dans les bassins sédimentaires de l'Europe. Cependant, desconcentrations dans l'eau interstitielle du sol peuvent être élevées lors de périodes de saturation du solcausées par la monté des eaux souterraines ou les inondations, prévues d'augmenter dû aux changementsclimatiques. La spectrométrie de fluorescence X quantitative et sans standard a été utilisée pour analyserl'arsenic dans des sols relativement contaminés de la plaine alluviale de la Saône au moyen de protocoles depréparation d'échantillons conçus pour optimiser la précision d'analyse et l'exactitude in situ aux bassesconcentrations d'arsenic. L'arsenic dans ces sols est associe aux (hydr)oxydes du fer et de manganèse de lataille d'argile colloïdale. Ceux-ci subissent une dissolution réductrice par les microorganismes lors desinondations, libérant une importante concentration d'arsenic dans la phase aqueuse. Si, par la suite, l'arsenicdégagé n'est pas éliminé avec l'eau de crue évacuée, il est ré-immobilisé pendant l'oxydation du sol et lareprécipitation des oxydes métalliques. Grâce à une combinaison novatrice d'analyses chimiques par voiehumide, d'écologie microbienne, de spectroscopie ainsi que de modélisation thermodynamique et cinétique,nous démontrons que les cycles d'oxydo-réduction séquentiels entraînent une atténuation d'arsenic aqueuxdans des conditions réductrices dû à la coprécipitation croissante, et a une diminution de l'activitémicrobienne causée par l'appauvrissement en matière organique labile. Des processus d'atténuationsimilaires sont observés en l'absence d'activité microbienne pour Cr et As dans des argiles pyriteuses lorsquecelles-ci sont exposés aux oscillations redox provoquées par l'ajout de substances humiques réduites. Ainsi,nous montrons que les effets cumulatifs de cycles redox successifs sont extrêmement importants pour lamobilité de divers contaminants dans l'environnement.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico
Os aqÃÃferos aluviais presentes na regiÃo semi-Ãrida do Nordeste brasileiro hospedam importantes recursos hÃdricos naturais para as populaÃÃes que vivem nessa regiÃo, devido a sua excelente qualidade, quando comparado aos aqÃÃferos localizados nas Ãreas de embasamento cristalino. No entanto, constituem recursos frÃgeis, sendo susceptÃveis a processos de degradaÃÃo da sua qualidade por aÃÃes antrÃpicas, variaÃÃes climÃticas ou modificaÃÃes hidrogeolÃgicas. Com o objetivo de identificar e quantificar os principais processos responsÃveis pelo aumento da salinidade observada no aqÃÃfero aluvial durante o perÃodo nÃo chuvoso usou-se, alÃm de estudos hidroquÃmicos (diagramas e estudo de razÃes iÃnicas), a anÃlise estatÃstica multivariada (agrupamento hierÃrquico e discriminante) e a modelagem geoquÃmica inversa. Os diagramas de Piper e Stiff mostraram a classificaÃÃo das Ãguas quanto à presenÃa dos Ãons dominantes, onde as Ãguas aluviais apresentaram caracterÃsticas intermediÃrias entre as Ãguas do aqÃÃfero fissural e Ãgua dos reservatÃrios. Com o diagrama de RAS obteve-se a mesma interpretaÃÃo. As relaÃÃes iÃnicas revelaram forte relaÃÃo das Ãguas aluviais com a litologia da regiÃo e a provÃvel dissoluÃÃo de aerossÃis contendo compostos de MgCl2 nos aqÃÃferos do embasamento cristalino. A anÃlise de agrupamento mostrou as similaridades entre os poÃos, enquanto a anÃlise discriminante ajudou a compreender o processo de salinizaÃÃo no aqÃÃfero aluvial. As modelagens geoquÃmicas inversas realizadas com o PHREEQC identificaram trocas catiÃnicas de CaX2, MgX2, NaX e KX, alÃm de precipitaÃÃes de K-mica e albita e dissoluÃÃes de anortita e K-feldspato, evidenciando a aÃÃo intempÃrica das Ãguas sobre as rochas. A grande dissoluÃÃo de CO2 nas Ãguas aluviais justifica a caracterÃstica bicarbonatada dessas Ãguas. A contribuiÃÃo volumÃtrica de Ãguas do aqÃÃfero fissural, como forma de justificar o aumento da salinidade nos poÃos aluviais, foi estimada entre 1,53% e 27,99% para diferentes pontos, na mÃdia foi de 15,8%. No entanto, esta contribuiÃÃo representa quase 64% da salinidade no aluviÃo.
The alluvial aquifers in the semi-arid region of Brazilâs Northeast host an important natural water resource for the populations that live in that region, owing to its excellent quality, when compared to the crystalline basement rock aquifers. However, they are fragile resources and are susceptible to processes of degradation of quality by anthropic action, climatic changes or hydrogeological modifications. The objective of this research is to identify and quantify the primary processes responsible for the increase in salinity observed in the alluvial aquifers during the dry season. Besides hydrochemical analysis (Piper and Stiff diagrams and ionic relations), multivariate statistical analysis (hierarchical clustering and discriminant analyses) and inverse geochemical modeling were also used. The Piper and Stiff diagrams presented water classification according to dominant ions, where the alluvial water showed intermediate characteristics between the hard-rock basement aquifer water and that from the reservoirs. With the SAR diagram, the same result was observed. The ionic relations revealed a strong relation of the alluvial water with the lithology of the region and the probable dissolution of aerosols containing composites of the MgCl2 type in the aquifers of the crystalline rock shield. Cluster analysis showed the similarities between the wells, whereas discriminant analysis helped to understand the process of salinization in the alluvial aquifer. The inverse geochemical modeling carried out with PHREEQC identified cationic exchanges of CaX2, MgX2, NaX and KX, as well as precipitation of K-mica and albite and dissolutions of anorthite and K-feldspar, evidencing the intemperic action of the water on the rocks. Strong dissolution of CO2 in the alluvial water justifies the bicarbonated characteristics of that water. The volume contribution from crystalline rock aquifer water was estimated as between 1.53% and 27.99% at different points with a mean value of 15.8%. However, this contribution represents nearly 64% of the salinity of the water in the alluvium.

Uganda is well endowed with economic quantities of salt evident in the interstitial brines and evaporite deposits of Lake Katwe, a closed saline lake located in the western branch of the great East African rift valley. Currently, rudimentally methods of salt mining based on solar evaporation of brine continue to be used for salt extraction at the lake. These have proved to be hazardous and unsustainable to the salt miners and the environment. In this work, literature concerning the occurrence of salt and the most common available technologies for salt extraction is documented. Field studies were undertaken to characterize the salt lake deposit and to devise strategies of improving salt mining and extraction from the salt lake raw materials. The mineral salt raw materials (brines and evaporites) were characterized to determine their physical, chemical, mineralogical, and morphological composition through field and laboratory analyses. In addition, laboratory extraction techniques were undertaken to evaluate possibilities of future sustainable salt extraction from the lake deposit. Also, PHREEQC simulations using Pitzer models were carried out to determine the present saturation state of the lake brine and to estimate which salts and the order in which they precipitate from the brine upon concentration by evaporation. Results reveal that the raw materials from the salt lake contain substantial amounts of salt which can be commercialized for optimum production. The brines are highly alkaline and rich in Na+, K+, Cl-, SO42-, CO32-, and HCO3-. Moreover, they contain trace amounts of Mg2+, Ca2+, Br-, and F-. The lake is hydro-chemically of a carbonate type with the brines showing an intermediate transition between Na-Cl and Na-HCO3 water types. The evaporites are composed of halite mixed with other salts such as hanksite, burkeite, trona etc, with their composition varying considerably within the same grades. The laboratory extraction experiments indicate that various types of economic salts such as thenardite, anhydrite, mirabilite, burkeite, hanksite, gypsum, trona, halite, nahcolite, soda ash, and thermonatrite precipitate from the brine of Lake Katwe. The salts crystallize in the order following the sequence starting with sulfates, followed by chlorides and carbonates, respectively. Moreover, thermodynamic modeling in PHREEQC accurately predicted the solubility and sequence of the salt precipitation from the lake brine. Understanding the sequence of salt precipitation from the brine helps to control its evolution during concentration and hence, will lead to an improved operating design scheme of the current extraction processes. The work providesinformation towards future mineral salt exploitation from the salt lake.

QC 20131129

Universidade Federal do CearÃ
A interaÃÃo entre a Ãgua subterrÃnea e as rochas, ocorre atravÃs de processos de dissoluÃÃo e precipitaÃÃo que atestam a evoluÃÃo hidroquÃmicas dentro do sistema aqÃÃfero com a influÃncia direta na qualidade da Ãgua. Nesse trabalho, foi utilizado o aplicativo PHREEQC para simular esses processos em Ãguas de 7 poÃos no cristalino coletadas nos perÃodos seco e chuvoso, com o objetivo de identificar a origem da salinidade dessas Ãguas. Os resultados mostram que (i) a salinidade varia no espaÃo e no tempo; (ii) predomina Ãgua do tipo cloretada mista; (iii) o tipo de Ãgua se mantÃm em cada poÃo (iv) a salinidade diminui no perÃodo chuvoso e aumenta no perÃodo seco, atingindo valores caracterÃsticos de cada poÃo, (v) Ãguas saturadas de goetita, hematita e hidrÃxido de ferro III ocorreram em dois poÃos; calcita, dolomita e aragonita em 3 poÃos e hematita em 2 poÃos. No perÃodo seco e chuvoso, ocorreram dissoluÃÃes de anortita e K-feldspato, precipitaÃÃo de K-mica e albita e trocas catiÃnicas dos tipos CaX2, MgX2, NaX e KX. As Ãguas mais salinas estÃo nos poÃos que receberam menores recargas e as diferenÃas nas recargas à caracterÃstica de Ãreas no cristalino.
The interaction between groundwater and rocks, occurs through processes of dissolution and precipitation that attest to the hydrochemical evolution within the aquifer system with direct influence on water quality. In this study, we used the application PHREEQC to simulate these processes in water from seven wells in crystalline collected during dry and wet, with the aim of identifying the origin of the salinity of these waters. The results show that (i) the salinity varies in space and time, (ii) are mainly chlorinated water from the mixed type, (iii) the type of water remains in each well (iv) the salinity decreases during the rainy season and increases in dry period, reaching values characteristic of each well, (v) water-saturated goethite, hematite and iron hydroxide III occurred in two wells, calcite, dolomite and aragonite in three wells and two wells in hematite. In the dry and rainy season, there were dissolution of anorthite and K-feldspar, precipitation of K-mica and albite and cationic exchange types CaX2, MgX2, NaX and KX. The waters are more saline in wells that received minor differences in recharges and refills is characteristic of areas in the lens

SANTIAGO, Roberto Namor Silva. Processos hidrogeoquímicos em águas subterrâneas no cristalino em Caucaia/CE. Contribuição da modelagem inversa através do PHREEQC. 2010. 77 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2010.
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The interaction between groundwater and rocks, occurs through processes of dissolution and precipitation that attest to the hydrochemical evolution within the aquifer system with direct influence on water quality. In this study, we used the application PHREEQC to simulate these processes in water from seven wells in crystalline collected during dry and wet, with the aim of identifying the origin of the salinity of these waters. The results show that (i) the salinity varies in space and time, (ii) are mainly chlorinated water from the mixed type, (iii) the type of water remains in each well (iv) the salinity decreases during the rainy season and increases in dry period, reaching values characteristic of each well, (v) water-saturated goethite, hematite and iron hydroxide III occurred in two wells, calcite, dolomite and aragonite in three wells and two wells in hematite. In the dry and rainy season, there were dissolution of anorthite and K-feldspar, precipitation of K-mica and albite and cationic exchange types CaX2, MgX2, NaX and KX. The waters are more saline in wells that received minor differences in recharges and refills is characteristic of areas in the lens.
A interação entre a água subterrânea e as rochas, ocorre através de processos de dissolução e precipitação que atestam a evolução hidroquímicas dentro do sistema aqüífero com a influência direta na qualidade da água. Nesse trabalho, foi utilizado o aplicativo PHREEQC para simular esses processos em águas de 7 poços no cristalino coletadas nos períodos seco e chuvoso, com o objetivo de identificar a origem da salinidade dessas águas. Os resultados mostram que (i) a salinidade varia no espaço e no tempo; (ii) predomina água do tipo cloretada mista; (iii) o tipo de água se mantém em cada poço (iv) a salinidade diminui no período chuvoso e aumenta no período seco, atingindo valores característicos de cada poço, (v) águas saturadas de goetita, hematita e hidróxido de ferro III ocorreram em dois poços; calcita, dolomita e aragonita em 3 poços e hematita em 2 poços. No período seco e chuvoso, ocorreram dissoluções de anortita e K-feldspato, precipitação de K-mica e albita e trocas catiônicas dos tipos CaX2, MgX2, NaX e KX. As águas mais salinas estão nos poços que receberam menores recargas e as diferenças nas recargas é característica de áreas no cristalino.

