Error models in hydrogeology applications

Notre consommation en eau souterraine, en particulier comme eau potable ou pour l'irrigation, a considérablement augmenté au cours des années. De nombreux problèmes font alors leur apparition, allant de la prospection de nouvelles ressources à la remédiation des aquifères pollués. Indépendamment du problème hydrogéologique considéré, le principal défi reste la caractérisation des propriétés du sous-sol. Une approche stochastique est alors nécessaire afin de représenter cette incertitude en considérant de multiples scénarios géologiques et en générant un grand nombre de réalisations géostatistiques. Nous rencontrons alors la principale limitation de ces approches qui est le coût de calcul dû à la simulation des processus d'écoulements complexes pour chacune de ces réalisations. Dans la première partie de la thèse, ce problème est investigué dans le contexte de propagation de l'incertitude, oú un ensemble de réalisations est identifié comme représentant les propriétés du sous-sol. Afin de propager cette incertitude à la quantité d'intérêt tout en limitant le coût de calcul, les méthodes actuelles font appel à des modèles d'écoulement approximés. Cela permet l'identification d'un sous-ensemble de réalisations représentant la variabilité de l'ensemble initial. Le modèle complexe d'écoulement est alors évalué uniquement pour ce sousensemble, et, sur la base de ces réponses complexes, l'inférence est faite. Notre objectif est d'améliorer la performance de cette approche en utilisant toute l'information à disposition. Pour cela, le sous-ensemble de réponses approximées et exactes est utilisé afin de construire un modèle d'erreur, qui sert ensuite à corriger le reste des réponses approximées et prédire la réponse du modèle complexe. Cette méthode permet de maximiser l'utilisation de l'information à disposition sans augmentation perceptible du temps de calcul. La propagation de l'incertitude est alors plus précise et plus robuste. La stratégie explorée dans le premier chapitre consiste à apprendre d'un sous-ensemble de réalisations la relation entre les modèles d'écoulement approximé et complexe. Dans la seconde partie de la thèse, cette méthodologie est formalisée mathématiquement en introduisant un modèle de régression entre les réponses fonctionnelles. Comme ce problème est mal posé, il est nécessaire d'en réduire la dimensionnalité. Dans cette optique, l'innovation du travail présenté provient de l'utilisation de l'analyse en composantes principales fonctionnelles (ACPF), qui non seulement effectue la réduction de dimensionnalités tout en maximisant l'information retenue, mais permet aussi de diagnostiquer la qualité du modèle d'erreur dans cet espace fonctionnel. La méthodologie proposée est appliquée à un problème de pollution par une phase liquide nonaqueuse et les résultats obtenus montrent que le modèle d'erreur permet une forte réduction du temps de calcul tout en estimant correctement l'incertitude. De plus, pour chaque réponse approximée, une prédiction de la réponse complexe est fournie par le modèle d'erreur. Le concept de modèle d'erreur fonctionnel est donc pertinent pour la propagation de l'incertitude, mais aussi pour les problèmes d'inférence bayésienne. Les méthodes de Monte Carlo par chaîne de Markov (MCMC) sont les algorithmes les plus communément utilisés afin de générer des réalisations géostatistiques en accord avec les observations. Cependant, ces méthodes souffrent d'un taux d'acceptation très bas pour les problèmes de grande dimensionnalité, résultant en un grand nombre de simulations d'écoulement gaspillées. Une approche en deux temps, le "MCMC en deux étapes", a été introduite afin d'éviter les simulations du modèle complexe inutiles par une évaluation préliminaire de la réalisation. Dans la troisième partie de la thèse, le modèle d'écoulement approximé couplé à un modèle d'erreur sert d'évaluation préliminaire pour le "MCMC en deux étapes". Nous démontrons une augmentation du taux d'acceptation par un facteur de 1.5 à 3 en comparaison avec une implémentation classique de MCMC. Une question reste sans réponse : comment choisir la taille de l'ensemble d'entrainement et comment identifier les réalisations permettant d'optimiser la construction du modèle d'erreur. Cela requiert une stratégie itérative afin que, à chaque nouvelle simulation d'écoulement, le modèle d'erreur soit amélioré en incorporant les nouvelles informations. Ceci est développé dans la quatrième partie de la thèse, oú cette méthodologie est appliquée à un problème d'intrusion saline dans un aquifère côtier. -- Our