Origin, seasonality and chemical characteristics of rainwater in Aveiro

Este trabalho teve como objectivo caracterizar quimicamente a água da chuva recolhida na cidade de Aveiro, localizada a sudoeste da Europa, no período de Setembro de 2008 a Setembro de 2009. Para matrizes diluídas como a da água da chuva, as metodologias analíticas a utilizar para se conseguir uma rigorosa caracterização química são de grande importância e ainda não estão uniformizadas. Assim, para caracterizar a fracção orgânica, primeiramente foram comparadas duas metodologias de filtração (0.22 e 0.45 μm) e foram estudados dois procedimentos de preservação da água da chuva (refrigeração e congelação), utilizando a espectroscopia de fluorescência molecular. Além disso, foram comparados dois procedimentos de isolamento e extracção da matéria orgânica dissolvida (DOM) da água da chuva, baseados na sorção nos sorbentes DAX-8 e C-18, utilizando as espectroscopias de ultravioleta-visível e fluorescência molecular. Relativamente aos resultados das metodologias de filtração e preservação, é recomendada a filtração por 0.45 μm, assim como, as amostras de água da chuva deverão ser mantidas no escuro a 4ºC, no máximo até 4 dias, até às análises espectroscópicas. Relativamente à metodologia de isolamento e extracção da DOM, os resultados mostraram que o procedimento de isolamento baseado na C-18 extraiu a DOM que é representativa da matriz global, enquanto que o procedimento da DAX-8 extraiu preferencialmente a fracção do tipo húmico. Como no presente trabalho pretendíamos caracterizar a fracção do tipo húmico da DOM da água da chuva, foi escolhida a metodologia de isolamento e extracção baseada na sorção no sorvente DAX-8. Previamente ao isolamento e extracção da DOM da água da chuva, toda a fracção orgânica das amostras de água da chuva foi caracterizada pelas técnicas de ultravioleta-visível e de fluorescência molecular. As amostras mostraram características semelhantes às de outras águas naturais, e a água da chuva do Verão e Outono apresentou maior conteúdo da matéria orgânica dissolvida cromofórica que a do Inverno e Primavera. Posteriormente, a fracção do tipo húmico de algumas amostras de água da chuva, isolada e extraída pelo procedimento baseado na DAX-8, foi caracterizada utilizando as técnicas espectroscópicas de ultravioleta-visível, fluorescência molecular e ressonância magnética nuclear de protão. Todos os extractos continham uma mistura complexa de compostos hidroxilados e ácidos carboxílicos, com uma predominância da componente alifática e um baixo conteúdo da componente aromática. A fracção inorgânica da água da chuva foi caracterizada determinando a concentração das seguintes espécies iónicas: H+, NH4 +, Cl-, NO3 -, SO4 2-. Os resultados foram comparados com os obtidos na chuva colectada no mesmo local entre 1986-1989 e mostraram que de todos os iões determinados a concentração de NO3 - foi a única que aumentou (cerca do dobro) em 20 anos, tendo sido atribuído ao aumento de veículos e emissões industriais na área de amostragem. Durante o período de amostragem cerca de 80% da precipitação esteve associada a massas de ar oceânicas, enquanto a restante esteve relacionada com massas que tiveram uma influência antropogénica e terrestre. De um modo geral, para as fracções orgânica e inorgânica da água da chuva analisadas, o conteúdo químico foi menor para as amostras que estiveram associadas a massas de ar marítimas do que para as amostras que tiveram contribuições terrestres e antropogénicas.

