In this diploma thesis, I deal with the influence of the sampling site on water quality in natural bathing lakes (Hostivar reservoir, Seberak pond and Vyzlovka pond) in this. I have established that hygienically significant kinds of phytoplankton may differ in terms of water quality especially where there are cyanobacteria constituting water bloom. Surface water bloom may be moved by wind to the lee side of the water body (Microcystis sp.). Aphanizomenon flos-aquae water bloom floating in water column can be affected by wind and by water flow (which may be partly affected by wind as well). With the prevailing fibrous Planktothrix agardhii which does not connstitute water bloom the concentration of chlorophyll-a and cyanobacterial cell abundance in individual sampling sites are similar although the concentration of chlorophyll-a a is about 200 g.l-1 . Microcystis sp. and Scenedesmus sp. survive under eutrophic conditions in competition. From the microbiological perspective, water quality can differ within a single sampling site in places at a distance of less than 100 m. Microbial contamination can be caused by bathers, water birds, farm animals and probably by the removing of microorganisms from sand, mud and sediments on the beach or shore. Rain episodes probably increase the abundance of E.coli...

Avec la hausse mondiale de la fréquence des floraisons de cyanobactéries (CB), dont certaines produisent des cyanotoxines (CT), le développement d’une méthode de détection/quantification rapide d’un maximum de CT s’impose. Cette méthode permettrait de faire un suivi quotidien de la toxicité de plans d’eau contaminés par des CB et ainsi d’émettre rapidement des avis d’alerte appropriés afin de protéger la santé publique. Une nouvelle technologie utilisant la désorption thermique induite par diode laser (LDTD) couplée à l’ionisation chimique sous pression atmosphérique (APCI) et reliée à la spectrométrie de masse en tandem (MS/MS) a déjà fait ses preuves avec des temps d'analyse de l’ordre de quelques secondes. Les analytes sont désorbés par la LDTD, ionisés en phase gazeuse par APCI et détectés par la MS/MS. Il n’y a donc pas de séparation chromatographique, et la préparation de l’échantillon avant l’analyse est minimale selon la complexité de la matrice contenant les analytes. Parmi les quatre CT testées (microcystine-LR, cylindrospermopsine, saxitoxine et anatoxine-a (ANA-a)), seule l’ANA-a a généré une désorption significative nécessaire au développement d’une méthode analytique avec l’interface LDTD-APCI. La forte polarité ou le poids moléculaire élevé des autres CT empêche probablement leur désorption. L’optimisation des paramètres instrumentaux, tout en tenant compte de l’interférence isobarique de l’acide aminé phénylalanine (PHE) lors de la détection de l’ANA-a par MS/MS, a généré une limite de détection d’ANA-a de l’ordre de 1 ug/L. Celle-ci a été évaluée à partir d’une matrice apparentée à une matrice réelle, démontrant qu’il serait possible d’utiliser la LDTD pour effectuer le suivi de l’ANA-a dans les eaux naturelles selon les normes environnementales applicables (1 à 12 ug/L). Il a été possible d’éviter l’interférence isobarique de la PHE en raison de sa très faible désorption avec l’interface LDTD-APCI. En effet, il a été démontré qu’une concentration aussi élevée que 500 ug/L de PHE ne causait aucune interférence sur le signal de l’ANA-a. / Within the context of the worldwide increasing frequency of cyanobacterial (CB) blooms, some containing cyanotoxins (CT), the development of a detection/quantification method for the fast analysis a maximum of CT is necessary. This method would allow daily tracking of the toxicity of CB-contaminated water such that, as warranted, appropriate measures can be taken quickly to protect public health. A new technology using laser diode thermal desorption (LDTD) coupled to atmospheric pressure chemical ionization (APCI)-tandem mass spectrometry (MS/MS) has shown great potential to reduce analysis time to seconds. Analytes are desorbed by the LDTD, ionized in gas-phase by APCI and detected by MS/MS. Therefore, there is no chromatographic separation and sample treatment prior to analysis is minimal, depending on the complexity of the sample matrix. Among the four CT tested (microcystin-LR, cylindrospermopsin, saxitoxin and anatoxin-a (ANA-a)), only ANA-a exhibited sufficient desorption which is necessary to develop an analytical method with the LDTD-APCI interface. The strong polarity or high molecular weight of the other CT probably inhibited their efficient desorption. Optimization of instrumental parameters, while accounting for the isobaric interference caused by the acid amino phenylalanine (PHE) in the detection of ANA-a by MS/MS, generated a detection limit of the order of 1 ug/L ANA-a. This value was obtained in a simulated natural matrix, demonstrating that it would be possible to use LDTD to monitor ANA-a in natural waters within the range of current applicable environmental guidelines (1 to 12 ug/L). Because PHE desorption is limited with the LDTD-APCI interface, this method avoids its interference on ANA-a analysis, even at PHE concentrations as high as 500 ug/L.

