Orientador: Rodrigo Sequinel / Coorientador: Danilo Luiz Flumignan / Banca: Edilene Cristina Ferreira / Banca: Erica Regina Filletti Nascimento / Banca: Mária Cristina Breitkreitz / Banca: Heron Dominguez Torres da Silva / Resumo: Segundo dados, de 2017, da Companhia Ambiental do Estado de São Paulo (CETESB), os postos de combustíveis são responsáveis pela contaminação ambiental de 72% das 5942 áreas contaminadas cadastradas no estado de São Paulo. A contaminação de solos e águas subterrâneas por combustíveis fósseis causam imensos danos ambientais devido à alta toxicidade dos constituintes destes combustíveis, além de apresentarem propriedades carcinogênicas e elevada permanência no solo. O monitoramento ambiental em áreas de risco potencial de contaminação, como postos de combustíveis, é realizado através da análise de hidrocarbonetos totais do petróleo (TPH), entre outros hidrocarbonetos individuais. Estas análises são realizadas através de métodos cromatográficos em fase gasosa que requerem etapas de extração com solventes halogenados, purificação e, muitas vezes, pré-concentração. O elevado custo e o tempo demandado para a quantificação de TPH em solo tornam-se barreiras para o crescimento do monitoramento e acompanhamento de processos de remediação das áreas contaminadas. Desta forma, este trabalho objetivou o desenvolvimento de métodos analíticos mais rápidos e de menor custo para a identificação e quantificação de TPH em solo através da espectroscopia na região do infravermelho próximo (NIR). Três métodos NIR foram desenvolvidos: (i) sem preparo de amostra; (ii) após extração por hexano; e (iii) após extração por etanol. Os modelos de classificação foram desenvolvidos pelo método de análise dis... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: According to the Environmental Company of the State of São Paulo (CETESB), the gas stations are responsible for the environmental contamination of 72% of the 5942 contaminated areas registered in the state of São Paulo. Contamination of soils and groundwater by fossil fuels causes immense environmental damages due to their high toxicity, carcinogenic properties and high permanence in the soil. Environmental monitoring in areas of potential contamination risk, such as gas stations, is carried out through the analysis of total petroleum hydrocarbons (TPH), among other individual compounds. These analyzes are performed by gas chromatographic methods which require some sample preparation steps, such as extraction with halogenated solvents, purification, and often preconcentration. The high cost and time demanded for the quantification of TPH in the soil become barriers for the growth of the monitoring program and remediation processes of the contaminated areas. Therefore, this work aimed at the development of faster and lower cost analytical methods for the identification and quantification of TPH in soil through near-infrared spectroscopy (NIR). Three NIR methods were developed: (i) without sample preparation; (ii) after hexane extraction; and (iii) after extraction with ethanol. The classification models were developed by partial least squares discriminant analysis (PLS-DA) method and the calibration models by partial least squares (PLS) method. In the development of the models... (Complete abstract click electronic access below) / Doutor

La complexité remarquable du sol et son importance pour un large panel de services écosystémiques présentent des défis majeurs pour évaluer les processus pédologiques. En dépit des progrès importants accomplis au cours des cinquante dernières années dans la caractérisation des propriétés hydriques, les méthodes analytiques demeurent coûteuses et chronophages. La spectroscopie proche infrarouge (SPIR) a été largement utilisée comme technique rapide, non destructive et peu coûteuse pour prédire différentes propriétés du sol y compris la teneur en eau. Toutefois, moins d’attention a été accordée à l’évaluation des propriétés hydriques et leurs variations en fonction des propriétés physiques du sol. L’objectif principal de ce travail est d’analyser la validité et la pertinence de la SPIR dans l’évaluation des propriétés hydriques et leur relation avec les caractéristiques du sol.Dans cette étude nous nous sommes focalisés sur la largeur à mi-hauteur de la bande d’absorption proche de 1920 nm pour identifier un nouvel indice spectral, noté SWSI pour caractériser l’état hydrique du sol. Nos résultats montrent une relation linéaire entre SWSI et la teneur en eau du sol (R2 >0.9). Ils ont monté aussi que SWSI est pertinent pour étudier les effets de la texture, de la teneur en carbone organique et des pratiques agricoles sur les propriétés de rétention en eau du sol. En outre, en utilisant les paramètres de cette relation linéaire, nous proposons une nouvelle approche pour caractériser les propriétés hydriques et la qualité physique des sols. En comparaison avec des méthodes clas / The remarkable complexity of soil and its importance for a wide range of ecosystem services present major challenges to the assessment of soil processes. Although major progress in characterizing water retention properties has occurred in the last fifty decades, analytical methods remain costly and time-consuming. Near infrared spectroscopy (NIRS) has been widely used as a rapid, non-destructive and cost-effective technique to predict different soil properties, including soil water content. However, less attention has been paid to assessing soil water retention properties and its variations depending on soil physical properties. The main objective of this work is to analyze the relevance and accuracy of NIRS for assessing soil water retention properties as they are related to soil characteristics.In this study, we focused on the full width at half maximum of the absorption band near 1920 nm to identify a new NIRS index (Soil water spectral index, SWSI) which can be used to characterize the soil water retention properties. Our results show a linear relation between SWSI and soil water content (R2 >0.9). They also shown that SWSI to be relevant to study the effects of texture, organic carbon content and agricultural practices on soil water retention properties. Furthermore, using the parameters (slope and intercept) of this linear relation, we propose a new approach to characterize water retention properties and physical quality of soils. Therefore, NIRS approach performs better or similar in assessing soil water retention properties and soil quality compared to conventiona

