The Pimpama estuarine plain in subtropical southeast Queensland is comprised of Quaternary sediments infilling older bedrock. These multilayered unconsolidated sediments have various depositional origins, and are highly heterogeneous. The plain is low-lying and the surface drainage is controlled by flood mitigation measures including tidal gates and channelised streams. The control of surface drainage potentially affects the shallow water table. This modification of hydrology has implications for future viability of agriculture and also the environmental health of waterways. Increased landscape modification and water management is likely in the coming years. The combination of sediment heterogeneity, low hydraulic gradients, and artificial drainage modification result in the plain being hydrogeologically complex. In order to understand hydrologic processes in this setting, a multi-disciplinary research programme was conducted which included a drilling program, overland electromagnetic induction and other geophysical surveys (downhole gamma log, electromagnetic induction and magnetic susceptibility) to initially establish the geologic framework. These surveys were followed by hydrogeochemical testing which includes for major and minor ions and also stable isotopes, and mineralogical analysis of drillhole material. Underlying basement rock occurs at up to 60 m depth. Unconsolidated gravel and sand deposits occur within incised paleo-valleys and are overlain by predominantly low-permeability fluvial sandy clays and estuarine and lagoonal muds. Fine-grained delta sands occur in the top 15 m of the sub-surface. Within the unconsolidated sediments, hydrodynamic trends clearly discriminated between upper unconfined and lower semi-confined aquifer systems. A comparison of surface water and shallow groundwater levels indicate limited interaction of groundwater and surface water. Hydrogeochemical analysis effectively distinguished between groundwater bodies, and also distinguished saline groundwater from seawater. Trends in major ion chemistry in the semi-confined system (particularly Na/Cl and Ca/Cl ratios) showed ion exchange accompanying saline intrusion. However, due to factors such as mineral dissolution, major ion chemistry does not clearly identify solute flux trends in the shallow aquifer system. Water stable isotope analysis (δ18O and δ2H) indicated the provenance of fresh and saline groundwater and also the relative importance of the principal hydrologic processes, i.e. evaporation and water uptake by plants. Groundwater exhibited a wide range in salinity, from very fresh to hypersaline. The formation of hypersaline groundwater was attributed largely to uptake of water by mangrove forests. Since mangrove forests were more extensive at the time of the Holocene maximum sea level (approximately 6,000 years ago) than at present, some of this groundwater may represent relict salinity from this earlier time. The relationship of relict salinity to low permeability sediments, particularly at intermediate depths, and their depositional history was examined. Vertical salinity gradients and hydrogeochemistry within these sediments varied according to position within the plain, suggesting deposition under various hydrological and sea level regimes. A preliminary investigation using analysis of stable sulfate isotopes (δ34S and δ18OSO4) was made. This study shows substantial potential for the application of this technique for quantification of solute flux and sulfur chemical transformations within settings such as this coastal plain. To establish shallow groundwater flow processes, a MODFLOW-based numerical model was used to inversely estimate aquifer parameters under various recharge scenarios. The model was designed to examine the relative importance of evapotranspiration and discharge to surface waters. However, largely due to the complexity of the drainage network and non-uniform surface water flows, the quantification of surface water- groundwater interaction by consideration of hydrodynamics is problematic. Therefore, the chemistry of groundwater and surface water was compared. While the estimated contribution of rainfall to groundwater level fluctuations was significant (46%), high evapotranspiration rates reduced net recharge and it was concluded that baseflow to drains and creeks during dry periods was insignificant, and groundwater velocities in the shallow aquifer are low. The study illustrates the value of both hydrodynamic and hydrogeochemical analyses in estuarine settings where relict salinity and groundwater-aquifer interactions impact significantly on water quality. Saline groundwater is chemically distinct from theoretical mixtures of seawater and freshwater. The study also demonstrates the value of particular chemical parameters, e.g. Na/Cl and SO4/Cl ratios and stable water isotopes, for identifying hydrologic processes in this setting.