Dans un contexte de stress hydrique, la micro-irrigation avec des eaux usées traitées constitue une solution visant à réduire les dépenses en eau. Cependant, le colmatage des goutteurs constitue une contrainte à l’utilisation de ces eaux bien chargées à cause des précipitations chimiques et du développement de biofilm. Les objectifs de cette étude sont de: a) Caractériser la précipitation des sels dissous en fonction des conditions opératoires, b) étudier le développement des biofilms sous différentes conditions hydrodynamiques, c) analyser l’interaction entre le carbonate de calcium et le développement du biofilm. En premier lieu une étude fut conduite sur l’impact de la température le pH et la pression partielle du CO2 sur la précipitation chimique. Cette étude a permis de quantifier l’augmentation de la masse du carbonate de calcium en fonction du pH et de la température. Les résultats expérimentaux ont permis de valider et de calibrer un modèle numérique (PHREEQC) qui permet de prédire la précipitation chimique pour une qualité d’eau donnée dans des conditions opératoire variées. Des expérimentations ont ensuite été réalisées à l’aide d’un banc d’essai d’irrigation pour étudier l’influence du carbonate de calcium sur la croissance des biofilms au niveau des conduites et des goutteurs. En parallèle un réacteur de Taylor-Couette fut utilisé pour étudier l’influence de la contrainte de cisaillement sur le développement des biofilms. Le biofilm a tendance à se développer selon la plus forte contrainte de cisaillement (4.4 Pa comparée à des contraintes de 2.2 et 0.7 Pa). Une précipitation du carbonate de calcium a été observée en interaction avec la croissance du biofilm
In a context of water stress, micro-irrigation with treated wastewater is a solution to reduce water expenditure. However, the clogging of micro-irrigation systems constitutes a constraint on the use of these well-laden waters due to chemical precipitation and the development of biofilm. The objectives of this study are to: a) characterize precipitation of dissolved salts as a function of operating conditions, b) study the development of biofilms under different hydrodynamic conditions and c) analyze the interaction between calcium carbonate and the development of biofilm. First, a study was conducted on the impact of pH, temperature and partial pressure of CO2 on chemical precipitation. This study permits the quantification of the increase in the mass of the precipitate produced in the form of calcite (calcium carbonate) as a function of the increase in pH and temperature. The experimental results allowed validation and calibration of the modeling of the precipitation under PHREEQC’s software. This numerical model allows prediction and quantification of chemical precipitation for a given water quality under various operating conditions. Experiments were then carried out using an irrigation set-up to study the influence of calcium carbonate on the growth of biofilms inside pipes and drippers. In parallel, a Taylor-Couette reactor was used to study the influence of shear stress on the development of biofilms. Biofilm tends to develop under the highest shear stress (4.4 Pa compared to 2.2 and 0.7 Pa). Precipitation of the calcium carbonate in the form of calcite was observed in interaction with the growth of the biofilm

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Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências - Geoquímica. Niterói, RJ
As águas minerais do Parque Salutaris no município de Paraíba do Sul, região centro-sul do estado do Rio de Janeiro, consistem em um recurso explorado para consumo humano desde 1887. Essas águas são provenientes de aquíferos fissurais com litologias variadas, tais como gnaisse, granulito e diabásio que lhes conferem características hidroquímicas excepcionais. O objetivo desse trabalho foi compreender os processos geoquímicos responsáveis pela mineralização das águas subterrâneas do Parque Salutaris e identificar possíveis riscos quanto ao consumo dessa água pela população. Para tanto, dentro do parque, foi realizado um monitoramento das águas minerais durante 10 meses, a partir de 3 poços tubulares que captam as águas, nas fontes de distribuição dessas águas e em uma cava que acumula água subterrânea dentro de uma gruta. Também foram realizadas amostragens no rio Paraíba do Sul e em uma nascente a montante do parque, como medidas de background. Foram realizadas medidas físico-químicas “in situ” e análises laboratoriais dos íons maiores Na, K, Mg, Ca, Cl, SO4, HCO3, constituintes menores e traços Al, Mn, Fe, e F, dos nutrientes, SiO2, N-NO2, N-NO3 e P-PO4, de coliformes totais e termotolerantes. Para os materiais geológicos considerados produtos do intemperismo na região foram realizadas análises mineralógicas por DRX da fração argila e comparadas com a modelagem das espécies minerais, disponíveis em água através do PHREEQC. Os tipos hidroquímicos das águas foram: águas bicarbonatada sódica na gruta, bicarbonatada sódica a mista para o poço Nilo Peçanha, bicarbonatada mista no poço Alexandre Abraão e bicarbonatada magnesiana a mista no poço Maria Rita. Verificou-se que as concentrações dos íons dissolvidos teriam origens principais a partir do intemperismo químico de minerais como micas, feldspatos, piroxênio e plagioclásio, presentes no embasamento gnáissico e granulítico. A modelagem hidrogeoquímica permitiu identificar que as espécies minerais carbonáticas tendem ao equilíbrio, enquanto os argilominerais e óxidos de ferro tendem a saturação. Os minerais secundários, identificados através do DRX, estão de acordo com a modelagem no PHREEQC, sendo encontrados principalmente a caulinita, gibbsita, goethita, calcita e clorita no material geológico. Também foram confirmadas que concentrações dissolvidas do flúor e manganês possuem origens naturais. Não foi identificado contaminação por efluentes nos poços de captação das águas minerais. A pesquisa considerou a ingestão de flúor e manganês das águas minerais por receptores residenciais na avaliação de risco a saúde humana, sendo constatado que bebês e infantes podem estar submetidos a riscos crônicos no que tange o desenvolvimento de fluorose dentária.
The mineral waters of Salutaris Park, located at the south-central part of Rio de Janeiro State, are exploited for human consumption since 1887. Those waters come from fractured aquifers as gneiss, granulite and diabase, yielding a variety of hydrogeochemical features. The aim of this study was to understand the geochemical processes responsible for the groundwater mineralization of Salutaris Park and identify the possible risks for human health through the population consumption of those waters. The monitoring of mineral waters was carried out in 3 wells and their respective sources of distribution, besides an ancient pit lake located in cave, inside the park. In order to considerate background measures for the mineral waters, were also collected samples from the Paraíba do Sul River and a spring in upstream of the park. The physicochemical parameters were directly measured in the field. In laboratory, were carried out the measures of major ions Na, K, Mg, Ca, Cl, SO4, HCO3, minor and traces constituents as Al, Mn, Fe and F, nutrients, SiO2, N- NO2, N-NO3, P-PO4 and total and fecal coliforms. The mineralogical characterization of the geological materials were performed by DRX of the clay fraction, which was posterior compared to the mineral species indicated by the PHREEQC hydrogeochemical modeling, through the measure of the minerals saturation indexes. Three different hydrochemical water types were identified in the studied area, namely: 1) sodium bicarbonate type from the pit lake; 2) sodium and mixed bicarbonate types from the Nilo Peçanha well; 3) mixed bicarbonate type from Alexandre Abraão well and 4) magnesium bicarbonate and mixed types from Maria Rita well. It is noticed that the increase of the dissolved concentrations is due to the weathering processes of primary minerals, mainly micaceous minerals, K-feldspar, pyroxene and plagioclase, which are the main constituents of the regional rocks (gneisses and granulites). The hydrogeochemical modeling identified the carbonate species are in equilibrium with those waters, while the clay minerals and iron oxides trend to be supersaturated. The secondary minerals, estimated by the DRX, are in according to the PHREEQC modeling, identifying mainly kaolinite, gibbsite, goethite, calcite and chlorite. Based on the results, there was no identification of anthropogenic impacts by effluents in the minerals waters wells. The fluoride and manganese have natural sources, although they present concentrations above of the standard potability. For that reason, in order to the accomplishment of a risk assessment for the mineral waters consumption, considering the fluoride and manganese intake by human beings, it was found that the babies and infants may be subjected to chronic risks of dental fluorosis development.

L’urbanisation est en forte croissance dans le monde, surtout en Afrique. Nourrir cette population urbaine nécessite de doubler la production agricole d’ici 2030. Une des solutions semble être l’agriculture urbaine. Le Gabon, comme d’autres pays d’Afrique, connait un essor de l’agriculture urbaine, en particulier à Libreville. Mais aucune étude concrète de l’impact dans le pays de l’agriculture en milieu urbain sur les propriétés bio-physico-chimiques, et le comportement des métaux dans les sols n’a encore été réalisée. Dans ce contexte, l’objectif de ce travail était d’étudier l’impact des cultures maraîchères urbaines sur les propriétés des sols, ainsi que la présence de certains métaux dans les sols et les plantes cultivées. Le maraîchage urbain est pratiqué sous abri ou en plein air et souffre encore de maux qui freinent son développement (niveau d’études des maraîchers, précarité du foncier, accès limité aux fertilisants, à l’eau d’irrigation…). Les sols de Libreville sont sablo-limoneux ou argilo-sablo-limoneux. La teneur des métaux est en général faible et les risques de contamination dans la chaîne alimentaire limités. Les sols cultivés depuis moins de 10 ans et les sols sous abri ne subissent pas un impact significatif vis-à-vis des sols non cultivés. En outre, les sols cultivés en plein air depuis au moins 10 ans sont acidifiés et leurs paramètres de fertilité et la teneur des métaux diminuent significativement. Le pH est bien corrélé à la spéciation chimique des métaux et il y a une bonne mobilité de Mn, Pb et Zn dans les sols. La teneur en métaux dans les légumes cultivés à Libreville était inférieure aux limites autorisées par la FAO. L’amarante et l’oseille accumulent bien les métaux, en particulier dans les feuilles qui sont consommées. La simulation du chaulage des sols cultivés en plein air depuis au moins 10 ans à l’aide du logiciel PHREEQC, montre qu’une stabilisation du pH à 6-7 améliorerait la fertilité des sols. Des expériences in situ et au laboratoire sont nécessaires pour confirmer ces résultats et tester d’autres apports minéraux et/ou organiques
Urbanization is growing rapidly worldwide, especially in Africa. Feed this urban population requires to double agricultural production before 2030. One of solution seems to be urban agriculture. Gabon, like other African countries, is experiencing a boom of urban agriculture, particularly in Libreville. But no concrete study of the impact of urban agriculture on the bio-physico-chemical properties and behavior of metals in soils has yet been carried out in the country. In this context, the objective of this work was to study the impact of urban gardening on soil properties, and the presence of metals in soils and crops.The urban gardening is practiced under cover or in open air and some factors hinder its development (instruction level of gardeners, land insecurity, fertilizers, limited access to water ...). Soils in Libreville are sandy-loam or clay-sandy-loam. The content of metals is generally low and the risk of contamination in the food is limited. Soils cultivated for less than 10 years and soils cultivated under cover do not undergo a significant impact of agricultural practices. In contrast, soils cultivated in open air for at least 10 years are acidified, their fertility parameters and metal content decreasing significantly. The pH is correlated with the chemical speciation of metals and there is a good mobility of Mn, Pb and Zn in soils. Metal content in vegetables grown in Libreville was below the limits allowed by the FAO. Amaranth and sorrel accumulated many metals, especially in the leaves that are consumed parts. The simulation of the liming of agricultural soils cultivated in open air for at least 10 years with the PHREEQC software shows that stabilization to pH 6-7 would improve soils fertility. Some experiments in situ and in laboratory are needed to confirm these results and other mineral and/or organics inputs tests