La planète Mars a connu une période où l'eau liquide était durablement stable. Outre les vestiges morphologiques d'une activité hydrologique en surface, l'interaction chimique de l'eau avec la croûte basaltique s'est traduite par la formation d'argiles et de sels hydratés en surface et en profondeur. Ces minéraux hydratés ont été détectés à la surface de Mars en 2004 grâce à l'instrument OMEGA, l'imageur hyperspectral infrarouge proche embarqué sur la sonde européenne Mars Express. Leur étude permet de reconstruire l'histoire de l'activité aqueuse sur Mars et de caractériser une période ancienne où l'environnement a pu être favorable à l'apparition d'une chimie pré-biotique. Ce travail de thèse s'intéresse aux environnements aqueux de Mars en couplant les données minéralogiques des imageurs hyperspectraux embarqués OMEGA/Mars Express et CRISM/Mars Reconnaissance Orbiter avec la morphologie. De nouveaux outils de traitement et d'analyse des données sont développés et ont permis la détection et la caractérisation spectrale de plus d'un millier de dépôts de minéraux hydratés sur Mars, fournissant une vue d'ensemble de l'altération. Celle-ci a eu lieu principalement dans la première partie du Noachien et a surtout formé des phyllosilicates ferro-magnésiens de la famille des vermiculites et smectites. Une importante diversité minérale est par ailleurs constatée avec une dizaine de familles minérales différentes, traçants des conditions géo-chimiques variées. Placés dans leur contexte géologique, certaines détections permettent de proposer l'existence passée d'un système hydrologique sur l'ensemble de la planète qui a donné naissance à un cycle des argiles similaire au cycle terrestre. Il apparait par ailleurs que les cratères d'impact sont le contexte privilégié des minéraux hydratés, mais le lien entre ces derniers et les processus d'impact demeure ambigu. La découverte d'un cycle des argiles est compatible avec l'hypothèse d'une planète potentiellement habitable au Noachien mais qui devra être vérifiée par l'exploration in-situ. / The planet Mars has experienced an era during which water was stable in its liquid state. In addition to morphological evidence for aqueous activity, the chemical interaction of water with the basaltic crust has led to the formation of hydrated clays and salts both on the surface and at depth. These hydrated minerals were first detected on the surface of Mars in 2004 with the OMEGA near infrared imaging spectrometer, onboard European probe Mars Express. Their study allows us to piece together the aqueous activity on Mars and to better understand an early era when the environment may have been conducive to prebiotic chemistry. This work focuses on the aqueous environments on Mars by coupling mineralogy data from the spaceborne imaging spectrometers OMEGA/Mars Express and CRISM/Mars Reconnaissance Orbiter to the surface morphology. The development of new data processing and analysis tools have led to the detection and spectral inquiry of over a thousand hydrated mineral exposures on Mars, thus providing a broad view of the aqueous alteration. The latter mostly took place during the Noachian era and formed primarily iron-magnesium bearing phyllosilicates of the vermiculite and smectite groups. In addition, great mineral diversity is found, implying varied geo-chemical formation conditions. Placed in their geological context, these detections show the likely existence of a past hydrological cycle on Mars which sustained a clay cycle similar to Earth's. It was also found that impact craters are the most common morphological context for these minerals, although the link between them remains unclear. The discovery of a clay cycle on Mars bodes well for the past habitability potential on Mars, but will need to be verified through in-situ exploration.

