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The time required for the identification of pathogens is an important determinant of infection-related mortality rates and disease spread for species of relevance in agriculture. Conventional identification methods require a processing time of at least one to twenty days. Therefore, inaccurate empirical treatments are often provided while awaiting further identification, such that most cases progress with further aggravation of symptoms, contamination of other animals or plants, generating economic loss from decreased yield, and increased mitigation costs. Thus, there is a need for innovative, non-destructive, and rapid analytical techniques that provide reagent-free, portable, reliable, and holistic approaches to detect diseases in real-time. Vibrational spectroscopy techniques have shown the capacity to provide relevant information for disease detection. In near infrared spectroscopy (NIRS), the absorbance from a sample is measured across several hundred wavelengths in the near infrared band (750-2500 nm) and is directly influenced by the number and type of chemical bonds present. In order to make NIRS an effective tool for field-based studies, a simplified procedure is needed such that NIRS can be used in minimally processed samples found in situ. Here, experiments involving the agricultural important bovine herpesvirus-1 (BoHV-1), bovine respiratory syncytial virus (BRSV), Mannheimia haemolytica (MH), Xanthomonas citri pv. malvacearum (Xcm) and Rhizoctonia solani (Rs) were carried out to determine if biological spectral signatures can be differentiated between samples from two classes (i.e., healthy vs. sick, control sample vs. test sample). The specific objectives were to (1) create a spectral library for each evaluated pathogen and disease, (2) identify and establish the characteristic NIR spectral signatures and trends by aquaphotomics and chemometrics-based MVA methods, (3) generate and evaluate models for discriminating representative spectra, (4) provide new biochemical information by the correlation of the results with pathogen development and disease states in living systems, and (5) support the groundwork for a portable, fast, non-destructive, and accurate diagnostic tool capable of reducing the existing time necessary for pathogen and disease detection.

Les projections concernant les changements climatiques dans les régions arctiques annoncent une augmentation disproportionnée des températures de surface pouvant influencer le cycle hydrologique et la fonte des pergélisols. Les hautes latitudes sont donc perçu comme des environnements potentiellement très sensibles aux modifications du climat. Ces modifications ont la capacité d’impacter les cycles biogéochimiques, en particulier la mobilisation du carbone vers les milieux aquatiques de la zone arctique. Dans les rivières arctiques, la période la plus importante du cycle hydrologique est la crue de printemps qui peut réaliser la majeure partie des transferts annuels de carbone organique vers l’océan dans un lapse de temps très court. L’objectif de cette thèse vise à suivre la dynamique des MOD en termes de quantité et de qualité au cours du cycle hydrologique du fleuve Ienisei, grâce à diverses techniques de caractérisation des MOD permettant de mettre en évidence les variations saisonniéres de leur composition, sources, âge et état de dégradation. La première étape a été d’examiner la large gamme de techniques de caractérisation des MOD dans les rivières du monde afin d’identifier les plus répendues,pértinentes et fiables. Grâce au développement d’une base de données des mesures des qualités des MOD, nous avons pu évaluer la couverture géographique des études de caractérisation des MOD, donner des estimations et gamme de valeurs des principales variables de caractérisation des MOD et observer des tendances générales des qualités des MOD selon un gradient latitudinal. La seconde étape a porté sur l’étude de la dynamique du COD dans le fleuve Ienisei concernant les variations de concentrations et les liens avec la chimie de l’eau et l’hydrologie. Nous avons mené des campagnes d’échantillonnage durant trois années consécutives (2014 à 2016), en couvrant avec une haute fréquence de prélèvement la période de la crue de printemps afin d’en capturer la dynamique rapide. Nous avons observé des concentrations en COD qui suivent l’hydrogramme avec les concentrations maximales mesurées quelques jours avant le pic de crue. Le COD a aussi répondu aux variations de débit (augmentation, probablement liée à des précipitations plus intenses du début d’automne. Nous avons enregistré un flux de COD moyen, durant les trois années de prélèvement, d’environ 4,53 Tg yr-1, ce qui est dans l’ordre de grandeur rapporté dans la littérature. Nous avons également observe ue variabilité interannuelle relativement importante avec les estimations d’exports annuels variant de 5,45 Tg yr-1 en 2014 à 3,57 Tg yr-1 en 2016, certainement influence par l’amplitude de débit. Nous avons confirmé le rôle prédominant de la crue de printemps dans les exports de COD avec en moyenne plus de 65% des exportations ayant lieu Durant cette période (approximatvement mai/juin). Le troisième point a consisté en l’étude de la qualité des MOD présentent dans les eaux du Ienisei et de son évolution