consumption of groundwater, in particular as drinking water and for irrigation, has considerably increased over the years and groundwater is becoming an increasingly scarce and endangered resource. Nofadays, we are facing many problems ranging from water prospection to sustainable management and remediation of polluted aquifers. Independently of the hydrogeological problem, the main challenge remains dealing with the incomplete knofledge of the underground properties. Stochastic approaches have been developed to represent this uncertainty by considering multiple geological scenarios and generating a large number of realizations. The main limitation of this approach is the computational cost associated with performing complex of simulations in each realization. In the first part of the thesis, we explore this issue in the context of uncertainty propagation, where an ensemble of geostatistical realizations is identified as representative of the subsurface uncertainty. To propagate this lack of knofledge to the quantity of interest (e.g., the concentration of pollutant in extracted water), it is necessary to evaluate the of response of each realization. Due to computational constraints, state-of-the-art methods make use of approximate of simulation, to identify a subset of realizations that represents the variability of the ensemble. The complex and computationally heavy of model is then run for this subset based on which inference is made. Our objective is to increase the performance of this approach by using all of the available information and not solely the subset of exact responses. Two error models are proposed to correct the approximate responses follofing a machine learning approach. For the subset identified by a classical approach (here the distance kernel method) both the approximate and the exact responses are knofn. This information is used to construct an error model and correct the ensemble of approximate responses to predict the "expected" responses of the exact model. The proposed methodology makes use of all the available information without perceptible additional computational costs and leads to an increase in accuracy and robustness of the uncertainty propagation. The strategy explored in the first chapter consists in learning from a subset of realizations the relationship between proxy and exact curves. In the second part of this thesis, the strategy is formalized in a rigorous mathematical framework by defining a regression model between functions. As this problem is ill-posed, it is necessary to reduce its dimensionality. The novelty of the work comes from the use of functional principal component analysis (FPCA), which not only performs the dimensionality reduction while maximizing the retained information, but also allofs a diagnostic of the quality of the error model in the functional space. The proposed methodology is applied to a pollution problem by a non-aqueous phase-liquid. The error model allofs a strong reduction of the computational cost while providing a good estimate of the uncertainty. The individual correction of the proxy response by the error model leads to an excellent prediction of the exact response, opening the door to many applications. The concept of functional error model is useful not only in the context of uncertainty propagation, but also, and maybe even more so, to perform Bayesian inference. Monte Carlo Markov Chain (MCMC) algorithms are the most common choice to ensure that the generated realizations are sampled in accordance with the observations. Hofever, this approach suffers from lof acceptance rate in high dimensional problems, resulting in a large number of wasted of simulations. This led to the introduction of two-stage MCMC, where the computational cost is decreased by avoiding unnecessary simulation of the exact of thanks to a preliminary evaluation of the proposal. In the third part of the thesis, a proxy is coupled to an error model to provide an approximate response for the two-stage MCMC set-up. We demonstrate an increase in acceptance rate by a factor three with respect to one-stage MCMC results. An open question remains: hof do we choose the size of the learning set and identify the realizations to optimize the construction of the error model. This requires devising an iterative strategy to construct the error model, such that, as new of simulations are performed, the error model is iteratively improved by incorporating the new information. This is discussed in the fourth part of the thesis, in which we apply this methodology to a problem of saline intrusion in a coastal aquifer.

