Geochemistry of natural chromium occurrence in a sandstone aquifer in Bauru Basin, Sao Paulo State, Brazil

Anomalous concentrations of Cr(VI) occur in groundwaters of the Adamantina Aquifer, in a large region in the western state of Sao Paulo, sometimes exceeding the potability limit (0.05 mg L(-1)). To identify the possible geochemical reactions responsible for the occurrence of Cr in groundwater in Urania, borehole rock samples were collected in order to carry out mineralogical and chemical analyses. In addition, multilevel monitoring wells were installed and groundwater samples were analyzed. Analyses of the borehole rock samples show the occurrence of a geochemical anomaly of Cr in the quartzose sandstones (average concentrations of 221 ppm). Chrome-diopside is one of the main minerals contributing to this anomaly, having an average Cr content of 1505 ppm. Sequential extraction experiments indicated weakly adsorbed Cr in the order of 0.54 ppm, and this quantity is enough to provide the Cr concentrations observed in groundwater. Groundwaters from the monitoring wells proved to be stratified, with the highest concentrations of Cr(VI) (0.13 mg L(-1)) being associated with high redox and pH values (over 10) and high concentrations of Na. Geochemical reactions that may explain the release of Cr from the solid phase to groundwater involve the release of Cr(III) from minerals (like chrome-diopside and Cr-Fe hydroxide), followed by oxidation of Cr(III) to Cr(VI), probably related to the reduction of Mn oxides present in the aquifer. Then cation exchange occurs and dissolution of carbonates which increases the pH of groundwater, resulting in the desorption and mobilization of Cr(VI) into groundwater. (C) 2011 Elsevier Ltd. All rights reserved.

Anomalous content of chromium in a Cretaceous sandstone aquifer of the Bauru Basin, state of Sao Paulo, Brazil

Anomalous and natural concentrations of Cr(6+), occasionally exceeding the permitted limit for human consumption (0.05 mg/L), have been detected in groundwater in the northwestern region of the state of Sao Paulo. As part of a water-rock interaction investigation, this article describes the chemical and mineralogical characterization of rock samples taken from boreholes in the municipality of Urania, with the objective of identifying Cr-bearing minerals and determining how chromium is associated with these minerals. Rock sample analysis were performed using X-ray Fluorescence, X-ray Diffraction, Scanning Electron Microscopy, electron microprobe and sequential extraction techniques. Chemical analyses indicated that the quartzose sandstones show a geochemical anomaly of chromium, with an average content of 221 ppm, which is higher than the reported chromium content of generic sandstones (35 ppm). Diopside was identified as the primary Cr-bearing mineral potentially subject to weathering processes, with a chromium content of up to 1.2% as Cr(2)O(3). Many of the diopside grains showed dissolution features, confirming the occurrence of weathering. Sequential extraction experiments indicated that 99.3% of the chromium in samples is tightly bonded to minerals, whereas 0.24% is weakly bonded via adsorption. Assuming hypothetically that all adsorbed chromium is released via desorption, the theoretical Cr concentration in water would be one order of magnitude higher than the concentrations of Cr(6+) detected in groundwater. (C) 2010 Elsevier Ltd. All rights reserved.

The low-lying electronic states of BeAs: a first principles characterization

The electronic structure and spectroscopic properties of a manifold of states of a new molecular species, BeAs, have been investigated theoretically at the complete active space self-consistent field/multireference single and double excitations configuration interaction (CASSCF/MRSDCI) approach, using the aug-cc-pV5Z-PP basis set for arsenic, which includes a relativistic effective core potential, and the cc-pV5Z set for beryllium. Potential energy curves of five quartet and eight doublet (I > + S) states correlating with the five lowest-lying dissociation limit are constructed. The effect of spin-orbit coupling is also included in the description of the ground state, and of the doublet states correlating with the second dissociation channel. Dipole moment functions and vibrationally averaged dipole moments are also evaluated. The similarities and differences between BeAs, BeP, and BeN are analyzed. Spin-orbit effects are small for the ground state close to the equilibrium distance, but avoided crossings between Omega = 1/2 states, and between Omega = 3/2 states changes significantly the I > + S curves for the lowest-lying doublets.