O trabalho apresenta resultados de um estudo sobre a dinâmica de cianobactérias e cianotoxinas e suas relações com variáveis climáticas, bióticas e abióticas do braço do reservatório da usina hidroelétrica Luiz Eduardo Magalhães (UHE Lajeado), em Palmas, Tocantins. O reservatório abrange 626 km2, extensão de 172 km, volume operacional de 4,9.109 m3, tempo de residência da água de 24 dias e uma área de drenagem de 184.219 km². O objetivo principal do estudo foi conhecer a dinâmica espacial e temporal de cianobactérias e cianotoxinas, bem como as suas implicações para o abastecimento público. Os resultados demonstraram que o ponto amostrado no período entre julho e dezembro de 2008, através do estudo de perfil vertical (PVJD), apresentou condições meso-eutróficas, com circulação do tipo polimítica, com estratificação transitória no final do período de seca e isotermia no período chuvoso. Os estudos nictemerais 1 (NIC-1), realizado em 29 de setembro de 2008, e 2 (NIC-2), realizado em 23 de março de 2009, comportaram-se sob condições climatológicas distintas, apresentando o segundo estudo características limnológicas inversas a do primeiro, marcadas principalmente pelas intrusões via tributários. As principais variáveis que influenciaram o padrão de distribuição das cianobactérias no sistema para os estudos foram: climáticas (ventos, precipitação e temperatura); físicas (turbidez e circulação térmica), e químicas (fósforo reativo solúvel e fósforo total). Em relação ao índice de estado trófico - IET, o ambiente foi classificado como eutrófico, para os estudos NIC-1 e 2, e oscilando entre mesotrófico e eutrófico em PVJD. O segundo estudo compreendeu uma avaliação mensal, entre os meses de janeiro de 2006 e dezembro de 2008. Os resultados demonstraram que o ponto 1 se comportou como ambiente em estado de meso-eutrofia, com regime de mistura polimítico, durante o ano de 2008. Neste mesmo ano, a temperatura do ar e a radiação solar foram as variáveis climáticas melhor correlacionadas positivamente com as variações de cianobactérias. Durante os períodos de estiagem dos três anos monitorados o nitrogênio total e o fósforo total definiram os padrões de distribuição de cianobactérias no ponto 1, através de razões inferiores a 10:1. Este ponto comportou-se como ambiente lêntico no período de estiagem, sofrendo influências do reservatório, e como ambiente lótico no período chuvoso, sob influências de fluxos do ribeirão Taquarussu Grande. O estudo também detectou a formação de três florações de cianobactérias no período de estiagem dos anos de 2007 e 2008 no ponto 1. A maior densidade de cianobactérias foi evidenciada em novembro de 2007 (28600 cél.mL-¹). A maior concentração de cianotoxinas ocorreu em julho de 2008, (>2,0 μg.L-¹ de microcistinas), nos pontos 1 e 3. Em relação à viabilidade para abastecimento público, os resultados de turbidez e clorofila-a sugerem a dupla-filtração como sendo a tecnologia capaz de remover cerca de 73,33% destas variáveis. De maneira geral, os dados obtidos neste trabalho sugerem a elaboração de um programa de avaliação sistemática destas toxinas e seus potenciais produtores nos pontos 1, 3, e foz do braço no reservatório. A modelagem ecológica subsidiaria a visualização de cenários futuros, e consequentemente, colaboraria na garantia da qualidade da água produzida pela empresa de abastecimento, no uso desta água para consumo humano. / This paper presents results of the study on the dynamic of cyanobacteria and cyanotoxins and their relationship with climatic, biotic and abiotic variables in the hydroelectric Luiz Eduardo Magalhães, Palmas (Tocantins-Brazil) reservoir. The reservoir has 626 km², is 172 km long, operating volume 4,9.109 m³, residence time 24 days, and adrainage area of 184.219 km². The main objective was to study the spatial and temporal dynamics of cyanobacteria and cyanotoxins, as well as its implications for public supply. The results showed that, between July and December 2008, the vertical profile of the studied site (PVJD) was meso-eutrophic, a polymictic mixing regime with stratification at the end of the dry season in a transitional period, and isotherm in the rainy season. Diel studies 1 (NIC-1) and 2 (NIC-2) revealed distinct climatic conditions, showed