Structural model for the biogenic Mn oxide produced by Pseudomonas putida

International audienceX-ray diffraction (XRD) and Mn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to elaborate a structural model for phyllomanganates (layer-type 18 Mn oxide) lacking 3D ordering (turbostratic stacking). These techniques were applied to a sample produced by a common soil and freshwater bacterium (Pseudomonas putida) and to two synthetic analogs, δ-MnO2 and “acid birnessite”, obtained by the reduction of potassium permanganate with MnCl2 and HCl, respectively. To interpret the diffraction and spectroscopic data, we applied an XRD simulation technique utilized previously for well-crystallized birnessite varieties, complementing this approach with single-scattering-path simulations of the Mn K-edge EXAFS spectra. Our structural analyses revealed that all three Mn oxides have an hexagonal layer symmetry with layers comprising edge-sharing Mn 4+O 6 26 octahedra and cation vacancies, but no layer Mn 3+O 6 octahedra. The proportion of cation vacancies in the layers ranged from 6 to 17 %, these vacancies being charge-compensated in the interlayer by protons, alkali metals, and Mn atoms, in amounts that vary with the phyllomanganate species and synthesis medium. Both vacancies and interlayer Mn were most abundant in the biogenic oxide. The diffracting crystallites contained three to six randomly stacked layers, and have coherent scattering domains of 19-42 Ä in the c* direction, and 60-85 Ä in the ab plane. Thus, the Mn oxides investigated here are nanoparticles that bear significant permanent structural charge resulting from cation layer vacancies and variable surface charge from unsaturated O atoms at layer edges

Eletroquímica das partículas coloidais e sua relação com a mineralogia de solos altamente intemperizados

O conhecimento das propriedades eletroquímicas das partículas minerais dos solos altamente intemperizados é imprescindível para o avanço dos estudos em diferente áreas da Ciência do Solo, como, Física, Manejo e Conservação, Fertilidade e Poluição do Solo. Nesse contexto, o comportamento das cargas superficiais e seu relacionamento com a mineralogia dos solos de carga variável é de importância fundamental para o entendimento e a melhoria da capacidade preditiva de diversos fenômenos, tais como dispersão e floculação de colóides, troca catiônica, adsorção de ânions, especialmente os fosfatos, adsorção de metais pesados, etc. Assim, essa revisão de literatura faz uma abordagem científica do tema "Eletroquímica das partículas coloidais e sua relação com a mineralogia de solos altamente intemperizados", na qual é contemplado o histórico da evolução do conhecimento nesse campo e os desafios para o aprofundamento das pesquisas futuras na área. As diferentes tendências e posicionamentos existentes na literatura sobre Pontos de Carga Zero (PCZs), Caracterização e Medição de Cargas, Nomenclatura e Simbologia de PCZs e Relacionamento entre Cargas e Minerais de solos altamente intemperizados são também apresentados. Conceituações básicas são revisitadas e conceitos novos ou pouco utilizados na Ciência do Solo são apresentados e discutidos, com o intuito de se melhorar o entendimento e aprimorar a interpretação de tão importante ramo da Química, Mineralogia e Poluição de Solos.The knowledge of the electrochemical properties of the mineral particles of highly weathered soils is indispensable for the advance of the studies in different Soil Science areas, like as, Soils Physics, Conservation and Management, Fertility and Pollution. In this context, the surface charge behavior and its relationship with the mineralogy of variable charge soils is of fundamental importance to the understanding and the improvement of the predictive capability of several phenomena, such as, floculation and dispersion of colloids, cations exchange, anion adsorption, specially phosphates, heavy metals adsorption, etc. Therefore, this literature review aims at to make a scientific approach of the topic "Electrochemistry of colloidal particles and its relationship with the mineralogy of highly weathered soils", in which, the historical evolution of the knowledge in this field is covered and the challenges to the development of the research in this area are raised. Different tendencies and views existing in the literature about Zero Points of Charge (ZPC), Charge Characterization and Measurement, ZPCs Terminology and Simbology and Relationship between Charge and Minerals of the highly weathered soils are also presented. Basic concepts are revisited and new or seldom used concepts in Soil Science are presented and discussed with the objective of improving the understanding and refining the interpretation of such important branch of the Soil Chemistry and Mineralogy field

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs(+ )formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs(+ )within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs(+ )for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs(+ )and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output

An integrated approach to seismic stimulation of oil reservoirs: laboratory, field and theoretical results from DOE/industry collaborations.

It has been observed repeatedly that low-frequency (10-500 Hz) seismic stress waves can enhance oil production from depleted reservoirs . Until recently, the majority of these observations have been anecdotal or at the proof-of-concept level. The physics coupling stress waves to multiphase fluid flow behavior in porous media is still poorly understood, even though numerous underlying physical mechanisms have been proposed to explain the observations . Basic research on the phenomenon is being conducted through a U .S. Department of Energy funded collaboration between Lawrence Berkeley National Laboratory, the University of California at Berkeley, Los Alamos National Laboratory and the U .S . oil and gas industry . The project has focused on three main areas of research: (1) laboratory core flow experiments, (2) field seismic monitoring of downhole stimulation tests, and (3) theoretical modeling of the coupled stress/flow phenomenon . The major goal is to obtain a comprehensive scientific understanding of the seismic stimulation phenomenon so that field application technologies can be improved. Initial developments and experimental results in all three research focus areas confirm historic observations that the stimulated flow phenomenon is real and that a fundamental scientific understanding can be obtained through continued research . Examples of project results and developments are presented here

Role of Adsorption Phenomena in Cubic Tricalcium Aluminate Dissolution

The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C₃A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C₃A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C₃A occurring at pH ∼12 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C₃A, reducing its zeta potential to negative values at pH >12. The S and Ca <i>K</i>-edge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of SO₄^2– on the partially dissolved C₃A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C₃A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich leached layer and the complexation of Ca–S ion pairs onto this leached layer provide the key inhibiting effect(s). This model reconciles the results obtained here with the existing literature, including the inhibiting action of macromolecules such as PNS and polyphosphonic acids upon C₃A dissolution. Therefore, this article advances the understanding of the rate-controlling mechanism in hydrated C₃A and thus PC systems, which is important to better controlling the workability of fresh PC concrete