durant le cycle hydrologique en combinant différentes outils de caractérisation. Associer les modes de caractérisation aide à renforcer les observations et à valider les interprétations. La plus part des variables mesurées avec les différentes techniques se sont confirmées les unes les autres. L’utilisation des biomarqueurs de la lignine, des propriétés optiques et de la datation 14C ont permis de tracer les sources prédominantes des MOD comme étant principalement dérivées de matières organiques récemment produites lixiviée depuis les litières forestières boréales et des horizons supèrieures pendant la crue de printemps et de matières organiques plus anciennes provenant des horizons plus profonds durant la période des basses eaux. / Arctic regions are expected to be highly sensitive to climate change regarding the prediction of disproportionately large increases in surface temperatures and their related influence over the hydrological cycle and permafrost thaw. These modifications have the potential to impact biogeochemical cycles in these regions and in particular the mobilization of organic carbon into rivers. The most crucial period in arctic rivers hydrological cycle is the spring freshet that can account for most of the annual organic carbon transfers to the ocean in a very short window of time. The focus of this thesis was to monitor the dynamic of DOM in terms of quantity and quality along the hydrological cycle of the Yenisei river, through DOM characterization approaches to reveal seasonal variations in its composition, sources, age and degradation state. The first step was to make a review of the full range of existing DOM characterization approaches in worldwide river systems to identify the most widely used, the most relevant and reliable ones. Through the development of a DOM quality measurements database, we have been able to evaluate the geographical coverage of DOM characterization studies, to give estimates and ranges of values of the main reported DOM characterization variables and to observe global trends of DOM quality across latitudinal gradient. Second stage was to investigate DOC dynamic in the Yenisei river with regard to quantity and links with water chemistry and hydrology. We conducted sampling campaigns during three consecutive years (2014 to 2016), covering with a high sampling frequency the spring flood period to capture its very dynamic evolution. We reported DOC concentrations that followed the hydrograph with highest concentrations observed a few days before peak discharge. DOC concentration also responded to discharge variation (increase, likely due to higher precipitation) in early autumn. We reported average DOC flux over the three sampling years of about 4.53 Tg yr-1 which is within the range of values reported in the literature. We observed interannual variability with annual export estimates ranging from 5.45 Tg yr-1 in 2014 to 3.57 Tg yr-1 in 2016, likely driven by discharge amplitude. We confirmed the important role of spring freshet in DOC export with on average more than 65% occurring during this period (roughly May/June). Third point was to determine DOM quality combining characterization techniques. Combination of approaches helped to strengthen observations and cross validate interpretations. Most of the variables reported from the different characterization techniques confirmed one each other. The use of lignin biomarkers, optical properties and radiocarbon age of DOM allowed us to trace DOM main sources has primarily deriving from recently produced organic matter leached from boreal forest litter and top soil horizon during the spring flood and older organic matter derived from deeper soil horizons during low flow period.

During recent decades many lakes have become browner in the northern hemisphere and more specific in Sweden. This process is called brownification. Brownification of lakes makes it more difficult to clean water to drinking water and may have negative ecological effects on biota. Browning of lakes is generally thought to be caused by an increase of humic substances that consist of organic matter which colour the water brown or yellow. However, more recent studies show that dissolved iron can interact with humic substances in browning lakes. Since the concentrations of dissolved iron have increased during recent years and the mechanisms behind brownification and the contribution of iron to this process is not clearly understood it is important to investigate this subject. In this study 17 lakes in south of Sweden were sampled for iron concentration, dissolved organic carbon (DOC), absorbance (420nm) and pH. Further, data was added about atmospheric sulphur deposition and additional data from 17 lakes in the north part of Sweden. Iron had a stronger significant correlation towards absorbance than DOC had in the south of Sweden. A similar amount of dissolved iron seems to colour lakes differently based on their location in Sweden. This indicates that different mechanisms are involved in the interaction between iron and absorbance. However, pH had a stronger relationship with absorbance than either DOC or iron. Overall results suggested that iron do have a strong browning effect on Swedish fresh water lakes in the presence of DOC and that iron-increase driven processes may be due to a change of pH.