Os projetos de assentamento da reforma agrária são empreendimentos que contemplam famílias de pequenos agricultores, para que tenham acesso a terra e o alcance de maior igualdade social, mas o que se observa é o descaso das autoridades governamentais frente a essa população. Na maioria dos assentamentos, a permanência do trabalhador rural é dificultada, devido a vários problemas e o principal é a precariedade no tratamento de água, que, afeta a saúde dos moradores. Assim, o objetivo deste trabalho foi avaliar a qualidade da água e as condições de saúde dos moradores do Projeto de Assentamento (PA) Dom José Mauro, Uberlândia-MG, relacionando essas análises aos fatores ambientais que podem afetar a qualidade de vida dos assentados. Para o desenvolvimento deste trabalho foram executadas as seguintes etapas: levantamento de dados de fonte primária (entrevista semiestruturada); levantamento de dados secundários com consultas em fontes oficiais dos sistemas de informações disponíveis, que foram os prontuários dos assentados, sendo a última etapa as análises da qualidade da água. Para verificar a qualidade da água, foram realizadas análises microbiológicas das águas superficial e subterrânea, para a detecção de coliformes totais e termotolerantes em específico para a pesquisa de E.coli, de acordo com o recomendado pela Resolução do Conama nº 357 (2005) e pela portaria MS 2914/2011. Para a determinação da presença dessas bactérias, foi utilizado o método das placas de petrifilm da 3M. Foram coletadas 13 amostras na época seca e 13 na época chuvosa, sendo que, as amostras de água superficial foram coletadas de represas e as das águas subterrâneas foram coletadas de nascentes, poços e cisternas. Os dados obtidos pela análise das amostras coletadas, detectaram contaminação de 76.9 % (10) de coliformes totais e 23.0 % (3) de E.coli na época seca, e na época chuvosa 92.3% (12) de coliformes totais e 69,2% (9) de E. coli. Estes resultados não atenderam ao padrão de potabilidade estabelecido pela portaria nº 2914/2011, evidenciando que água fica mais contaminada na época chuvosa, aumentando o risco de doenças. Já em relação à presença de sintomas associados a doenças de veiculação hídrica, a diarreia foi o sintoma mais prevalente, ocorrendo nos pontos onde a contaminação por E.coli estava presente. Concluiu-se que grande parte das famílias assentadas está consumindo água fora dos padrões de potabilidade estabelecidos pela legislação brasileira, por isso esta população está vulnerável a contrair doenças de veiculação hídrica. A melhoria na qualidade da água depende da existência de um saneamento básico, de melhoria na infraestrutura de captação e armazenamento da água e do uso de metodologias eficientes para a educação ambiental e higiênico-sanitária das famílias assentadas. / The land reform settlement developments are projects that include families of small farmers, to have access to social equality, but what has been observed is the indifference of government authorities to forward this population, therefore. In most settlements the permanence of rural workers is hampered because there are several problems and the main issue is the precariousness in water treatment, which further affects the health of residents. So the aim of this study was to evaluate the water quality and the health conditions of the residents of Settlement Project (PA) Dom José Mauro, Uberlândia, Minas Gerais, relating these analyses to the environmental factors that can affect the settler’s quality of live. In order to develop this project, the following steps were taken: Primary research of data (structured interviews); collection of secondary data, based on official sources analyses of information available, such as, the records of the settlers and analysis of water quality. For the purpose of checking the water quality, microbiological analysis of surface water and groundwater have been made for the detection of total and fecal coliforms in particular for the detection of E. coli, according to the recommendations of the CONAMA Resolution nº 357 (2005) and by MS 2914/2011 concierge. For the determination of the presence of these bacteria, we used the method of 3M Petrifilm plates. 