Strategies for halogen determination and isotopic analysis via ICP-MS

Dit werk presenteert nieuwe methodes voor de kwantitatieve bepaling van halogenen door middel van inductief gekoppeld plasma massaspectrometrie (ICP-MS) en voor de meting van isotopen verhoudingen gebruikmakend van multicollector (MC) ICP-MS. Vier methodes voor directe vastestofanalyse (SS) door middel van ICP-MS – drie met behulp van elektrothermische vervluchtiging (ETV) en één middels laser ablatie (LA) – en twee methodes voor de isotopenanalyse van Br en Cl in zeewater met MC-ICP-MS werden ontwikkeld. Deze methodes werden toegepast op stalen afkomstig uit concrete studies en geven als dusdanig relevante resultaten met betrekking tot milieuprocessen. In alle methodes waarin SS-ETV-ICP-MS toegepast werd, werden de vaste stalen direct afgewogen in grafietbuisjes en ingebracht in de grafietoven. De instrumentele parameters werden geoptimaliseerd voor het bekomen van een hoge gevoeligheid en efficiënte verwijdering van de matrix. Chloorbepaling in biologische stalen kon uitgevoerd worden via kalibratie tegenover waterige standaardoplossingen, in de aanwezigheid van vooraf gedroogde modifiers (Pd + Nd of Pd + Ca) of met gecertificeerde vaste referentiematerialen (CRMs), eveneens in de aanwezigheid van vooraf gedroogde modifiers of zonder gebruik te maken van modifiers, wat leidt tot een kwantificatielimiet (LOQ) van 5 µg g-1. Voor de bepaling van Br en Cl in steenkoolstalen werd Cl accuraat gemeten middels kalibratie met vaste standaarden, terwijl Br ook succesvol werd gekwantificeerd via kalibratie met waterige standaardoplossingen, in beide gevallen met vooraf gedroogde modifiers (Pd + Ca). Kwantificatielimieten van 0.03 µg g-1 en 7 µg g-1 werden bereikt voor respectievelijk Br en Cl. In een derde deel van dit werk werden F, Cl, Br en I bepaald in fijn stof (PM10). Fluor werd bepaald middels hoge resolutie moleculaire absorbtiespectrometrie (HR-CS MAS), waarbij de CaF molecule geobserveerd werd, terwijl Cl, Br en I bepaald werd door middel van SS-ETV-ICP-MS. De methode liet de kwantificatie van halogenen toe in 14 PM10-stalen verzameld in een noordoostelijke kuststad in Brazilië. De resultaten toonden variaties in halogeengehalte naargelang de meteorologische omstandigheden, in het bijzonder gerelateerd aan regenval, relatieve luchtvochtigheid en zonneschijn. In een vierde deel wordt de bepaling van broom in polymeerstalen met LA-ICP-MS behandeld. Onder geoptimaliseerde omstandigheden kon Br accuraat bepaald worden in vijf verschillende polymeerstandaarden (CRM) en vijf ‘echte’ polymeerstalen door externe calibratie tegenover verschillende CRMs en eveneens door externe calibratie tegenover slechts één CRM, mits gebruik van het 12C+ als interne standaard. De LOQ werd bepaald op 110 µg g-1 Br. Daarnaast werd aangetoond dat de accurate en precieze meting van broom- en chloorisotopen verhoudingen in zeewater via MC-ICP-MS mogelijk is mits het gebruik van hoge massaresolutie, en door toevoeging van 5 mmol L-1 NH4OH aan alle staal-, standaard- en wasoplossingen (voor analietconcentraties van ≥ 3 mg L-1 voor Br en ≥ 70 mg L-1 voor Cl). Het overgrote deel van de kationen in zeewater werd voorafgaand aan de analyse verwijderd door kationenuitwisselingschromatografie (Dowex 50WX8 hars). In het geval van Br liet het uitdampen van de stalen bij 90°C toe om de stalen op te concentreren zonder analietverlies of isotopische fractionatie. Voor beide elementen werd gecorrigeerd voor massadiscriminatie door externe correctie in een staal-standaard ‘bracketing’ benadering, en tevens werd ook nagegaan of Sr, Ge of Se kunnen aangewend worden als potentiële interne standaarden voor Br-isotopenanalyse. Vergelijking van de bekomen resultaten bij de analyse van CRMs met de referentiewaarden of waarden uit de literatuur, toonde aan dat beide methodes aanleiding geven tot precieze en accurate resultaten. Tot slot werden deze methodes toegepast als onderdeel van een milieustudie rond de aanwezigheid van Br en Cl in zeeijs verzameld op verschillende dieptes en locaties tijdens de Sea Ice Physics and Ecosystem eXperiment 2012 expeditie. De concentratie van deze elementen in de stalen bedroeg 700 tot 31000 µg L-1 Br en 200 tot 8000 mg L-1 Cl en er werd een relatie aangetoond tussen de Br en Cl concentraties in de stalen en de overeenkomstige δ81Br en δ37Cl waarden. De lagere concentraties en δ-waarden werden geobserveerd in diep zeeijs, wat waarschijnlijk verklaard kan worden door de optredende ontzoutingsprocessen