Pregnancy and newborns disorders followed by urine metabolomics

Chapter 1 introduces the scope of the work by identifying the clinically relevant prenatal disorders and presently available diagnostic methods. The methodology followed in this work is presented, along with a brief account of the principles of the analytical and statistical tools employed. A thorough description of the state of the art of metabolomics in prenatal research concludes the chapter, highlighting the merit of this novel strategy to identify robust disease biomarkers. The scarce use of maternal and newborn urine in previous reports enlightens the relevance of this work. Chapter 2 presents a description of all the experimental details involved in the work performed, comprising sampling, sample collection and preparation issues, data acquisition protocols and data analysis procedures. The proton Nuclear Magnetic Resonance (NMR) characterization of maternal urine composition in healthy pregnancies is presented in Chapter 3. The urinary metabolic profile characteristic of each pregnancy trimester was defined and a 21-metabolite signature found descriptive of the metabolic adaptations occurring throughout pregnancy. 8 metabolites were found, for the first time to our knowledge, to vary in connection to pregnancy, while known metabolic effects were confirmed. This chapter includes a study of the effects of non-fasting (used in this work) as a possible confounder. Chapter 4 describes the metabolomic study of 2nd trimester maternal urine for the diagnosis of fetal disorders and prediction of later-developing complications. This was achieved by applying a novel variable selection method developed in the context of this work. It was found that fetal malformations (FM) (and, specifically those of the central nervous system, CNS) and chromosomal disorders (CD) (and, specifically, trisomy 21, T21) are accompanied by changes in energy, amino acids, lipids and nucleotides metabolic pathways, with CD causing a further deregulation in sugars metabolism, urea cycle and/or creatinine biosynthesis. Multivariate analysis models´ validation revealed classification rates (CR) of 84% for FM (87%, CNS) and 85% for CD (94%, T21). For later-diagnosed preterm delivery (PTD), preeclampsia (PE) and intrauterine growth restriction (IUGR), it is found that urinary NMR profiles have early predictive value, with CRs ranging from 84% for PTD (11-20 gestational weeks, g.w., prior to diagnosis), 94% for PE (18-24 g.w. pre-diagnosis) and 94% for IUGR (2-22 g.w. pre-diagnosis). This chapter includes results obtained for an ultraperformance liquid chromatography-mass spectrometry (UPLC-MS) study of pre-PTD samples and correlation with NMR data. One possible marker was detected, although its identification was not possible. Chapter 5 relates to the NMR metabolomic study of gestational diabetes mellitus (GDM), establishing a potentially predictive urinary metabolic profile for GDM, 2-21 g.w. prior to diagnosis (CR 83%). Furthermore, the NMR spectrum was shown to carry information on individual phenotypes, able to predict future insulin treatment requirement (CR 94%). Chapter 6 describes results that demonstrate the impact of delivery mode (CR 88%) and gender (CR 76%) on newborn urinary profile. It was also found that newborn prematurity, respiratory depression, large for gestational age growth and malformations induce relevant metabolic perturbations (CR 82-92%), as well as maternal conditions, namely GDM (CR 82%) and maternal psychiatric disorders (CR 91%). Finally, the main conclusions of this thesis are presented in Chapter 7, highlighting the value of maternal or newborn urine metabolomics for pregnancy monitoring and disease prediction, towards the development of new early and non-invasive diagnostic methods.

Metabolic signature of lung cancer: a metabolomic study of human tissues and biofluids

