Environmental analysis of polar herbicides in complex organic-rich matrices by high performance liquid chromatography atmospheric pressure ionization mass spectrometry (HPLC-API-MS)

A comprehensive forensic investigation of sensitive ecosystems in the Everglades Area is presented. Assessing the background levels of contamination in these ecosystems represents a vital resource to build up forensic evidence required to enforce future environmental crimes within the studied areas. This investigation presents the development and validation of a fractionation and isolation method for two families of herbicides commonly applied in the vicinity of the study area, including phenoxy acids like 2,4-D, MCPA, and silvex; as well as the most common triazine-based herbicides like atrazine, prometyne, simazine and related metabolites like DIA and DEA. Accelerated solvent extraction (ASE) and solid phase extraction (SPE) were used to isolate the analytes from abiotic matrices containing large amounts of organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-), and Chemical Ionization in the positive mode (APCI+) were used to perform the characterization of the herbicides of interest.

Experiências subjetivadoras no limite da pele: Uma análise de práticas discursivas inscritas em tatuagens

This research aims to study the constitution of subjectivities in discursive practices included in imagistic and verbal texts of tattoos. Seeks to grasp the effects of meanings which translate emotions, experiences and disaffection that marked and / or transformed the lives of tattooed subjects. This thesis was anchored in Foucault's theories (1990, 2010, 2012) that address ways of subjectivity from the writing itself, transgression technologies as overshoot, opening new possibilities for discursive subject producing care of itself. Still notions from this analysis of French discourse (AD), as interdiscourse and discursive memory are used. The nature of qualitative research intends to contribute to the understanding of discourse as social practice constitutive of meaning in ways of being of the subject, as well as production of discourses about social norms. The corpus is composed of testimonials and imagistic and verbal texts of five subjects, among the ten respondents who tattooed experiences in the skin. The results show data demonstrating the constitution itself through lived experiences and printed on the skin. The meanings generated in the skin are types of subjectivities that reflect happiness, resilience, protection and immortality. We conclude that our subjects are positioned discursively in order to rebuild their bodies and experiences as necessary and that the images and statements recorded in bodies produce effects felt around the reflection about the ways of life and the existence choices of each one of the tattooed subjects.

Representações discursivas de Câmara Cascudo por Mário de Andrade

This piece of research aims to address the issue on the construction and reconstruction of Câmara Cascudo´s discursive representations in Mário de Andrade´s discourse. In order to describe, analyze and interpret these representations, we recur to some semantic categories from the Discourse Textual Analysis (DTA) by articulating them with other categories, notably, Grize´s Logic (1996,1997), Text Linguistics and Semantics. Therefore, the purpose is to analyze how these representations are constructed discursively, in written letters, by means of semantic categories such as referentiation, predication, modification, connection and spatial and temporal locations. In the theoretical foundation, proposals of Textual Analysis of Discourses, conceived by the linguist Jean-Michel Adam (1990, 2008a, 2011a), Text Linguistics, Semantics and Logic, focusing, especially, on the phenomenon of discursive representations, are articulated. The research approach is of qualitative nature supported by some quantitative data (OLIVEIRA, 2012); option which makes the analysis richer and comprehensive. As a hypothesis, it is presented the fact that these categories used by Mário de Andrade, in his discourse, do not only enable the (re)construction of the interlocutor´s images, discursively constructed, but they also provide a multiplicity of information and viewpoints about the RN writer´s personality. The study corpus is constituted of 20 texts written by Mário de Andrade and sent to Câmara Cascudo between 1924 and 1944, of which 35 fragments were selected and analyzed. However, it can be verified that, in the analyzed corpus, a set of discursive representations is constructed for Câmara Cascudo, from semantic categories proposed for analysis and used in Mário de Andrade´s discourse. These categories enable to construct and reconstruct the representations that emerge in the texts. Therefore, the analysis points out the construction of a set of different representations, highlighting the representation of the writer, the intellectual and the friend.