Postmortem interval (PMI) estimation is a necessary but often difficult task that must completed during a death investigation. The level of difficulty rises as time since death increases, especially with the case of skeletonized remains (long PMI). While challenging, a reliable PMI estimate may be of great importance for investigative direction and cost-savings (e.g. suspect identification, tailoring missing persons searches, non-forensic remains exclusion). Long PMI can be estimated by assessing changes in the organic content of bone (i.e. collagen), which degrades and is lost as the PMI lengthens. Visible-near infrared (VNIR) spectroscopy is one method that can be used for analyzing organic constituents, including proteins, in solid specimens. A 2013 preliminary investigation using a limited number of human cortical bone samples suggested that VNIR spectroscopy could provide a fast, reliable technique for assessing PMI in human skeletal remains. Clear separation was noted between "forensic" and "archaeological" specimen spectra within the near-infrared (NIR) bands. The goal of this research was to develop reliable multivariate classification models that could assign skeletal remains to appropriate PMI classes (e.g. "forensic" and "non-forensic"), based on NIR spectra collected from human cortical bone. Working with a large set of cortical samples (n=341), absorbance spectra were collected with an ASD/PANalytical LabSpec® 4 full range spectrometer. Sample spectra were then randomly assigned to training and test sets, where training set spectra were used to build internally cross-validated models in Camo Unscrambler® X 10.4; external validations of the models were then performed on test set spectra. Selected model algorithms included soft independent modeling of class analogy (SIMCA), linear discriminant analysis on principal components (LDA-PCA), and partial least squares discriminant analysis (PLSDA); an application of support vector machines on principal components (SVM-PCA) was attempted as well. Multivariate classification models were built using both raw and transformed spectra (standard normal variate, Savitzky-Golay) that were collected from the longitudinally cut cortical surfaces (Set A models) and the superficial cortical surface following light grinding (Set B models). SIMCA models were consistently the poorest performers, as were many of the SVM-PCA models; LDA-PCA models were generally the best performers for these data. Transformed-spectra model classification accuracies were generally the same or lower than corresponding raw spectral models. Set A models out-performed Set B counterparts in most cases; Set B models often yielded lower classification accuracy for older forensic and non-forensic spectra. A limited number of Set B transformed-spectra models out-performed the raw model counterparts, suggesting that these transformations may be removing scattering-related noise, leading to improvements in model accuracy. This study suggests that NIR spectroscopy may represent a reliable technique for assessing the PMI of unknown human skeletal remains. Future work will require identifying new sources of remains with established extended PMI values. Broadening the number of spectra collected from older forensic samples would allow for the determination of how many narrower potential PMI classes can be discriminated within the forensic time-frame.

No description available.

Repeat sprint ability has been investigated thoroughly, however optimal training methodology to improve RSA remains elusive. Both kinetic and physiological viewpoints have been used to scrutinize aspects of RSA including, initial sprint performance (anaerobic power), maximal cardiorespiratory fitness (VO2max), lactate threshold, anaerobic capacity (mean power), muscle activation (EMG), and local muscle oxygenation kinetics. To our knowledge no study has utilized maximal strength levels as a separate factor among a homogenous group of cardiorespiratory fitness individuals (as determined by peak VO2 during RSA). The purpose of this study was to better understand the relationship between maximal strength, muscular characteristics, and cycling RSA- respective to muscle oxygenation responses. Fifteen participants completed fifteen 10-second maximal effort sprints on a cycle ergometer interspersed with 30-seconds passive recovery. Respiratory, muscle oxygenation, and kinetic responses were monitored continuously and evaluated relationships with maximal strength and muscular architecture as determined by isometric mid-thigh pull and ultrasonography respectively. A series of 2 x 15 mixed design, group x time, ANOVA’s were used to evaluate the effects of group and or sprint on muscle oxygenation kinetics. Strong individuals were found to have significantly greater levels of muscle oxygenation usage, recovery and the respective rates; p = 0.01, p = 0.02, p

No description available.