O líquido denominado “lixiviado”, formado pela disposição de resíduos em aterros sanitários e lixões, apresenta composição complexa, dada principalmente pela presença de compostos orgânicos extremamente recalcitrantes. O tratamento consorciado deste efluente com esgotos domésticos em ETE’s municipais carece de estudos, tendo em vista que são líquidos com características diferentes. Neste trabalho foi avaliado o desempenho de um processo biológico de tratamento de efluentes, composto por 3 sistemas de banhados construídos (B1, B2 e B3) operados em paralelo, tratando a combinação de esgoto doméstico (90%) + lixiviado de aterro sanitário (10%), no que diz respeito a remoção de matéria orgânica de lenta degradação. Cada sistema foi composto por 4 leitos cultivados com as macrófitas emergentes Luziola peruviana e Typha latifolia, recebendo afluente proveniente de diferentes níveis de pré-tratamento, nomeadamente: B1 - processo biológico anaeróbio (UASB) seguido de aeróbio (CBR); B2 - processo biológico aneróbio (UASB) e B3 - sem prévio tratamento. Para tal, além das análises da matéria orgânica pelos parâmetros não específicos, foi também empregada análise de absorbância e fluorescência para analisar a presença de substâncias húmicas e o uso da respirometria para avaliação da DQO lentamente biodegradável. As eficiências médias de remoção dos sistemas B1, B2 e B3 foi de 97,4, 96,1 e 96,6 % para DBO5, 66,9, 70,9 e 80,6% para DQOT, 61,9, 69 e 62,8 % para DQOFil e de 60,3, 72,8 e 72 % para COT, respectivamente. A avaliação destes parâmetros permitiu inferir que o nível de pré-tratamento não influenciou na eficiência de remoção pelos sistemas de banhados. Os espectros de absorbância foram marcados por maior absorbância na região λ < 400 nm, com diminuição progressiva até 700 nm. A aplicação de coeficientes de absortividade indicaram a predominância de matéria orgânica dissolvida proveniente de esgoto doméstico, com pouca influência de SH’s. Nos espectros de emissão de fluorescência, o aparecimento de bandas na região de 450 nm indicou a presença de substâncias húmicas no afluente e efluente do sistema de banhados construídos, sem diferença significativa entre a intensidade de fluorescência emitida em 450 nm nas amostras analisadas, indicando que a substância em questão passou pelo tratamento sem ser degradada. Os resultados observados pela análise de fluorescência sincronizada do B1 apresentaram contribuição positiva do pré-tratamento (menor concentração de DQOFil) para o desempenho do banhado, devido a menor presença de ácidos húmicos no efluente. / The liquid known as "leachate", produced by the disposal of waste in landfills and dumps, has a complex composition, characterized mainly by the presence of recalcitrant organic compounds. Currently, there is a lack of knowledge regarding the co-treatment of leachate with municipal wastewater in WWTP's, considering that these are effluents with different characteristics. This study evaluated the performance of a biological treatment process of wastewater consisting of 3 constructed wetlands systems (B1, B2 and B3), operated in parallel, treating a combination of domestic sewage (90%) + landfill leachate (10 %). Each system was comprised of four beds cultured with emerging macrophytes Luziola peruviana and Typha latifolia receiving affluent from different levels of pre-treatment, namely: B1 - anaerobic biological process (UASB) followed by aerobic biological process (CBR); B2 - anaerobic biological process (UASB). B3 received the untreated effluents. The content of organic matter and humic substances was analyzed by non-specific parameters, absorbance and fluorescence methods. Respirometry test were conducted to evaluate the content of slowly biodegradable COD. The average removal efficiencies of systems B1, B2 and B3 was of 97.4, 96.1 and 96.6% for BOD5, 66.9, 70.9 and 80.6% for CODT, 61,9, 69 and 62.8% for CODFil and 60.3, 72.8 and 72% of TOC, respectively. The evaluation of these parameters allowed to infer that the level of pre-treatment did not influenced the removal efficiency by wetland systems. Absorbance spectra were marked by greater absorbance in the region λ = <400 nm with progressive decrease up to 700 nm. Absorptivity coefficients indicated the predominance of domestic sewage, with little influence of SH's. In the fluorescence emission spectra, the appearance of bands in the 450 nm region indicated the presence of humic substances in the influent and effluent of the constructed wetland systems without a significant. This indicates that the substance in question went through the treatment without being degraded. The results obtained by synchronous fluorescence analysis showed a positive contribution of the B1 pretreatment (lowest concentration DQOFil) to the observed performance due to less presence of humic acids in the effluent. The authors did not have success during evaluation of the slowly biodegradable COD using the method proposed before.