Processing of Rainfall Time Series Data in the State of Rio de Janeiro

The goal was to perform the filling, consistency and processing of the rainfall time series data from 1943 to 2013 in five regions of the state. Data were obtained from several sources (ANA, CPRM, INMET, SERLA and LIGHT), totaling 23 stations. The time series (raw data) showed failures that were filled with data from TRMM satellite via 3B43 product, and with the climatological normal from INMET. The 3B43 product was used from 1998 to 2013 and the climatological normal over the 1947- 1997 period. Data were submitted to descriptive and exploratory analysis, parametric tests (Shapiro-Wilks and Bartlett), cluster analysis (CA), and data processing (Box Cox) in the 23 stations. Descriptive analysis of the raw data consistency showed a probability of occurrence above 75% (high time variability). Through the CA, two homogeneous rainfall groups (G1 and G2) were defined. The group G1 and G2 represent 77.01% and 22.99% of the rainfall occurring in SRJ, respectively. Box Cox Processing was effective in stabilizing the normality of the residuals and homogeneity of variance of the monthly rainfall time series of the five regions of the state. Data from 3B43 product and the climatological normal can be used as an alternative source of quality data for gap filling

Uncertainty relations from graph theory

Quantum measurements are inherently probabilistic and quantum theory often forbids to precisely predict the outcomes of simultaneous measurements. This phenomenon is captured and quantified through uncertainty relations. Although studied since the inception of quantum theory, the problem of determining the possible expectation values of a collection of quantum measurements remains, in general, unsolved. By constructing a close connection between observables and graph theory, we derive uncertainty relations valid for any set of dichotomic observables. These relations are, in many cases, tight, and related to the size of the maximum clique of the associated graph. As applications, our results can be straightforwardly used to formulate entropic uncertainty relations, separability criteria and entanglement witnesses.Comment: A counterexample to a conjecture was found by Xu et a