13 samples were collected during the dry season and 13 in the rainy season, and the surface water samples were collected from dam and groundwater was collected from springs, wells and cisterns. The data obtained by the analysis of the collected samples, detected contamination 76.9% (10) of total coliforms and 23.0% (3) E.coli in the dry season and the rainy season 92.3% (12) of total coliforms and 69.2% (9) of E. coli. These results did not meet the potability standards established by decree nº 2914/2011, showing that water is more contaminated during the rainy season, increasing the risk of acquiring disease. Regarding the presence of symptoms associated with waterborne diseases, diarrhea was the most prevalent symptom, occurring at the points where contamination by E.coli was present. Overall, most of the settled families are consuming water without the potability standards established by Brazilian law increasing the settled families, vulnerability to contract waterborne diseases. As it was mentioned above improvement in water quality depends on the existence of sanitation in the settlement, also an enhanced infrastructure capture and storage of water, and the use of efficient methodologies for environmental education, hygiene and better sanitary conditions for settled families. / Dissertação (Mestrado)

La présente étude est une contribution à la connaissance de la géochimie des eaux de la partie inférieure du bassin versant de la rivière N’djili située à l’Est de Kinshasa (République Démocratique du Congo). Les eaux de surface ont été échantillonnées sur six sites de prélèvements au cours de la période allant d’avril 2005 à février 2006, deux sites supplémentaires ont été ajoutés sur le fleuve Congo à partir de 2007. Onze campagnes d’échantillonnages ont permis un suivi annuel (avril 2005 à février 2006), trois autres ont eu lieu de mai à juillet 2007 et vingt-deux autres d’octobre 2008 à octobre 2009. Les paramètres physico-chimiques suivants ont été mesurés :température, pH, conductivité, alcalinité, oxygène dissous. Les dosages des éléments majeurs (anioniques et cationiques) et de certains éléments traces ont été effectués pour étayer cette étude géochimique. <p><p>Il ressort de cette étude que la température de l’eau prélevée est proche de la température moyenne atmosphérique dans la zone d’étude, ce qui indique un équilibre thermique entre les eaux de surface et l’atmosphère.<p><p>Dans certains cas, les valeurs de pH mesurées peuvent être très basses à cause du lessivage des acides organiques provenant de la végétation en décomposition et de la présence d’anhydride carbonique dissous (Burler et Ison, 1966). A la vue des résultats d’analyse des eaux de pluies, nous pouvons remarquer que l’acidité des eaux prélevées de cette partie du bassin versant serait en partie due à la contribution des précipitations.<p><p>Pour ce qui est de la conductivité, à l’exception du site Matete, les valeurs mesurées sont inférieures à 100 µS/cm, ce qui correspond aux eaux de surface très faiblement minéralisées. Il n’y a pas beaucoup de variation de conductivité entre la saison des pluies, période des hautes eaux, et la saison sèche, période des basses eaux. Ceci nous montre à nouveau qu’il y a une contribution importante des précipitations dans la composition des eaux échantillonnées puisqu’il n’y a pas de grand écart de valeur en l’absence de précipitation.<p><p>La solubilité de l’oxygène dans l’eau diminue lorsque la température augmente, ce qui induit une diminution de la concentration en oxygène à saturation. Le calcul du taux de saturation dans nos échantillons montre que les eaux sont sous-saturées en oxygène. Ceci peut s’expliquer par le fait que ce bassin versant, du moins dans la zone d’étude, subit des rejets d’eaux usées et des rejets de l’usine de traitement des eaux (REGIDESO). Nous soupçonnons la présence d’une pollution organique induisant la consommation de l’oxygène dissous par respiration. <p>Les teneurs des éléments ne sont pas constantes au cours du temps. Certains sont plus abondants que d’autres (en particulier HCO3-, Ca+, Na+, K+, SiO2 et Cl-). Il n’y a pas de variations saisonnières importantes des éléments majeurs. L’ordre d’abondance décroissant pour les cations est Na+>Ca2+>K+>Mg2+ et pour les anions est HCO3->Cl-≈NO3->SO42-.