L’augmentation considérable de l’eutrophisation des eaux de surface dans les dernières décennies a mené à la création de stations de récupération des ressources de l’eau (StaRRE) de plus en plus instrumentées pouvant procéder à l’élimination des nutriments. Pour assurer l’efficacité des procédés de récupération, plusieurs paramètres de qualité des eaux doivent être surveillés. Des méthodes en ligne et hors-ligne existent pour réaliser cette surveillance. Cependant, certains paramètres sont difficilement mesurés en ligne, alors des analyses en laboratoire sont toujours de mise. La titrimétrie est une méthode hors-ligne permettant la surveillance de la qualité des eaux en laboratoire. Un appareil Titrino a été installé afin de procéder à l’analyse titrimétrique des eaux usées de l’usine pilEAUte, une StaRRE de traitement expérimentale de 12 m3 située sur le campus de l’Université Laval. L’eau usée de cette station provient d’une résidence étudiante du campus et de ses environs. L’eau pompée vers la station est stockée dans un bassin de 5 m3 avant d’être acheminée à un décanteur primaire. L’effluent du décanteur est alors envoyé vers deux chaînes de traitement biologique composées de cinq bioréacteurs chacune. Enfin, l’eau est acheminée vers deux décanteurs secondaires. Dans le cadre de ce projet, des campagnes de mesure ont été réalisées afin de comparer les données provenant de capteurs en ligne avec l’information extraite d’expériences de titrimétrie pour la mesure de la qualité des eaux usées de la station. Ces campagnes de mesure ont été réalisées en lien avec de projets menés avec des partenaires industriels. L’objectif de cette étude est d’évaluer l’efficacité des analyses de titrimétrie pour la mesure de la qualité de l’eau à l’affluent et à l’effluent d’une StaRRE. Les données extraites de la titrimétrie sont analysées de deux façons différentes: la modélisation de la capacité tampon de l’eau et la modélisation de l’équilibre chimique via le logiciel PHREEQC. Ces méthodes ont été mises en place, puis comparées sur la base de leur efficacité pour mesurer la concentration de certaines substances tampon présentes dans les eaux usées. Pour améliorer les estimations des modèles, des améliorations au protocole d’utilisation du Titrino ont été développées. Il a été déterminé que l’utilisation d’une couverture d’azote gazeux et le stripage du CO2 dissout dans les échantillons sont nécessaires à la réalisation de titrations fiables, et sont donc aussi nécessaires à la mesure de substances tampon autre que l’alcalinité, soit l’ammoniaque et les acides gras volatils (AGV). Afin de valider les résultats obtenus à l’aide du modèle de capacité tampon et afin d’obtenir une description complète de l’équilibre chimique des solutions analysées, un modèle de simulation de la procédure de titration a été développé avec le logiciel PHREEQC et l’interface PHREEQXCEL. Cet environnement de simulation a été supplémenté du solveur OpenSolver, un complément Excel à licence libre capable de réaliser les estimations de paramètres requises pour estimer la concentration de chaque espèce chimique présente dans les échantillons. De plus, la base de données de réactions chimiques de PHREEQC a été modifiée afin d’inclure toute l’information chimique nécessaire à la modélisation des spéciations se produisant dans les eaux usées. Après avoir proposé ces améliorations et avoir comparé les résultats des analyses de titration à des analyses chimiques conventionnelles, il a été déterminé que la titrimétrie est une alternative fiable pour la surveillance de la performance des procédés de récupération des nutriments des eaux usées.
The considerable rise of eutrophication in water bodies has led to highly instrumented water resource recovery facilities (WRRFs) that can perform nutrient removal processes. To ensure the efficiency of these processes, several parameters that influence the performance of WRRFs need to be well thought out. The latter requires monitoring strategies composed of on-line and off-line methods. Lately, on-line measurements have contributed significantly to monitor and characterize the quality of water and wastewater. However, on-line measurements are not applicable or not implemented yet for some specific areas. For this, off-line laboratory methods are welcome alternatives. Titrimetry is one of the examples of a low-cost off-line method that allows characterizing aquatic streams. Concerning titrimetric monitoring of wastewater, a Titrino device was installed in the laboratory of the 12 m3 pilEAUte WRRF located at Université Laval. The wastewater feeding the plant is coming from a student residence building on campus. The water pumped to the station is feeding a storage tank with a volume of 5 m3 , from which it is then pumped to a primary clarifier. The influent stream is then split into two similar treatment lines, composed of several bioreactors. These two lanes are followed by two secondary settling tanks. In this work, sampling campaigns were performed to compare the sensor data and the off-line titrimetric measurements in a framework of research projects in which industrial partners are involved. The goal of this study was to investigate the efficiency of using titrimetry to analyze and characterize influent and effluent samples of a WRRF. Two data interpretation methods, buffer capacity and PHREEQC, were tested and their performances in estimating the concentration of the concerned buffers were evaluated. For better model estimation, first, some of the lab procedures were improved. It was found out that nitrogen blanketing and CO2 stripping are necessary to perform reliable titration, and thus, to measure other concerned buffers besides alkalinity, such as ammonia and volatile fatty acids (VFA). Moreover, to validate the results of the buffer capacity model and to have a complete description of the equilibrium reactions of the chemical system under study, a titration simulation model was successfully built in PHREEQC with the PHREEQXCEL interface. This titration lab simulation was extended with the OpenSolver, an open-source Excel add-in, which allows to reliably perform the parameter estimation needed to find the concentration of the different species in the sample. In addition, PHREEQC’s database was modified to include all the model components and their essential chemical information for the speciation calculations.After introducing the mentioned lab and modelling improvements, the reliability of the titrimetric measurements for monitoring the performance of nutrient removal was enhanced.

L'arsenic est un élément toxique présent naturellement dans l'environnement. Parfois en fortes concentrations dans les eaux souterraines, utilisées comme eaux de boisson, il est responsable d'une des plus grandes mortalités au monde. Il est donc important de mieux comprendre les interactions de l'As avec l'environnement et son mode de transfert jusqu'aux aquifères. Cette thèse a pour objectif de comprendre les mécanismes de complexation direct et indirect de l'As(III) par la matière organique (MO) en milieu anoxique, notamment via les groupements thiols de la MO et sous forme de complexes ternaires faisant intervenir le Fe ionique. La première partie de ce travail a été consacrée à la complexation de l'As(III) par les groupements thiols de la MO. Des expériences de complexation d'As(III) par un acide humique (AH) naturel greffé ou non en sites thiols ont été réalisées. L'As(III) se complexe à la MO directement mais les concentrations complexées sont faibles et dépendantes de la densité en site thiol. La modélisation à l'aide de PHREEQC-Model VI modifié afin de tenir compte des sites thiols, a mis en évidence que l'As était complexé à la MO sous forme de complexes monodentates. Il existe, un autre mécanisme qui propose une complexation indirecte via la formation d'un pont cationique. Nous nous sommes intéressés ici, en conditions anoxiques, à la possibilité que ce pont soit un pont de Fe(II). Il n'existe cependant que très peu d'information sur la complexation du Fe(II) par la MO. Des expériences de complexation du Fe(II) par des substances humiques (SH) ont donc été réalisées. Les résultats expérimentaux ont montré que le Fe(II) est faiblement complexé aux SH lorsque le pH était acide et les groupements fonctionnels protonés. Au contraire à pH neutre à basique, 100% du Fe(II) est complexé aux SH. La modélisation a montré que le Fe(II) forme majoritairement des complexes bidentates carboxyliques à pH acides et des complexes bidentates carboxy-phénoliques et phénoliques à pH basiques. Dans la dernière partie, la complexation de l'As(III) par des complexes ternaires As(III)-Fe(II, III) ionique-MO a été testée. Les résultats expérimentaux ont montré que des complexes ternaires As(III)-Fe(II)-MO pouvaient se former en milieu anoxique. La modélisation a permis de tester différentes conformations structurales de complexes ternaires. Le complexe le plus probable est un complexe bidentate mononucléaire d'As(III) sur un complexe bidentate de Fe(II)-AH. Cependant, PHREEQC-Model VI doit être amélioré car la distribution des sites bidentate n'est pas réaliste en comparaison des données spectroscopiques. Au contraire pour de faibles concentrations en Fe(III), l'As(III) ne forme pas de complexes ternaires As(III)-Fe(III) ionique-MO. La spéciation de l'As et du Fe est particulièrement importante dans l'étude du transfert de l'As. Si l'As(III) est complexée à la MO, son transfert dépendra totalement des mécanismes de transfert de la MO
Arsenic occurs naturally in groundwater used as drinking water. It is thus responsible of a great mortality in the world. Understand the As interactions with its environment and its transfer mode to the aquifers is therefore crucial. This work was focused on the direct and indirect binding mechanisms of As(III) by organic matter (OM) in anoxic environments, in particular via OM thiol groups and as ternary complexes involving ionic Fe. The first part of this work was dedicated to the complexation of As(III) by the OM thiol. Binding experiments of As(III) by a humic acid (HA) grafted or not by thiol were thus performed. Grafted or not OM were able to bind As(III) but bound As(III) concentrations were low and dependant on the thiol site density. Modeling with PHREEQC-Model VI modified to take into account thiol site demonstrated that As(III) was bound as monodentate complexes to OM thiol sites. Another indirect binding mechanism involving ternary complex via cationic bridge was however described to explain larger binding of As(III, V) to natural OM. Here under anoxic conditions, we speculated that this bridge was an ionic Fe(II) bridge. However, little information exists about the binding of Fe(II) by OM. Complexation experiments of Fe(II) by humic substances (HS) were thus conducted. The experimental results showed that Fe(II) was weakly complexed to HS at acidic pH, when the functional groups were protonated. By contrast, at basic pH, 100% of Fe(II) were complexed to HS. Modeling calculations demonstrated that Fe(II) formed mainly carboxylic bidentate at acidic pH and carboxy-phenolic and phenolic bidentate at basic pH. In the last part, the complexation of As(III) as As(III)-ionic Fe(II, III)-OM ternary complexes was tested. Experimental results showed that As(III)-Fe(II)-OM ternary complexes could form in anoxic environments. Modeling allowed to test several ternary complexes conformations. The most potential was the binding of As(III) as mononuclear bidentate complex onto a bidentate Fe(II)-AH complex. However, another definition of the model that should be constrained by XAS data is required. By contrast, at low concentrations of Fe (III), when the oxidizing and reduced species coexist, As(III) does not form As(III)-ionic Fe(III)-OM ternary complexes. Speciation of As and Fe is particularly important in the study of the As(III) transfer. When As(III) is bound to OM as ternary complexes, its transfer is entirely controlled by the own OM transfer mechanisms. Here, we calculated, however, that much of As(III) remains as labile species and can therefore reach underlying aquifers as long as anoxic conditions exist

Dans les mois les plus pluvieux de l'année, les inondations provoquent souvent des dégâts importants, en particulier dans les grandes villes tropicales, comme au Brésil. Les Systèmes Compensatoires d'infiltration d'Eau de Pluie (SCIEP) ont été développés pour soutenir les systèmes classiques de macro et micro drainage, en accélérant l'infiltration et en minimisant le ruissellement. L’avantage de l’amélioration de l'infiltration des eaux pluviales, est associé à des inconvénients importants tels que des infiltrations rapides de polluants comme les métaux lourds qui sont connus pour être mobilisables par les eaux pluviales, notamment en zone urbaine, et peuvent donc s’infiltrer dans les sols urbains. La principale préoccupation concernant la mobilité de ces polluants est le risque de contamination des nappes phréatiques. La ville de Recife étant seulement quelques mètres au-dessus du niveau de la mer, les eaux souterraines sont peu profondes et sont largement exploitées à travers de nombreux puits. Cette ressource en eau potable facilement accessible est donc particulièrement vulnérable aux eaux de mauvaise qualité chimique, notamment en lien avec la présence de polluants inorganiques, très fréquents en zones urbaines à cause de la nature des matériaux de construction et des rejets des populations. Les métaux lourds tels que le zinc, le cuivre, le chrome ou encore le cadmium sont considérés comme polluants modèles représentatifs car ils sont souvent détectés en mélange et en concentrations importantes dans les eaux de ruissèlement. Afin d'évaluer la réactivité et la mobilité des métaux dans les urbains inondés, le comportement de ces trois métaux Zinc, le Chrome et le Cadmium a été étudié. La sorption de ces métaux a été étudiée sur 2 horizons d’un sol supportant un SCIEP : le sol de surface (0-20cm, SS) et le sol de profondeur (60-80cm, SP). Les deux sols varient en termes de composition et donc en termes de réactivité. En particulier, le sol SS a un taux de matière organique et une CEC plus élevé que le sol SP. Des isothermes d'adsorption ont été réalisées et modélisées avec le modèle de Langmuir, ainsi que des tests de transfert des métaux en colonnes de sol. Les effets de compétition des métaux pour les sites de sorption ont été étudiés en comparant les isothermes de sorption (i) des métaux Zn, Cr et Cd seuls (condition mono-métal MM), (ii) de 2 métaux combinés (DM : Zn[+Cd]; Zn[+Cr]; Cd[+Zn]; Cd[+Cr]; Cr[+Cd] e Cr[+Zn] et (iii) de trois métaux combinés (TM: Zn[+Cd+Cr]; Cd[+Zn+Cr] et Cr[+Cd+Zn]). Des phénomènes de compétition ont été observés entre le Cd et le Zn (augmentant ainsi leur mobilité) mais pas le chrome. En revanche le Cr a présenté une mobilité très forte dans les deux sols et surtout le sol de surface, pourtant plus réactif. Nos résultats montrent clairement le risque associé à la mobilisation de métaux entrainés par les eaux de ruissèlement et infiltrées dans les SCIEP
In the rainiest months of the year, floods often cause significant damage, especially in large tropical cities, such as in Brazil. Compensatory Rainwater Infiltration Systems (RWIS) have been developed to support conventional macro- and micro-drainage systems, accelerating infiltration and minimizing runoff. The advantage of improving rainwater infiltration is associated with significant disadvantages such as rapid infiltration of pollutants such as heavy metals which are known to be mobilized by rainwater, especially in urban areas, and can therefore infiltrate into urban soils. The main concern regarding the mobility of these pollutants is the risk of groundwater contamination. As the city of Recife is only a few metres above sea level, the groundwater is shallow and is largely exploited through numerous wells. This easily accessible drinking water resource is therefore particularly vulnerable to water of poor chemical quality, especially in connection with the presence of inorganic pollutants, which are very frequent in urban areas due to the nature of the construction materials and the population's discharges. Heavy metals such as zinc, copper, chromium and cadmium are considered as representative model pollutants because they are often detected in mixtures and in high concentrations in runoff water. In order to assess the reactivity and mobility of metals in flooded urban areas, the behaviour of the three metals Zinc, Chromium and Cadmium was studied. The sorption of these metals was studied on 2 horizons of a soil supporting a SCIEP: the surface soil (0-20cm, SS) and the deep soil (60-80cm, SP). The two soils vary in terms of composition and thus in terms of reactivity. In particular, the SS soil has a higher organic matter content and CEC than the SP soil. Adsorption isotherms were carried out and modelled with the Langmuir model, as well as soil column metal transfer tests. Metal competition effects for sorption sites were investigated by comparing the sorption isotherms of (i) Zn, Cr and Cd alone (single metal MM condition), (ii) 2 combined metals (DM : Zn[+Cd]; Zn[+Cr]; Cd[+Zn]; Cd[+Cr]; Cr[+Cd] and Cr[+Zn]; and (iii) three combined metals (TM: Zn[+Cd+Cr]; Cd[+Zn+Cr] and Cr[+Cd+Zn]). Competition was observed between Cd and Zn (thus increasing their mobility) but not chromium. On the other hand, Cr showed a very high mobility in both soils and especially in the surface soil, which is more reactive. Our results clearly show the risk associated with the mobilization of metals entrained by runoff water and infiltrated in SCIEP

This study evaluated SO4 2- removal from circumneutral mine water (CMW) collected from Middleburg coal mine using coal FA collected from Hendrina power station. The following parameters were investigated: the effect of the amount of FA, the effect of the final pH achieved during treatment, the effect of the initial pH of the mine water and the effect of Fe and Al on SO4 2- removal from mine water. The precipitation of ettringite at alkaline pH was evaluated to further reduce the SO4 2- concentration to below the DWAF limit for potable water. Removal of SO4 2- from mine water was found to be dependent on: the final pH achieved during treatment, the amount of FA used to treat the mine water and the presence of Fe and Al in the mine water. Treatment of CMW using different CMW:FA ratios
5:1, 4:1, 3:1, and 2:1 resulted in 55, 60, 70 and 71 % SO4 2- removal respectively. Treatment of CMW to pH 8.98, 9.88, 10.21, 10.96, 11.77 and 12.35 resulted in 6, 19, 37, 45, 63 and 71 % SO4 2- removal respectively. When the CMW was modified by adding Fe and Al by mixing with Navigation coal mine AMD and treated to pH 10, 93 % SO4 2- removal was observed. Further studies were done to evaluate the effects of Fe and Al separately. Treatment of simulated Fe containing AMD (Fe-AMD) to pH 9.54, 10.2, 11.8, and 12.1 resulted in 47, 52, 65, and 68 % SO4 2- removal respectively. When Al containing AMD was treated to pH 9.46, 10.3, 11.5 and 12 percentage SO4 2- removal of 39, 51, 55 and 67 % was observed respectively.