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2014-08-01T11:50:31Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao Daniela Cristina Vinhal.pdf: 4105984 bytes, checksum: f00413027a2eaed20e59defa2239af07 (MD5) / Made available in DSpace on 2014-08-01T11:50:31Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao Daniela Cristina Vinhal.pdf: 4105984 bytes, checksum: f00413027a2eaed20e59defa2239af07 (MD5) Previous issue date: 2012 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In Brazil, the estimates for the year 2012 point to approximately 134,000 new cases of skin cancer, being mostly related to exposure to ultraviolet radiation. According to current consensus, such damage can be minimized by prophylactic use of sunscreens, which aims to protect human skin against harmful effects of UV radiation. This way, this study proposed to plan, synthesize, characterize and evaluate a new compound to be a sunscreen (17). The structural planning is made from photoprotective triazona ethylhexyl prototypes (12) and cinnamate (4) having the compound 15 which was produced from vanillin, a natural abundant and low cost product. In addition, 17 compound has molecular weight above 800 Daltons, which is in accordance with the photoprotective recently launched on the market, because it minimizes or even prevents its absorption through the skin. The synthetic route proposal consisted of two stages, which after optimized lead to obtain the 17 compound in 78.6% overall yield. It is noteworthy that the 15 compound was obtained in quantitative yield and the 17 compound was purified by Soxhlet extractor, using amyl alcohol as solvent. These facts make its synthesis a bit laborious and inexpensive, fundamental characteristics of a technological product, from the financial point of view. All the synthesized compounds were characterized by spectrometric techniques of nuclear magnetic resonance of hydrogen-dimensional and two-dimensional, infrared, mass and ultraviolet, in equal ways. From the spectrophotometric absorption technique it was identified that 17 compound had two peaks of maximum absorption (λmax.) in the UV, and 306 nm in the region of UVB and 344 nm for UVA. It is also possible to calculate the parameters of the molar absorptivity (ε) and specific extinction coefficient (E), whose values were above 104 -1 cm-1 for ε and 5,843 4,337 for E. Moreover, the 15 and 17 compounds were also M evaluated on their redox profile using the technique of cyclic voltammetry which showed that the 17 compound keeps stable considering the applied potential. The thermogravimetric thermal analysis the 17 compound showed a weight loss of 47.88% in the range of 330 °C under an atmosphere of synthetic air, characterized as a stable compound at high temperatures. From the in vitro evaluation by the spectrophotometric method described by Mansur it presented SPF equal to 4.58, while under the same conditions the methoxycinnamato of octyl (4), sunscreen sold worldwide, presented SPF equal to 2.79. At the end of this work it is possible to observe that the proposed synthetic route to obtain the 17 compound was effective, given the obtained high yields, laborious and low cost steps. Finally, we conclude that the structural planning employee was ratified, since the described physical-chemicals organic evaluated had great similarities with the prototype sunscreen (12) and (4) used in its planning. / No Brasil, as estimativas para o ano de 2012 apontam para a ocorrência de, aproximadamente, 134 mil casos novos de câncer de pele, sendo em sua maioria relacionados com exposição à radiação ultravioleta. Segundo consenso atual, tais danos podem ser minimizados através do uso profilático de protetores solares, cujo objetivo é proteger a pele humana contra efeitos nocivos da radiação UV. Neste sentido, o presente trabalho se propôs planejar, sintetizar, caracterizar e avaliar um novo composto candidato a fotoprotetor (17). O planejamento estrutural se deu a partir dos protótipos fotoprotetores etilhexil triazona (12) e cinamato (4), tendo como partida o composto 15 que foi produzido a partir da vanilina, um produto natural abundante e de baixo custo. Ademais, o composto 17 apresenta peso molecular acima de 800 Daltons, o que está de acordo com os fotoprotetores lançados no mercado recentemente, pois minimiza ou mesmo impede sua absorção através da pele. A rota sintética proposta constituiu-se por duas etapas, que após otimizadas levaram a obtenção do composto 17 em rendimento global de 78,6%. Vale salientar que o composto 15 foi obtido em rendimento quantitativo e o composto 17 foi purificado através do extrator de Soxhlet, empregando álcool amílico como solvente. Tais fatos tornam sua síntese pouco laboriosa e pouco onerosa, características fundamentais a um produto tecnológico, sob o ponto de vista financeiro. Todos os compostos sintetizados