<p><p>La corrélation entre la conductivité électrique et les teneurs en composés chimiques majeurs montre que la conductivité est surtout contrôlée par les bicarbonates, les nitrates, les chlorures, les sulfates, le sodium, le magnésium, le calcium et le potassium. Ces eaux sont particulièrement peu chargées en éléments minéraux dissous, la moyenne des TDS (Total Dissolved Salts) pour chaque site étant largement inférieure à la moyenne mondiale des eaux de rivière, qui est 100 mg/l (Berner et Berner, 1987), tendance également observée pour le calcium (5,7 mg/l pour les rivières africaines et 13,4 mg/l pour la moyenne mondiale). Seul le site de Matete présente une moyenne supérieure à ces valeurs. Pour la silice dissoute, par contre, les concentrations observées sont voisines de la moyenne mondiale (10,4 mg/l).<p><p>Les valeurs du bilan ionique sont en majorité négatives, c’est-à-dire qu’elles traduisent un excès d’anions. Le calcul du bilan ionique a été effectué pour chaque point de prélèvements, pour les deux dernières séries de campagnes de prélèvements, soit de mai à juillet 2007 et d’octobre 2008 à octobre 2009.<p><p>Cette étude nous a permis de dégager des groupes au comportement commun qui reflètent des faciès géochimiques différents et dont les plus importants sont les suivants :(1) Le faciès bicarbonaté calcique :il correspond aux eaux provenant des écoulements sur des roches hypersiliceuses (grès, quartzites). Le magnésium est le deuxième cation dominant après le calcium pour le site de prélèvements CFAM (Confluence Fleuve Amont) représentant plus de 20% de la teneur en cations. Et, (2) Le faciès bicarbonaté sodique :il correspond au point de prélèvement Kwambila qui, bien que situé sur une roche hypersiliceuse, présente le sodium comme cation dominant et les nitrates comme anions dominants après les bicarbonates. Ce point de prélèvement est caractérisé par une activité agricole induisant l’utilisation de fertilisants azotés. L’élevage porcin est également pratiqué dans cette région. Ces activités humaines pourraient expliquer la prédominance du sodium et du nitrate dans cette région pour toutes les saisons confondues. <p> <p>SUMMARY<p>The present study contributes to a better understanding of the water<p>geochemistry in the N’djili river catchment, East from Kinshasa (Democratic<p>Republic of Congo). Surface waters have been collected at six sampling sites during the period from April 2005 and February 2006. Two additional sampling sites have been added since 2007. Eleven sampling campaigns allowed an annual<p>follow-up (April 2005 to February 2006), three others took place from May to<p>July 2007 and twenty-two additional ones from October 2008 to October 2009.<p>The physico-chemical parameters that have been measured are as follows:<p>temperature, pH, conductivity, alkalinity, dissolved oxygen. The measurement of<p>major elements (anions and cations) and some trace elements has been<p>performed in order to support this geochemical investigation.<p>The temperature of the riverine waters appears to be close to the mean air<p>temperature in the study area, indicating a thermal equilibrium between surface<p>waters and the atmosphere.<p>In some cases, values pH measured can be very low due to the leaching of<p>organic acids originating from both decomposing vegetation and the presence of<p>dissolved carbon dioxide (Burler and Ison, 1966). Based on the analyses of the<p>rain waters, one can note that the acidity of riverine waters results partially from<p>the atmospheric precipitation.<p>Regarding conductivity, with the exception of Matete area, the values are below<p>100 μS/cm, which corresponds to weakly mineralized surface waters. Little<p>variation in conductivity was observed between rainy and dry seasons is low,<p>suggesting again an important control of the riverine water composition by the<p>precipitation.<p>Oxygen solubility in the riverine waters decreases with increasing temperature,<p>which results in a decrease of dissolved oxygen content. The calculation of the<p>saturation state in our samples show that the riverine waters are undersaturated<p>with oxygen. This phenomenon can be explained by the fact that the river<p>catchment, at least for the study area, is subjected to untreated and treated<p>sewage effluent releases. One may expect an organic pollution leading to a<p>consumption of dissolved oxygen by respiration.