This thesis reports the application of metabolomics to human tissues and biofluids (blood plasma and urine) to unveil the metabolic signature of primary lung cancer. In Chapter 1, a brief introduction on lung cancer epidemiology and pathogenesis, together with a review of the main metabolic dysregulations known to be associated with cancer, is presented. The metabolomics approach is also described, addressing the analytical and statistical methods employed, as well as the current state of the art on its application to clinical lung cancer studies. Chapter 2 provides the experimental details of this work, in regard to the subjects enrolled, sample collection and analysis, and data processing. In Chapter 3, the metabolic characterization of intact lung tissues (from 56 patients) by proton High Resolution Magic Angle Spinning (HRMAS) Nuclear Magnetic Resonance (NMR) spectroscopy is described. After careful assessment of acquisition conditions and thorough spectral assignment (over 50 metabolites identified), the metabolic profiles of tumour and adjacent control tissues were compared through multivariate analysis. The two tissue classes could be discriminated with 97% accuracy, with 13 metabolites significantly accounting for this discrimination: glucose and acetate (depleted in tumours), together with lactate, alanine, glutamate, GSH, taurine, creatine, phosphocholine, glycerophosphocholine, phosphoethanolamine, uracil nucleotides and peptides (increased in tumours). Some of these variations corroborated typical features of cancer metabolism (e.g., upregulated glycolysis and glutaminolysis), while others suggested less known pathways (e.g., antioxidant protection, protein degradation) to play important roles. Another major and novel finding described in this chapter was the dependence of this metabolic signature on tumour histological subtype. While main alterations in adenocarcinomas (AdC) related to phospholipid and protein metabolisms, squamous cell carcinomas (SqCC) were found to have stronger glycolytic and glutaminolytic profiles, making it possible to build a valid classification model to discriminate these two subtypes. Chapter 4 reports the NMR metabolomic study of blood plasma from over 100 patients and near 100 healthy controls, the multivariate model built having afforded a classification rate of 87%. The two groups were found to differ significantly in the levels of lactate, pyruvate, acetoacetate, LDL+VLDL lipoproteins and glycoproteins (increased in patients), together with glutamine, histidine, valine, methanol, HDL lipoproteins and two unassigned compounds (decreased in patients). Interestingly, these variations were detected from initial disease stages and the magnitude of some of them depended on the histological type, although not allowing AdC vs. SqCC discrimination. Moreover, it is shown in this chapter that age mismatch between control and cancer groups could not be ruled out as a possible confounding factor, and exploratory external validation afforded a classification rate of 85%. The NMR profiling of urine from lung cancer patients and healthy controls is presented in Chapter 5. Compared to plasma, the classification model built with urinary profiles resulted in a superior classification rate (97%). After careful assessment of possible bias from gender, age and smoking habits, a set of 19 metabolites was proposed to be cancer-related (out of which 3 were unknowns and 6 were partially identified as N-acetylated metabolites). As for plasma, these variations were detected regardless of disease stage and showed some dependency on histological subtype, the AdC vs. SqCC model built showing modest predictive power. In addition, preliminary external validation of the urine-based classification model afforded 100% sensitivity and 90% specificity, which are exciting results in terms of potential for future clinical application. Chapter 6 describes the analysis of urine from a subset of patients by a different profiling technique, namely, Ultra-Performance Liquid Chromatography coupled to Mass Spectrometry (UPLC-MS). Although the identification of discriminant metabolites was very limited, multivariate models showed high classification rate and predictive power, thus reinforcing the value of urine in the context of lung cancer diagnosis. Finally, the main conclusions of this thesis are presented in Chapter 7, highlighting the potential of integrated metabolomics of tissues and biofluids to improve current understanding of lung cancer altered metabolism and to reveal new marker profiles with diagnostic value.

Challenges and Potentials for Keyword Extraction from Company Websites for the Development of Regional Knowledge Maps

Regional Innovation Systems describe the relations between actors, structures and infrastructures in a region in order to stimulate innovation and regional development. For these systems the collection and organization of information is crucial. In the present paper we investigate the possibilities to extract information from websites of companies. First we describe regional innovation systems and the information types that are necessary to create them. Then we discuss the possibilities of text mining and keyword extraction techniques to extract this information from company websites. Finally, we describe a small scale experiment in which keywords related to economic sectors and commodities are extracted from the websites of over 200 companies. This experiment shows what the main challenges are for information extraction from websites for regional innovation systems.

Variations in the Work and Lives of Teachers: Relative and Relational Effectiveness

The VITAE project is a four‐year (2001–2005) research study, commissioned by the Department for Education and Skills, conducted with 300 teachers in 100 schools in seven local education authorities in England. The project aimed to identify factors that may affect their work and lives over time and how these factors may, in turn, impact on their teaching and subsequent pupil progress and outcomes. It combined quantitative and qualitative methods of data collection and analysis in order to define and examine notions of teachers' relational and relative effectiveness. The first part of the paper addresses the nature of effectiveness and three key themes relating to the changing contexts of teachers' work, lives and effectiveness: the challenge of reform to notions of professionalism; professional identities; changes in teachers' work and lives. The research design and early findings and their effects upon the development of the research form the second part. The final part of the paper discusses three sets of understandings which are fundamental to any consideration of teachers' work, lives and effectiveness: relative and relational effectiveness; teacher identities; teachers' life and work contexts. The research suggests that policy‐makers, school leaders and teachers themselves need to attend to these if teacher recruitment, retention and standards are to improve.