characteristics opposite, mainly by advection of intrusions via tributaries. In both occasions the main variables that affected the pattern of distribution of cyanobacteria were wind, precipitation and temperature), physical (turbidity, residence time, thermal circulation, orthophosphate and total phosphorus. The sampled area was classified as eutrophic, for studies NIC-1 and 2, and ranged from mesotrophic and eutrophic in PVJD. The second study included a monthly assessment, between January 2006 and December 2008. The results showed that sampling station 1 behaved as a meso-eutrophic environment in 2008. In that same year, the air temperature and solar radiation were the climatic variables that correlated most positively with changes in cyanobacteria. During the dry periods for the three monitored years the total nitrogen and total phosphorus defined the distribution patterns of cyanobacteria dynamics in the sampling station 1. This sampling station behaved as a lentic habitat in the dry season, associated with the reservoir, and as lotic in the rainy season, associated with the river Taquarussu Grande. The study also detected the occurrence of three cyanobacterial blooms in the dry season of the years 2007 and 2008 in section 1. The highest density of cyanobacteria was found in November 2007 (28600 cell.mL-¹). The highest concentration of cyanotoxins occurred in July 2008, (<2.0 μg.L-¹ microcystins) in sampling stations 1 and 3. Regarding the feasibility of this area for public supply, the results suggested the adoption of conventional treatment system. However, some peculiarities of water quality suggested that dual-filtration would be more adequate, due to the incoming effluents of the sewage treatment station Aureny in the sampling station 1. Overall, the data obtained throughout this study points to the maintenance of another two years of systematic evaluation of these toxins and their potential producers form sampling points1 and 3 to the estuary of the arm in the reservoir. The hydrological modelling of future scenarios will help to evaluate this area as source of water for human supply.

O trabalho apresenta resultados de um estudo sobre a dinâmica de cianobactérias e cianotoxinas e suas relações com variáveis climáticas, bióticas e abióticas do braço do reservatório da usina hidroelétrica Luiz Eduardo Magalhães (UHE Lajeado), em Palmas, Tocantins. O reservatório abrange 626 km2, extensão de 172 km, volume operacional de 4,9.109 m3, tempo de residência da água de 24 dias e uma área de drenagem de 184.219 km². O objetivo principal do estudo foi conhecer a dinâmica espacial e temporal de cianobactérias e cianotoxinas, bem como as suas implicações para o abastecimento público. Os resultados demonstraram que o ponto amostrado no período entre julho e dezembro de 2008, através do estudo de perfil vertical (PVJD), apresentou condições meso-eutróficas, com circulação do tipo polimítica, com estratificação transitória no final do período de seca e isotermia no período chuvoso. Os estudos nictemerais 1 (NIC-1), realizado em 29 de setembro de 2008, e 2 (NIC-2), realizado em 23 de março de 2009, comportaram-se sob condições climatológicas distintas, apresentando o segundo estudo características limnológicas inversas a do primeiro, marcadas principalmente pelas intrusões via tributários. As principais variáveis que influenciaram o padrão de distribuição das cianobactérias no sistema para os estudos foram: climáticas (ventos, precipitação e temperatura); físicas (turbidez e circulação térmica), e químicas (fósforo reativo solúvel e fósforo total). Em relação ao índice de estado trófico - IET, o ambiente foi classificado como eutrófico, para os estudos NIC-1 e 2, e oscilando entre mesotrófico e eutrófico em PVJD. O segundo estudo compreendeu uma avaliação mensal, entre os meses de janeiro de 2006 e dezembro de 2008. Os resultados demonstraram que o ponto 1 se comportou como ambiente em estado de meso-eutrofia, com regime de mistura polimítico, durante o ano de 2008. Neste mesmo ano, a temperatura do ar e a radiação solar foram as variáveis climáticas melhor correlacionadas positivamente com as variações de cianobactérias. Durante os períodos de estiagem dos três anos monitorados o nitrogênio total