New Relativistic Atomic Natural Orbital Basis Sets for Lanthanide Atoms with Applications to the Ce Diatom and LuF3

New basis sets of the atomic natural orbital (ANO) type have been developed for the lanthanide atoms La-Lu. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies and some excitation energies. Computed ionization energies have an accuracy better than 0.1 eV in most cases. Two molecular applications are inluded as illustration: the cerium diatom and the LuF3 molecule. In both cases it is shown that 4f orbitals are not involved in the chemical bond in contrast to an earlier claim for the latter molecule.

A green flow-based procedure for fluorimetric determination of acid-dissociable cyanide in natural waters exploiting multicommutation

A flow system designed with solenoid valves is proposed for determination of weak acid dissociable cyanide, based on the reaction with o-phthalaldehyde (OPA) and glycine yielding a highly fluorescent isoindole derivative. The proposed procedure minimizes the main drawbacks related to the reference batch procedure, based on reaction with barbituric acid and pyridine followed by spectrophotometric detection, i.e., use of toxic reagents, high reagent consumption and waste generation, low sampling rate, and poor sensitivity. Retention of the sample zone was exploited to increase the conversion rate of the analyte with minimized sample dispersion. Linear response (r=0.999) was observed for cyanide concentrations in the range 1-200 mu g L(-1), with a detection limit (99.7% confidence level) of 0.5 mu g L(-1)(19 nmol L(-1)). The sampling rate and coefficient of variation (n=10) were estimated as 22 measurements per hour and 1.4%, respectively. The results of determination of weak acid dissociable cyanide in natural water samples were in agreement with those achieved by the batch reference procedure at the 95% confidence level. Additionally to the improvement in the analytical features in comparison with those of the flow system with continuous reagent addition (sensitivity and sampling rate 90 and 83% higher, respectively), the consumption of OPA was 230-fold lower.

A New Indirect Electroanalytical Method to Monitor the Contamination of Natural Waters with 4-Nitrophenol Using Multiwall Carbon Nanotubes

The electrochemical detection of the hazardous pollutant 4-nitrophenol (4-NP) at low potentials, in order to avoid matrix interferences, is an important research challenge. This study describes the development, electrochemical characterization and utilization of a multiwall carbon nanotube (MWCNT) film electrode for the quantitative determination of 4-NP in natural water. Electrochemical impedence spectroscopy measurements showed that the modified surface exhibits a decrease of ca. 13 times in the charge transfer resistance when compared with a bare glassy carbon (GC) surface. Voltammetric experiments showed the possibility to oxidize a hydroxylamine layer (produced by the electrochemical reduction of 4-NP on the GC/MWNCT surface) in a potential region which is approximately 700 mV less positive than that needed to oxidize 4-NP, thus minimizing the interference of matrix components. The limit of detection for 4-NP obtained using square-wave voltammetry (0.12 mu mol L(-1)) was lower than the value advised by EPA. A natural water sample from a dam located in Sao Carlos (Brazil) was spiked with 4-NP and analyzed by the standard addition method using thee GC/MWCNT electrode, without any further purification step. the recovery procedure yielded a value of 96.5% for such sample, thus confirming the suitability of the developed method to determine 4-NP in natural water samples. The electrochemical determination was compared with that obtained by HPLC with UV-vis detection.

The use of polyacrylamides (PAMs) for removing natural organic matter (NOM) from Paraiba do Sul River (Brazil)

This work assesses the efficiency of polyacrylamides for natural organic matter (NOM) removal from Paraiba do Sul River (Brazil) raw water for drinking purposes. Jar tests were performed following an experimental design protocol. Three kinds of polyacrylamides (anionic, cationic, and non-ionic) at 0.2 mg L(-1) were tested. After coagulation, turbidity, DOC, UVA(254) and SCAN (UV-absorbing material) were determined. Color and pH were also measured. It was found that polyacrylamides did not reduce the amounts of alum and lime needed in the process and that the amount of alum alone for removing UV-absorbing organic matter is significantly higher. Efficiency of the coagulation process decreased as follows: non-ionic -> cationic -> anionic -> no polyacrylamide. Removal efficiencies for the best case were: 100%, 90%, 83%, and 68% for turbidity, DOC, UVA(254), and SCAN, respectively.

