Cobalt incorporation in calcite: Thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.

Partitions selection strategy for set of clustering solutions

Clustering is a difficult task: there is no single cluster definition and the data can have more than one underlying structure. Pareto-based multi-objective genetic algorithms (e.g., MOCK Multi-Objective Clustering with automatic K-determination and MOCLE-Multi-Objective Clustering Ensemble) were proposed to tackle these problems. However, the output of such algorithms can often contains a high number of partitions, becoming difficult for an expert to manually analyze all of them. In order to deal with this problem, we present two selection strategies, which are based on the corrected Rand, to choose a subset of solutions. To test them, they are applied to the set of solutions produced by MOCK and MOCLE in the context of several datasets. The study was also extended to select a reduced set of partitions from the initial population of MOCLE. These analysis show that both versions of selection strategy proposed are very effective. They can significantly reduce the number of solutions and, at the same time, keep the quality and the diversity of the partitions in the original set of solutions. (C) 2010 Elsevier B.V. All rights reserved.

Comments on regularization of identity based solutions in string field theory

We analyze the consistency of the recently proposed regularization of an identity based solution in open bosonic string field theory. We show that the equation of motion is satisfied when it is contracted with the regularized solution itself. Additionally, we propose a similar regularization of an identity based solution in the modified cubic superstring field theory.

Efficient solutions to robust, semi-implicit discretizations of the immersed boundary method

The immersed boundary method is a versatile tool for the investigation of flow-structure interaction. In a large number of applications, the immersed boundaries or structures are very stiff and strong tangential forces on these interfaces induce a well-known, severe time-step restriction for explicit discretizations. This excessive stability constraint can be removed with fully implicit or suitable semi-implicit schemes but at a seemingly prohibitive computational cost. While economical alternatives have been proposed recently for some special cases, there is a practical need for a computationally efficient approach that can be applied more broadly. In this context, we revisit a robust semi-implicit discretization introduced by Peskin in the late 1970s which has received renewed attention recently. This discretization, in which the spreading and interpolation operators are lagged. leads to a linear system of equations for the inter-face configuration at the future time, when the interfacial force is linear. However, this linear system is large and dense and thus it is challenging to streamline its solution. Moreover, while the same linear system or one of similar structure could potentially be used in Newton-type iterations, nonlinear and highly stiff immersed structures pose additional challenges to iterative methods. In this work, we address these problems and propose cost-effective computational strategies for solving Peskin`s lagged-operators type of discretization. We do this by first constructing a sufficiently accurate approximation to the system`s matrix and we obtain a rigorous estimate for this approximation. This matrix is expeditiously computed by using a combination of pre-calculated values and interpolation. The availability of a matrix allows for more efficient matrix-vector products and facilitates the design of effective iterative schemes. We propose efficient iterative approaches to deal with both linear and nonlinear interfacial forces and simple or complex immersed structures with tethered or untethered points. One of these iterative approaches employs a splitting in which we first solve a linear problem for the interfacial force and then we use a nonlinear iteration to find the interface configuration corresponding to this force. We demonstrate that the proposed approach is several orders of magnitude more efficient than the standard explicit method. In addition to considering the standard elliptical drop test case, we show both the robustness and efficacy of the proposed methodology with a 2D model of a heart valve. (C) 2009 Elsevier Inc. All rights reserved.

A proposed EPR approach to evaluating agonist binding site of a peptide receptor

Angiotensin II (Ang II) and its transmembrane AT(1) receptor were selected in order to test an innovative strategy that might allow the assessment of the agonist binding site in the receptor molecule. With the use of the 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (TOAC) paramagnetic probe, a biologically active agonist (TOAC(1)-Ang II), as well as an inactive control (TOAC(4)-Ang II) analogs were mixed in solution with various synthesized AT(1) fragments. Comparative intermolecular interactions, as estimated by analyzing the EPR spectra of solutions, suggested the existence of an agonist binding site containing a sequence composed of portions of the N-terminal (13-17) and the third extracellular loop (266-278) fragments of the AT(1) molecule. Therefore, this combined EPR-TOAC approach shows promise as an alternative for use also in other applications related to specific intermolecular association processes.