It is important to understand the processes that regulate phosphorus (P) fluxes to coastal environments, because P is an important nutrient in coastal ecosystems. Phosphorus adsorbs to the surface of minerals in sediment and bedrock, and an influx of seawater can cause some of that P to desorb, raising the P concentration of ambient water. Although seawater-induced P desorption is thought to be an important source of P to coastal environments, the chemical reactions that underlie it have not been established. Previous work provides some relevant surface reactions and associated affinity constants between various aqueous P species and the surface of calcite and in dilute calcium carbonate-P solutions. However, these reactions with their respective affinity constants from the literature fail to predict the behavior of P with calcite in seawater. In this study, we conducted a series of batch experiments involving both adsorption and desorption of P in seawater, freshwater, dilute seawater, and mixtures of seawater and freshwater. We used these results in the geochemical model PHREEQC and the parameter estimation model PEST to optimize the affinity constants for the existing surface reactions. We found that after making minor adjustments to the affinity constants, the existing surface complexation models of calcite surface reactions from the published literature are sufficient to explain seawater-induced P desorption. Specifically, our results suggest that CaPO4- and either CaHPO40 or HPO42- may be important species in the P adsorption/desorption reactions in freshwater-seawater mixing.

The objective of the work described in this thesis was to understand sorption reactions of uranium occurring at the water-clay mineral interfaces in the presence and absence of arsenic and other inorganic ligands. Uranium(VI) removal by clay minerals is influenced by a large number of factors including: type of clay mineral, pH, ionic strength, partial pressure of CO2, load of the sorbent, total amount of U present, and the presence of arsenate and other inorganic ligands such as sulfate, carbonate, and phosphate. Both sulfate and carbonate reduced uranium sorption onto IBECO bentonite due to the competition between SO42- or CO32- ions and the uranyl ion for sorption sites, or the formation of uranyl-sulfate or uranyl-carbonate complexes. Phosphate is a successful ligand to promote U(VI) removal from the aqueous solution through formation of ternary surface complexes with a surface site of bentonite. In terms of the type of clay mineral used, KGa-1b and KGa-2 kaolinites showed much greater uranium sorption than the other clay minerals (STx-1b, SWy-2, and IBECO montmorillonites) due to more aluminol sites available, which have higher affinity toward uranium than silanol sites. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. A multisite layer surface complexation model was able to account for U uptake on different clay minerals under a wide range of experimental conditions. The model involved eight surface reactions binding to aluminol and silanol edge sites of montmorillonite and to aluminol and titanol surface sites of kaolinite, respectively. The sorption constants were determined from the experimental data by using the parameter estimation code PEST together with PHREEQC. The PEST- PHREEQC approach indicated an extremely powerful tool compared to FITEQL. In column experiments, U(VI) was also significantly retarded due to adsorptive interaction with the porous media, requiring hundreds of pore volumes to achieve breakthrough. Concerning the U(VI) desorption, columns packed with STx-1b and SWy-2 exhibited irreversible sorption, whereas columns packed with KGa-1b and KGa-2 demonstrated slow, but complete desorption. Furthermore, most phenomena observed in batch experiments were recognized in the column experiments, too. The affinity of uranium to clay minerals was higher than that of arsenate. In systems containing uranium and arsenate, the period required to achieve the breakthrough in all columns was significantly longer when the solution was adjusted to pH 6, due to the formation of the uranyl-arsenate complex. In contrast, when pH was adjusted to 3, competitive sorption for U(VI) and As(V) accelerated the breakthrough for both elements. Finally, experiments without sorbing material conducted for higher concentrations of uranium and arsenic showed no loss of total arsenic and uranium in non-filtered samples. In contrast, significant loss was observed after filtration probably indicating the precipitation of a U/As 1:1 phase.

This study was made to increase the understanding of how heavy metals in the aqueous phase are removed at low initial concentrations in different pH and Eh values. The reaction that has been studied is mainly hydroxide precipitation and adsorption in a condensate treatment. In the study, data from one of Vattenfalls waste incinerators was analysed and the results from the data were then compared to previous studies. To increase the understanding, modelling of the heavy metals behaviour in the given concentrations was then made with Medusa and PHREEQC. The heavy metals that were analysed were Sb, As, Pb, Zn, Cr, and Cd. The low initial concentration that vary between 36.1-23600 μg/l complicates the removal process because it corresponds in a low driving force and the results are hard to compare to other studies since the initial concentrations vary between 10-100 mg/l. From the modelling and the measurement data it can be seen that Pb, Zn, Cr, and Cd was removed by hydroxide precipitation at pH 10. According to the speciation calculations, the dominant species at this pH are Pb(OH) 2 , Cd(OH)2, Zn(OH)2 and Cr(OH)3. For arsenic a clear conclusion could not be drawn from the modelling and the measurement data because of low precision. Due to the limited thermodynamic parameters of antimony in comparison with other heavy metals in the database of Medusa and PHREEQC, the modelling of antimony behaviour in condensate treatment has relatively larger uncertainty is low. The modelling results show that the main species in acidic solutions for antimony is Sb(OH)3 and in basic solutions Sb(OH)-6. Further investigation for antimony in needed for a clear conclusions to be drawn

The primary aim of these coal fired industries for co-disposing fly ash and brine was to use the fly ash as a sustainable salt sink. It is therefore important to study the interaction chemistry of the fly ash-brine systems to fully understand the leaching and mobility of the contaminant species, and to determine the possibility of capturing the salts from the brine solution when fly ash and brine are co-disposed. In order to achieve the aims and objectives of this study, several leaching procedures such as batch reaction tests, long-term fly ash-brine interaction tests, acid neutralization capacity (ANC) tests, up-flow percolation tests and sequential extraction tests were employed. The geochemical modeling software was applied to predict the formation of secondary mineral phases controlling the release of species in the fly ash-brine systems. Several analytical techniques such as x-ray diffraction (XRD), x-ray fluorescence (XRF), scanning electron microscopy-energy dispersion spectroscopy (SEM-EDS), inductively coupled plasma-mass spectroscopy (ICP-MS) and ion chromatography (IC) were applied to characterize the fresh fly ashes, solid residues recovered from the fly ash-brine interaction tests, the brine sample used in this study and the leachate samples in order to determine the chemical and mineralogical compositions and speciation of the waste materials.

In my thesis work, 0D geochemical numerical models were implemented in order to qualitatively and quantitatively understand the results of a set of experiments obtained from a physical model, to simulate the concretion effects on high enthalpy geothermal wells. In particular a set of flow-through simulation results based on the physical model were used to reproduce the precipitation of metallic copper resulting from steel corrosion in a geothermal production well positioned at Groß Schönebeck, Germany. The numerical models were implemented with PHREEQC hydrogeochemical simulator (Appelo and Parkhurst, 1999). Although the predications obtained from the numerical simulations have not systematically matched the experimental data obtained by physical model, nevertheless, very useful information on the behaviours of these kind of processes has been obtained. Now this useful information is used at the German Research Center for Geosciences (GFZ) in Potsdam to develop more accurate new research lines.

Mercury (Hg) is a global contaminant of ecosystems and human health risk, with complicated biogeochemical processes. Mercury sulfide (HgS) dissolution has been suggested as a key process in Hg cycling, as it could potentially increase the pool of inorganic Hg (iHg) for the production of methylmercury (MeHg). Despite previous sporadic observations of enhanced HgS dissolution under certain conditions, much remains unclear on mechanisms of HgS dissolution. The objective of my research was to advance the mechanistic understanding of HgS dissolution, concerning re-adsorption of released Hg, effects of thiol-ligands, and Hg speciation. Considering the lack of feasible techniques to differentiate dissolution and re-adsorption processes, I first developed an efficient method using isotope tracer and isotope dilution techniques to investigate the re-adsorption of released Hg during HgS dissolution. The HgS dissolution rate with consideration of re-adsorption was two times the rate calculated from detecting Hg alone in the presence of O2, indicating the importance of Hg re-adsorption during HgS dissolution. I further examined the role of Hg-ligand complexation in HgS dissolution and Hg(II) re-adsorption using a thermodynamic adsorption method, selecting L-cysteine (Cys) as a model compound for low molecular weight ligands and Waskish fulvic acid (FA) for natural dissolved organic matter (DOM). My results suggest that the presence of Cys enhanced HgS dissolution through the decreased re-adsorption of Hg-Cys complex, whereas Waskish FA inhibited HgS dissolution, possibly because of the adsorption of FA on HgS surface that covered dissolution sites. I further employed a geochemical modeling method to study Hg speciation and the relation of iHg speciation to MeHg, aiming to provide a methodological example for potentially evaluating the implications of Hg species distribution during HgS dissolution on MeHg production. I applied geochemical model PHREEQC to the Florida Everglades, a well-studied wetland with model input parameters available, to determine the distribution of iHg in surface water at different sites. The modeling results suggest that sulfide and DOM govern iHg speciation, and the Hg-sulfide and Hg-DOM species are related to MeHg in environmental media but not fish, suggesting the importance of iHg speciation in MeHg production and the complexity of Hg bioaccumulation.

Variable groundwater quality in complex aquifer-aquitard systems presents a challenge for sustainable groundwater development. In the Lower Murrumbidgee alluvial fan of the Murray-Darling Basin in semi arid inland Australia, shallow groundwater is saline (12000 µ S/cm) and locally contaminated by nitrate. Deep fresh aquifers (150 µ S/cm), developed as an irrigation water supply, were thought to be protected from downwards leakage by laterally extensive aquitards. However, hydrochemical sampling, augmented by historic data, revealed that aquifer salinisation (400 to 4000 µ S/cm) had occurred at some sites to 50 m depth since the mid 1980s. Aquitard windows, landscape depositional features at a scale of 10s to 100s of metres which are rarely detected by conventional investigations, were proposed as conduits for rapid downwards leakage in stressed systems. Intensive research was conducted at the Tubbo site where downhole geophysical logging and minimally disturbed cores were used to describe a saline clayey silt to 15m depth, an indurated clayey sand and 2 deep deposits of hard clayey silt. Fracturing was inferred by the scale dependency of aquitard permeability (Kv 10E-11 to 10E-6 m/s). Lithological variation near the surface was delineated by electrical imaging which revealed a 40m wide aquitard window beneath a veneer of smectite clay. Intensive monitoring of groundwater pressures in six piezometers (23-96 m depth) near the Tubbo irrigation bore and two other peizometers upgradient, indicated that the indurated clayey sand formed an effective hydraulic barrier but the deep silty deposits were spatially discontinuous. Groundwater samples were collected before, three times during, and after the 1998-99 irrigation season. A large, but delayed TDS increase occurred in the shallow aquifer and small pulses of saline water were sustained in the middle aquifer but shortlived in the deep aquifer. Hydrochemical and isotopic data dC-13, dH-2, dO-18, C-14 and H-3) showed the middle aquifer mixing with the deep aquifer, though retaining the signature of a palaeowater. Hydrochemical changes were accounted for with PHREEQC inverse mass balance models for the shallow aquifer. Mixing of aquifer water with 20-70% saline porewater from the upper aquitard occurred, together with ion exchange and NaCl dissolution. Based on an axisymmetric radial FEFLOW model, 5-30% of the volume pumped was accounted for by vertical leakage from the middle aquifer. Leakage from the shallow aquifer was small but significant, as it allowed high salinity water to migrate. Permeability and compressible storage measurements (Ss 10E-5 to 10E-4 /m) were used to constrain model calibration, and to show that direct mixing occurred mainly via aquitard windows at depth, and between the shallow and middle aquifers via leaky boreholes. Fracture flow and aquifer-aquitard interaction by diffusion were of secondary importance.