Quenching of excited states of red-pigment zinc protoporphyrin IX by hemin and natural reductors in dry-cured hams

Zinc protoporphyrin IX (ZnPP), the major red pigment in hams dry-cured without nitrates/nitrites, is an efficient photosensitizer, which upon absorption of visible light forms short-lived excited singlet state ((1)ZnPP*) and by intersystem crossing yields the very reactive triplet-excited state ((3)ZnPP*). Using nano-second laser flash photolysis and transient absorption spectroscopy NADH, ascorbic acid, hemin and dehydroascorbic acid were each found to be efficient quenchers of (3)ZnPP*. The deactivation followed, in homogeneous dimethyl sulfoxide (DMSO) or DMSO:water (1:1) solutions, second-order kinetics. The rate constant for ascorbic acid and NADH for reductive quenching of (3)ZnPP* was at 25 A degrees C found to be 7.5 +/- A 0.1 x 10(4) L mol(-1) s(-1) and 6.3 +/- A 0.1 x 10(5) L mol(-1) s(-1), respectively. The polyphenols catechin and quercetin had no effect on (3)ZnPP*. The quenching rate constant for oxidative deactivation of (3)ZnPP* by dehydroascorbic acid and hemin was at 25 A degrees C: 1.6 +/- A 0.1 x 10(5) L mol(-1) s(-1) and 1.47 +/- A 0.1 x 10(9) L mol(-1) s(-1), respectively. Oxidized glutathione did not act as an oxidative quencher for (3)ZnPP*. After photoexcitation of ZnPP to (1)ZnPP*, fluorescence was only found to be quenched by the presence of hemin in a diffusion-controlled reaction. The efficient deactivation of (3)ZnPP* and (1)ZnPP* by the metalloporphyrin (hemin) naturally present in meat may accordingly inherently protect meat proteins and lipids against ZnPP photosensitized oxidation.

Qualidade de vida no serviço público: um programa para a Agência Nacional do Petróleo, Gás Natural e Biocombustíveis - ANP

This study aimed to verify which are the main factors for a Quality of Working Life Program in context of the Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (ANP). For this, a descriptive, an explanatory, a literature, a documentary and a field research was applied. ANP was the universe of the research. The sample consists of 2 Quality of Working Life Program¿s managers: one of Agência Nacional de Águas (ANA), and another one from Agência Nacional de Saúde Suplementar (ANS), as well as managers and servers from ANP. Two semi structured interviews, a mixed questionnaire and a words evoke test were applied. The Quality of Working Life Factors used in this study were: working conditions, health, moral, compensation, participation, internal communication, organization image, headmansubaltern relationship and working organization. It was concluded that relevant factors for a Quality of Working Life Program in ANP are: working organization, working condition, moral, health and organization image.