Does working memory training affect decision making ? : a neuroeconomic study

We all make decisions of varying levels of importance every day. Because making a decision implies that there are alternative choices to be considered, almost all decision involves some conflicts or dissatisfaction. Traditional economic models esteem that a person must weight the positive and negative outcomes of each option, and based on all these inferences, determines which option is the best for that particular situation. However, individuals rather act as irrational agents and tend to deviate from these rational choices. They somewhat evaluate the outcomes' subjective value, namely, when they face a risky choice leading to losses, people are inclined to have some preference for risk over certainty, while when facing a risky choice leading to gains, people often avoid to take risks and choose the most certain option. Yet, it is assumed that decision making is balanced between deliberative and emotional components. Distinct neural regions underpin these factors: the deliberative pathway that corresponds to executive functions, implies the activation of the prefrontal cortex, while the emotional pathway tends to activate the limbic system. These circuits appear to be altered in individuals with ADHD, and result, amongst others, in impaired decision making capacities. Their impulsive and inattentive behaviors are likely to be the cause of their irrational attitude towards risk taking. Still, a possible solution is to administrate these individuals a drug treatment, with the knowledge that it might have several side effects. However, an alternative treatment that relies on cognitive rehabilitation might be appropriate. This project was therefore aimed at investigate whether an intensive working memory training could have a spillover effect on decision making in adults with ADHD and in age-matched healthy controls. We designed a decision making task where the participants had to select an amount to gamble with the chance of 1/3 to win four times the chosen amount, while in the other cases they could loose their investment. Their performances were recorded using electroencephalography prior and after a one-month Dual N-Back training and the possible near and far transfer effects were investigated. Overall, we found that the performance during the gambling task was modulated by personality factors and by the importance of the symptoms at the pretest session. At posttest, we found that all individuals demonstrated an improvement on the Dual N-Back and on similar untrained dimensions. In addition, we discovered that not only the adults with ADHD showed a stable decrease of the symptomatology, as evaluated by the CAARS inventory, but this reduction was also detected in the control samples. In addition, Event-Related Potential (ERP) data are in favor of an change within prefrontal and parietal cortices. These results suggest that cognitive remediation can be effective in adults with ADHD, and in healthy controls. An important complement of this work would be the examination of the data in regard to the attentional networks, which could empower the fact that complex programs covering the remediation of several executive functions' dimensions is not required, a unique working memory training can be sufficient. -- Nous prenons tous chaque jour des décisions ayant des niveaux d'importance variables. Toutes les décisions ont une composante conflictuelle et d'insatisfaction, car prendre une décision implique qu'il y ait des choix alternatifs à considérer. Les modèles économiques traditionnels estiment qu'une personne doit peser les conséquences positives et négatives de chaque option et en se basant sur ces inférences, détermine quelle option est la meilleure dans une situation particulière. Cependant, les individus peuvent dévier de ces choix rationnels. Ils évaluent plutôt les valeur subjective des résultats, c'est-à-dire que lorsqu'ils sont face à un choix risqué pouvant les mener à des pertes, les gens ont tendance à avoir des préférences pour le risque à la place de la certitude, tandis que lorsqu'ils sont face à un choix risqué pouvant les conduire à un gain, ils évitent de prendre des risques et choisissent l'option la plus su^re. De nos jours, il est considéré que la prise de décision est balancée entre des composantes délibératives et émotionnelles. Ces facteurs sont sous-tendus par des régions neurales distinctes: le chemin délibératif, correspondant aux fonctions exécutives, implique l'activation du cortex préfrontal, tandis que le chemin émotionnel active le système limbique. Ces circuits semblent être dysfonctionnels chez les individus ayant un TDAH, et résulte, entre autres, en des capacités de prise de décision altérées. Leurs comportements impulsifs et inattentifs sont probablement la cause de ces attitudes irrationnelles face au risque. Cependant, une solution possible est de leur administrer un traitement médicamenteux, en prenant en compte les potentiels effets secondaires. Un traitement alternatif se reposant sur une réhabilitation cognitive pourrait être appropriée. Le but de ce projet est donc de déterminer si un entrainement intensif de la mémoire de travail peut avoir un effet sur la prise de décision chez des adultes ayant un TDAH et chez des contrôles sains du même âge. Nous avons conçu une tâche de prise de décision dans laquelle les participants devaient sélectionner un montant à jouer en ayant une chance sur trois de gagner quatre fois le montant choisi, alors que dans l'autre cas, ils pouvaient perdre leur investissement. Leurs performances ont été enregistrées en utilisant l'électroencéphalographie avant et après un entrainement d'un mois au Dual N-Back, et nous avons étudié les possibles effets de transfert. Dans l'ensemble, nous avons trouvé au pré-test que les performances au cours du jeu d'argent étaient modulées par les facteurs de personnalité, et par le degré des sympt^omes. Au post-test, nous avons non seulement trouvé que les adultes ayant un TDAH montraient une diminutions stable des symptômes, qui étaient évalués par le questionnaire du CAARS, mais que cette réduction était également perçue dans l'échantillon des contrôles. Les rsultats expérimentaux mesurés à l'aide de l'éléctroencéphalographie suggèrent un changement dans les cortex préfrontaux et pariétaux. Ces résultats suggèrent que la remédiation cognitive est efficace chez les adultes ayant un TDAH, mais produit aussi un effet chez les contrôles sains. Un complément important de ce travail pourrait examiner les données sur l'attention, qui pourraient renforcer l'idée qu'il n'est pas nécessaire d'utiliser des programmes complexes englobant la remédiation de plusieurs dimensions des fonctions exécutives, un simple entraiment de la mémoire de travail devrait suffire.