e o fósforo total definiram os padrões de distribuição de cianobactérias no ponto 1, através de razões inferiores a 10:1. Este ponto comportou-se como ambiente lêntico no período de estiagem, sofrendo influências do reservatório, e como ambiente lótico no período chuvoso, sob influências de fluxos do ribeirão Taquarussu Grande. O estudo também detectou a formação de três florações de cianobactérias no período de estiagem dos anos de 2007 e 2008 no ponto 1. A maior densidade de cianobactérias foi evidenciada em novembro de 2007 (28600 cél.mL-¹). A maior concentração de cianotoxinas ocorreu em julho de 2008, (>2,0 μg.L-¹ de microcistinas), nos pontos 1 e 3. Em relação à viabilidade para abastecimento público, os resultados de turbidez e clorofila-a sugerem a dupla-filtração como sendo a tecnologia capaz de remover cerca de 73,33% destas variáveis. De maneira geral, os dados obtidos neste trabalho sugerem a elaboração de um programa de avaliação sistemática destas toxinas e seus potenciais produtores nos pontos 1, 3, e foz do braço no reservatório. A modelagem ecológica subsidiaria a visualização de cenários futuros, e consequentemente, colaboraria na garantia da qualidade da água produzida pela empresa de abastecimento, no uso desta água para consumo humano. / This paper presents results of the study on the dynamic of cyanobacteria and cyanotoxins and their relationship with climatic, biotic and abiotic variables in the hydroelectric Luiz Eduardo Magalhães, Palmas (Tocantins-Brazil) reservoir. The reservoir has 626 km², is 172 km long, operating volume 4,9.109 m³, residence time 24 days, and adrainage area of 184.219 km². The main objective was to study the spatial and temporal dynamics of cyanobacteria and cyanotoxins, as well as its implications for public supply. The results showed that, between July and December 2008, the vertical profile of the studied site (PVJD) was meso-eutrophic, a polymictic mixing regime with stratification at the end of the dry season in a transitional period, and isotherm in the rainy season. Diel studies 1 (NIC-1) and 2 (NIC-2) revealed distinct climatic conditions, showed characteristics opposite, mainly by advection of intrusions via tributaries. In both occasions the main variables that affected the pattern of distribution of cyanobacteria were wind, precipitation and temperature), physical (turbidity, residence time, thermal circulation, orthophosphate and total phosphorus. The sampled area was classified as eutrophic, for studies NIC-1 and 2, and ranged from mesotrophic and eutrophic in PVJD. The second study included a monthly assessment, between January 2006 and December 2008. The results showed that sampling station 1 behaved as a meso-eutrophic environment in 2008. In that same year, the air temperature and solar radiation were the climatic variables that correlated most positively with changes in cyanobacteria. During the dry periods for the three monitored years the total nitrogen and total phosphorus defined the distribution patterns of cyanobacteria dynamics in the sampling station 1. This sampling station behaved as a lentic habitat in the dry season, associated with the reservoir, and as lotic in the rainy season, associated with the river Taquarussu Grande. The study also detected the occurrence of three cyanobacterial blooms in the dry season of the years 2007 and 2008 in section 1. The highest density of cyanobacteria was found in November 2007 (28600 cell.mL-¹). The highest concentration of cyanotoxins occurred in July 2008, (<2.0 μg.L-¹ microcystins) in sampling stations 1 and 3. Regarding the feasibility of this area for public supply, the results suggested the adoption of conventional treatment system. However, some peculiarities of water quality suggested that dual-filtration would be more adequate, due to the incoming effluents of the sewage treatment station Aureny in the sampling station 1. Overall, the data obtained throughout this study points to the maintenance of another two years of systematic evaluation of these toxins and their potential producers form sampling points1 and 3 to the estuary of the arm in the reservoir. The hydrological modelling of future scenarios will help to evaluate this area as source of water for human supply.