Simulação numérica da combustão turbulenta de gás natural em câmara cilíndrica

O presente trabalho apresenta uma modelagem detalhada de processos de combustao turbulentos para um jato concentrico de combustıvel e ar. A modelagem é fundamentada nas equacões de conservacão de massa, de quantidade de movimento, de energia e de espécies quımicas. A turbulencia é resolvida pela utilizacão do modelo k- padrão. Dois modelos de reacões quımicas são apresentados. O modelo SCRS – Simple Chemically-Reacting Systems, que assume taxas instantâneas de reacões quımicas. Também é abordado o modelo E-A – Eddy Breakup - Arrhenius, que assume taxas finitas de reacões quımicas. A radiacão térmica, fenômeno de grande importância devido as altas temperaturas alcancadas em processos de combustão,é modelada através do Método das Zonas. O modelo da soma ponderada de gases cinzas – WSGGM,é usado para determinar o espectro de emissão e absorcão dos gases no processo. Para a solucão destas equacões diferenciais, juntamente com os modelos de turbulência, de reaçõoes químicas e radiação térmica, faz-se o uso do Método dos Volumes Finitos. Para validar a modelagem apresentada resolve-se o processo de combustão em uma câmara cilíndrica. A câmara de combustão usada áa mesma abordada no First Workshop on Aerodynamics of Steady State Combustion Chambers and Furnaces, organizado pela ERCORTAC - European Research Community On Flow Turbulence And Combustion, em outubro de 1994, que apresenta dados experimentais de temperatura e concentração das espécies químicas para várias posições de interesse no interior da câmara. Utiliza-se o gás natural como combustível e o ar atmosférico como oxidante. O processo de combustão sem pré-mistura é resolvido para a condição de excesso de combustível de 5 % para ambos os modelos, onde o gás natural é injetado por um duto circular central, e o ar atmosférico por um orifício anular externo a esse duto, no mesmo plano Uma reação química não estagiada é assumida para o modelo SCRS. Para o modelo E-A duas situações são resolvidas: combustão não estagiada, com uma etapa global de reação química; e reação quımica estagiada, com duas etapas globais. Os resultados obtidos com o modelo SCRS para a distribuição de temperaturas, em termos de tendências gerais, são razoáveis. Já as concentrações de espécies químicas não apresentam dados satisfatórios para este modelo. Para o modelo E-A os resultados apresentam boa concordância com os dados experimentais, principalmente para a situação em que o processo de combustão é assumido em duas etapas globais. ´E analisado em detalhe o papel desempenhado pela transferencia de calor por radiacao, com meio participante. Para melhor verificar as trocas de calor, assume-se uma camara de combustao cilındrica com paredes d’agua. A injecao do combustıvel e do oxidante e feita atraves de um queimador central, semelhante ao usado para validar a modelagem, porem com dois orifıcios concentricos para injecao de combustıvel. Nesta situação o efeito do turbilhonamento (swril), assumido como 20 % da velocidade axial de entrada, sobre a injecao de ar e computado atraves da condicao contorno da equacao de conservacao da quantidade de movimento angular. Nesta fase apenas o modelo E-A, com duas etapas globais de reacoes quımicas, e considerado, ja que o mesmo apresenta os melhores resultados. O processo de combustao e simulado com e sem a presenca da radiacao termica. Verifica-se que a presenca da radiacao termica homogeneiza a temperatura dos gases no interior da camara. Com isso verifica-se tambem alterações nas taxas de reacoes quımicas, modificando a magnitude das fracoes das especies quımicas Quando a radiacao termica e considerada efeitos de extinção local da chama sao verificados nas regioes de temperaturas mais altas, diminuindo o consumo de oxigenio e aumentando a producao de monoxido de carbono, caracterizando assim uma combustao incompleta. Em algumas situacoes tem-se uma variacao de temperatura de ate 500 K, a montante da chama. A radiacao termica tambem aumenta a taxa de transferencia de calor dos gases quentes para as paredes da camara, e desta para o seu exterior. Com os resultados obtidos a partir desta modelagem e possıvel determinar o perfil da zona de combustao, a distribuicao de concentracoes de especies quımicas, o campo de velocidades e as taxas de transferencia de calor para as paredes da camara de combustao, total, por conveccao superficial e por radiacao. Estes resultados sao de extrema importancia para prever a performance de camaras de combustao, assim como auxiliar na sua otimizacao.

O mercado de gás natural veicular em Curitiba : visão dos taxistas

O tema do presente estudo consiste na análise da demanda do mercado de taxistas de Curitiba frente à possibilidade de utilização de um combustível alternativo menos oneroso e poluente: o Gás Natural Veicular – GNV. O objetivo principal deste trabalho foi de analisar o mercado atual do GNV entre os taxistas de Curitiba, verificando a possibilidade de ampliar do uso do GNV por esta frota através de uma pesquisa de mercado. Os dados da pesquisa servirão de subsídios para campanhas de marketing orientadas à ampliação acelerada do uso desta tecnologia. Para tanto, realizou-se uma pesquisa de satisfação para levantar os fatores determinantes para a tomada de decisão dos taxistas de Curitiba de utilizarem ou não um combustível alternativo menos oneroso e poluente como o Gás Natural Veicular – GNV. O estudo visou obter a percepção dos taxistas de Curitiba. Com base nos resultados da pesquisa foi possível estabelecer subsídios para campanhas de marketing orientadas à ampliação acelerada do uso desta tecnologia. Para realização da pesquisa, utilizou-se uma pesquisa exploratória, com entrevistas individuais da cúpula das organizações que trabalham com o Gás Natural, prospectando novos projetos para o futuro e as perspectivas de evolução do mercado de GNV em Curitiba, a qual forneceu subsídios para a pesquisa quantitativa junto aos taxistas da cidade de Curitiba. Constatou-se que somente 36% do público estudado é usuário de gás natural veicular, mas entre os não usuários, 82% já pensou em instalar o kit gás. As principais razões pelas quais os taxistas pesquisados não utilizam o GNV são a perda de espaço no porta-malas e a perda de potência do veículo. Entre os taxistas que utilizam o GNV, no que tange aos atributos relacionados à rede de distribuição, a maior insatisfação refere-se à localização dos postos e a maior satisfação às eventuais filas para abastecimento. Nesses mesmos atributos o que obteve maior índice de importância foi justamente a localização dos postos. Entre os atributos relacionados ao produto, o maior índice de satisfação foi o nível de poluição ambiental e a maior insatisfação espaço para armazenamento, sendo o desempenho do veículo considerado o mais importante. Quanto aos atributos relacionados aos equipamentos, verificou-se a segurança com o maior índice de satisfação e de importância.