Defining Spatial and Temporal Hydromorphological Sampling Strategies for the Leigh Brook River Site

Detailed surveys of depth and velocity are undertaken to describe hydro-ecological status of rivers. Fieldwork for these surveys is time consuming and expensive. This paper aims to describe the methodology applied in order to determine the most suitable depth sampling strategy for effective field data collection and river representation in time and space at the Leigh Brook river site, Worcester, UK. The accuracy of three different sampling strategies for predicting depth at non-measured points has been compared and the mesohabitats that better characterise depth changes due to variations in discharge have been identified. The results show that depth changes due to discharge change are mainly located at shallow and deep glide mesohabitat types. The analysis for the comparison of sampling strategies indicates that grid sampling strategies give better results than regular transects. Since the results also show that higher errors in predictions are obtained in the deepest areas, higher sampling densities should be applied in these locations.

Receptivity to Self-Service Technology (SST): A Research Overview and the Way Forward

In a digital era characterised by the need for efficiency and value, self-service technology rises as a delivery interface offered by public and private sector service providers. With the assumption of a win-win situation for both the provider and customers who can ‘do it themselves’ online/offsite and offline/onsite, stereotypes arise concerning antecedents for positive receptivity and impediments in adopting SSTs. The present paper offers a literature-based discussion of some of the existing and emerging perspectives in this domain; it delivers a contextual review of studies conducted, highlights controversial viewpoints that need to be reconsidered, and suggests future research themes that can make use of the emergent digital sources in data collection and analysis. The purpose is to spark future research on the extent to which SST is a champion for different service types, and to systematically study the customer profile to be targeted for its optimal use in value co-creation.

A Bilingual Thesaurus of Everyday Life in Medieval England: Some Issues at the Interface of Semantics and Lexicography

This paper reports on issues at the interface between semantics and lexicography that arose out of the data collection and classification of vocabulary in Anglo-Norman and Middle English in order to create a bilingual thesaurus of everyday life in medieval England. The Bilingual Thesaurus project is based at Birmingham City University and the University of Westminster. Issues to be resolved included the definition of an occupational domain; the creation of a methodology of data collection; the delimitation of domain-specific vocabulary; making distinctions between sense and usage; and the categorisation of the lexical items. Some of these issues are general to thesaurus-making, some are specific to the making of historical thesauruses, while some are unique to the production of a thesaurus of two languages whose use overlapped for several centuries in the late medieval period in England.

RadiaLE: A framework for designing and assessing link quality estimators in wireless sensor networks

Stringent cost and energy constraints impose the use of low-cost and low-power radio transceivers in large-scale wireless sensor networks (WSNs). This fact, together with the harsh characteristics of the physical environment, requires a rigorous WSN design. Mechanisms for WSN deployment and topology control, MAC and routing, resource and mobility management, greatly depend on reliable link quality estimators (LQEs). This paper describes the RadiaLE framework, which enables the experimental assessment, design and optimization of LQEs. RadiaLE comprises (i) the hardware components of the WSN testbed and (ii) a software tool for setting-up and controlling the experiments, automating link measurements gathering through packets-statistics collection, and analyzing the collected data, allowing for LQEs evaluation. We also propose a methodology that allows (i) to properly set different types of links and different types of traffic, (ii) to collect rich link measurements, and (iii) to validate LQEs using a holistic and unified approach. To demonstrate the validity and usefulness of RadiaLE, we present two case studies: the characterization of low-power links and a comparison between six representative LQEs. We also extend the second study for evaluating the accuracy of the TOSSIM 2 channel model.

Influence of transport and time on blood variables commonly measured for the athlete biological passport.

Some recent studies have characterized the stability of blood variables commonly measured for the Athlete Biological Passport. The aim of this study was to characterize the impact of different shipments conditions and the quality of the results returned by the haematological analyzer. Twenty-two healthy male subjects provided five EDTA tubes each. Four shipment conditions (24, 36, 48, 72 h) under refrigerated conditions were tested and compared to a set of samples left in the laboratory also under refrigerated conditions (group control). All measurements were conducted using two Sysmex XT-2000i analyzers. Haemoglobin concentration, reticulocytes percentage, and OFF-score numerical data were the same for samples analyzed just after collection and after a shipment under refrigerated conditions up to 72 h. Detailed information reported especially by the differential (DIFF) channel scatterplot of the Sysmex XT-2000i indicated that there were signs of blood deterioration, but were not of relevance for the variables used in the Athlete Biological Passport. As long as the cold chain is guaranteed, the time delay between the collection and the analyses of blood variables can be extended. Copyright© 2015 John Wiley & Sons, Ltd.