<p>The concentrations of dissolved elements are variable with time. Some are more<p>abundant than others (especially HCO3-, Ca+, Na+, K+, SiO2 and Cl-). There is no<p>major seasonal variability for the major dissolved elements. The abundance<p>decreases in the orders Na+>Ca2+>K+>Mg2+ and HCO3->Cl-≈NO3->SO42- for<p>cations and anions, respectively.<p>Correlation between conductivity and major element concentrations show that<p>the former is mainly dictated by bicarbonates, nitrates, chlorides, sulfates,<p>sodium, magnesium, calcium and potassium. These riverine waters are<p>particularly low in dissolved minerals, the mean TDS (Total Dissolved Salts) for<p>each site being largely lower than the global average for rivers (i.e. 100 mg/l,<p>Berner and Berner, 1987). Calcium displays the same trend, with 5.7 mg/l for<p>African rivers in comparison with a global average of 13.4 mg/l. Only Matete area<p>exhibits a mean higher than these values. For dissolved silica, however, the<p>measured contents are close to the global average (i.e. 10.4 mg/l).<p>The values of the ionic balance are negative most of the time, suggesting an<p>excess in anions. The calculation of the charge balance has been realised for<p>each sampling location, during the two last campaigns (i.e. May 2007 - July 2007<p>and October 2008 – October 2009).<p>This study sheds some light on the groups of elements exhibiting a common<p>behaviour but reflecting different geochemical facies. The most important ones<p>are the following: (1) calcium bicarbonate facies: it corresponds to the water<p>run-off from silicate rocks (sandstone, quartzite). Magnesium is the second<p>dominant cation (after calcium) for the CFAM (“Confluence Fleuve Amont”)<p>sampling site, accounting for more than 20% of cation load. And (2) sodium<p>bicarbonate facies: it corresponds to the Kwambila sampling site, where sodium<p>is present as dominant cation and nitrates as dominant anion (after<p>bicarbonates). This sampling site is characterized by agricultural activities<p>entailing the use of nitrogen-rich fertilizers. Pig farming is also practiced in this<p>region. Theses human activities could therefore explain the predominance of<p>both sodium and nitrate in this area, irrespective of the season.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

This work is based on the current issue of increasing concentrations of pharmaceutical residues in various components of the environment. These new environmental contaminants continuously enter the environment. The most affected environmental component is the aquatic environment. This study is focused on the development and optimization of reliable analytical method, which can determine selected drugs in the aquatic environment (waste waters and surface waters) qualitatively and quantitatively. The target compounds were selected mainly from the group of non-steroidal anti-inflammatory drugs (NSAID): salicylic acid, acetylsalicylic acid, clofibric acid, ibuprofen, acetaminophen, caffeine, naproxen, mefenamic acid, ketoprofen and diclofenac. NSAIDs are one of the most used drugs in Czech Republic. For the final analysis of this study was used the comprehensive two-dimensional gas chromatography with mass spectrometric detection Time-of-Flight (GCxGC-TOF MS). It is a very sensitive and reliable analytical method for trace and ultra-trace analysis. Simultaneously, solid phase extraction (SPE) and derivatization are optimized in this work. Optimized analytical method including SPE, derivatization with MSTFA (N-methyl-N-(trimethylsilyl) trifluoroacetamide) and final analysis by GCxGC-TOF MS were applied successfully for the analysis of real samples. Samples of waste water were collected from the waste water treatment plant in Brno – Modřice and samples of surface water were collected from two river streams Svratka and Svitava in Moravian region. The range of concentrations of selected drug residues varied from one to tens of g/L in wastewater and from tens to hundreds of ng/L in surface waters. The degree of wastewater and surface waters contamination by drug residues is assessed in conclusions of the work. Simultaneously, spontaneous degradation of selected drugs in water and removal efficiency of the wastewater treatment plant is assessed in conclusions of the work. The developed method is usable for monitoring and environmental analysis of water ecosystems. It is usable not only for selected drugs, but even for other organic compounds with similar properties.