O trabalho apresenta resultados de um estudo sobre a dinâmica de cianobactérias e cianotoxinas e suas relações com variáveis climáticas, bióticas e abióticas do braço do reservatório da usina hidroelétrica Luiz Eduardo Magalhães (UHE Lajeado), em Palmas, Tocantins. O reservatório abrange 626 km2, extensão de 172 km, volume operacional de 4,9.109 m3, tempo de residência da água de 24 dias e uma área de drenagem de 184.219 km². O objetivo principal do estudo foi conhecer a dinâmica espacial e temporal de cianobactérias e cianotoxinas, bem como as suas implicações para o abastecimento público. Os resultados demonstraram que o ponto amostrado no período entre julho e dezembro de 2008, através do estudo de perfil vertical (PVJD), apresentou condições meso-eutróficas, com circulação do tipo polimítica, com estratificação transitória no final do período de seca e isotermia no período chuvoso. Os estudos nictemerais 1 (NIC-1), realizado em 29 de setembro de 2008, e 2 (NIC-2), realizado em 23 de março de 2009, comportaram-se sob condições climatológicas distintas, apresentando o segundo estudo características limnológicas inversas a do primeiro, marcadas principalmente pelas intrusões via tributários. As principais variáveis que influenciaram o padrão de distribuição das cianobactérias no sistema para os estudos foram: climáticas (ventos, precipitação e temperatura); físicas (turbidez e circulação térmica), e químicas (fósforo reativo solúvel e fósforo total). Em relação ao índice de estado trófico - IET, o ambiente foi classificado como eutrófico, para os estudos NIC-1 e 2, e oscilando entre mesotrófico e eutrófico em PVJD. O segundo estudo compreendeu uma avaliação mensal, entre os meses de janeiro de 2006 e dezembro de 2008. Os resultados demonstraram que o ponto 1 se comportou como ambiente em estado de meso-eutrofia, com regime de mistura polimítico, durante o ano de 2008. Neste mesmo ano, a temperatura do ar e a radiação solar foram as variáveis climáticas melhor correlacionadas positivamente com as variações de cianobactérias. Durante os períodos de estiagem dos três anos monitorados o nitrogênio total e o fósforo total definiram os padrões de distribuição de cianobactérias no ponto 1, através de razões inferiores a 10:1. Este ponto comportou-se como ambiente lêntico no período de estiagem, sofrendo influências do reservatório, e como ambiente lótico no período chuvoso, sob influências de fluxos do ribeirão Taquarussu Grande. O estudo também detectou a formação de três florações de cianobactérias no período de estiagem dos anos de 2007 e 2008 no ponto 1. A maior densidade de cianobactérias foi evidenciada em novembro de 2007 (28600 cél.mL-¹). A maior concentração de cianotoxinas ocorreu em julho de 2008, (>2,0 μg.L-¹ de microcistinas), nos pontos 1 e 3. Em relação à viabilidade para abastecimento público, os resultados de turbidez e clorofila-a sugerem a dupla-filtração como sendo a tecnologia capaz de remover cerca de 73,33% destas variáveis. De maneira geral, os dados obtidos neste trabalho sugerem a elaboração de um programa de avaliação sistemática destas toxinas e seus potenciais produtores nos pontos 1, 3, e foz do braço no reservatório. A modelagem ecológica subsidiaria a visualização de cenários futuros, e consequentemente, colaboraria na garantia da qualidade da água produzida pela empresa de abastecimento, no uso desta água para consumo humano. / This paper presents results of the study on the dynamic of cyanobacteria and cyanotoxins and their relationship with climatic, biotic and abiotic variables in the hydroelectric Luiz Eduardo Magalhães, Palmas (Tocantins-Brazil) reservoir. The reservoir has 626 km², is 172 km long, operating volume 4,9.109 m³, residence time 24 days, and adrainage area of 184.219 km². The main objective was to study the spatial and temporal dynamics of cyanobacteria and cyanotoxins, as well as its implications for public supply. The results showed that, between July and December 2008, the vertical profile of the studied site (PVJD) was meso-eutrophic, a polymictic mixing regime with stratification at the end of the dry season in a transitional period, and isotherm in the rainy season. Diel studies 1 (NIC-1) and 2 (NIC-2) revealed distinct climatic conditions, showed characteristics opposite, mainly by advection of intrusions via tributaries. In both occasions the main variables that affected the pattern of distribution of cyanobacteria were wind, precipitation and temperature), physical (turbidity, residence time, thermal circulation, orthophosphate and total phosphorus. The sampled area was classified as eutrophic, for studies NIC-1 and 2, and ranged from mesotrophic and eutrophic in PVJD. The second study included a monthly assessment, between January 2006 and December 2008. The results showed that sampling station 1 behaved as a meso-eutrophic environment in 2008. In that same year, the air temperature and solar radiation were the climatic variables that correlated most positively with changes in cyanobacteria. During the dry periods for the three monitored years the total nitrogen and total phosphorus defined the distribution patterns of cyanobacteria dynamics in the sampling station 1. This sampling station behaved as a lentic habitat in the dry season, associated with the reservoir, and as lotic in the rainy season, associated with the river Taquarussu Grande. The study also detected the occurrence of three cyanobacterial blooms in the dry season of the years 2007 and 2008 in section 1. The highest density of cyanobacteria was found in November 2007 (28600 cell.mL-¹). The highest concentration of cyanotoxins occurred in July 2008, (<2.0 μg.L-¹ microcystins) in sampling stations 1 and 3. Regarding the feasibility of this area for public supply, the results suggested the adoption of conventional treatment system. However, some peculiarities of water quality suggested that dual-filtration would be more adequate, due to the incoming effluents of the sewage treatment station Aureny in the sampling station 1. Overall, the data obtained throughout this study points to the maintenance of another two years of systematic evaluation of these toxins and their potential producers form sampling points1 and 3 to the estuary of the arm in the reservoir. The hydrological modelling of future scenarios will help to evaluate this area as source of water for human supply.