Onondaga chert : geological and palynological studies as applied to archaeology /

Cherts from the Middle Devonian Onondaga Formation of the Niagara Peninsula in Southern Ontario and Western New York State can now be distinguished from those of the Early Devonian Bois Blanc Formation of the same area based on differences in petrology, acritarchs, spores, and "Preservation Ratio" values. The finely crystalline, carbonate sediments of the Bois Blanc Formation were deposited under shallow, low energy conditions characterised by the acritarchs Leiofusa bacillum and L. minuta and a high relative abundance of the spore, Apiculiretusispora minor. The medio crystalline and bioclastic carbonate sediments of the Onondaga Formation were deposited under shallow, high energy conditions except for the finely crystalline lagoonal sediments of the Clarence Member which is characterised by the acritarchs Leiofusa navicula, L. sp. B, and L. tomaculata . The author has subdivided and correlated the Clarence Member of the Onondaga Formation using the "Preservation Ratio" values derived from the palynomorphs contained in the cherts. Clarence Member cherts were used by the Archaic people of the Niagara Peninsula for chipped-stone tools. The source area for the chert is considered to be the cobble beach deposits along the north shore of Lake Erie from Port Maitland to Nanticoke

An impact evaluation of the Ontario ban on smoking in schools and on school property : does the ban on smoking influence high school students' intentions to smoke cigarettes?

The Ontario Tobacco Control Act of 1994 imposed a total ban on smoking in schools, and on school property for every school in the province. The imposition of this policy created problems for school administrators. For instance, students who were smoking on walkways and properties adjacent to school boundaries, clashed with neighbouring property owners who were angry about the resulting damage and disruption. The enforcement of this policy consumes valuable resources at each school; therefore, knowledge about the impact of the policy is important. If effective, this policy has the potential to improve the health of students over their lifetime, by preventing or delaying smoking behaviour. Alternatively, an ineffective policy will continue to create administrative problems for the school and serve no legitimate purpose. Therefore, knowledge about the impact of the smoking ban policy on students' smoking intentions assists policy makers and school administrators in their understanding of the policy's impact within the schools. This research provided an impact evaluation of the ban on smoking in schools and on school property in Ontario. A total of 2069 students, from five high schools, in the Niagara Region, provided complete responses to a survey, designed to test whether smoking intentions were affected by the imposition of the policy. The study used Ajzen's theory of planned behaviour (Ajzen, 1991), specifically, the perceived behavioural control measure, to gain some understanding of students' perceptions of control over smoking imposed by the ban. The findings indicate the policy has the potential to influence students' overall smoking intentions. The ban on smoking policy was found to be a significant predictor of the smoking intentions of high school students. As well, attitude, social norms, and perceptions of control were significant predictors of smoking intentions. Exploratory findings also indicated differences between the control beliefs of students from different high schools, indicating potential differences in the enforcement of the smoking ban between schools. The findings also support the utility of the theory of planned behaviour as a methodology for evaluating the influence of punitive policies. This research study should be continued by utilizing the full theory of planned behaviour, including two phases of data collection and the measurement of actual smoking behaviour.