Uganda is well endowed with economic quantities of mineral salts present in the interstitial brines and evaporite deposits of Lake Katwe, a closed (endorheic) saline lake located in the western branch of the great East African rift valley. Currently, rudimentally and artisanal methods continue to be used for salt extraction from the lake raw materials. These have proved to be risky and unsustainable to the salt miners and the environment and they have a low productivity and poor product quality. This work involves the investigation of the salt raw materials that naturally occur in the brines and evaporites of Lake Katwe. The purpose is to propose strategies for the extraction of improved salt products for the domestic and commercial industry in Uganda. The literature concerning the occurrence of salt and the most common available technologies for salt extraction was documented. Also, field investigations were undertaken to characterize the salt lake deposits and to assess the salt processing methods and practices. The mineral salt raw materials (brines and evaporites) were characterized to assess their quality in terms of the physical, chemical, mineralogical, and morphological composition through field and laboratory analyses. An evaluation of the potential of future sustainable salt extraction from the lake deposits was done through field, experimental, and modeling methods. Moreover, the mineral solubilities in the lake brine systems and dissolution kinetics aspects were investigated. The results reveal that the salt lake raw materials contain substantial amounts of salt, which can be commercialized to enable an optimum production. The brines are highly alkaline and rich in Na+, K+, Cl-, SO42-, CO32-, and HCO3-. Moreover, they contain trace amounts of Mg2+, Ca2+, Br-, and F-. The lake is hydro-chemically of a carbonate type with the brines showing an intermediate transition between Na-Cl and Na-HCO3 water types. Also, the evaporation-crystallization is the main mechanism controlling the lake brine chemistry. These evaporites are composed of halite mixed with other salts such as hanksite, burkeite, trona etc, but with a composition that varies considerably within the same grades. The laboratory isothermal extraction experiments indicate that various types of economic salts such as thenardite, anhydrite, mirabilite, burkeite, hanksite, gypsum, trona, halite, nahcolite, soda ash, and thermonatrite exist in the brine of Lake Katwe. In addition, the salts were found to crystallize in the following the sequence: sulfates, chlorides, and carbonates. A combination of results from the Pitzer’s ion-interaction model in PHREEQC and experimental data provided a valuable insight into the thermodynamic conditions of the brine and the sequence of salt precipitation during an isothermal evaporation. A good agreement between the theoretical and experimental results of the mineral solubilities in the lake brine systems was observed with an average deviation ranging between 8-28%. The understanding of the mineral solubility and sequence of salt precipitation from the brine helps to control its evolution during concentration. Hence, it will lead to an improved operating design scheme of the current extraction processes. The dissolution rate of the salt raw materials was found to increase with an increased temperature, agitation speed and to decrease with an increased particle size and solid-to-liquid ratio. Moreover, the Avrami model provided the best agreement with the obtained experimental data (R2 = 0.9127-0.9731). In addition, the dissolution process was found to be controlled by a diffusion mechanism, with an activation energy of 33.3 kJ/mol. Under natural field conditions, the evaporative-crystallization process at Lake Katwe is influenced by in-situ weather conditions. Especially, the depth of the brine layer in the salt pans and the temperature play a significant role on the brine evaporation rates. With the optimal use of solar energy, it was established that the brine evaporation flux can be speeded up in the salt pans, which could increase the production rates. Moreover, recrystallization can be a viable technique to improve the salt product purity. Overall, it is believed that the current work provides useful information on how to exploit the mineral salts from the salt lake resources in the future.

QC 20151217

Les doublets géothermiques sur aquifères superficiels jouent un rôle important en France pour le chauffage, le rafraichissement et la production d’eau chaude sanitaire des bâtiments. La pérennité de ces installations est cependant conditionnée par la possibilité de pouvoir garantir dans le temps la production puis la réinjection de l’eau souterraine. Le colmatage de la boucle géothermale est un problème majeur qui affecte de nombreuses installations sur l’ensemble du territoire français et remet en cause leur viabilité technico-économique. La compréhension et la prédiction de ce phénomène nécessite de nouveaux moyens de caractérisation et de modélisation des processus biogéochimiques couplés au fonctionnement des boucles géothermales dans des environnements de subsurface hétérogènes. Cette thèse a ainsi fait l’objet d’une nouvelle collaboration entre le laboratoire Géosciences Rennes et l’entreprise Antea group pour identifier les mécanismes à l’origine de ces phénomènes de colmatage et d’en caractériser les paramètres influents dans le but de construire un outil d’analyse des risques permettant l’anticipation de ces processus de colmatage. Le premier volet de la thèse expose la synthèse des typologies de colmatage (biogéochimique, chimique, biologique et physique). Cette synthèse est issue de l’étude de la littérature sur la problématique de colmatage des forages d’eau et des retours d’expérience concernant les doublets géothermiques recensés et étudiés durant cette thèse. Le second volet présente les inventaires régionaux des problématiques de colmatage recensées en France dans différents contextes hydrogéologiques. Ces inventaires ont permis de délivrer un état des lieux à grande échelle de la problématique de colmatage et d’étudier les contextes associés à chaque type de colmatage. Dans le troisième volet, de nouvelles méthodologies de caractérisation in-situ des phénomènes de colmatage biogéochimique liés à l’oxydation du manganèse et du fer sont présentées. Elles ont été développées dans le cadre de ces travaux de thèse à partir des investigations menées sur différents sites confrontés à des problèmes d’exploitation. Ces méthodologies d’investigations pluridisciplinaires couplent la mesure des propriétés hydrauliques, des concentrations en éléments chimiques et de la diversité microbienne afin d’identifier la problématique impactant le fonctionnement de l’installation et d’en définir in fine les causes. Le quatrième volet expose les résultats d’une campagne de terrain effectuée sur un doublet géothermique impacté par un processus de colmatage biogéochimique. Cette campagne a permis d’identifier les composantes clés de la réactivité biochimique impliquée dans le colmatage : distribution du flux, hétérogénéité chimique et diversité microbiologique. A l’aide du code de calcul PHREEQC, un modèle géochimique simulant les cinétiques de précipitation observées a été développé. Il permet l’étude quantitative des mécanismes biogéochimiques favorisant l’apparition rapide du colmatage. Enfin, les retours d’expériences de l’exploitation des doublets sur nappes superficielles ont démontré le besoin d’une méthodologie fiable d’analyse des risques, permettant d’anticiper l’apparition des processus de colmatage à chaque étape de la vie du projet. Ainsi, à partir de la synthèse de la littérature scientifique et technique et des conclusions des études menées durant cette thèse, les facteurs de risques d’apparition des phénomènes de colmatage ont été déterminés. L’analyse des risques de colmatage intégrant ces différents facteurs a été implémentée à travers l’élaboration de méthodes développées sous Python 3. L’outil ARCADE (Analyse des Risques de Colmatage et Aide à la Décision) a été conçu d’une part pour évaluer le risque et d’autre part pour informer l’utilisateur averti des bonnes pratiques et moyens préventifs. Ces bonnes pratiques d’analyse et de gestion préventive sont présentées dans le dernier volet de cette thèse
The sustainability of geothermal systems using shallow aquifers for heating, cooling and hot water production depends on the possibility to ensure, over long time-scales, the production and the reinjection of groundwater in the aquifer. Clogging of the geothermal loop is a major issue affecting the technical and economic viabilities of numerous operations in France. The understanding and prediction of this phenomenon requires new methods of characterization and modelling of biogeochemical processes coupled to the operation of geothermal loops in heterogeneous subsurface environments. This thesis is thus the result of a new collaboration between the Géosciences Rennes lab and Antea group to identify the mechanisms at the origin of clogging phenomena and characterize their controlling parameters, in order to establish a risk assessment tool allowing the anticipation of clogging processes. The first part of the thesis describes the main clogging processes (biogeochemical, chemical, biological and physical). This synthesis is the result of (1) the study of the literature dealing with the clogging of water wells and (2) our feedbacks on the geothermal doublets identified and studied during this thesis. The second part presents the regional inventories of shallow geothermal systems impacted by clogging problems identified in different hydrogeological contexts in France. These inventories provide a large-scale perspective of clogging phenomena and allow to study the contexts associated with each type of clogging processes. In the third part, new methodologies for the in-situ characterization of biogeochemical clogging phenomena linked to manganese and iron oxidation are presented through case studies of sites affected by clogging issues. These interdisciplinary studies couple the measurement of hydraulic properties, chemical element concentrations and bacterial diversity, to identify the specific issue impacting the operation and to define its causes. The fourth part presents the results of an interdisciplinary field campaign carried out on a geothermal doublet impacted by a biogeochemical clogging process. This campaign documented the key components involved in mixing induced biogeochemical reactivity: flow distribution, chemical heterogeneity and microbiological diversity. Using PHREEQC, a geochemical model simulating observed kinetics of precipitation was developed in order to quantitatively explore the biogeochemical mechanisms favoring rapid clogging. Feedback from shallow geothermal systems operation has demonstrated the need for a reliable risk analysis methodology that allowed to anticipate the apparition of clogging processes at each stage of the project life (part 5). From the synthesis of the scientific & technical literature and the conclusions of the studies carried out during this thesis, the risk factors for the appearance of clogging phenomena were determined. A clogging risk analysis integrating these factors was implemented through the development of methods developed under Python 3. The methodology of the ARCADE tool (Analyse des Risques de Colmatage et Aide à la Décision) is designed to assess the risk and to inform users of good practices and preventive methods. These good practices for analysis and preventive methods are presented in the last part of this thesis

Impacts from mining waste deposits on groundwater resources have been recognized invarious parts of the world; though varied in scale depending on the composition of mineralsbeing mined, the level of technology employed and environmental commitment of thedevelopers. Mining activities usually involve milling, concentrating, and processing of oreswhich will result in a huge amount of waste, called tailings, usually deposited inimpoundments as a slurry, composed of fine grained geological material (uneconomicalminerals), chemicals utilized in the processs, and water. Oxidation of these deposits, usuallycontaining sulphide minerals, may result in generation of an acidic, metal laden leachate,callled Acid Mine Drainage (AMD), which may have a devastating impact on thesurrounding groundwater resources. In this study, the stochastic LaSAR-PHREEQC reactive transport modeling approach is usedin order to evaluate the coupled effect of geochemical reactions and physical heterogeneity ofthe subsurface in the breakthrough of acidity and metal downstream of the source while theAMD transported in the water saturated zone of an impoundment. The tailings depositcalled Impoundment 1 at the Kristineberg mining site at the Skellefteå field, in northernSweden, is used as a case study to simulate pH buffering processes and attenuation of Zn.The objectives of the study are 1) to evaluate the relevance of different possible geochemicalprocesses in pH buffering and Zn attenuation; 2) to evaluate the effect of spatial variability ofthe physical processes of the groundwater system on the breakthrough of contaminants; and3) to evaluate the effect of the location and distribution of the source zone in terms of thedistance from the impoundment boundary. Simulation results of the presented model revealed that pH buffering from calcite andchlorite are important processes capable of counteracting the acidification from AMD.Dissolution of secondary Al(OH)3(s) is another important process capable of buffering pH.Precipitation of smithsonite, ZnCO3, is an important process for attenuation of Zn2+.Moreover, sorption of Zn2+ on ferric iron surfaces is found to be an important process forattenuation of the metal, depending on the available sorption surface sites. Flow variabilityhighly affects the breakthrough of the contaminants such that with increasing subsurfaceheterogeneity, earlier breakthrough of contaminants occurs. Moreover, increased variabilityresults in decreased peak loads, but longer duration of the load.
www.ima.kth.se