Posibles beneficios fisiológicos y psicológicos del método madre canguro (MMC) en bebés prematuros y sus madres

Objetivos: La preocupación por la crisis económica que azota España y por lo tanto, a la comunidad autónoma de Navarra, sumado a la evidencia científica de las consecuencias que sufre el bebé al ser separado de su madre tras el nacimiento, siendo más notable por debajo de las 37 semanas de gestación, y al elevado estrés y sufrimiento de los padres cuando su hijo está encerrado en una incubadora, llevó al planteamiento de querer demostrar los posibles beneficios fisiológicos y psicológicos del método madre canguro (MMC) en bebés prematuros y sus madres. Metodología: Será un estudio experimental, longitudinal y prospectivo dirigido a 40 mujeres y a sus bebés prematuros, que den a luz en el hospital Virgen del Camino. El grado de satisfacción se determinará con preguntas extraídas de la escala validada Caring Assement Instrument (CARE- Q) y con otro cuestionario no validado. Los parámetros fisiológicos se medirán con un termómetro de mercurio y una cinta métrica. El programa informático SPSS® vs 21.0. será el elegido para el análisis estadístico. Limitaciones del estudio: La larga duración de la participación de la unidad madre-hijo, la tercera etapa domiciliaria del MMC, las restricciones de la UCIN del hospital Virgen del Camino junto al uso de una escala no validada, podría conllevar a la aparición de obstáculos a la hora, tanto de poder llevar a cabo el proyecto, como de la obtención de sus resultados.

El mercuri s'ha triplicat als nostres oceans

L"ACTIVITAT INDUSTRIAL INCLOU PROCESSOS molt diversos que sovint generen productes potencialment contaminants, que s"han estat abocant al medi ambient amb més o menys control des de l"inici de la Revolució Industrial. Alguns d"aquests productes poden ser reciclats pels mateixos cicles naturals, geoquímics i biològics, però d"altres es van acumulant, com és el cas del mercuri. Un estudi publicat a la revista Nature, encapçalat per Carl H. Lamborg, de la Woods Hole Oceanographic Institution de Massachusetts, als EUA, indica que la quantitat de mercuri als oceans s"ha triplicat des de la Revolució Industrial i, malgrat que el nivell actual encara és raonablement lluny de ser considerat tòxic per a les persones, pot començar a alterar els ecosistemes marins. A més, com assenyalen els autors del treball, la capacitat dels oceans per dissoldre el mercuri acumulat es podria estar esgotant, la qual cosa implicaria que, si no es prenen mesures que evitin els abocaments incontrolats, el seu ritme de penetració dins els ecosistemes i, a la llarga, en l"alimentació humana, podria augmentar de manera exponencial.