京都大学 / 0048 / 新制・課程博士 / 博士(人間健康科学) / 甲第20294号 / 人健博第42号 / 新制||人健||4(附属図書館) / 京都大学大学院医学研究科人間健康科学系専攻 / (主査)教授 二木 淑子, 教授 精山 明敏, 教授 村井 俊哉 / 学位規則第4条第1項該当 / Doctor of Human Health Sciences / Kyoto University / DFAM

Sustainability has gained a lot of attention in the field of research. Researchers and consumers both prioritize sustainability and environmental issues over previously dominant materials, such as plastic. Packaging and disposable items that used to be made of plastic have largely been replaced with paper. Unfortunately, paper does not perform as well as plastic regarding barrier properties against grease, oxygen, or water vapor. Barrier properties are an important factor when choosing packaging material for food, among other things, as they help maintain the shelf life of the product. In order to improve the properties of the paper packaging and expand its use, the paper is coated with a polymer. However, the polymer contributes to challenges in the recycling of the products as some of the polymer attaches to the fibers, causing difficulties in the separation of each material. Small fragments of plastic may end up in the material streams and the recycled pulp due to the existing challenges in completely removing plastic from cellulosic substrates during recycling. This thesis analyzes the possibilities of identifying and classifying plastic fragments of polyethylene (PE) and polyvinyl alcohol (PVOH) in recycled paper sheets using near-infrared spectroscopy together with multivariate data analysis. The purpose of the work is to develop models that can identify possible residues that may appear in recycled products from various industries. Paper sheets of two different grammages and six different compositions of recycled fiber and virgin fiber were created and scanned by NIR, with and without plastic film under the sheets. The scans were used to develop classification models to identify and categorize scans not included in the calibration data set. The performance of the models was tested by applying them to images of sheets of paper with plastic fragments of different sizes and different type underneath. The results indicated potential in the method. The prediction of the paper sheets with a lower grammage was mostly correct, whereas the classification of polyethylene showed the best performance. There was some noise in the prediction of the plastic fragments, regardless of the grammage of the paper. The noise may be due to a wide variation in the calibration data set since it consisted of paper sheets of six different compositions. A large part of the noise was incorrectly classified as polyvinyl alcohol, which can be due to differences in the manufacturing process of the plastic films. The conclusion of the thesis is that it is feasible to identify and categorize plastic fragments of polyethylene and polyvinyl alcohol in recycled paper sheets with a certain margin of error. It can be stated that the method shows promise, but further research and development in the field is required to build models that can be applied to a wider range of samples.

<p>The natural chemical and physical variations that occur within volcanic rocks (petrology) provide critical insights into mantle and crust conditions on terrestrial bodies. Visible/near-infrared (VNIR; 0.3-2.5 µm) and thermal infrared (TIR; 5-50 µm) spectroscopy are the main tools available to remotely characterize these materials from satellites in orbit. However, the accuracy of petrologic information that can be gained from spectra when rocks exhibit complex variations in mineralogy, crystallinity, microtexture, and oxidation state occurring together in natural settings is not well constrained. Here, we compare the spectra of a suite of volcanic planetary analog rocks from the Three Sisters, OR to their mineralogy, chemistry, and microtexture from X-ray diffraction, X-ray fluorescence, and electron microprobe analysis. Our results indicate that TIR spectroscopy is an effective petrologic tool in such rocks for modeling bulk mineralogy, crystallinity, and mineral chemistry. Given a library with appropriate glass endmembers, TIR modeling can derive glass abundance with similar accuracy as other major mineral groups and provide first-order estimates of glass wt.% SiO2 in glass-rich samples, but cannot effectively detect variations in microtexture and minor oxide minerals. In contrast, VNIR spectra often yield non-unique mineralogic interpretations due to overlapping absorption bands from olivine, glass, and Fe-bearing plagioclase. In addition, we find that sub-micron oxides hosted in transparent matrix material that are common in fine-grained extrusive rocks can lower albedo and partially to fully suppress mafic absorption bands, leading to very different VNIR spectra in rocks with the same mineralogy and chemistry. Mineralogical interpretations from VNIR spectra should not be treated as rigorous petrologic indicators, but can supplement TIR-based petrology by providing unique constraints on oxide minerals, microtexture, and alteration processes.</p>