Magnésium | EPFL Graph Search

Le magnésium est l'élément chimique de numéro atomique 12, de symbole Mg. Le magnésium est un métal alcalino-terreux. Il s’agit du neuvième élément le plus abondant de l'univers. Il est le produit, dans de grandes étoiles vieillissantes, de l'addition séquentielle de trois noyaux d'hélium à un noyau carboné. Lorsque de telles étoiles explosent en tant que supernovas, une grande partie du magnésium est expulsé dans le milieu interstellaire où il peut se recycler dans de nouveaux systèmes stellaires. Le magnésium est le huitième élément le plus abondant de la croûte terrestre et le quatrième élément le plus commun de la Terre (après le fer, l'oxygène et le silicium), constituant 13 % de la masse de la planète et une grande partie du manteau de la planète. C'est le troisième élément le plus abondant dissous dans l'eau de mer, après le sodium et le chlore. Les atomes de magnésium existent dans la nature uniquement sous forme de combinaisons avec d'autres éléments, où il présente invaria

Influence of pH on dehalorespiring consortia & first steps in the development of a methodology for acid neutralization in enhanced in situ bioremediation

Nicole Munz

Enhanced in situ bioremediation of chlorinated solvents is, especially in source zone remediation, often limited through the accompanied high acidification of groundwater. This acid built-up originating from the dechlorination itself and fermentation products, such as organic acids, presents a draw-back in the efficiency of dehalorespiring bacteria. It is therefore indispensable to develop and implement appropriate buffering strategies to ensure a constant transformation of toxic chloroethenes to the final non-toxic product ethene. In this study pH tolerance of different dehalorespiring bacteria was tested. The limiting acidic pH varies significantly among the consortia. The consortium SL23b4 (PCE to ethene) grows at all the examined pH (pH 5 to pH 7.5) with a pH optimum between 6 and 7 (depending on the dechlorination step), whereas Maroc 6b (PCE to ethene) was only found to grow at incubation pH of 7, and very slowly at pH 6.5. The consortium 2SO (cis-DCE to ethene) seems to be inhibited at acidic pH (no growth at pH 5 and 5.5) having a pH optimum above neutral pH. In most cases incomplete dechlorination was observed in cultures growing at acidic pH or below the pH optima, accumulating toxic intermediate dechlorination products as a consequence. Additionally, high rates of dechlorination were always accompanied by pH drops up to 1.2 pH units, giving evidence of high acid production. pH had also influence on the community composition. In the consortium SL23b4 a shift from a Dehalococcoides- (pH 6-7.5) to a Sulfurospirillum spp.- (pH5 -5.5) dominated community was observed. Consortium Maroc 6b showed significantly different community compositions due to a pH change of only 0.5 pH units. Dehalococcoides spp. and Dehalobacter spp. were dominating at pH 7 and pH 6.5, respectively. Consortium 2SO is dominated by Dehalococcoides spp. at all pH, although at pH 7 a much higher diversity seems to prevail, with the threefold number of OTUs. Tests on the tolerance of the dehalorespiring consortia for elevated PCE concentration showed similar patterns for the different dechlorination steps, as for pH cultures, and confirmed a generally higher sensitivity towards PCE and pH changes for the last steps of dechlorination. Conclusively, Dehalococcoides spp., the only known genera able to perform complete dechlorination, seem to be highly sensitive to pH and PCE changes. Further, abiotic experiments on silicate mineral dissolution, using forsteritic olivine, were performed to simulate the buffer capacity of the minerals for the acid production during microbial reductive dechlorination. In these experiments, the buffer capacity was insufficient to counterbalance the constant acid titration rate, resulting in a final pH between 3 and 4 (initial pH of 7). The formation of precipitates, such as iron oxide, and the re-precipitation of magnesium were observed in some cases, showing a decrease in magnesium concentrations.

2010

Design of Surface-Supported Bio-inspired Networks for CO2 and O2 Activation at Room Temperature