Establishing International Blood Pressure References Among Nonoverweight Children and Adolescents Aged 6 to 17 Years.

BACKGROUND: Several distributions of country-specific blood pressure (BP) percentiles by sex, age, and height for children and adolescents have been established worldwide. However, there are no globally unified BP references for defining elevated BP in children and adolescents, which limits international comparisons of the prevalence of pediatric elevated BP. We aimed to establish international BP references for children and adolescents by using 7 nationally representative data sets (China, India, Iran, Korea, Poland, Tunisia, and the United States). METHODS AND RESULTS: Data on BP for 52 636 nonoverweight children and adolescents aged 6 to 19 years were obtained from 7 large nationally representative cross-sectional surveys in China, India, Iran, Korea, Poland, Tunisia, and the United States. BP values were obtained with certified mercury sphygmomanometers in all 7 countries by using standard procedures for BP measurement. Smoothed BP percentiles (50th, 90th, 95th, and 99th) by age and height were estimated by using the Generalized Additive Model for Location Scale and Shape model. BP values were similar between males and females until the age of 13 years and were higher in males than females thereafter. In comparison with the BP levels of the 90th and 95th percentiles of the US Fourth Report at median height, systolic BP of the corresponding percentiles of these international references was lower, whereas diastolic BP was similar. CONCLUSIONS: These international BP references will be a useful tool for international comparison of the prevalence of elevated BP in children and adolescents and may help to identify hypertensive youths in diverse populations.

Contaminação por mercúrio no Brasil: fontes industriais vs garimpo de ouro

This paper reviews the history of Hg contamination in Brazil by characterizing and quantifying two major sources of Hg emissions to the environment: industrial sources and gold mining. Industry was responsible for nearly 100% of total Hg emissions from the late 1940's to the early 1970's, when efficient control policies were enforced, leading to a decrease in emissions. Gold mining, on the other hand was nearly insignificant as a Hg source up to the late 1970's, but presently is responsible for over 80% of total emissions. Presently, over 115 tons of Hg are released into the atmosphere in Brazil annually. Nearly 78 tons come from gold mining operations, 12 tons come from chlor-alkali industry and 25 tons come from all other industrial uses. Inputs to soils and waters however, are still unknown, due to lack of detailed data base. However, emissions from diffuse sources rather than well studied classical industrial sources are probably responsible for the major inputs of mercury to these compartments.

A presença de mercúrio em casa constitui um risco de contaminação humana e / ou ambiental? Relato de um caso

Mercury kept in a garage of a residencial building in Rio de Janeiro was accidentally released and caused local (environmental and human) contamination. The concentration of mercury in indoor air of the most critical site reached 15.5 mg/m³. Outdoor air samples showed concentrations ranging from 0.37 to 6.6 mg/m³ . Seventy five per cent of the urine samples collected from 22 residents in the contaminated building showed levels of mercury higher than those observed in non exposed individuals (>6.9 mg/L); in 30% of these samples, the concentration was higher than 20 mg/L. These values show a high level of human contamination and the final consequences were not so serious owing to the quick action taken by one of the residents.

Os três princípios e as doenças: a visão de dois filósofos químicos

Paracelsus (1493 - 1541) developed a theory about three principles (sulphur, mercury, and salt) that would constitute matter, and whose mutual interactions within man's body could cause diseases. This paper discusses the influence of this theory on the work of two chemical philosophers. Oswald Crollius (1560 - 1609) considered that the conceptions of matter and disease were strongly related because of the macro - microcosm analogy, and classified diseases in sulphurean, mercurial and saline. On the other hand, J. B. Van Helmont (1579 - 1644) stated that sulphur, mercury, and salt were not true principles, and that every disease would have a specific origin. Instead of the principles, Van Helmont put the Archeus at the center of both his medical and matter theories.