Análise textual das representações discursivas no discurso político brasileiro: o discurso da primeira posse da presidenta Dilma Rousseff (1°/01/2011)

Cette recherche décrit la représentation discursive que la présidente Dilma Rousseff fait de soi-même, dans son discours devant le Congrès National, lors de la journée d’investiture, le 1/1/2011. Notre travail se situe dans le domaine théorique et méthodologique de la linguistique du texte et, plus spécialement, dans la perspective de l’Analyse Textuelle des Discours – ATD (ADAM, 2011 [2008a]), qui se définit comme « une théorie de la production co(n)textuelle de sens qui doit se fonder sur l’analyse de textes concrets ». Elle nous fournit la notion théorique et analytique de « représentation discursive », qui se focalise sur la dimension sémantique du texte. Nous nous appuyons, aussi, sur des travaux récents sur les représentations discursives, réalisés dans la recherche brésilienne sur l’ATD (RODRIGUES, PASSEGGI, SILVA NETO, 2010, 2012; RAMOS, 2011; OLIVEIRA, 2013; QUEIROZ, 2013; ZAMBLANO-OLIVEIRA, PASSEGGI, 2013). Les principales opérations sémantiques de construction de la représentation discursive utilisées dans notre travail sont la Référenciation et la Prédication. L’approche méthodologique est, en même temps, qualitative et quantitative, priorisant l’identification des occurrences, ainsi que la description détaillée de leurs valeurs sémantiques et textuelles. Les résultats de la recherche sont de trois ordres : méthodologique, théorique et descriptif-interprétatif. Méthodologique : nous proposons une approche que nous désignons comme « marquage textuel » (ou « mappage textuel ») qui permet de marquer (étiqueter) les valeurs sémantiques des formes linguistiques, permettant leur identification dans le flux textuel, c.-à-d., dans la dimension séquentiellecompositionnelle du texte. Théorique : nous introduisons la notion de « domaines de la représentation discursive » qui organisent et articulent les différents éléments qui composent la représentation discursive de la présidente. Quant aux résultats descriptifsinterprétatifs du discours de l’investiture, ils indiquent que la représentation discursive de la présidente se configure au moyen de différents domaines conceptuels, explicités par les référenciations et les prédications. Ils mettent en relief les désignations et les actions / états, aussi bien de la femme – domaine du genre – que de la présidente – domaine du rôle politique et institutionnel. La présidente se représente explicitement et avec emphase comme l’agent responsable par les actions exprimées par les prédications verbales (verbes d’action), consciente de l’importance de son rôle politique et social. Les prédications nominales signalent clairement une représentation discursive qui englobe les domaines conceptuels politique, moral, éthique, comportemental et émotionnel (forte, accueillante, pionnière, consolidatrice, infatigable, humble, engagée, démocrate, victorieuse et courageuse). Le discours d’investiture réalise, donc, des désignations positives de la présidente, lesquelles se situent dans un temps présent et prospectif – avec des perspectives de futur – comme leader politique du Brésil, avec une participation active dans la transformation du pays, tenant compte aussi de son histoire de vie, sa biographie de luttes. Ainsi, la description empirique et l’interprétation de ce discours particulier contribue à l’analyse textuelle des représentations discursives dans le discours politique brésilien contemporain. Elle soulève, aussi, des questions théoriques et méthodologiques qui nous semblent pertinentes pour le développement de cette aproche.

Representações discursivas de Lula nas capas das revistas Época e Veja

This doctoral dissertation proposes to analyze the discursive representations of Lula, as they appear on the covers of the magazines, Época and Veja, targeting the verbo visual elements that comprise the genre, magazine covers. In this way, we seek to describe and interpret the discursive representations (Drs), using a theoretical framework based on the Textual Discourse Analysis –TDA, developed by Jean Michel Adam (2011a), focusing on the semantic level of the text, that is, on the dimension that allows for the comprehension of Drs present in a text. For a discussion about the Drs and their categories of analysis referencing, predication, modification, relation and spatial localization and time we use as a starting point, the study by Brize about the logical discursive operations (1990, 1996), and continue through the studies that discuss linguistic, textual, and discursive operations in concrete utterances, such as Castilho (2010), Rodrigues; Passeggi; Silva Neto (2010), Neves (2011), Rodrigues et al. (2012), Passeggi (2001; 2012), Queiroz (2013), among others. In addition, we rely on Multimodal Discourse for the verbo visual aspects present on magazine covers (KRESS; van LEEUWEN, 2006; DIONISIO, 2011; DIONISIO; VASCONCELOS, 2013). Using aresearch approach that is qualitative with quantitative support, and which is documental, and based on deductive inductive methods, we describe and interpret a corpus (SEVERINO, 2007; CHIZZOTTI, 2010; OLIVEIRA, M., 2013), aiming to reconstruct Lula’s Drs. The cor pusis comprised of forty one magazine covers sixteen from Época and twenty four from Veja. The covers date from the election period in which the candidate, Lula, was elected President of Brazil in 2002, the last mandate after his reelection in 2006, and in the year 2010 a period of 9 years. Based on the analysis carried out, we can affirm that the magazines, Época and Veja, construct diverse Drs by Lula, such as: candidate; elected candidate; governing member and member of a political party; reelected president; politics; workers party acronym PT; international governments as allies; accomplices and participants in scandals of corruption; friend, brother, cousin, nephew, father, parent and man; among others that unfold throughout these by the mediation of the modifiers of the referents and processes, and by the very processes and connections, and analogies made on the object of discourse, Lula. Nonetheless, the reconstruction of these is derived from the description and interpretation of the textual linguistic and discursive choices that the magazines make to produce the proposition utterances, as well as by the choices of images and other visual resources, all operating as co(n)textually articulated to produce the magazine’s desired effect. In conclusion, the Drs verified demand the reflection, description and interpretation of the referencing, prediction, the relationship and spatial temporal localization, which was only possible through the textual discursive analysis of the verbo visual arrangements that comprise texts in the genre magazine cover.