New Molecular Species of Potential Interest to Atmospheric Chemistry: Isomers on the [H, S(2), Br] Potential Energy Surface

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

Road Sign Recognition based onInvariant Features using SupportVector Machine

Since last two decades researches have been working on developing systems that can assistsdrivers in the best way possible and make driving safe. Computer vision has played a crucialpart in design of these systems. With the introduction of vision techniques variousautonomous and robust real-time traffic automation systems have been designed such asTraffic monitoring, Traffic related parameter estimation and intelligent vehicles. Among theseautomatic detection and recognition of road signs has became an interesting research topic.The system can assist drivers about signs they don’t recognize before passing them.Aim of this research project is to present an Intelligent Road Sign Recognition System basedon state-of-the-art technique, the Support Vector Machine. The project is an extension to thework done at ITS research Platform at Dalarna University [25]. Focus of this research work ison the recognition of road signs under analysis. When classifying an image its location, sizeand orientation in the image plane are its irrelevant features and one way to get rid of thisambiguity is to extract those features which are invariant under the above mentionedtransformation. These invariant features are then used in Support Vector Machine forclassification. Support Vector Machine is a supervised learning machine that solves problemin higher dimension with the help of Kernel functions and is best know for classificationproblems.

A Gradient-Type Method For Real-Time State Estimation Of Water Distribution Networks

Drinking water distribution networks risk exposure to malicious or accidental contamination. Several levels of responses are conceivable. One of them consists to install a sensor network to monitor the system on real time. Once a contamination has been detected, this is also important to take appropriate counter-measures. In the SMaRT-OnlineWDN project, this relies on modeling to predict both hydraulics and water quality. An online model use makes identification of the contaminant source and simulation of the contaminated area possible. The objective of this paper is to present SMaRT-OnlineWDN experience and research results for hydraulic state estimation with sampling frequency of few minutes. A least squares problem with bound constraints is formulated to adjust demand class coefficient to best fit the observed values at a given time. The criterion is a Huber function to limit the influence of outliers. A Tikhonov regularization is introduced for consideration of prior information on the parameter vector. Then the Levenberg-Marquardt algorithm is applied that use derivative information for limiting the number of iterations. Confidence intervals for the state prediction are also given. The results are presented and discussed on real networks in France and Germany.

Central limit theorem for asymmetric kernel functionals

Asymmetric kernels are quite useful for the estimation of density functions with bounded support. Gamma kernels are designed to handle density functions whose supports are bounded from one end only, whereas beta kernels are particularly convenient for the estimation of density functions with compact support. These asymmetric kernels are nonnegative and free of boundary bias. Moreover, their shape varies according to the location of the data point, thus also changing the amount of smoothing. This paper applies the central limit theorem for degenerate U-statistics to compute the limiting distribution of a class of asymmetric kernel functionals.

As desventuras do duty to mitigate the loss no Brasil : nascimento (e morte) de um brocardo

Primeiramente, o trabalho descreve sinteticamente a tradição common law, inserindo o o duty to mitigate the loss em contexto próprio. Então, traça as linhas gerais que, naquele cenário, conformam o instituto. Atenção é dada aos fundamentos do duty to mitigate the loss e às funções por ele desempenhadas, inclusive nos casos subordinados à United Nations Convention on Contracts for the International Sale of Goods (CISG). No contexto próprio, o duty to mitigate the loss tem por fundamento primeiro a causation e funciona como um limitador do quantum indenizatório; não trata de um “dever”; cabe ao demandante; tem na razoabilidade das medidas mitigadoras e no reembolso das despesas incorridas características essenciais. Em segundo lugar, a dissertação investiga o duty to mitigate the loss no Brasil, a partir da doutrina selecionada e de decisões do Superior Tribunal de Justiça e de diversos tribunais estaduais. As pesquisas demonstram que o duty to mitigate the loss, sob o nome de mitigation doctrine, ingressou no Brasil pela doutrina, mas desta forma repercutiu pouco nos tribunais. Desprovido desta influência doutrinária anterior, o duty to mitigate the loss retornou ao Brasil por meio de enunciado do Conselho da Justiça Federal, proposto em documento cujo conteúdo é objeto de reflexões neste trabalho, notadamente na questão da íntima relação entre o duty to mitigate the loss e a boa-fé objetiva. A partir do leading case no Superior Tribunal de Justiça, que adotou o enunciado e o documento que lhe serviu de proposta, o duty to mitigate the loss expandiu rapidamente no Brasil. Em São Paulo, foi alçado à princípio e brocardo. No Superior Tribunal e Justiça, foi considerado sub-princípio da boa-fé e aplicado em questões adjetivas e substantivas criminais. Comparativamente, o duty to mitigate the loss no Brasil guarda remotas semelhanças ao instituto homônimo da common law. Este trabalho aponta as diferenças entre os intitutos e concluí com a sistematização das funções que o duty to mitigate the loss desempenha no Brasil, formulando proposta para a reedição de enunciado do Conselho da Justiça Federal.