EDUCAR PARA O VIVER E O MORRER

The absence of the pertinent subjects to the death in the educational ways must to a large extent, the terms in the moved away one from the death, virtue of a society that cultivates the curative omnipotence, the maintenance of the life whatever the cost and of any form. We changed ourselves into a society that closes the eyes and silences ahead of the Suicide and the Euthanasia, which exist of kept out of society form, neglected form, renegade form to the edges of the academic and social quarrels. To see human being as a whole, is to congregate physicist, biological, psycho-emotional, spiritual, in all complexity, and, thus to produce knowledge that leaves of an Inter base, multi and to transdisciplinary, is to understand that, when does not have explanation, when it does not have words to describe, is there that the “human being” of the being meets, and is in this scope that we find the subject of the death that must be boarded in the educational environment. This does not imply in having “Doctors in Thanatology” in the Schools, but, only in understanding that of form multi and to interdisciplinary, of critical and reflexive form, any person with maturity and educative formation is apt to dialogue on this thematic one.La ausencia de las cuestiones relativas a la muerte en los ambientes educativos se debe en gran parte a los términos de distancia de la muerte como resultado de una sociedad que cultiva la omnipotencia de la curación, mantenimiento de la vida a cualquier precio y en cualquier caso. Nos hemos convertido en una sociedad que cierra sus ojos y no se pronuncia sobre el suicidio y la eutanasia, que están tan marginados, en el abandono, para que los bordes de renegados de los debates académicos y sociales. Ver al ser humano como un todo es el cumplimiento de los físicos, biológicos, piscó-espiritual, emocional, en todas su complejidad, y por lo tanto producir un conocimiento que sale de una base internacional y multidisciplinar, se entiende que cuando no hay explicación, si no hay palabras para describirlo es que no es el "ser humano y, en este contexto que se encuentra el tema de la muerte que debe abordarse en el ámbito educativo. Esto no implica que "Los médicos de Tanatología en las escuelas, pero sólo para darse cuenta de que en un multi e interdisciplinaria, crítica y reflexiva, a nadie con la madurez y la formación profesional es capaz de hablar sobre esta cuestión.A ausência dos temas pertinentes à morte nos meios educacionais deve-se em grande parte, a termos nos afastado da morte, em virtude de uma sociedade que cultiva a onipotência curativa, a manutenção da vida a qualquer preço e de qualquer forma. Transformamo-nos em uma sociedade que fecha os olhos e silencia diante do Suicídio e da Eutanásia, os quais existem de forma marginalizada, de forma negligenciada, de forma renegada às margens das discussões acadêmicas e sociais. Ver o ser humano como um todo, é reunir o físico, biológico, psicoemocional, espiritual, em toda complexidade, e, assim produzir conhecimentos que partam de uma base inter, multi e transdisciplinar, é compreender que, quando não há explicação, quando não há palavras para descrever, é aí que se encontra o “humano” do ser, e é nesse âmbito que encontramos o tema da morte que deve ser abordado no ambiente educacional. Isto não implica em haver “Doutores em Tanatologia” nas Escolas, mas, apenas em compreender que de forma multi e interdisciplinar, de forma crítica e reflexiva, qualquer pessoa com maturidade e formação educativa está apta a dialogar sobre esta temática

A Terapia Comunitária Integrativa na abordagem da saúde mental na atenção primária: um relato de experiência

The Integrative Community Therapy (ICT), in addition to being a therapeutic method, is considered a community space to user embracement, where people can share their sufferings, life experiences, knowledge, problems, tough situations, victories and overcoming stories. The objective of this work is to report the experience and present the process of an ICT group’s insertion in a primary care unit located in Curitiba-PR. The themes and achievements presented by the participants are discussed, as well as the role of the primary care professional as a therapist in an ICT circle, and its reverberations in the workplace and clinical practice. It is concluded that ICT has great value because it can be understood as a technology for mental health, as well as a collaborative practice of social intervention, given the greatness of its possibilities since it empowers the community in solving their problems, and humanizes the work of the health team.La Terapia Comunitaria Integrativa (TCI), además de ser un método terapéutico, se considera un espacio comunitario de acogida, donde los participantes comparten sus sufrimientos, vivencias, conocimientos, problemas, situaciones difíciles, victorias y superaciones. El objetivo de este trabajo es reportar la experiencia y presentar el proceso de inserción de un grupo de TCI en una unidad básica de salud ubicada en Curitiba-PR. Se discuten los temas y superaciones presentados por los participantes, así como el papel del profesional de atención primaria como terapeuta en una rueda de TCI, y sus repercusiones en el ámbito laboral y en la práctica clínica. Se concluye que la TCI tiene capilaridad y puede entenderse como una tecnología para la salud mental, así como una práctica colaborativa de intervención social, dada la grandeza de sus posibilidades ya que empodera a la comunidad en las soluciones de sus problemas, y humaniza el trabajo del equipo de salud.A Terapia Comunitária Integrativa (TCI), além de método terapêutico, é considerada um espaço comunitário de acolhimento, no qual ocorre partilha dos participantes de seus sofrimentos, experiências de vida, sabedorias, problemas, situações difíceis, vitórias e superações. O objetivo deste trabalho é relatar a experiência e apresentar o processo de inserção de um grupo de TCI em uma unidade básica de saúde localizada em Curitiba-PR. Os temas e superações apresentados pelos participantes são discutidos, assim como o papel do profissional de atenção primária como terapeuta de uma roda de TCI, e suas reverberações no local de trabalho e prática clínica. Conclui-se que a TCI tem capilaridade e pode ser entendida como uma tecnologia para a saúde mental, assim como também uma prática colaborativa de intervenção social dada a grandeza de suas possibilidades, uma vez que empodera a comunidade na resolução de seus problemas, e humaniza o trabalho da equipe de saúde