Análise da volatilidade de preço do mercado da borracha natural

O foco central deste estudo foi desenvolver uma análise da trajetória dos prsços da borracha natural bensflciada ao longo do século XX, através da utilização dos testes econométricos da dasse - ARCH: GARCH, E-GARCH e TARCH para o da Malásia, principal entidade de formação do preço intemacional da commodity. Como resultado dos testes estatísticos dos dados disponíveis no mercado, observouse uma forte incidência de ciclos de sazonalidade no preço intemacional da borracha impactando diretamente na produção mundial. Observa se ainda a baixa capacidade de resposta da produção a choques de demanda devido ao longo prazo de maturação das pfantações

Coordenação no sistema agroindustrial da borracha natural : um estudo das relações entre produtores rurais e usinas beneficiadoras paulistas

O enfoque da Nova Economia Institucional é utilizado no estudo de sistemas agroindustriais brasileiros, mas ainda há poucos trabalhos sobre as relações entre produtores rurais e indústrias processadoras. O objetivo deste estudo é aferir o alinhamento das características das transações com os modos de governança adotados na comercialização de borracha natural entre produtores rurais e indústrias de beneficiamento primário. Busca-se confrontar os resultados com as previsões da teoria da Economia dos Custos de Transação, que prevê a adoção da governança mais eficiente, contingenciada ao ambiente transacional. Esta pesquisa utiliza um enfoque pioneiro para o setor. A primeira parte consiste na exploração qualitativa das transações entre produtores rurais e usinas beneficiadoras e na descrição dos elementos que compõe o sistema agroindustrial da borracha natural no Estado de São Paulo. Os resultados desta etapa são utilizados para refinar as hipóteses da etapa quantitativa, que relacionam os modos de governança adotados aos investimentos em ativos específicos, como o plantio de seringueiras, à frequência, à incerteza e à assistência técnica associadas à transação. Os resultados, apesar das limitações devido ao tamanho pequeno da amostra, sugerem que a quantidade de borracha comercializada influi positivamente na adoção de modos de governança mais coordenados e que a recorrência das transações provavelmente está associada a contratos relacionais. A hipótese da endogeneidade é rejeitada.

Natural disasters and their impacts on supply chains

This research aimed to understand how Brazilian organizations, located in areas affected by natural disasters were impacted in their operations and the impacts to their whole supply chain. Based on documentary analysis, the study identified the major events that happened in Brazil between 2003 and 2012 and the most affected supply chains, as well as key players during the disaster and the greatest impacts on economic activities. The results suggest that natural disasters are still not considered in the risk management by companies, despite the effects on their activities

Humanitarian operations in Brazil: a review of natural disasters in the last decade

This research used documentary analysis to identify the main natural disasters in Brazil in the last decade (2003 to 2013). Results provided evidence that operations and impacts differ in sudden-onset and slow-onset disasters and that Government is the main player in the Humanitarian Operations in Brazi

Atração e retenção de talentos em empresas de engenharia consultiva no setor de petróleo e gás natural da cidade de Natal