Operações linguístico-discursivas em relatos retextualizados por alunos do ensino fundamental

The following paper attempted to investigate and discuss the possible improvements in the writing of students from the public network in the 6th grade of elementary school. This research was run in the professional master degree In Portuguese Language. Also based upon Genetic Criticism, this study attempting to analyze in which way and in which proportions the alterations done in the texts reveal and perspective capacity in the students as they replace, broad, remove or just move terms in their assignments. We tried to develop our analysis in the pragmatic perspective in which Textual Linguistic is included, investigating the texts and appreciating them as a construction process of meaning. Our theoretical discussion will be based on and socio-interactional conception of language (MARCUSCHI, 2008), as well as in the postulates of Analyze of Discursion (ADAM, 2010, 2008). It has also been used the theoretical assumptions taken from Genetic Criticism which regard the relation between text and genesis, due to the fact that it considers the text and a the result of a construction of progressive elaboration and the writing as an activity of constant movement (DE BIASI, [2000] 2010; GRÉSILLON, 1989; [1990] 2008; [1992] 2002; SALLES, 2008a). To assemble the data in this research we took into consideration the social variables related to the students and the sociocultural context. Nonetheless, this investigation point towards a real classroom situation where we tried to analyze the language functioning in application conditions, thus, giving us authority to describe more precisely the reality we lived in, which provided us with a more attentive look to the observed particularities. This description of the reality appreciated built a path that point to a research of qualitative data approach to which meanings deriving from interpretation were attributed. To conduct this research we resourced to the Action-Research process. The data are comprised of ten personal reports that were created from rewriting assignments, which constitutes a range of twenty texts assessed starting from the linguistic operations acknowledged by Generative Grammar and continued by Lebrave and Grésillon (2009). As result of this analysis, we identified the operation of adding more often than the other ones. The replacement and removal operations display a very close offspring. Nevertheless, the moving operation was scarcely used. These results, besides demonstrating linguistic creativity of the students, revealed that for a text to be seen as “concluded”, the writing student articulates new elaborations through these linguistic operators and that these movements of coming and going, of erasures and amendments contribute significantly for the teacher to approach the relationship the student keeps with his textual and discursive expression, and then, with that, to hold information that eventually provides individual and collective directions in school productions.

Representações discursivas sobre lampião e seu bando em notícias de jornais mossoroenses (1927): “O mais audaz e miserável de todos os bandidos” e o seu “grupo de asseclas”