In the presented PhD. thesis, problems covering occurrence of polybrominated diphenyl ethers (PBDE) and perfluorinated compounds in the environment were solved. The study was focused on identification and further verification of optimal methods in order to determine PBDEs and perfluorinated compounds sampled from the aquatic ecosystem. Polybrominated diphenyl ethers belong to persistent compounds classified as main pollutants; within the environmental constituents, they have been observed particularly in the last decade. For these studies, there were selected surface water matrices and sediments taken in various localities within the river Svratka basin. The analyses were to demonstrate whether they accumulate and remain in these specific matrices for longer time. There we assessed the congeners of polybrominated diphenyl ethers as follows: BDE-28, 47, 66, 85, 99, 100, 153, 154 and 183. In order to isolate them from matrices, various extraction techniques were used, i.e., ultrasonic extraction, microwave extraction, and pressure solvent extraction. Gas chromatography method with electron capture detection (GC/ECD) was selected for determination. The accomplished studies also assessed basic chemical, physical and environmental characteristics of diphenyl ethers in the environmental constituents. The attention was also paid to perfluorooctanoic compounds (PFOA), (PFOS) and (FOSA); physico-chemical properties of these organic pollutants were characterised and their toxicological and environmental aspects were evaluated. Usability of extraction techniques (ultrasonic extraction, pressure solvent extraction, solid phase extraction) applied to PFCs isolation from sediments samples was assessed. Identification and quantification of these analytes were performed using a high performance liquid chromatography/mass spectrometry method (HPLC/MS). After that, the optimized methods applied to real samples. Surface water and sediments were sampled within the river Svratka basin, in particular, from 19 sampling localities. PBDE occurrence was confirmed in sediments samples from the Svratka river (g.kg-1), PBDE were not detected in the surface water samples, their concentrations were below the detection limit, resp.; perfluorinated compounds were not detected in sediments and water samples at all.

Blastodinium, a genus of the phytoplanktonic dinoflagellates, was found to be inhabiting the gut region of the copepod species Labidocera. Copepods are ubiquitous in aquatic environments, being the most numerous multicellular organisms on planet earth. Being primary consumers, they play important ecological roles, passing energy from one trophic level to the next. As zooplankton, estuarine copepods contribute substantially to carbon cycling as they undergo diurnal migration to avoid daylight UV-B damage and surface water predation. Blastodinium are presumed to infect copepods via ingestion of zoospores by juvenile hosts, who function as microhabitats for acquiring nutrients in non-photosynthetic species or in nutrient-limited environments. Blastodinium may hinder reproduction of copepod hosts, thereby influencing local copepod populations and, by extension, food webs up to humanity. Copepod populations may also help contain disease spread, such as malaria and Dengue fever, through their consumption of mosquito larvae in standing water. Further evaluation of copepods for Blastodinium may help shed light on the limited knowledge of this species and the nature of its relationship with copepods, as well as its effects on copepod populations and the higher order consequences of its parasitism.

No description available.