The occurrences of cyanotoxin and organic contaminants threaten drinking water sources and are a serious human health and environmental concern. The control of these problematic contaminants and the remediation of the associated contaminants are critical for ensuring safe drinking water to significant populations. Advanced oxidation processes (AOPs) have received considerable attention as a potential water treatment for various pollutants. In this dissertation, advanced oxidative degradation of four problematic water toxic contaminants (CYN, iopamidol, 4-methylcyclohexane methanol and propylene glycol phenyl ether) were studied to develop the fundamental understanding required to assess AOPs as a potential water treatment process. UV and visible light activated (VLA) TiO2 photocatalysis using nitrogen and fluorine-TiO2 (NF-TiO2), phosphorus and fluorine-TiO2 (PF-TiO2) and sulfur-TiO2 (S-TiO2) were employed for degradation of 6-hydroxymethyl uracil (6-HOMU), a model compound for the potent cyanotoxin cylindrospermopsin (CYN). NF-TiO2 exhibits the most photoactive, followed by marginally active PF-TiO2 and inactive S-TiO2 under visible light irradiation. Our results indicate that O2-• plays an important role in VLA TiO2 photocatalysis. Fe (VI), an environmentally friendly oxidant, was employed for the degradation of CYN and 6-HOMU over a range of pH (7 ~ 9.5). The second order rate constants for the reaction of Fe (VI) with CYN decrease from 38.83 ± 0.07 M-1s-1 at pH 7 to 5.02 ± 0.04 M-1s-1 at pH 9.5. Fe (VI) mediated reactions primarily occur via oxidation of the uracil ring in CYN. ELISA results demonstrate that Fe (VI) oxidation process leads to a significant decrease in the bioactivity of CYN as a function of treatment time. Fe (III)-oxalate/H2O2 process was employed for the remediation of iopamidol, a model for ICM, to determine the formation rates and steady concentrations of •OH and O2-• under UV and visible light irradiation. Reduction by CO2-• and oxidation by •OH contribute to the degradation pathways. Pulse and gamma radiolysis of 4-methylcyclohexane methanol (MCHM) and propylene glycol phenyl ether (PPh) were studied to determine the bimolecular rate constants and reaction pathways. •OH addition to ortho and para positions in PPh are the predominant reaction pathways; H-abstraction are the primary reaction mechanisms for ∙OH mediated oxidation of MCHM

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Due to an ever-increasing global population and limited resource availability, there is a constant need for detection of both natural and anthropogenic hazards in water, air, food, and material goods. Traditionally a different instrument would be used to detect each class of contaminant, often after a concentration or separation protocol to extract the analyte from its matrix. Raman spectroscopy is unique in its ability to detect organic or inorganic, airborne or waterborne, and embedded or adsorbed analytes within environmental systems. This ability comes from the inherent abilities of the Raman spectrometer combined with concentration, separation, and signal enhancement provided by drop coating deposition Raman (DCDR) and surface-enhanced Raman spectroscopy (SERS). Herein the capacity of DCDR to differentiate between cyanotoxin variants in aqueous solutions was demonstrated using principal component analysis (PCA) to statistically demonstrate spectral differentiation. A set of rules was outlined based on Raman peak ratios to allow an inexperienced user to determine the toxin variant identity from its Raman spectrum. DCDR was also employed for microcystin-LR (MC-LR) detection in environmental waters at environmentally relevant concentrations, after pre-concentration with solid-phase extraction (SPE). In a cellulose matrix, SERS and normal Raman spectral imaging revealed nanoparticle transport and deposition patterns, illustrating that nanoparticle surface coating dictated the observed transport properties. Both SERS spectral imaging and insight into analyte transport in wax-printed paper microfluidic channels will ultimately be useful for microfluidic paper-based analytical device (𝜇PAD) development. Within algal cells, SERS produced 3D cellular images in the presence of intracellularly biosynthesized gold nanoparticles (AuNP), documenting in detail the molecular vibrations of biomolecules at the AuNP surfaces. Molecules involved in nanoparticle biosynthesis were identified at AuNP surfaces within algal cells, thus aiding in mechanism elucidation. The capabilities of Raman spectroscopy are endless, especially in light of SERS tag design, coordinating detection of analytes that do not inherently produce strong Raman vibrations. The increase in portable Raman spectrometer availability will only facilitate cheaper, more frequent application of Raman spectrometry both in the field and the lab. The tremendous detection power of the Raman spectrometer cannot be ignored. / Ph. D.