In this doctoral thesis analyzed the discursive representations of the bandit Lampião, the Lantern and his bandits gang in news mossoroenses newspapers published in the twenties of the last century (1927), when the gang invasion of the city of Mossoro in the state of Rio Grande do Norte, on June 13 of that year. To this end, we take as basis the theoretical assumptions of linguistics Textual, especially the narrower context of what is known today as Textual Analysis of the Discourses (ADT), theoretical and descriptive approach to linguistic studies of the text proposed by the French linguist Jean-Michel Adam. In this approach, we are interested in, specifically, the semantic level of the text, highlighting the notion of discursive representation, studied based on benchmarking operations, predication, modification, spatial location and temporal connection and analogy (ADAM, 2011; CASTILHO, 2010; KOCH, 2002, 2006; MARCUSCHI, 1998, 2008; NEVES, 2007; RODRIGUES, PASSEGGI & SILVA NETO, 2010). The corpus of this research consists of three reports in the twenties of the last century in newspapers The Mossoroense, Correio do Povo and the Northeast, and reconstituted through the collection held in the Municipal Museum Lauro Scotland files, Memorial Resistance Mossoro, both located in Natal, and in the news collection of Lampião newspapers in Natal, north of Rio Grande Raimundo Nonato historian. The discursive representations are built from the use of semantic analysis operations. Lampião to, the following representations are built: bandit, head of bandits, briber, defeated, Captain and Lord. To the outlaws of Lampião bunch of the following discursive representations were built: group, gang, gangsters, mates, bloodthirsty pack, brigands, bandits, criminals, burglar horde, and wild beasts. These representations reveal mainly the views of the newspapers of that time, which represented mainly the interests of traders, politicians, the government itself and generally Mossoró population.

Optimización de la factorización de matrices no negativas en Bioinformática

En los últimos años se ha incrementado el interés de la comunidad científica en la Factorización de matrices no negativas (Non-negative Matrix Factorization, NMF). Este método permite transformar un conjunto de datos de grandes dimensiones en una pequeña colección de elementos que poseen semántica propia en el contexto del análisis. En el caso de Bioinformática, NMF suele emplearse como base de algunos métodos de agrupamiento de datos, que emplean un modelo estadístico para determinar el número de clases más favorable. Este modelo requiere de una gran cantidad de ejecuciones de NMF con distintos parámetros de entrada, lo que representa una enorme carga de trabajo a nivel computacional. La mayoría de las implementaciones de NMF han ido quedando obsoletas ante el constante crecimiento de los datos que la comunidad científica busca analizar, bien sea porque los tiempos de cómputo llegan a alargarse hasta convertirse en inviables, o porque el tamaño de esos datos desborda los recursos del sistema. Por ello, esta tesis doctoral se centra en la optimización y paralelización de la factorización NMF, pero no solo a nivel teórico, sino con el objetivo de proporcionarle a la comunidad científica una nueva herramienta para el análisis de datos de origen biológico. NMF expone un alto grado de paralelismo a nivel de datos, de granularidad variable; mientras que los métodos de agrupamiento mencionados anteriormente presentan un paralelismo a nivel de cómputo, ya que las diversas instancias de NMF que se ejecutan son independientes. Por tanto, desde un punto de vista global, se plantea un modelo de optimización por capas donde se emplean diferentes tecnologías de alto rendimiento...

Stabilisation of dehydrated nanoemulsions using sugar - protein matrices

There are numerous review papers discussing liquid nanoemulsions and how they compare to other emulsion systems. Little research is available on dried nanoemulsions. The objectives of this research were to (i) study the effect of varying the continuous phase of nanoemulsions with different carbohydrate/protein ratios on subsequent emulsion stability, and (ii) compare the physicochemical properties, lactose crystallisation properties, microstructure, and lipid oxidation of spray dried nanoemulsions compared to spray dried conventional emulsions having different water and sugar contents. Nanoemulsions containing sunflower oil (10% w/w), β-casein (2.5–10% w/w) and lactose or trehalose (10–17.5%) were produced following optimisation of the continuous phase by maximising and minimising viscosity and glass transition temperature (Tg’) using mixture design software. Increasing levels of β-casein from caused a significant increase in viscosity, particle size, and nanoemulsion stability, while resulting in a decrease in Tg’. Powders were made from spray drying emulsions/nanoemulsions consisting of lactose or a 70:30 mixture of lactose:sucrose (23.9%), sodium caseinate (5.1%) and sunflower oil (11.5%) in water. Nanoemulsions, produced by microfluidisation (100 MPa), had higher stability and lower viscosity than control emulsions (homogenization at 17 MPa) with lower solvent extractable free fat in the resulting powder. Partial replacement of lactose with sucrose decreased Tg and delayed Tcr. DVS and PLM showed that in powdered nanoemulsions, lactose crystallises faster than in powdered conventional emulsions. Microstructure of both powders (CLSM and cryo-SEM) showed different FGS in powders and different structure post lactose crystallisation. Powdered nanoemulsions had lower pentanal and hexanal (indicators of lipid oxidation) after 24 months storage due to their lower free fat and porosity, measured using a validated GC HS-SPME method, This research has shown the effect of altering the continuous phase of nanoemulsions on microstructure of spray dried nanoemulsions, which affects physical properties, sugar crystallisation, and lipid oxidation.