foram caracterizados através das técnicas espectrométricas de ressonância magnética nuclear de 1H unidimensional e 1H-13C bidimensional, infravermelho, massas e ultravioleta, de forma inambígua. A partir da técnica de absorção espectrofotométrica, indentificou-se para o composto 17 dois picos de absorção máxima (λmáx.) no UV, sendo 306 nm na região da UVB e 344 nm na UVA. Também pode-se calcular os parâmetros de absortividade molar (ε) e coeficiente de extinção específico (E), cujos valores foram acima de 104 para ε e 5.843 e 4.337 para E. Por conseguinte, os compostos 15 e 17 também foram avaliados quanto ao seu perfil redox através da técnica de voltametria cíclica, a qual ilustrou que o composto 17 mantém-se estável frente aos potenciais aplicados. Quanto a análise térmica termogravimétrica, o composto 17 apresentou uma perda de massa de 47,88% na faixa de 330 °C sob atmosfera de ar sintético, caracterizando-o como composto estável sob temperaturas elevadas, visto que seu ponto de fusão ocorre em 186 oC. A partir da avaliação in vitro pelo método espectrofotométrico descrito por Mansur o mesmo apresentou FPS igual a 4,58 ao passo que sob as mesmas condições o para-metoxicinamato de octila (4), filtro solar comercializado mundialmente, apresentou FPS de 2,79. Ao término deste trabalho podemos observar que a rota sintética proposta para a obtenção do composto 17 se mostrou eficaz, face aos altos rendimentos obtidos, etapas pouco laboriosas e de baixo custo. Por fim, podemos concluir que o planejamento estrutural empregado foi ratificado, uma vez que os descritos físico- químicos orgânicos avaliados apresentaram grandes similaridades com os protótipos fotoprotetores (12) e (4) empregados no seu planejamento.

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<p>The aim of this thesis was to determine whether there has been a trend of increasing or decreasing water colour, absorbance, in Lake Mälaren during the last 35 years and whether it could be correlated with water discharge. The discharge was accounted for using regression analysis. The data material was analyzed for trends using a nonparametric test, the so-called seasonal Mann- Kendall test. The regression model could only account for a small (maximum of 24%) variation due to discharge. Thisindicates that discharge single-handedly can not explain the variation in absorbance. The trend analysis indicated a significant yearly increase in absorbance of 0.93% - 2.43% yr-¹ for three out of four investigated sub-basins, namely, Galten, Ekoln and Skarven. This strongly implies that there has been an increase of absorbance and a change in the amount of organic material in Lake Mälaren during the last 35 years.</p>

Detta examensarbete är en förundersökning till Glafos undersökning angående rening av glasbrukens processvatten från antimon med zeolit. Förundersökningen gick ut på att via experiment ta reda på hur mycket antimon som adsorberas av behandlad (för optimering: dels med NaNO3 och dels med NaCl) och obehandlad zeolit (porstorlek 0.4 nm). pH mättes och ställdes eftersom det har betydelse för adsorptionen, åtminstone vid väldigt lågt pH. När lösningarna hade filtrerats mättes den kvarvarande antimonhalten med atomabsorptionsspektrofotometri. Mätningarna visade att i genomsnitt 53 % av Sb-halten i lösningarna hade adsorberats av zeoliten. Förundersökningen visade att det inte blir någon adsorption då pH är väldigt lågt (under 1). Den visade också att när pH är över 4 verkar det inte ha någon betydelse om zeoliten är behandlad eller inte. Zeoliten bör behandlas med NaCl först i en tank med omrörning, sedan blandas i processvattnet (vars pH justerats till pH 4) i en tank eller bassäng och därefter filtreras. Tidsfaktorn för hur lång tid det tar för zeoliten att nå jämvikt och temperaturens inverkan bör även undersökas. / The aim of this diploma work is to study the removal of antimony from glassworks process water using zeolites. The experimental part of the studies were carried out to find the quantity of antimony adsorbed by the zeolite. The studies included treated (for optimization: partly with NaNO3 and partly with NaCl) and untreated zeolite. The pore size is 0.4 nm. pH was measured and adjusted because it is important for the antimony adsorption. When the solutions were filtrated the content of antimony left was measured with atomic absorption spectrophotometry. The measurements showed an average uptake of antimony by the zeolite of 53 %.The preinvestigation indicates that with a very low pH (below 1) there is no antimony adsorption. It also indicates that with pH above 4 it does not matter if the zeolite are treated or not. In further investigations the zeolite should be treated with NaCl in a stirred tank, then be mixed in the process water (pH is set to 4) in a tank or basin and then be filtrated. The time to reach equilibrium and the influence of temperature should also be investigated.