Daniel Eduardo Hurtado Salinas

The structure of a biological system defines its function. Therefore, nature has developed sophisticated systems that catalyze chemical reactions that are vital for life on earth. For instance, the photosynthesis is a biological process that is partially regulated by the metallo-enzyme RuBisCO (Ribulose-1,5-bisphosphate carboxylase/oxygenase), whose function is to catalyze the capture and transfer of CO2 into organic molecules. This carboxylation reaction occurs at the active site, where a magnesium ion (Mg2+) is bound to organic molecules with carboxylate (COO-) and amine (NH2) functional groups. In the last decades, supramolecular chemistry has proven to be a valid approach to replicate the structural characteristics of these natural metal-organic systems. Metal atoms and organic molecules are used as building blocks to form two-dimensional (2D) metal-organic networks (MONs) on metal surfaces, through a self-assembly process that occurs spontaneously. In these systems the molecules bind to the metal centers and control their oxidation states that, as found in metallo-enzymes, is crucial to perform a catalytic task. Therefore, these supramolecular assemblies show promising features to be explored for heterogeneous catalysis. The main objective of this thesis is to reverse the structure-function equation, that is: instead of finding specific functions of well-known 2D structures for future applications, 2D structures are designed to reproduce the specific functions of well-known bio-systems. Thus, inspired in the structure of the active site of RuBisCO, 2D Mg-based supramolecular assemblies are rationally designed on Cu(100) or Mg(0001) surfaces at room temperature (RT) as a platform for CO2 adsorption. This work is the first study of self-assembly of alkaline earth metal atoms (Mg) with organic molecules ((1,4-benzenedicarboxylic acid (TPA) and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT)) on metal surfaces. The first part of this thesis investigates the self-assembly of TAPT molecules. Scanning Tunneling Microscopy (STM) and High Resolution X-ray Photoemission Spectroscopy (HR-XPS) demonstrate that the molecules typically semi-deprotonate to form MONs with the adatoms from the host substrates. The exposure of these structures to CO2 results in the carboxylation of the amino groups. The second part proves that the COOH moieties of TPA molecules fully-deprotonate to form homo-molecular structures. The incorporation of Mg adatoms result in ionic MONs, which reproduce the carboxylate environment of the active site of RuBiSCO. STM, XPS and Density Functional Theory (DFT) analyze the structural changes, the chemical reactions and charge transfer during either the CO2 or O2 adsorption on the Mg2+ centers. The last part focusses on the co-deposition of both molecules to form 2D metallic-hetero-molecular networks with Mg2+ centers. The role of the Mg2+ centers as active sites for molecular adsorption and model systems for gas storage is studied. STM reveals that CO2 partially modifies the network towards a configuration that resembles the active site of RuBisCO. The formation of 3D structures to enhance CO2 adsorption is also evaluated.

EPFL2018

Investigation of Sulfate Attack by Experimental and Thermodynamic Means

Wolfgang Kunther

This work investigates sulfate attack in complex sulfate environments by exposing different binder types to various sulfate solutions and comparing predicted phase and volume changes with experimental data. The most important aspects of this work can be grouped in three topics: The comparison of the predicted volume increase with the experimentally observed length changes. This part of the work shows that volume increase cannot be linked directly to the observed expansions. Additionally, the volume increase model does not provide an explanation for the driving force for the space filling to overcome mechanical constraints. A more plausible explanation of expansion lies in the theory of crystallization pressure, in which crystals forming from a supersaturated solution seem to be a more applicable explanation for the deterioration differences. However, this is difficult to verify directly as it is impossible to measure the solution concentration or individual crystals exert pressure on their surroundings. It is observed that expansion occurs in systems where thermodynamic modelling predicts the co-existence of ettringite with gypsum. In such a case, if monosulfate and gypsum are both present locally, the solution can be highly supersaturated with respect to ettringite within the exposed materials. An increase of sulfate contents in the C-S-H phase has been observed for these cases, indicating increased sulfate concentrations in the pore solution while providing the necessary confinement for the crystals in intimate phase mixtures to exceed pressure. The presence of bicarbonate ions in the sulfate solution reduces the expansion significantly for the CEM I and CEM III/B binders, and reduced the sulfate uptake in the phase assemblage. The CEM III/B mortars showed a highly leached zone at the surface in which also calcite was observed, this is attributed to the destabilisation of ettringite in the presence of high concentrations of bicarbonate ions. The microstructural characterization combined with the information from thermodynamic modelling suggests that conditions of high supersaturation with respect to ettringite are unlikely to occur in samples exposed to solutions containing bicarbonate ions. Degradation of mortars exposed to complex magnesium containing sulfate solutions showed that the presence of sodium, potassium and calcium in a magnesium solution reduce the deterioration symptoms significantly for the CEM I and CEM III/B mortars. The experimental observations suggest that sulfate attack in natural environments is not only less severe, due to reduced sulfate concentrations in the field, but are likely to be affected by the presence of bicarbonate anions and the common occurrence of different cations. Both of these aspects reduce the deterioration significantly and can be assumed to occur in most natural waters.

EPFL2012