Mining of lignite in Lusatia has a long history of over 100 years. The extracted brown coal is utilized to generate electricity in three large power plants: Jänschwalde, Boxberg, and Schwarze Pumpe. With an annual carbon dioxide (CO2) output of approximately 50 million tons, these power plants are among Germany’s large-scale CO2 emitters. The environmental impact from open-pit mining is of a considerable degree and currently poses a challenging problem. The groundwater deficit in 1990 was 7 billion m3 over a surface area of approximately 2100 km2 (Luckner, 2006a) and was bisected in value until today. Due to the decline of mining activity and the termination of mine drainage at most open pits in the Lusatian region, the groundwater table has recovered forming 28 pit lakes (Zschiedrich, 2011). The majority of the post mining lakes do not meet the quality standards for pH, iron or sulfate parameters; because of pyrite oxidation that produces acid mine drainage (Luckner, 2006b, Klapper and Schultze, 1995, Schultze et al., 2010). The post mining lakes in Lusatia have low pH values (3 – 4), high sulfate contents (up to 2800 ppm) as well as high iron concentrations (100 – 150 ppm). Lakes are flooded by groundwater and using surface water from Spree and Neisse River to achieve fast filling and dilution; however, due to the limited availability of surface water, further rehabilitation strategies for the region had to be investigated. Between 1970 and 1990, approximately 26 million m3 of suspended fly ash were deposited in the lake Burghammer and settled as an ash body at its base; where it may be used for rehabilitation. In a first experiment conducted in 2001 material from the ash body was picked up and redistributed throughout the lake. By this treatment the pH of the lake was raised temporarily; however, a sustainable remediation was not achieved. Based on these experiments it was investigated whether the ash reacts more sufficiently through additional CO2 injection or not. Aim was to combine the rehabilitation of acid mine lakes with the utilization of atmospheric carbon dioxide emissions from coal-fired power plants. The CO2 sequestration is achieved through the generation and accumulation of carbonates in the lake. The following equations describe the precipitation of carbonate by using CO2 and alkaline earth cations M: CO2 + MO → MCO3 (s) CO2 + M(OH)2 → MCO3 (s) + H2O Therefore, neutral pH conditions are necessary for the long-term accumulation of carbonates in the lakes. In laboratory investigations it was shown, that the 20 to 30 years old fly ash deposits of lake Burghammer can be used for carbonate sequestration and lake water treatment. Bivalent ions (Ca2+, Mg2+) are eluable and available for carbonate precipitation; on average we assumed 1 wt.-% of reactive calcium to be contained in the settled ash sediments. Settled fly ash sediments are less reactive than fresh fly ash from a power plant (e.g. Schwarze Pumpe). During batch experiments, we increased the buffering capacity to maximum values of 7 mmol/L. Beforehand no buffering capacity exists due to the low pH of 2.9 in the lake. Batch investigations provided a sequestration potential of 17 g CO2/kg ash sediment; in comparison fresh fly ash results in a sequestration potential of 33 g CO2/kg ash (Schipek and Merkel, 2008b, Schipek and Merkel, 2008a, Schipek, 2009). Based on the laboratory results a field experiment was conducted. In this field experiment gas injection lances were installed to a sediment depth of 12 m. Gaseous CO2 was applied with a pressure of 2.2 bar and 2.2 m³/h for 3 months and lake water was monitored during injection. Variations in total inorganic carbon due to diffusion processes of CO2 saturated pore waters could be observed. As the pilot experiment comprised only a small area of lake Burghammer no initial neutralisition (e.g. by a suction excavator) was possible. Thus, no further changes in water chemistry were observed. Drilling cores in the vicinity of the injection area provided mineralogical and geochemical conditions before and after CO2 treatment. No trace metal mobilization was found during CO2 injection. Most elements showed decreasing trends or didn’t change significantly. Calculated saturation indices for calcite indicated equilibrium conditions or slightly oversaturated conditions (SICalcite,average +0.12; SICalcite,median +0.31). Geochemical and mineralogical investigations proved that CO2 sequestration is possible with an average precipitation rate of 0.5 wt.-% (2.2 g CO2/kg). The maximum rate for carbonate precipitation was determined with 7.4 wt.-% Calcite, according to 32.6 g CO2 per kilogram treated ash. Besides the use of the settled fly ash as neutralizing agent in acidic mining lakes, laboratory and field investigations were conducted in order to improve in-lake liming. In batch and columns experiments, different liming agents (synthetic marble powder and industrial products) were tested and investigated. Significant differences in reactivity were obvious at pCO2 > 3.8 • 10-4 atm. Ions typical for acid mine drainage (e.g. Mn2+, Cd2+, SO42-) do have different effects on the kinetic of carbonate dissolution. Manganese concentrations typical for acidic mining lakes inhibit calcite dissolution. Cadmium has as well a significant influence on dissolution and kinetics. Only circa 50 % of the calcium concentration was reached with cadmium as inhibitor compared to the dissolution in pure water. Increased CO2 partial pressure might be used to compensate inhibtion by material impurities and/or water constituents. Column experiments showed that a multi-stage application of liming agent increases the efficiency of a lake treatment. The combination of a first application of calcite (up to pH 4.5) and further application of Ca(OH)2 seemed to be the most promising method. This treatment sheme was successfully applied in lake Burghammer from March 2009 – December 2010 (initial neutralisation and 6 follow-up treatments). Finally, it can be concluded, that in lignite mining districts in-lake treatment of acidic mining lakes is a seminal method to handle water quality problems. Using gaseous CO2 in combination with industrial by-products can be accounted as sustainable method for CO2 sequestration and for treatment of AMD. The advantage for mining areas lays in the prevention during treatment of acid mine lakes. Nevertheless, this method presents only a niche solution due to the dependence on alkaline materials, e.g. fly ash. The development of further strategies and optimization during lake water treatment by in-lake liming might improve the effectiveness of the method. Using calcite instead of NaOH or CaO as liming agent will provide advantages in being more economic and ecological (CO2 bilance). In order to enhance efficiency the use of calcite in combination with CO2 can be a worth considering suggesting. If meteorological parameters (wind) and lake specific characteristics (morphology, currents, etc.) will be considered efforts and costs for in-lake liming will be minimized
Der Abbau von Braunkohle im Lausitzer Bergbaurevier hat seit über 100 Jahren Tradition. Die abgebaute Braunkohle wird dabei hauptsächliche zur Energieerzeugung in den drei großen Kraftwerken Jänschwalde, Boxberg und Schwarze Pumpe genutzt. Mit einem jährlichen Kohlenstoffdioxid (CO2) – Ausstoß von circa 50 Millionen Tonnen gehören diese Kraftwerke zu Deutschlands größten CO2-Emittenten. Der Einfluss auf die Umwelt durch Tagebau-Betrieb ist von beträchtlichem Ausmaß und bringt große Probleme mit sich. Im Jahr 1990 betrug das Grundwasser-Defizit im Lausitzer Bergbaurevier 7 Milliarden m³ auf einer Fläche von circa 2100 km² (Luckner, 2006a). Dieses Defizit hat sich bis zum heutigen Zeitpunkt halbiert. Durch den Rückgang der Bergbauaktivitäten und die Beendigung der Wasserhaltungsmaßnahmen in den meisten Tagebauen, hat der ansteigende Grundwasserspiegel 28 Tagebaufolgeseen geschaffen (Zschiedrich, 2011). Der überwiegende Teil der Tagebaufolgeseen ist aufgrund der Pyritoxidation, welche AMD (acid mine drainage) produziert, hinsichtlich der Wasserqualitätsparameter stark beeinflusst (Luckner, 2006b, Klapper and Schultze, 1995, Schultze et al., 2010). Die Tagebaufolgeseen im Lausitzer Bergbaurevier sind durch niedrige pH-Werte (3 – 4), hoche Sulfat-Konzentrationen (bis zu 2800 ppm) und hohe Eisengehalte (100 – 150 ppm) gekennzeichnet. Die entstehenden Seen sind hauptsächlich durch aufsteigendes Grundwasser und Oberflächenwasser aus den Flüssen Spree und Neisse geflutet. Aufgrund der geringen Verfügbarkeit von Oberflächenwasser mussten weitere Sanierungsmaßnahmen für die Region untersucht werden. Zwischen 1970 und 1990 wurden im Tagebaufolgesee Burghammer circa 26 Millionen m³ Flugasche-Suspension als Aschekörper abgelagert, wobei eine Nutzung zu Sanierungszwecken angedacht war. Im Rahmen einer Aschesedimentumlagerung im Jahr 2001 wurde der pH-Wert des Seewassers kurzzeitig angehoben, eine nachhaltige Sanierung fand jedoch nicht statt. Auf Grundlage dieser Ergebnisse wurde im Rahmen dieser Dissertation untersucht, ob die abgelagerten Aschesedimente nachhaltiger durch Einsatz von CO2 reagieren. Ziel war es die Sanierung von Tagebaufolgeseen mit der Reduktion von CO2-Emissionen aus Kohlekraftwerken zu kombinieren. Diese CO2-Sequestrierung sollte durch die Bildung und Ablagerung von Carbonaten im Seesediment erfolgen. Die Gleichungen (1) und (2) beschreiben dabei die Fällungsreaktion von Carbonaten aus CO2 mit dem Alkalimetall M (aus Oxiden bzw. Hydroxiden): CO2 + MO → MCO3 (s) CO2 + M(OH)2 → MCO3 (s) + H2O Zur Carbonatfällung und nachhaltigen Ablagerung sind neutrale pH-Bedingungen notwendig. In Laboruntersuchungen konnte gezeigt werden, dass die 20 bis 30 Jahre alten Flugaschesedimente zur CO2-Sequestrierung in Kombination mit Seewasserbehandlung genutzt werden können. Zweiwertige Ionen (Ca2+, Mg2+) sind aus den Aschesedimenten eluierbar und stehen für die Fällungsreaktion zur Verfügung. Durchschnittlich 1 Masse-% reaktives Calcium befindet sich in den Sedimenten. Die abgelagerten Aschesedimente sind dabei weniger reaktiv als frische Flugaschen aus Kohlekraftwerken (z.B. Schwarze Pumpe). In Batch-Versuchen mit Tagebaufolgesee-Wasser konnte die Säure-Pufferkapazität auf maximal 7 mmol/L erhöht werden. Sequestrierungs-Raten von 17 g CO2/kg Aschesediment wurden im Rahmen der Versuche erreicht. Im Vergleich dazu betrugen die Sequestrierungs-Raten in Versuchen mit frischen Flugaschen bis 33 g CO2/kg Asche (Schipek and Merkel, 2008b, Schipek and Merkel, 2008a, Schipek, 2009). Auf Grundlage dieser Laborergebnisse wurde ein Feldversuch im Tagebaufolgesee Burghammer geplant. Während diesem wurden Gasinjektionslanzen bis in eine Sedimenttiefe von 12 m im abgelagerten Aschesediment installiert. Gasförmiges CO2 wurde mit einem durchschnittlichen Druck von 2.2 bar und 2.2 m³/h für eine Dauer von 3 Monaten injiziert. Während dieser Zeit fand ein kontinuierliches Monitoring des Seewassers im Bereich der Injektion statt. Veränderungen des Gehaltes an TIC (total inorganic carbon) aufgrund von Diffusionprozessen von CO2-gesättigtem Porenwasser aus dem Aschekörper waren beobachtbar. Da der Feldversuch nur in einem begrenzten Bereich des Tagebaufolgesees Burghammer stattfand und keine Initialneutralisierung vorsah, konnten keine weiteren, großmaßstäblichen Veränderungen im Wasserkörper festgestellt werden. Bohrkernentnahmen im Umfeld des Behandlungsgebietes lieferten Aussagen bezüglich der mineralogischen und geochemischen Beschaffenheit vor und nach CO2-Injektion. Im Porenwasser wurde keine Spurenmetall-(re)-mobilisierung durch die Behandlung mit CO2 festgestellt. Nahezu alle Elemente zeigten einen abnehmenden Trend durch die Behandlung mit CO2, bzw. keine signifikanten Veränderungen. Modellierte Sättigungsindizes für Calcit wiesen auf Gleichgewichtsbedingungen oder leichte Übersättigung bzgl. Calcit hin (SICalcit, Mittelwert +0.12; SICalcit, Median +0.31). Geochemische und mineralogische Untersuchungen zeigten, daß CO2-Sequestrierung mit einer durchschnittlichen Fällungsrate von 0.5 Masse-% (2.2 g CO2/kg Aschesediment) erreicht wurde. Die maximale Fällungsrate wurde mit 7.4 Masse-% Calcit bestimmt, dies entspricht einer Festlegung von 32.6 g CO2/ kg Aschesediment. Neben der Nutzung der abgelagerten Aschesedimente zur Behandlung des Tagebaufolgeseewassers wurden desweiteren Labor- und Feldversuche durchgeführt um In-Lake-Behandlungen mit industriellen Kalkprodukten zu optimieren. In Batch- und Säulenversuchen wurden verschiedene Kalkprodukte (synthetisches Marmorpulver und industrielle Produkte) getestet und untersucht. Signifikante Unterschiede auf die Reaktivität wurde bei erhöhten CO2-Partialdrücken (pCO2 > 3.8 • 10-4 bar) beobachtet. Wasserinhaltsstoffe, die typisch für AMD sind (z.B.. Mn2+, Cd2+, SO42-) zeigten einen signifikanten Einfluss auf die Calcit-Lösungskinetik. Mangankonzentrationen, wie sie in Lausitzer Tagebaufolgeseen vorkommen, zeigten – ebenso wie Cadmium - eine inhibitierende Wirkung auf die Kinetik. Im Vergleich zu Versuchen mit destilliertem Wasser wurden nur ungefähr 50 % der Calcium-Gleichgewichtskonzentration mit Cadmium als Inhibitor erreicht. Erhöhte CO2-Partialdrücke könnten genutzt werden, um die inhibitierende Wirkung von vorhanden Materialverunreinigungen und/oder Wasserinhaltsstoffen zu kompensieren. Säulenversuche zeigten, dass der mehrstufige Einsatz von Kalkprodukten die Effizienz während einer Seewasserbehandlung erhöht. Die Kombination einer Erstbehandlung mit Kalksteinmehl (bis pH 4.5), und einer Behandlungsfortsetzung mit Ca(OH)2 erwies sich als wirkungsvollste Methode. Dieses Behandlungsschema (Initialneutralisation, 6 Nachfolgebehandlungen) wurde im Tagebaufolgesee Burghammer von März 2009 – Dezember 2010 erfolgreich angewandt. Zusammenfassend lässt sich sagen, dass in ehemaligen Bergbaurevieren die In-Lake-Behandlung von Tagebaufolgeseen eine zukunftsträchtige Methode zur Behandlung von Wasserqualitätsproblemen darstellt. Die Nutzung von gasförmigen CO2 in Kombination mit industriellen „Abfall-Produkten“ kann als nachhaltige Methode zur CO2-Sequestrierung und zur Behandlung von AMD bezeichnet werden. Der Vorteil in Bergbaurevieren liegt dabei in der Vorbeugung der Entstehung von Wasserqualitätsproblemen. Dennoch stellt diese Methode nur eine Nischenlösung aufgrund der Verfügbarkeit der alkalischen Materialien (Flugasche) dar. Die Entwicklung und Optimierung weiterführender Strategien zur In-Lake-Behandlung durch Kalkung wird zur Effizienzerhöhung beitragen. Die Nutzung von Kalksteinmehl anstelle von NaOH bzw. CaO als Neutralisationsprodukt wird Vorteile hinsichtlich ökonomischer und ökologischer Sicht (CO2-Bilanz) mit sich führen. Um die Effizienz beim Einsatz von Kalksteinmehl zu steigern, kann der Einsatz von CO2 in Betracht gezogen werden. Sobald meteorologische Parameter (Wind) und see-spezifische Merkmale (Morphologie, Strömungen, etc.) berücksichtigt werden, kann der Aufwand und die Kosten für In-Lake-Behandlungen minimiert werden