Analyse simultanée des hormones stéroïdiennes et leurs formes chimiques dans les matrices d'eau et d'urine par SPE-LC-MS/MS en ligne.

Dans les dernières années, les perturbateurs endocriniens ont été observés dans les rivières qui reçoivent des entrées importantes d’eaux usées. Parmi les perturbateurs endocriniens, les hormones stéroïdiennes naturelles et synthétiques sont des composés dont le potentiel d'imiter ou d'interférer avec les fonctions hormonales normales (développement, croissance et reproduction), est reconnu même au niveau ultra-traces (ng L-1). Bien que les hormones conjuguées soient moins actives que les hormones libres, elles peuvent être clivées et redevenir libres une fois exposées aux processus microbiens avant ou pendant le traitement des eaux usées. En raison de la nécessité d'identifier et de quantifier ces composés dans l'eau, une nouvelle méthode, entièrement automatisée, a été développée pour la détermination simultanée des deux formes de plusieurs hormones stéroïdiennes (conjuguées et libres) dans les matrices d'eau et dans l’urine des femmes. La méthode est basée sur l'extraction en phase solide couplée en ligne à la chromatographie liquide et la spectrométrie de masse en tandem (SPE-LC-MS/MS). Plusieurs paramètres ont été évalués dans le but d'optimiser l'efficacité de la méthode, tels que le type et le débit de la phase mobile, des différentes colonnes de SPE et de chromatographie, ainsi que différentes sources et modes d'ionisation des échantillons pour la MS. La méthode démontre une bonne linéarité (R2 > 0.993), ainsi qu'une précision avec un coefficient de variance inférieure à 10%. Les limites de quantification varient d’un minimum de 3 à 15 ng L-1 pour un volume d'injection entre 1 mL et 5 mL et le recouvrement des composés varie de 72 % à 117 %.

Elemental Analysis of Biological Matrices by Laser Ablation High Resolution Inductively Coupled Plasma Mass Spectrometry (LA-HR-ICP-MS) and High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICP-MS)

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of aterials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar16O1H+, and 40Ca16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the nalytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 ìg g-1 and 0.14 ìg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis)samples was achieved using the developed method.

Practicas discursivas sobre el cuerpo en la Universidad de los Llanos

El estudio aquí presentado intentó comprender las concepciones que de cuerpo subyace en la formación de maestros del programa de Licenciatura en Educación Física y Deportes de la Universidad de los Llanos, y cómo estos se develaron en el currículo. Para dicho análisis se acudió a la aplicación de una metodología que permitiera vislumbrar la tendencia y la agenda investigativa de docentes, para prospectar con objetividad dicha situación. Se debió, entonces, abordar la metodología del rastreo arqueológico a partir de la descripción de las condiciones conceptuales del saber objeto de estudio. Los resultados se antojan inquietantes e interesantes en tanto revelación documental partiendo de ciertas categorías de análisis que da cuenta del trasegar del cuerpo en el currículo a partir de 1998

Practicas discursivas sobre el cuerpo en la Universidad de los Llanos

El estudio aquí presentado intentó comprender las concepciones que de cuerpo subyace en la formación de maestros del programa de Licenciatura en Educación Física y Deportes de la Universidad de los Llanos, y cómo estos se develaron en el currículo. Para dicho análisis se acudió a la aplicación de una metodología que permitiera vislumbrar la tendencia y la agenda investigativa de docentes, para prospectar con objetividad dicha situación. Se debió, entonces, abordar la metodología del rastreo arqueológico a partir de la descripción de las condiciones conceptuales del saber objeto de estudio. Los resultados se antojan inquietantes e interesantes en tanto revelación documental partiendo de ciertas categorías de análisis que da cuenta del trasegar del cuerpo en el currículo a partir de 1998

Reglas discursivas y normas morales

El objetivo de este trabajo es explicar la conexión entre reglas discursivas y normas morales en el marco de la ética del discurso. El trabajo comienza con un análisis de la diferencia entre acción y operación y con una reconstrucción del concepto de discurso. Luego es presentada la diferencia y la relación entre ley y obligación. La conclusión es que la conexión entre acción y discurso posible está implícita en la noción de responsabilidad moral.