Determinação de elementos-traço: relatório de dois exercícios interlaboratoriais

Results of two intercomparison exercises are reported. In the first one, the participants were asked to determine Cd, Cu, Pb and Zn, at the sub mg mL-1 level, in an acidified aqueous solution. In the second one, the participants were asked to determine mercury (total) in two homogeneous biological samples, hair and fish. The exercises were considered satisfactory and few reported results were discharged (3s criteria).

Metals and Selenium as bioindicators of geographic and trophic segregation in Giant Petrels Macronectes spp.

We analysed concentrations of cadmium, lead, mercury and selenium in blood from males and females of the 2 sibling species of giant petrels, the northern Macronectes halli and the southern M. giganteus, breeding sympatrically at Bird Island (South Georgia, Antarctica). Blood samples were collected in 1998 during the incubation period, from 5 November to 10 December. Between species, cadmium and lead concentrations were significantly higher for northern than for southern giant petrels, which probably resulted from northern giant petrels wintering in more polluted areas (mainly on the Patagonian Shelf and Falkland Islands) compared to southern giant petrels (wintering mainly around South Georgia and the South Sandwich Islands). Between sexes, cadmium concentrations were significantly higher for females than for males in both species, corresponding to the more pelagic habits of females compared to the more scavenging habits of males. Lead and cadmium concentrations in circulating blood decreased significantly over the incubation period, suggesting that when breeding at Bird Island, exposure to the source of pollution had ended, and these metals had been cleared from the blood and excreted, or rapidly transferred to other tissues. Association of lead and cadmium with a common source of pollution was further corroborated by a significant positive correlation between the levels of the 2 elements found. Mercury levels were similar between the species, but showed an opposite trend between sexes, with males showing higher levels than females in northern giant petrels, and the opposite was true in southern giant petrels, with no changes throughout incubation. Selenium levels were similar between sexes, but significantly greater for northern than for southern giant petrels. Moreover, there was a significant increase in the selenium levels over the incubation period in northern giant petrels. Age of adult birds did not affect metal concentrations. Coefficients of variation of metal levels were consistently lower for northern than for southern giant petrels, particularly for mercury, suggesting that the former species is more dietary specialised than the latter. Contaminant analyses, when combined with accurate information on seabird movements, obtained through geolocation or satellite tracking, help us to understand geographic variation of pollution in the marine environment.

Redução seletiva aplicada à especiação de mercúrio em peixes: uma adaptação do método de Magos

In the selective reduction procedure proposed by Magos SnCl2 was used as reductant for inorganic mercury while total mercury was determined after reduction with a mixture of SnCl2 and CdCl2. The difference between total mercury and inorganic mercury determines the content of organic mercury. The procedure of the present work differs of Magos in that the mercury vapour is carried to the absorption cell after magnetic stirring of the solution in the reaction flask; in the Magos procedure, mercury vapour is carried by bubbling the gas in to the solution. In contrast to the Magos procedure this slight modification overcame the necessity of at calibration by analyte addition, saving time and gainning accuracy.