Effect of the chain length in the structure of imidazolic ionic liquids and dimethylformamide solutions probed by Raman spectroscopy

The Raman band assigned to the nu(C=O)mode in N,N-dimethylformamide (at ca. 1660 cm(-1)) was used as a probe to study a group of ionic liquids 1-alkyl-3-methylimidazolium bromide ([C(n)Mlm]Br) with different alkyl groups (n = 2, 4, 6, 8 and 10 carbons) in binary equimolar binary mixtures with dimethylformamide. Due to the high electric dipole moment of the group C=O, there is a substantial coupling between adjacent molecules in the solution, and the corresponding Raman band involves both vibrational and reorientational modes. Different chain lengths of the ILs lead to different extents of the uncoupling of adjacent molecules of dimethylformamide, resulting in different shifts for this band in the mixtures. Information about the organization of ionic liquids in solution was obtained and a model of aggregation for these systems is proposed. (C) 2010 Elsevier B.V. All rights reserved.

Analysis and Evaluation of EndpointSecurity Solutions

The main objective for this degree project was to analyze the Endpoint Security Solutions developed by Cisco, Microsoft and a third minor company solution represented by InfoExpress. The different solutions proposed are Cisco Network Admission Control, Microsoft Network Access Protection and InfoExpress CyberGatekeeper. An explanation of each solution functioning is proposed as well as an analysis of the differences between those solutions. This thesis work also proposes a tutorial for the installation of Cisco Network Admission Control for an easier implementation. The research was done by reading articles on the internet and by experimenting the Cisco Network Admission Control solution. My background knowledge about Cisco routing and ACL was also used. Based on the actual analysis done in this thesis, a conclusion was drawn that all existing solutions are not yet ready for large-scale use in corporate networks. Moreover all solutions are proprietary and incompatible. The future possible standard for Endpoint solution might be driven by Cisco and Microsoft and a rude competition begins between those two giants.

Optimization heuristic solutions, how good can they be? : With empirical applications in location problems

Combinatorial optimization problems, are one of the most important types of problems in operational research. Heuristic and metaheuristics algorithms are widely applied to find a good solution. However, a common problem is that these algorithms do not guarantee that the solution will coincide with the optimum and, hence, many solutions to real world OR-problems are afflicted with an uncertainty about the quality of the solution. The main aim of this thesis is to investigate the usability of statistical bounds to evaluate the quality of heuristic solutions applied to large combinatorial problems. The contributions of this thesis are both methodological and empirical. From a methodological point of view, the usefulness of statistical bounds on p-median problems is thoroughly investigated. The statistical bounds have good performance in providing informative quality assessment under appropriate parameter settings. Also, they outperform the commonly used Lagrangian bounds. It is demonstrated that the statistical bounds are shown to be comparable with the deterministic bounds in quadratic assignment problems. As to empirical research, environment pollution has become a worldwide problem, and transportation can cause a great amount of pollution. A new method for calculating and comparing the CO2-emissions of online and brick-and-mortar retailing is proposed. It leads to the conclusion that online retailing has significantly lesser CO2-emissions. Another problem is that the Swedish regional division is under revision and the border effect to public service accessibility is concerned of both residents and politicians. After analysis, it is shown that borders hinder the optimal location of public services and consequently the highest achievable economic and social utility may not be attained.

Exact static soliton solutions of (3+1)-dimensional integrable theory with nonzero Hopf numbers

In this paper, we explicitly construct an infinite number of Hopfions (static, soliton solutions with nonzero Hopf topological charges) within the recently proposed (3 + 1)-dimensional, integrable, and relativistically invariant field theory. Two integers label the family of Hopfions we have found. Their product is equal to the Hopf charge which provides a lower bound to the soliton's finite energy. The Hopfions are explicitly constructed in terms of the toroidal coordinates and shown to have a form of linked closed vortices.

A class of soliton solutions for the N=2 super mKdV/Sinh-Gordon hierarchy

Employing Hirota's method, a class of soliton solutions for the N = 2 super mKdV equations is proposed in terms of a single Grassmann parameter. Such solutions are shown to satisfy two copies of N = 1 supersymmetric mKdV equations connected by nontrivial algebraic identities. Using the super Miura transformation, we obtain solutions of the N = 2 super KdV equations. These are shown to generalize solutions derived previously. By using them KdV/sinh-Gordon hierarchy properties we generate the solutions of the N = 2 super sinh-Gordon as well.