This study addresses the question of attraction and retention of talent in companies that produce engineering projects in the area of oil and natural gas in the city of Natal. The objectives were to identify the mechanisms that these companies use to attract and retain talented professionals and what the relationship between these practices and performance of these organizations in the market. This is a case study of a qualitative nature which were included in the fullness of companies that work in that class in the capital Potiguar. Have been applied to the managers of these companies structured questionnaires with eleven issues orientativas based on theoretical reference adopted. The research finds that managers understand the word "talent", recognize the importance of the appreciation of its employees and the development of their innate abilities to better organizational performance, much due to the fact they are acting in a market of fierce competition. His companies - though not submit the formal procedures related to the subject in question - have mechanisms that can be characterized as the attraction and retention of talent. The relationships identified in this study are consistent with the results found in other studies and put the information here can serve as the basis for that other managers, including other areas, to reach excellence in their respective industries

Avaliação Pós-Ocupação da iluminação natural das salas dos setores de aulas teóricas da Universidade Federal do Rio Grande do Norte

The objective of this study is to assess the natural light of the classrooms sectors, at Universidade Federal do Rio Grande do Norte. It was applied the Post-Occupation Evaluation technique, by using questionnaires and brightness levels measurements inside the classrooms. In order to check the users satisfaction degree, it was initially done a general approach on the related aspects to natural light: their characteristics, availability, sources, opening systems and evaluating tools. It was also determined the necessary brightness levels for the activities development in the classroom and the Post-Occupation Evaluation technique used in the search analyses. Then, it was made the UFRN Campus` characterization; the models` definition which formed the data collection basis; the detailing of the procedures used in the research, the processing description and the data analysis. Subsequently, the results that clarify the issues raised were shown through quantitative and / or qualitative data analyses. This research notes a high level of satisfaction by the users, despite some problems such as the reflections occurrence on the board, the lack of uniformity and, occasionally, the brightness low levels

Paisagem, um patrimônio esquecido: subsídios para a construção de uma metodologia de valoração e proteção do cenário natural litorâneo

The so-called "residential tourism" came to intensify the previous occupation of the coastal zones, characterized by traditional beach houses, and brought significant consequences for their spatial configuration, and especially for its scenic value of the landscape. Although there is the intention to regulate the activities of enterprising groups by some legal instruments to control the use and occupation of land, and to contain some negative effects, the actions of government are still inefficient in trying to follow the implications on the landscape from the accelerated growth of the real estate and touristic sectors. Supported in the speech of economic development and income generation, public managers prioritize areas to attract tourists to the detriment of preserving important physical attributes of the natural environment that contribute significantly to the quality of life. The result can be noticed in the use of natural elements as one of the major components in the land valorization, and in the immediate attraction of investors and enterprising. Therefore, the objective of this work is to contribute to the debate on the landscape preservation a little detailed thematic in view of their relevance in the current context - by indicating subsidies to the creation of a methodology for the evaluation and protection of coastal zones that may assist the government in creating new instruments, and better prepare it in control of the occupation of these areas. For such, was followed two ways to analysis: the indirect method and the direct method. The first is grounded in the evaluation of landscape attributes, which is based on the work of Raquel Tardin (2008) and Eduardo Cuesta, Encarnación Algarra and Isabel Pastor (2001). The second, based on the research of Leticia and Carlos Hardt (2010) and on the concepts of phenomenology - expressed by Antonio Christofoletti (1985) and Yi-Fu Tuan (1983) - considers the population perspective on the quality of the natural scenery. Developed through cartographic materials, photographic collections and quantitative tables, this dissertation utilized as a case study the beaches of Barra de Tabatinga and Camurupim, located in the city of Nísia Floresta/RN. Despite already being sighted spaces of advanced stage of landscape degradation in these locations, areas of remarkable scenic value can still be found, what reinforce the urgency in adopting preservationists actions. The absence of laws focused on the management and protection of the landscape singularities associated with the inefficiency of the government to invigilate the land occupation in coastal zones, encourage the excessive action of the real estate-tourism, and consequently make the government the main responsible for the environmental and landscape impacts in these areas - by its omission or by their connivance. Therefore, the legislation permeates this entire process and constitutes itself as the most effective way to guarantee the right to the landscape to present and future generations. Are also pointed some important considerations to build a methodology, especially concerning possibilities of improvements and adaptations of its applicability in each case