O princípio da vedação ao retrocesso social e o papel dos poderes públicos na efetivação dos direitos fundamentais sociais

The purpose of this dissertation is to analyze the role of Public Powers in the enforcement of fundamental social rights, according to the principle of prohibition to social regression. The Federal Constitution of Brazil, situated in a position normative hierarchical superior, disciplines the legal and political process of the country, determining how Public Powers (Legislative, Executive and Judiciary) should act to enforce fundamental rights (social). Thus, features a cast of fundamental rights that aim to ensure social justice, highlighting the concern to ensure social values aimed at reducing social inequalities. The will of the state should be prevented by controlling the constitutionality of measures which restrict fundamental social rights, assuming the principle of human dignity, pillar of Social and Democratic State of Right, a dual role in the brazilian legal system, acting as the presupposition of jurisdictional control of the constitutionality of restrictive acts and as supervisory of omission or insufficient action of the State in the fulfillment of their fundamental duties. The constitutional determinations remove from the legislator the option to create or not the law that prints effectiveness to the social rights, as well as from the Executive the option of to execute or not rules directed at realization of the constitutional parameters, and Judiciary to behave or not in accordance with the Constitution, being given to the Powers only the arbitrariness of "how" to do, so that all functions performed by public actors to use the Constitution as a repository of the foundational values of the collectivity. Any situation that does not conform the principle of proportionality in relation to the enforcement of fundamental rights, especially the social, represents an unacceptable social regression unconstitutional. The constitutional rules and principles postulated by the realization of the rights, freedoms and guarantees of the human person, acting the principle of prohibition to social regression to regulate a concrete situation, whenever it is intended to change, reducing or deleting, the content of a social right. This paper of limit of state action serves to provide to the society legal security and protection of trust, ensuring the core of every social right. This should be effected to be sheltered the existential minimum, as a guarantee of the inviolability of human life, respecting the constitutional will, not falling into social regression

A Competência normativa das agências reguladoras e seus limites principiológicos no direito brasileiro

The transition of the liberal state to welfare state, globalization and the crisis of funding from the government spending on the multiple roles demanded an overhaul of the means of intervention in the economic domain and structure organizational of the Public Administration by enhancing the performance of regulatory functions. Therefore appear in Brazilian law independent regulatory agencies with legal administrative particular that gives autonomy increased, with fixed terms and stability of its leaders, police and competencies, normative and administrative judges. In this scenario, given the autonomy granted by the laws of the creation of regulatory agencies, the legislative competence becomes the most contentious issue, as not infrequently is innovation in the legal system. The main foundations of innovative extension producible by regulatory agencies, which diverges doctrine, are the constitutional attribution of own competence of the Public Administration and the discretionary power. Thus, it is necessary to delimit the constitutional and legal foundations of special legislative powers of these autarchies in our legal system, seeking ways to limit and control the production rules of those entities, for the purpose of position them before the powers constitutionally constituted. We note that with the constitutionalisation of administrative law regulatory agencies found limits to its performance in the normative constitutional principles, especially through the principles of efficiency, morality and proportionality, which has enabled a more effective control of their normative acts

Superconducting state in a mesoscopic segment ring

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Less Conservative Control Design for Linear Systems with Polytopic Uncertainties via State-Derivative Feedback

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Heaviside generalized functions and shock waves for a Burger kind equation

The purpose of the work is to study the existence and nonexistence of shock wave solutions for the Burger equations. The study is developed in the context of Colombeau's theory of generalized functions (GFs). This study uses the equality in the strict sense and the weak equality of GFs. The shock wave solutions are given in terms of GFs that have the Heaviside function, in x and ( x, t) variables, as macroscopic aspect. This means that solutions are sought in the form of sequences of regularizations to the Heaviside function, in R-n and R-n x R, in the distributional limit sense.

Abundance and distribution of juvenile pink shrimps Farfantepenaeus spp. in a mangrove estuary and adjacent bay on the northern shore of São Paulo State, southeastern Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Amphibia, Anura, Hylidae, Dendropsophus melanargyreus (Cope, 1887): distribution extension, new state record and geographic distribution map.

We present the first record of Dendropsophus melanargyreus for the state of São Paulo and a distribution map for this species. This new record represents the southeastern limit of distribution, which is 106 Km from the nearest locality previously recorded for this species and is the fourth new register of anuran to northwestern region of São Paulo in the last two years, increasing species list of the region from 33 to 36 species. This results evidence the importance of this region as priority area for inventory.