Excess of arsenic in groundwater is a worldwide problem threatening the health of the millions of people directly exposed to Arsenic-rich water intake. The problem is particularly acute in naturally occurring unconsolidated aquifers where Arsenic-rich groundwater is an easily accessible resource of drinking water, such arsenic in India, Bangladesh and Vietnam. In Italy, arsenic is found in aquifers from north to south and it is associated to different geological settings (i.e. volcanic areas and alluvial plains). The shallow aquifer of Venetian Alluvial Plain (VAP) is notoriously affected by arsenic contamination, characterized by a patchy distribution with variable extensions and concentrations. With concentrations exceeding the WHO limit of 10 μg/L, this metal poses a risk for locals, arsenic the aquifer is exploited for agricultural purposes. Although empirical evidences exist about the relationship between arsenic occurrence and other factors, several aspects regarding the physical and geochemical processes controlling arsenic in the VAP aquifers remain unclear. In this line, the present study aims to elucidate both the geochemical processes fostering arsenic mobility and their correlation with the subsurface heterogeneity, in order to improve the knowledge about arsenic-controlling processes and use them arsenic aid for the environmental management. To this end, we focused in detail on an agricultural zone nearby the Venice lagoon, affected by arsenic contamination (called “Western Agricultural Areas”, WAA). The available data, collected by several hydrogeological surveys, show a spatial and temporal variability of arsenic concentration, which can be associated to a variety of hydro-geochemical processes such arsenic redox variations, sorption or reductive dissolution of Arsenic-rich iron oxy-hydroxides. In order to point out the consistency and the importance of these processes, we structured the study in two main phases: 1) evaluation of geochemical processes by means of a PHREEQC batch-like reactive model and 2) creation of a 3D reactive transport model based on previous results. The former allows us for testing whether the supposed geochemical processes are able to fit the geochemical conditions of the study system, identifying the main actors for arsenic mobility. The latter couples the obtained reactive processes with a 3D flow model, in order to evaluate the spatial and temporal distribution of dissolved arsenic as function of the subsurface heterogeneity. The results highlighted a strong effect of oxy-reductive potential on arsenic mobility, and it seems to be strictly correlated to organic matter degradation. The uprising of reduced condition, then, affects other mechanism such arsenic reductive dissolution of iron hydroxides, ion exchange and sorption processes, causing arsenic mobilization. Moreover, this study shaded light on the existence of oxygen ingress arsenic function of local water recharge events, which seems to be responsible of space/time redox variation. The 3D reactive transport model showed a strong dependence between the aforementioned processes and subsurface heterogeneity. The material distribution, indeed, plays an import role affecting the arising of the main chemical reactions.

The Biscayne Aquifer is a primary source of water supply in Southeast Florida. As a coastal aquifer, it is threatened by saltwater intrusion (SWI) when the natural groundwater flow is altered by over-pumping of groundwater. SWI is detrimental to the quality of fresh groundwater sources, making the water unfit for drinking due to mixing and reactions with aquifer minerals. Increasing water demand and complex environmental issues thus force water utilities in South Florida to sustainably manage saltwater intrusion and develop alternative water supplies (e.g., aquifer storage and recovery, ASR). The objectives of this study were to develop and use calibrated geochemical models to estimate water quality changes during saline intrusion and during ASR in south Florida. A batch-reaction model of saltwater intrusion was developed and important geochemical reactions were inferred. Additionally, a reactive transport model was developed to assess fate and transport of major ions and trace metals (Fe, As) at the Kissimmee River ASR. Finally, a cost-effective management of saltwater intrusion that involves using abstraction and recharge wells was implemented and optimized for the case of the Biscayne Aquifer. Major processes in the SWI areas were found to be mixing and dissolution-precipitation reactions with calcite and dolomite. Most of the major ions (Cl, Na, K, Mg, SO4) behaved conservatively during ASR while Ca and alkalinity were affected by carbonate reactions and cation exchange. A complex set of reactions involving thermodynamic equilibrium, kinetics and surface complexation reactions was required in the ASR model to simulate observed concentrations of Fe and As. The saltwater management model aimed at finding optimal locations and flow rates for abstraction and recharge wells. Optimal solutions (i.e., minimum total salt and total cost Pareto front) were produced for the Biscayne Aquifer for scenarios of surface recharge induced by climate change-affected precipitation. In general, abstraction at the maximum rate near the coast and artificial recharge at locations much further inland were found to be optimal. Knowledge developed herein directly supports the understanding of SWI caused by anthropogenic stressors, such as over-pumping and sea level rise, on coastal aquifers.

La modélisation du transport réactif dans les milieux poreux implique la simulation de plusieurs processus physico-chimiques : écoulement de phases fluides, transport de chaleur, réactions chimiques entre espèces en phases identiques ou différentes. La résolution du système d'équations qui décrit le problème peut être obtenue par une approche soit totalement couplée soit découplée. Les approches découplées simplifient le système d'équations en décomposant le problème sous-parties plus faciles à gérer. Chacune de ces sous-parties peut être résolue avec des techniques d'intégration appropriées. Les techniques de découplage peuvent être non‑itératives (operator splitting methods) ou itératives (fixed‑point iteration), chacunes ayant des avantages et des inconvénients. Les approches non‑iteratives génèrent une erreur associée à la séparation des sous­-parties couplées, et les approaches itératives peuvent présenter des problèmes de convergence. Dans cette thèse, nous développons un code sous licence libre en langage MATLAB (https://github.com/TReacLab/TReacLab) dédie à la modélisation du la problématique de la carbonatation atmosphérique du béton, dans le cadre du stockage de déchets de moyenne activité et longue vie en couche géologique profonde. Le code propose un ensemble d'approche découplée : classique, comme les approches de fractionnement séquentiel, alternatif ou Strang, et moins classique, comme les approches de fractionnement additif ou par répartition symétrique. En outre, deux approches itératives basées sur une formulation spécifique (SIA CC et SIA TC) ont également été implémentées. Le code été interfacé de manière générique avec différents solveurs de transport (COMSOL, pdepe MATLAB, FVTool, FD scripts) et géochimiques (iPhreeqc, PhreeqcRM). Afin de valider l'implémentations des différentes approches, plusieurs bancs d'essais classiques dans le domaine du transport réactif ont été utilises avec succès. L'erreur associée à la combinaison du fractionnement de l'opérateur et des techniques numériques étant complexe à évaluer, nous explorons les outils mathématiques existants permettant de l'estimer. Enfin, nous structurons le problème de la carbonatation atmosphérique et présentons des simulations préliminaires, en détaillant les problèmes pertinents et les étapes futures à suivre
Reactive transport modeling in porous media involves the simulation of several physico‑chemical processes: flow of fluid phases, transport of species, heat transport, chemical reactions between species in the same phase or in different phases. The resolution of the system of equations that describes the problem can be obtained by a fully coupled approach or by a decoupled approach. Decoupled approaches can simplify the system of equations by breaking down the problem into smaller parts that are easier to handle. Each of the smaller parts can be solved with suitable integration techniques. The decoupling techniques might be non‑iterative (operator splitting methods) or iterative (fixed‑point iteration), having each its advantages and disadvantages. Non‑iterative approaches have an error associated with the separation of the coupled effects, and iterative approaches might have problems to converge. In this thesis, we develop an open‑source code written in MATLAB (https://github.com/TReacLab/TReacLab) in order to model the problematic of concrete atmospheric carbonation for an intermediate‑level long‑lived nuclear waste package in a deep geological repository. The code uses a decoupled approach. Classical operator splitting approaches, such as sequential, alternating or Strang splitting, and less classical splitting approaches, such as additive or symmetrically weighted splitting, have been implemented. Besides, two iterative approaches based on an specific formulation (SIA CC, and SIA TC) have also been implemented. The code has been interfaced in a generic way with different transport solvers (COMSOL, pdepe MATLAB, FVTool, FD scripts) and geochemical solvers (iPhreeqc, PhreeqcRM). In order to validate the implementation of the different approaches, a series of classical benchmarks in the field of reactive transport have been solved successfully and compared with analytical and external numerical solutions. Since the associated error due to the combination of operator splitting and numerical techniques may be complex to assess, we explore the existing mathematical tools used to evaluate it. Finally, we frame the atmospheric carbonation problem and run preliminary simulations, stating the relevant problems and future steps to follow

Cette thèse a permis de mieux comprendre les mécanismes de complexation des terres rares par les acides humiques afin d'expliquer la variabilité des spectres de terres rares observée dans les eaux riches en matière organique. Cette étude montre que l'hétérogénéité des groupements fonctionnels complexants des acides humiques peut induire différents types de spectres de complexation des terres rares en fonction des conditions physico-chimiques. En effet, à pH acide, lorsque le rapport terres rares/acides humiques augmente, les terres rares se lient majoritairement à des sites carboxyliques multidentates puis monodentates qui ont, respectivement, une plus forte affinité pour les terres rares lourdes et intermédiaires. Lorsque le pH augmente, la participation de sites phénoliques devient plus importante pour les terres rares lourdes tandis que les légères restent liées à des sites carboxyliques. Des expériences de compétition entre les terres rares et le fer ou l'aluminium pour la complexation par les acides humiques ont également été réalisées. A pH neutre, Al est un plus fort compétiteur pour les terres rares légères, et se lie donc préférentiellement à des sites carboxyliques, tandis que Fe est un compétiteur pour toutes les terres rares, et se lie donc aussi bien aux sites carboxyliques que phénoliques. Ainsi, le rapport cation dissous/acides humiques, le pH et la natures des cations compétiteurs peuvent expliquer la variabilité des spectres de terres rares observée dans les eaux naturelles. De plus, les terres rares peuvent être utilisées comme sonde des mécanismes de complexation des cations par les acides humiques, comme ici pour Al et Fe.

Water from Mantua reservoir has, during some years, exhibited reddish-brown staining when used by Brigham City for irrigation. I propose that seasonal fluctuations in the reservoir chemistry create an environment conducive to dissolving iron from the iron-rich sediments, which subsequently precipitate during irrigation, resulting in a staining event. These conditions are produced by chemical and biological decomposition of organic matter, coupled with isolation of the hypolimnetic waters, which results in seasonal low concentrations of dissolved oxygen in these waters. Under these specific circumstances, anaerobic conditions develop creating a geochemical environment that causes iron and manganese reduction from Fe(III) to Fe(II) and Mn(IV) to Mn(II), respectively. These reducing conditions facilitate reduction-oxidation (redox) chemical reactions that convert insoluble forms of iron and manganese found in the reservoir sediments into more soluble forms. Consequently, relatively high amounts of dissolved iron and manganese are generated in the bottom waters immediately adjacent to the benthic sediments of the reservoir. Water withdrawn from a bottom intake pipe during these periods introduces iron-rich water into the distribution system. When this water is exposed to oxygen, reoxidation shifts redox equilibrium causing precipitation of soluble Fe(II) and Mn(III) back to highly insoluble Fe(III) and Mn(IV). The precipitant appears on contact surfaces as the aforementioned ferric stain. This research focuses specifically on the iron chemistry involved and evaluates this hypothesis using various measurements and models including field data collection, computer simulations, and bench-scale testing to validate the processes proposed.