Diese Dissertation ist ein Beitrag zum Forschungsfeld der Stressökologie, im Spe-ziellen der Verhaltensökotoxikologie. Das spontane lokomotorische Verhalten der Fischarten Danio rerio und Leucaspius delineatus wurde unter sublethaler Expo-sition mit dem Cyanobakterientoxin Microcystin-LR (MC-LR) und dem Xenobio-tikums 2.4.4`-Trichlorobiphenyl (PCB 28) quantifiziert. Die Schwimmgeschwin-digkeit und Anzahl der Wendungen wurden kontinuierlich mit einem automati-schen Video-Monitoringsystem unter Laborbedingungen aufgezeichnet. In Hin-blick auf zyklische Aspekte wurden die Verhaltensanalysen mit chronobiologi-schen Methoden kombiniert. Hiermit wurde gezeigt, dass MC-LR und PCB 28 zu signifikanten Effekten in Verhalten und Aktivitätsrhythmik beider Fischarten führten. Höhere Konzentrati-onen beider Untersuchungssubstanzen verursachten eine deutliche Aktivitätsredu-zierung bei Danio rerio und Leucaspius delineatus. Einige der festgestellten Do-sis-Wirkungsbeziehungen entsprechen der Hormesistheorie, z. B. war bei geringe-ren MC-LR Konzentrationen ein Aktivitätsanstieg und bei höheren ein Aktivitäts-abfall beider Fischarten zu verzeichnen. Die Exposition mit MC-LR und PCB 28 verringerte bei beiden Testfischarten die Synchronisation der Aktivität mit dem Zeitgeber Licht. Dies führte bei beiden Fischarten zu einer Phasenverschiebung. Bei Leucaspius delineatus war unter dem Einfluss von MC-LR eine Phasenumkehr zu verzeichnen, die Fische wechselten von Tag- zu Nachtaktivität. Die Cosinor Analyse zeigte Dosis abhängige Veränderungen der circadianen Rhythmen der Schwimmaktivität (z.B. MESOR, Akrophase) unter Einfluss von MC-LR und PCB 28 an. Die Power Spektral Analyse indizierte für beide Fischar-ten unter Einwirkung von MC-LR and PCB 28 eine reduzierte Dominanz des cir-cadianen Rhythmuspeaks. Da die registrierten Unterschiede in der Reaktion beider Fischarten auf MC-LR und PCB 28 eher gering waren, sind Ergebnisse der Art Danio rerio, die häufig in Toxizitätstests verwendet wird, mit denen der einheimischen Art Leucaspius deli-neatus vergleichbar. Die Ergebnisse belegen, dass Verhaltensuntersuchungen in Kombination mit chronobiologischen Auswertemethoden eine sensitive und zuverlässige Abschät-zung des Gefährdungspotentials von Substanzen sowohl auf dem Gebiet der Öko-toxikologie als auch für Biomonitoring ermöglichen. / This thesis contributes to the field of stress ecology specifically behavioural ecotoxicology. The spontaneous locomotor behavior of two fish species Danio re-rio and Leucaspius delineatus was recorded and quantified continuously under sublethal exposure to the cyanotoxin microcystin-LR (MC-LR) and the xenobioti-cum 2.4.4`-trichlorobiphenyl (PCB 28). By using an automated video-monitoring system, the swimming velocity and the number of turns were assessed under labo-ratory conditions. For analysing cyclic aspects basic behavioural analyses were combined with chronobiological procedures as cosinor analysis and power spec-tral analysis. Both MC-LR and PCB 28 acted as stressors and caused significant changes in the behaviour and circadian activity rhythms of Danio rerio as well as Leucaspius de-lineatus. So for both species elevated concentrations of the stressors led to a re-duction of their activity. Some dose-responses correspond to the hormesis theory, e.g., there was an increase of daytime activity at lower MC-LR concentrations and a decrease at elevated concentrations of MC-LR for both species. A degree of desynchronisation of activity to the zeitgeber light, which led to a phase shift was caused by the chemicals in both fish species. In Leucaspius de-lineatus this shift was so drastic that this species reversed their significant diurnal activity and became nocturnal under the influence of MC-LR. The Cosinor analysis revealed MC-LR- and PCB 28-induced, dose-dependent al-terations of the circadian rhythms of activity (e.g., MESOR, acrophase). The power spectral analysis showed that the dominance of the circadian rhythmic peak (of 24 h) was reduced under MC-LR and PCB 28 for both species. Since the observed differences in the reactions of both species to MC-LR and PCB 28 were rather small, the results of the species Danio rerio which is widely used for environmental risk assessment tests, are comparable to those of the native European species Leucaspius delineatus. The findings of this study proved that the basic behavioural analyses combined with chronobiological procedures could be valuable tools for the study of stressful or even harmful environmental factors in the field of ecotoxicology as well as for biomonitoring.