Fluorescence study of the interaction between metal ions and methyl methacrylate methacrylic acid copolymers in aqueous solutions: thallium(I), calcium(II), and terbium(III)

The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

Temperature and concentration dependence of heat capacity of model aqueous solutions

Heat capacities of binary aqueous solutions of different concentrations of sucrose, glucose, fructose, citric acid, malic acid, and inorganic salts were measured with a differential scanning calorimeter in the temperature range from 5degreesC to 65degreesC. Heat capacity increased with increasing water content and increasing temperature. At low concentrations, heat capacity approached that of pure water, with a less pronounced effect of temperature, and similar abnormal behavior of pure water with a minimum around 30degreesC-40degreesC. Literature data, when available agreed relatively well with experimental values. A correction factor, based on the assumption of chemical equilibrium between liquid and gas phase in the Differential Scanning Calorimeter, was proposed to correct for the water evaporation due to temperature rise. Experimental data were fitted to predictive models. Excess molar heat capacity was calculated using the Redlich-Kister equation to represent the deviation from the additive ideal model.

Environmental solutions of recovery of Amazonian forest mining operations

In order for the projects of recovery of degraded areas to be successful, it is necessary to have a perfect recovery of the soil where the revegetation will be implanted as an initial action in the recovery of the whole process. The use of native forest species fully adapted to these types of terrain is another aspect of great importance, once the non-selection of these species, even if abundant in the surrounding areas, as it is in our case, implies great mortality of individuals during the planting and their low fixation during the process. The establishment of a monitoring program that contemplates the advancements obtained in the soil, the vegetation and the return of wild animals also collaborate in the evaluation of the success of the process. And, finally, the effective participation of the mining company, accepting and applying the techniques tested and indicated by research, even if, initially, the return time is longer than expected, also guarantees the success of the process. The mining company not only implemented a partnership with important universities in Brazil to obtain solutions for the environmental problems but also applied the developed techniques and the monitoring program. In the present work, we have attempted to summarize important aspects to evaluate the advancements in the rehabilitation plan for those areas, being here presented some results of the monitoring of areas under different levels of recovery, in accordance with the techniques adopted. Biological parameters of the soil were used to verify the efficiency of these different techniques in the recovery process. This work is part of the monitoring program of areas in rehabilitation by the mining company, implemented as of 1999 and in partnership with universities. The microbial activity was determined through the quantification of the carbon and nitrogen microbial biomass (BMC and BMN) and the activity of the dehydrogenase evaluated in the mining floor and tailing areas in different levels of soil preparation and planting of native species. The analysis of the parameters studied revealed that the preparation of the soil, following the three years proposed by the methodology, was important for the success in establishing the rehabilitation process. Some of the areas analyzed already show some parameters with values close or superior to those found in the capoeira (secondary forest), the latter being the non-treated area. © 2010 WIT Press.

Growth of TiO2 nanotubes by anodization of Ti-7.5Mo in NH 4F solutions

Titanium and its alloys are widely used as biomaterials due to their mechanical, chemical and biological properties. To enhance the biocompatibility of titanium alloys, various surface treatments have been proposed. In particular, the formation of titanium oxide nanotubes layers has been extensively examined. According to the literature, it is possible to induce the growth of TiO2 on the surface of titanium, employing the aqueous anodizing electrolyte. This Ti-7.5Mo alloy was anodized in glycerol electrolytes containg 0.25 wt% of NH4F, with variations in time, voltage and calcinations temperature. After anodization, the sample surfaces were analyzed with a field emission scanning electron microscopy, DRX and contact angle measurements. It was possible to observe the formation of TiO2 on the surface and these findings represent a simple surface treatment for Ti alloys that has high potential for biomedical applications. Copyright © 2013 American Scientific Publishers. All rights reserved.

On the regularity of the pressure field of relaxed solutions to Euler equations with variable density

In this paper we improve the regularity in time of the gradient of the pressure field in the solution of relaxed version of variational formulation proposed by V. I. Arnold and by Y. Brenier, for the incompressible Euler equations with variable density. We obtain that the pressure field is not only a measure, but a function in Lloc2((0,T);BVloc(D)) as an extension of the work of Ambrosio and Figalli (2008) in [1] to the variable density case. © 2013 Elsevier Ltd.