Introduction : Les patients dépendant d’une ventilation artificielle sont principalement placés sous ventilation mécanique. Si leur nerf phrénique et leur diaphragme demeurent fonctionnels, un implant de stimulation du diaphragme (DP) peut permettre une respiration plus naturelle. Mais les systèmes DP existants ne peuvent monitorer la respiration induite du patient et ne permettent que de stimuler à intensité et à fréquence constantes. Ajouter une capacité d’adaptation à ces systèmes pourrait améliorer l’efficacité de la stimulation. Une méthode de monitoring respiratoire basée sur l’enregistrement de sons trachéaux via un microphone a été introduite dans cette thèse. Cette méthode a été conçue pour être portable et non-invasive, et capable de fonctionner une journée complète et en temps réel.Méthodes : Les sons trachéaux ont été enregistrés à l’aide d’un microphone placé dans un support en forme de cloche réalisé par impression 3D, et placé sur le cou du patient. Les signaux récupérés ont été filtrés et pré-amplifiés puis enregistrés et traités sur ordinateur. Quatre protocoles ont été conçus pour enregistrer des sons trachéaux dans divers contextes : (1) 15 sujets sains ; (2) 1 patient ayant une tétraplégie haute sous IT-PNS ; (3) 13 sujets sains assis puis couchés, avec des signaux de référence ; (4) 30 patients souffrant d’apnée du sommeil et 10 patients avec un système IT-PNS implanté seront includes prochainement. Un algorithme de traitement du signal en temps réel a permis de détecter toutes les phases d’inspiration et d’expiration par détection d’enveloppe dans les domaines temporel, fréquentiel, et également une détection à partir du PDR (PCG-derived respiration : la variation d’amplitude des pics cardiaques correspond à la respiration). La combinaison de ces trois détections permet une meilleure spécificité du système (moins de faux-positifs).Résultats : L’application de l’algorithme aux données des protocoles 1 et 3 a conduit à de bons résultats de détection qui satisfont le minimum requis pour système. Ces résultats ont aussi montré que les bruits tels que la parole ou l’environnement extérieur, et les différentes position du corps n’influencent pas le résultat de la détection. La nouvelle méthode d’évaluation de l’effort respiratoire proposé – PDR montre une bonne corrélation avec EDR, ce qui démontre la faisabilité de l’utilisation de PDR pour le monitoring de la respiration. Une bonne corrélation entre des intervalles R-R et S-S montre également qu'il serait donc également possible de monitorer l’activité du cœur à partir des sons trachéaux.Conclusions : Cette thèse a démontré la faisabilité de détecter des épisodes d’apnée à partir de sons trachéaux et de monitorer l’activité cardiaque. Le signal extrait PDR peut permettre d’identifier le type d’apnée (obstructive / centrale). De plus, le système d’enregistrement par microphone peut permettre d’observer les signaux de stimulation électrique chez les patients implantés et indiquer un dysfonctionnement éventuel du système implanté. Les sons trachéaux peuvent aussi fournir un retour sur la qualité de l’électroventilation. La prochaine étape sera donc d’obtenir les enregistrements de patients et de tester si ce même algorithme fonctionne dans ce cas (protocole 4). Le monitoring des sons trachéaux peut fournir une méthode non-invasive pour estimer le flux inspiratoire dans le cas de patients nécessitant un monitoring respiratoire dans les situations extrêmes (e.g. comme une mesure de sécurité pour l’administration de morphine pour les douleurs aiguës) et dans les situations chroniques (e.g. la ventilation mécanique à domicile). Et dans le cas de maisons connectées, en particulier pour les maisons de retraite, les applications de monitoring des sons trachéaux peut permettre un monitoring robuste et efficace des signes multi-vitaux
Introduction: Patients who have an artificial ventilation dependence are usually treated with mechanical ventilation. If their phrenic nerves and diaphragms are still functional, implanted diaphragm pacing (DP) can provide them a more natural respiration. But existing DP systems cannot monitor patient’s induced respiration and stimulate with a current of constant intensity and frequency. Adding adaptive abilities to existing systems would improve the efficiency of the delivered stimulation and could also deliver an alarm in case of an apnea detection. A respiratory monitoring method based on recordings from tracheal sounds by microphone is introduced. This method aims at being ambulatory and non-invasive for all-day long real-time use.Methods: Tracheal sounds were recorded by a microphone inserted into a 3D printed bell-shape support, which was stuck over patient’s neck. Recorded signals were filtered and pre-amplified then saved and processed in a computer. Four protocols were designed to record and analyze respiration in different contexts: (1) 15 healthy subjects; (2) 1 patient with high tetraplegia under IT-PNS; (3) 13 healthy subjects in sitting and lying positions with reference signals; (4) 30 patients with sleep apnoea and 10 patients with implanted IT-PNS will be included in short future. One real-time processing algorithm detected all inspiration/expiration phases by combining results from temporal envelope detection, frequency detection, and also PDR detection (PCG-derived respiration: variation of cardiac peak amplitude corresponds to respiration). Combining the detection results in these 3 domains allowed for a better specificity of system (less false positives).Results: The application of the algorithms to protocols 1 to 3 data lead to good detection results that met the minimum requirements for the system. These result also showed that noises like speech or environments and different body position do not influence much the detection results. The new proposed respiratory effort evaluation method -- PDR showed a good correlation with EDR, this demonstrates the feasibility to use the PDR to monitor respiration. At a good correlation between R-R intervals and S-S intervals also showed that it would also be possible to monitor heart activity from tracheal sounds.Conclusions: This thesis shows the feasibility of detecting the apnoea and of monitoring cardiac activity from tracheal sounds. The extracted signal PDR could be used to identify the type of apnoea (obstructive/central). Furthermore, the microphone-based recording system could capture stimulation signals which can indicate a dysfunction of the pacing system and recorded tracheal sounds could give a feedback of the electro-ventilation quality. The next step is to record patient's tracheal sounds signals and test if the same algorithm could still work well in this context (the protocol 4).Monitoring tracheal sounds could provide a non-invasive way to approximate inspiratory flow that would be useful in all patients requiring respiratory monitoring in acute situations (e.g. as a safety measure during the administration of morphine for acute pain) and in chronic situations (e.g. home mechanical ventilation). And in the construction of smart house, especially for nursing/retirement home, application of tracheal sounds monitoring could provide convenient, robust multi-vital signals monitoring

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Na atualidade, enquanto diminuem as reservas dos recursos naturais, aumentam as quantidade e extensão dos danos ambientais decorrentes desta exploração. Entre as diversas atividades produtivas a mineração é uma das que também causam perdas à qualidade do ar, águas e solos, entre outras razões, por extravio de minério em rejeitos, cujo significado pode ser traduzido como contaminação. Este é o cenário que se observada hoje, no entorno da pequena cidade de Lavras do sul, distante 320 Km a oeste da capital do estado do Rio Grande do Sul, onde três séculos de vocação mineira e o sonhos de riquezas fartas produziram incontável número de escavações, acompanhadas de grandes quantidades de rejeitos e estéril, em pilhas ou espalhados na superfície. Sob este contexto é que foi escolhida a área “Mina Cerro Rico” (MCR), distante cerca de seis Km a leste da cidade, com o objetivo de avaliar como se comportam os íons dos metais como o cobre, chumbo, zinco e o metaloíde arsênio, nos solos do entorno destas áreas exploradas durante tantos anos, para produção de ouro e prata. Os trabalhos visaram inicialmente entender da capacidade em reter os íons dos metais escolhidos, que as substancias húmicas do solo podem possuir. A seguir, foi reproduzido em laboratório, o processo de lixiviação da camada superior de solo total (0,00 a 0,15 m), por águas que simularam aproximadamente as mesmas condições de chuvas, com emprego da técnica de colunas de percolação. O trabalho foi acompanhado de análises químicas da concentração de metais e metalóide, por FRX e ICP-OES, para deste modo apreciar a existência eventual de contaminação segundo critérios FEPAM, CONAMA e USEPA. O comportamento dos íons de Cu, Pb, e Zn, metais escolhidos para o estudo, assim como e do As, foi estimado pelo reconhecimento da especiação e a mobilidade das espécies, empregando o software PHREEQC aos percolados obtidos na lixiviação do solos.
At the present time, while decreasing natural resources reserves, the amount and extent of environmental damages resulting from this exploitation increase. Among the various productive activities mining is one of those that also cause losses to the quality of air, water and soil, among other reasons, due to the loss of ore in tailings, whose meaning can be translated as contamination. This is the scenario that is observed today, around the small town of Lavras do Sul, 320 km west of the capital of the state of Rio Grande do Sul, where three centuries of mining vocation and the dreams of riches have produced countless Excavations, accompanied by large quantities of tailings and sterile, in piles or scattered on the surface. In this context, the "Cerro Rico Mine" (MCR) area was chosen, about six kilometers east of the city, with the objective of evaluating the behavior of metals ions such as copper, lead, zinc and metalloid arsenic, in the soils surrounding these areas exploited for so many years, for the production of gold and silver. The works initially aimed at understanding the ability to retain the ions of the chosen metals, which soil humic substances may possess. Next, the leaching process of the upper layer of total soil (0,00 to 0,15 m) was reproduced in the laboratory, by water that simulated approximately the same rainfall conditions, using the technique of percolation columns. The work was accompanied by chemical analyzes of the concentration of metals and metalloid, by FRX and ICP-OES, in order to evaluate the possible existence of contamination according to FEPAM, CONAMA and USEPA criteria. The behavior of the Cu, Pb, and Zn ions, metals chosen for the study, as well as of the As, was estimated by the recognition of speciation and species mobility, using the PHREEQC software to percolates obtained in soil leaching.

Orientador: Lea Rodrigues Simioni
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Ciencias Medicas
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Resumo: A espécie Micrurus pyrrhocryptus, classificada anteriormente como subespécie da Micrurus frontalis, foi recentemente classificada como espécie plena baseada nas diferenças morfológicas. Esta serpente é especialmente encontrada no continente Sul Americano. No presente trabalho foram analisados os efeitos farmacológicos do veneno de M. pyrrhocryptus sob métodos para caracterização de efeitos neurotóxico e miotóxico em preparações biventer cervicis de pintainho (BCP) (0,5, 1, 5, 10, 20, 30 e 50 µg/mL, n=6 para cada concentração) e nervo frênicodiafragma de camundongo (NFD) (1, 5, 10, 20, 30 e 50 µg/mL, n=6 para cada concentração). Também foram realizados estudos sobre a capacidade de neutralização do antiveneno específico e comercial. O veneno induziu um irreversível bloqueio neuromuscular (pós-sináptico, como demonstrado pela resposta contrátil sob estímulo de alta frequência - 50 Hz, n=6 em NFD), tempo e concentração-dependente em ambas as preparações (10 µg/mL induziu 50% de bloqueio neuromuscular em 22±3 min vs 62±4 min em BCP e NFD respectivamente, n=6 para cada preparação); as contraturas em resposta a adição exógena de KCl (20 mM) não foram afetadas significativamente depois da incubação com o veneno, bem como, a determinação da atividade de CK quando comparados com os valores controle (25,8±1,75 U/L vs 24,3±2,2 U/L) ou também com o registro da resposta contrátil em preparações curarizadas (n=6). O veneno apresentou um baixo valor de atividade fosfolipásica quando comparado com o veneno de Crotalus durissus terrificus em 37ºC. Nos testes de neutralização, os antivenenos específico e comercial foram eficientes, contra o efeito bloqueador neuromuscular induzido pelo veneno, quando usados na concentração recomendada pelo fabricante (1,5 mg de veneno para 1,0 mL de antiveneno). A análise histológica mostrou apenas uma discreta alteração mesmo quando usado em alta concentração (50 µg/mL - n=5; 3,5±0,8% em mamífero e 4,3±1,5% em ave vs 1,2±0,5% em mamífero e 1,1±0,7% em ave do controle, ambos p<0,05 em relação ao controle), corroborando com as características de outros venenos de Micrurus. A razão da potência do veneno vs sensibilidade de receptores colinérgicos presentes no sítio extra juncional da preparação do músculo biventer, foi demonstrada quando usado em baixa concentração (0,5 µg/mL) aboliu totalmente em 30 min a contratura induzida pela adição ACh exógena (110 µM). O conjunto dos resultados indica que o veneno de M. pyrrhocryptus causa bloqueio pós-sináptico envolvendo os receptores nicotínicos, como as ?- neurotoxinas, sem determinar alteração significativa na membrana da fibra muscular
Abstract: Micrurus pyrrhocryptus, originally known as a Micrurus frontalis subspecies, was recently classified as a species based on selected morphological features. It can be found in the South America. Only two studies are apparently available on its venom effects. Herein, pharmacological approaches were used to characterize the neurotoxic and myotoxic effects of M. pyrrhocryptus venom in chick biventer cervicis (BC, 0.5, 1, 5, 10 and 50 µg/mL, n=6 for each concentration) and mouse phrenic nerve-diaphragm preparations (NFD, 1, 5, 10 and 50 µg/mL, n=6 for each concentration). In addition, studies on neutralization capacity of specific and commercial antivenom were performed. The venom induced an irreversible, time and concentrationdependent neuromuscular blockade (postsynaptic, as demonstrated by the high frequency twitch tension response - 50Hz, n=6 in NFD) in both preparations (10 µg/mL induced 50% neuromuscular blockade in 22±3 min vs 62±4 min in BC and NFD respectively, n=6 for each preparation); the contractures in response to exogenous KCl (20 mM) were not significant after venom incubation as well as the value of CK released when compared with control values (25.8±1.75 U/L vs 24.3±2.2 U/L) or also twitch tension record in curarized preparations (n=6). The venom showed a very low PLA2 activity when compared with c. d. terrificus venom at 37ºC. In neutralization test the specific and Brazilian commercial antielapidic serum were efficient when used in concentration recommended by the producer (1.5 of venom to 1.0 mL of antivenom). The histological analysis showed a mild myotoxic effect, even using high venom concentration (50 µg/mL - n=5, 3.5±0.8% in mammalian and 4.3±1.5% on avian vs 1.2±0.5% in mammalian and 1.1±0.7% in avian of control), corroborating characteristics of other Micrurus venoms). The ratio venom potency vs preparation sensitivity was shown when a concentration as low as 0.5 µg/mL totally abolished within only 30 min the contracture induced by the exogenously added ACh (110µM) to chick preparation. Altogether the results indicate that M. pyrrhocryptus venom has a postsynaptic blocking effect involving nicotinic receptors as does the ?-neurotoxins, and without any significant myotoxic effect
Mestrado
Mestre em Farmacologia