Uma das principais preocupações em relação à crescente ocorrência de cianobactérias em sistemas aquáticos está relacionada à capacidade de algumas espécies em produzir e liberar toxinas, entre elas as microcistinas, que podem afetar a saúde humana. O processo convencional de tratamento de água é muitas vezes insuficiente para remover a toxina dissolvida na água. Entre as tecnologias que podem ser utilizadas para removê-la, estão os filtros de carvão ativado granular (CAG). Essa pesquisa se dedicou ao aprofundamento do conhecimento sobre o desempenho de colunas de CAG quando operadas para remover microcistina de águas de abastecimento. A água de estudo foi composta por água de poço artesiano contaminada por extrato de microcistina (MC), produzindo soluções com concentrações iniciais de MC-LR que variaram entre 14 &#181;g/L e 92 &#181;g/L. Em ensaios de adsorção em colunas de leito fixo, sob regime contínuo, foram avaliados três tipos de CAG, de origens diferentes, sendo um vegetal (CAG-Ccoco) e dois minerais (CAG-Hulha e CAG-Linhito). A partir das curvas de ruptura dos ensaios, foram avaliadas as remoções de microcistina e a capacidade de adsorção desse poluente pelos carvões ativados. Ao ajustar modelos matemáticos (Bohart-Adams, Thomas e Yoon-Nelson) às curvas de ruptura, foi possível obter informações sobre a capacidade de adsorção dos carvões. Os resultados mostraram que o CAG-Linhito possui melhor capacidade de adsorção (164 &#181;g/g), seguido pelo CAG-Ccoco (79 &#181;g/g) e, por último, GAG-Hulha (62 &#181;g/g). A maior capacidade de adsorção de microcistina do CAG-Linhito foi atribuída ao maior volume de mesoporos (0,53 cm³/g) presente em sua estrutura (CAG-Ccoco = 0,05 cm³/g e CAG-Hulha = 0,06 cm³/g). A adsorção de microcistina por colunas de CAG se mostrou eficiente para remoção do poluente do meio líquido, em especial com a utilização do CAG-Linhito. / One of the main concerns about the increasing occurrence of cyanobacteria in aquatic systems is related to the ability of some species to produce and release toxins, including microcystins, which may affect human health. The conventional water treatment process is often insufficient to remove the toxin dissolved in the water. Among the technologies that can be used to remove microcystins are granular activated carbon (GAC) filters. This research focused on knowledge enhancement about the performance of GAC columns when operated to remove microcystin from supply water. The study water was composed of artesian well water contaminated by microcystin (MC) extract, producing solutions with initial concentrations of MC-LR that varied between 14 &#181;g / L and 92 &#181;g / L. In adsorption tests on fixed bed columns, under continuos regime, three types of GAC were evaluated, from different sources, being one vegetal (GAC-Ccoco) and two minerals (GAC-Hulha and GAC-Linhito). From the breakthrough curves, the microcystin removals and the adsorption capacity of this pollutant by activated carbons were evaluated. By adjusting mathematical models (Bohart-Adams, Thomas and Yoon-Nelson) to the breakthrough curves, it was possible to obtain information about the adsorption capacity of the GAC. The results showed that GAC-Linhito had better adsorption capacity (164 &#181;g/g), followed by GAC-Ccoco (79 &#181;g/g) and, finally, GAC-Hulha (62 &#181;g/g). The highest adsorption capacity of GAC-Linhito was attributed to the higher volume of mesopores (0.53 cm³/g) present in its structure (GAC-Ccoco = 0.05 cm³/g GAC-Coal = 0.06 cm³/g). The adsorption of microcystin by GAC columns proved to be efficient for removal of the pollutant from the liquid medium, especially with the use of GAC-Linhito.