Ympäristöteknologioiden verifioinnin mahdollisuudet pilaantuneiden maiden laadukkaan käsittelyn edistämisessä

EU on käynnistämässä ympäristöteknologioiden verifiointijärjestelmää, jonka avulla voidaan tarjota käyttäjille ja sijoittajille riippumatonta tietoa innovatiivisten teknologioiden toimivuudesta ja suorituskyvystä ja parantaa niiden markkina-asemaa. Verifioinnilla tarkoitetaan kolmannen osapuolen suorittamaa prosessia tai mekanismia, jonka avulla tuotteen toiminta ja suorituskyky voidaan todentaa. Kansallinen ympäristöteknologioiden verifiointijärjestelmä on käytössä mm. Yhdysvalloissa ja Kanadassa. Euroopassa järjestelmä otettaneen käyttöön vuonna 2011–2012. Suomessa tehdään nykyisin noin 300 pilaantuneen maan puhdistushanketta koskevaa lupa- ja ilmoituspäätöstä vuosittain. Noin 85 prosentissa kohteista käytetään kunnostusmenetelmänä massanvaihtoa. Massanvaihto tulee ainakin toistaiseksi säilymään yleisimpänä kunnostusmenetelmänä, mutta mm. in situ -menetelmien käytön arvioidaan lisääntyvän. Tämän diplomityön tavoitteena oli arvioida voidaanko verifiointia hyödyntää pilaantuneiden maiden laadukkaan käsittelyn edistämisessä ja voiko verifiointi nopeuttaa innovatiivisten kunnostusmenetelmien markkinoillepääsyä. Aihetta tarkasteltiin mm. kahden erityyppisen pilaantuneen maan ja pohjaveden kunnostusmenetelmän, reaktiivisten seinämien (in situ) ja bitumistabiloinnin (ex situ) kautta. Pilaantuneiden maiden kunnostusmenetelmien toimivuus riippuu monista eri tekijöistä, joista osaa ei voida hallita tai mallintaa luotettavasti. Verifiointi soveltuukin parhaiten laitteiden tai PIMA-menetelmiä yksinkertaisempien puhdistusmenetelmien suorituskyvyn todentamiseen. Verifiointi saattaa kuitenkin hyvin toimia PIMA-kunnostuksen kohdalla esimerkiksi tiedollisena ohjauskeinona. Reaktiivisten seinämien ja bitumistabiloinnin verifioinnin työvaiheet ovat hyvin samankaltaiset, suurimpana erona seinämien kohdalla tulee kuvata myös kohde johon seinämä on asennettu. Reaktiivisten seinämien toiminta on riippuvaista monista ympäristötekijöistä, toisin kuin erillisellä laitteistolla suoritettavan bitumistabiloinnin. Tulosten perusteella voidaan yleistää, että verifiointi soveltuu paremmin ex situ -, kuin in situ -kunnostusmenetelmille.

Investigação espectroscópica dos carbonilos heterobimetálicos cis-[Fe(CO)4(HgX)2], X = Cl, Br,I

The series of compounds cis-[Fe(CO)4(HgX)2], X=Cl,Br,I shows an octahedral geometry around the iron atom with the two HgX groups cis to each other. In this paper the assignment for the carbonyl stretching modes and the calculation of their force constants were performed on the basis of the Cotton-Krainhanzel model. Taking into account all the data from the IR, 199Hg NMR and UV-vis spectra it is possible to verify the influence of X on the electronic densities at the metallic centers.

Compostos de mercúrio. Revisão de métodos de determinação, tratamento e descarte

This review article on mercury compounds deals with the differences on toxicity of different forms of this metal, the Brazilian regulation for its disposal and the usual methods of determination. Besides that, the text gives special emphasis on the methods used for the treatment and disposal of residues containing mercury, as well as the new developments being made in this area.

O uso de sílica gel organofuncionalizada como agente sequestrante para metais

An overview about the homogeneous and heterogeneous methods of synthesizing silylating agents and applications of the organofunctionalized silica-gel samples was explored. The pendant molecules attached covalently to the inorganic surface displayed important properties to act as sequestrating agents for metals in aqueous and non-aqueous solutions. The large variety of basic centres anchored on organic molecules improve the capacity in adsorbing cations. The increase in adsorption is dependent on the number of basic atoms disposed on the pendant molecules on the surface. The combination of acidic and basicity properties favours the selectivity, such is exemplified by the thiol modified silicas towards mercury (II) cations.