Business Benefits Associated With Improving Fatigue Regulations for Cargo Pilots

The central idea of this research is to assess business-related factors in the Pilots ́ Fatigue Regulations and evaluate if a more flexible regulation would improve productivity of airline cargo pilots in Brazil. The results of the study have indicated that Brazilian Civil Aviation Authority (ANAC) can create a regulatory environment that may lead up to 34,28% of improved productivity of pilots ́ availability in cargo operations, which may contribute for gains up to USD $3.6 million for an airline with cargo 70 pilots flying 16.500 hours per year. Aviation fatigue regulations are an extremely important subject in the aviation industry as they are a part of an evolution of operational processes within the Safety Management System (SMS). However, some restrictions in regulation may produce some business-related inefficiencies in terms of additional costs or revenue loss to airline companies. The research conducted revised the bibliography available with regards this subject of pilots ́ fatigue regulation in the USA and Brazil. The Group also compared important business-related indicators related to cargo pilots ́ operations in Brazil and calculated potential gains of a hypothetical scenario with an adjusted pilot ́s schedule in line with FAA CFR 177. At last, the research included evaluation of The National Transportation Safety Board (NTSB) records of events of cargo operations in the USA to compare if safety is impacted by fatigue in an environment of an optimized schedule of cargo pilot. A crucial finding of this research is that the proposed changes shall not impact current safety levels caused by fatigue of pilots

Complete hierarchy for high-dimensional steering certification

High-dimensional quantum steering can be seen as a test for the dimensionality of entanglement, where the devices at one side are not characterized. As such, it is an important component in quantum informational protocols that make use of high-dimensional entanglement. Although it has been recently observed experimentally, the phenomenon of high-dimensional steering is lacking a general certification procedure. We provide necessary and sufficient conditions to certify the entanglement dimension in a steering scenario. These conditions are stated in terms of a hierarchy of semidefinite programs, which can also be used to quantify the phenomenon using the steering dimension robustness. To demonstrate the practical viability of our method, we characterize the dimensionality of entanglement in steering scenarios prepared with maximally entangled states measured in mutually unbiased bases. Our methods give significantly stronger bounds on the noise robustness necessary to experimentally certify high-dimensional entanglement.Comment: 5 + 2 pages, 3 figures, comments are welcom

O efeito da identidade social na relação das percepções de impacto social e autenticidade da marca com as intenções de compra e recomendação