School integration and the friendships of youth with developmental disabilities

- The present study was an investigation into the effect ofschool integration on the friendships ofyouth with developmental disabilities and their peers without disabilities. The youths, their parents, and their teachers provided insights into the youths' friendships. A qualitative paradigm was used in this research. The researcher guided the collection and analysis ofthe data with the phenomenologicallifeworld existentials of body, space, time, and human relation (Van Manen, 1990). Individual interviews were conducted with each youth, and group interviews were conducted with each triad (a youth, their parent(s), and their teacher) to discuss the youth's friendships and the supports necessary to facilitate the friendships. Through phenomenological analysis of the data, four thematic statements emerged: friendships are far from perfect, to have a friend you have to be a friend, parents as choreographers offriendship, and teachers as reluctant partners in friendship facilitation. Based on the results ofthis study, it was concluded that the development of friendships between youth with developmental disabilities and their peers without disabilities was happening in integrated school settings. However, it was also evident that the support ofteachers and parents alike were required to facilitate the development and maintenance ofsuch friendships. Recommendations for practice are discussed, including the need for active participation by the youth's parents in the facilitation offriendships, and the use ofa "circle offriends" to facilitate friendship development. Also discussed are the recommendations for further research, including the need for the youth's friends to be interviewed regarding their friendships with the youth with disabilities, and the need for researcher observation ofth~ friendships in action. Further research could also explore the role ofthe mother versus the father in facilitating friendships, and the role of recreation and leisure opportunities in the ,development offriendships.

Therapeutic riding : learning and recovery for people with disabilities

The purpose ofthis study was to explore the process oftherapeutic riding as an experiential and holistic approach to learning and recovery for people with disabilities as perceived by the providers oftherapeutic riding. To enhance the connection between theory and practice and to suggest future research, the researcher endeavoured to develop a theory that contributed to the knowledge base oftherapeutic riding, animal-assisted therapy and education, experiential education, and experiential therapy in addition to contributing to connections among them. This topic was investigated because ofthe lack ofresearch about the process of therapeutic riding, particularly from learning and a recovery perspective. Few studies have addressed how therapeutic riding outcomes are achieved or how the therapeutic riding process actually works. This study was identified as grounded theory using qualitative data through interviews and narrative reflections with therapeutic riding providers, a researcher's journal, field notes, and written documents. Grounded theory analysis was used to analyze the qualitative data. This consisted ofdoing open, axial, and selective coding. This study provided detailed descriptions ofthe research approach, researcher's involvement, participant and site selection, data collection and analysis, methodological assumptions and limitations, credibility established, and ethical considerations. The findings ofthe data analysis revealed the theme ofrelationships as central to the learning and recovery process oftherapeutic riding for people with disabilities. The significance ofthe team relationships, the horse and rider relationship, and the providers and rider relationship was found. The essential components ofthe learning and recovery process were presented in a diagram in the selective coding phase. Goals oftherapeutic riding included psycho-education; behavioural and social; physical; and equestrian. Parts ofthe process ofhow outcomes were achieved included motivation; "opens new doors;" risk; task analysis; control; communication; and environmental factors. Outcomes of therapeutic riding included independence and mobility; confidence; and transfer abilities or skills. The implications ofthese findings for theory, practice, and further research were also. explored.

Dinocyst biochronology and palynofacies : inferred systems tract character of Miocene sequences from New Jersey mid-Atlantic transect (ODP legs 174A and 174AX) /

One of the main objectives of the mid-Atlantic transect is to improve dating resolution of sequences and unconfonnity surfaces. Dinoflagellate cysts from two Ocean Drilling Program boreholes, the onshore Leg 174AX Ocean View Site and Leg 174A continental shelf Site 1071, are used to provide age estimates for sequences and unconfonnities fonned on the New Jersey continental margin during the Miocene epoch. Despite the occasional lack of dinocysts in barren and oxidized sections, dinocyst biochronology still offers greater age control than that provided by other microfossils in marginal marine environments. An early Miocene to late Miocene chronology based on ages detennined for the two study sites is presented. In addition, .palynofacies are used to unravel the systems tract character of the Miocene sequences and provide insight into the effects of taphonomy and preservation of palynomorphs in marginal marine and shelf environments under different ~ea level conditions. More precise placement of maximum flooding surfaces is possible through the identification of condensed sections and palynofacies shifts can also reveal subaerially exposed sections and surfaces not apparent in seismic or lithological analyses. The problems with the application of the pollen record in the interpretation of Miocene climate are also discussed. Palynomorphs provide evidence for a second-order lowering of sea level during the Miocene, onto which higher order sea level fluctuations are super-imposed. Correlation of sequences and unconfonnities is attempted between onshore boreholes and from the onshore Ocean View borehole to offshore Site 1071.