Esta dissertação teve como objetivo investigar o efeito da identificação social dos consumidores como membros das comunidades-alvo, utilizadas nas ações afirmativas comunicadas pela empresa, na relação das percepções de impacto social e autenticidade da marca com as intenções de compra e recomendação. Este trabalho abordou os temas de ações afirmativas e os seus impactos sociais, bem como a influência destes na percepção de autenticidade da marca. Além de tratar sobre o fato de que a autenticidade da marca pode ser influenciada pela identidade social do consumidor. Como também, expõe que essas influências supracitadas podem aumentar as intenções de compra e as intenções de recomendação do consumidor sobre a marca. Através de dois estudos experimentais feitos com pessoas que se identificam socialmente como pessoas LGBTQIAP+ e pessoas que não se identificam socialmente desta forma, os resultados desta pesquisa quanto maior o impacto social percebido (ISP) maior será a percepção de autenticidade da marca (AMP) pelo consumidor; A identificação social do consumidor como membro da comunidade-alvo da ação afirmativa comunicada pela empresa acentua a relação entre impacto social percebido e autenticidade percebida; O efeito de mediação da percepção de autenticidade da marca na relação entre impacto social percebido e intenção de compra é moderado pela identificação social do consumidor, bem como o efeito de mediação da percepção de autenticidade da marca na relação entre impacto social percebido e intenção de recomendação é moderado pela identificação social do consumidor. Baseado nisto, esta dissertação contribui para a literatura de marketing, de autenticidade da marca, de identidade social ao evidenciar que quando os indivíduos independentemente da sua identidade social percebem uma ação afirmativa como uma ação de alto impacto social, eles também percebem a empresa como mais autêntica e possuem uma intenção de compra e recomendação maior, o mesmo acontece quando ocorre o inverso. Contudo, outro fator importante foi o fato de que quando as pessoas que se identificam socialmente como membros da comunidade-alvo (ex.: pessoa negra), percebem a ação afirmativa como uma ação de alto impacto social, a marca como mais autêntica e possuem uma maior intenção de compra e recomendação normalmente esses valores são maiores do que os dos consumidores que não se identificam socialmente dessa maneira (ex.: pessoa branca). Do mesmo modo acontece com o inverso (quando for avaliado de forma menor e/ou negativa). Este fato reforça o achado de que os consumidores que se identificam socialmente com a comunidade-alvo são mais críticos do que os demais.This thesis investigates the effect of consumers' social identification as members of the target communities, used in the affirmative actions communicated by the company, on the relationship of social impact perceptions and brand authenticity with purchase intentions and recommendation. It addresses the issues of affirmative action and its social impacts, as well as their influence on the perception of brand authenticity. In addition to dealing with the fact that brand authenticity can be influenced by the consumer's social identity. It also exposes that these aforementioned influences can increase consumers' purchase intentions and recommendation intentions about the brand. Through two experimental studies with people who socially identify themselves as LGBTQIAP+ and also with people who do not socially identify themselves this way, the results of this research showed that the higher the perceived social impact (PSI) the higher the consumer's perception of brand authenticity (PBA); The consumer's social identification as a member of the target community of the affirmative action communicated by the company accentuates the relationship between perceived social impact and perceived authenticity. The mediating effect of perceived brand authenticity on the relationship between perceived social impact and purchase intention is moderated by consumer social identification, as well as the mediating effect of perceived brand authenticity on the relationship between perceived social impact and recommendation intention is moderated by consumer social identification. Based on this, this study contributes to the marketing literature, brand authenticity, and social identity by highlighting that when individuals regardless of their social identity perceive an affirmative action as an action of high social impact, they also perceive the company as more authentic and have a higher purchase intention and recommendation, the same happens when the reverse occurs. However, another important factor was the fact that when people who socially identify themselves as members of the target community (e.g., black people), perceive affirmative action as a high social impact action, the brand as more authentic and have a higher purchase intention and recommendation, these values are usually higher than those consumers who do not socially identify themselves this way (e.g., white people). Likewise, the opposite happens (when it is evaluated in a lower and/or negative way). This reinforces the finding that consumers who identify socially with the target community are more critical than others