Il apparaît au grand jour que de nombreuses substances telles que les perturbateurs endocriniens sont introduites quotidiennement dans l’environnement. Ces molécules organiques bien souvent d’origine anthropique peuvent être employées dans d’innombrables circonstances : pharmaceutique, médecine, agriculture, cosmétique, agroalimentaire pour citer quelques exemples. Parmi ce large panel de composés, se trouvent les hormones stéroïdiennes. Un certain nombre de maladies et de modifications aussi bien comportementales que physiologiques tant chez l’humain que sur la faune aquatique sont attribuées à l’usage et aux rejets chroniques de ces perturbateurs endocriniens. Il est donc indispensable de développer une approche portée sur la prévention et l’étude des niveaux de contamination selon un seul maître-mot : précaution. Dans ce contexte, ce projet de doctorat visait à développer de nouvelles méthodes de détection des hormones stéroïdiennes à niveau ultra-trace dans diverses matrices environnementales. La sélection des composés ciblés dans ce projet s’est basée sur la nouvelle liste de perturbateurs endocriniens prioritaires de l’agence de protection de l’environnement des États-Unis (US EPA), récemment élargie à d’autres classes de substances dont le bisphénol A. Les méthodes analytiques ont été développées non seulement dans l’eau du robinet (EPA 539), mais également dans d’autres matrices plus complexes (eaux de surface, eaux usées). Commune à l’ensemble des procédures testées, la phase de validation analytique a permis de vérifier la conformité avec les exigences de performance de l’EPA. La première méthode mise au point repose sur une pré-concentration rapide de l’échantillon par extraction sur phase solide en ligne (on-line SPE) couplée à la chromatographie liquide à ultra-haute performance (UHPLC) et à la spectrométrie de masse en tandem (MS/MS). La méthode validée présente de nombreux avantages—reproductibilité, automatisation, temps d’analyse minimal, logistique réduite et surtout des limites de détection de 0,10 ng·L-1 à 7,5 ng·L-1 selon les différentes matrices étudiées. Cette méthode apparaît particulièrement adaptée pour la détection des hormones dans les eaux usées, en lien avec les plus fortes concentrations attendues. Cependant, il est apparu pertinent d’améliorer encore la sensibilité des méthodes dans certains contextes, notamment dans le cadre des iv analyses d’eau de surface, compte tenu des critères de qualité applicables. La principale modification fut apportée au niveau de l’extraction et de la purification des échantillons. Amendée à la faveur des différentes matrices, l’étape d’extraction par SPE hors-ligne automatisée (off-line SPE) a permis d’atteindre des limites de détection adéquates variant de 0,010 ng·L-1 à 6,0 ng·L-1 dépendamment de la matrice et du composé. Un aspect original de cette étude a consisté à étudier de façon plus systématique les facteurs de robustesse de la méthode lorsque soumise à certaines variations, tant au niveau de l’analyse instrumentale (phases mobiles, volume d’injection) que des protocoles (emploi de différents agents de conservation, par exemple). L’analyse de la phase dissoute ne saurait être suffisante pour comprendre le devenir environnemental des perturbateurs endocriniens dans les milieux aquatiques, notamment leur distribution. Dans cette optique, la phase particulaire en suspension dans la colonne d’eau (SPM) fut également étudiée après optimisation et validation de la méthode d’extraction. Les limites de détection obtenues étaient comprises entre 0,10 ng/g et 3,0 ng/g, un degré de performance adéquat au regard des teneurs attendues dans l’environnement. De telles méthodes ne trouveraient pas de fondement si elles n’étaient pas employées à l’analyse d’échantillons réels. C’est pourquoi, pour chaque méthode développée, une série d’échantillons d’eau a été analysée pour toutes les matrices étudiées. La quantification des hormones stéroïdiennes a permis de rendre compte des niveaux de concentrations retrouvés dans l’environnement. Une étude saisonnière d’un cours d’eau a également été réalisée durant quatre saisons (hiver, printemps, été et automne) afin d’évaluer les éventuelles variations saisonnières en termes d’occurrence et de concentration. / It is now admitted that many substances such as endocrine disruptors are released daily into the environment. This process can be of natural origin but is predominantly linked to human activity. Endocrine disruptors originate from numerous fields: medicine, agriculture, cosmetics, and the food industry, to name a few. Steroid hormones belong to this wide array of compounds. A significant number of human diseases and behavioral and physiological changes in both humans and aquatic life have been attributed to the use and chronic release of these endocrine disruptors. The effects of such a cocktail of substances are difficult to understand and evaluate. To date, the synergistic mechanisms or the potential cumulative effects are not well known. It remains essential to develop an approach focused on the prevention and the study of contamination levels with one key word in mind: precaution. In this context and aiming to detect steroid hormones in tap water, surface water and wastewater at trace levels, new analytical methods have been developed within the framework of this project. The first method developed is based on high performance liquid chromatography (HPLC) coupled with tandem mass spectrometry (MS / MS). LC-MS/MS hyphenation involved using an electrospray ionization source at atmospheric pressure with heating element (H-ESI). Pre-concentration and purification of the samples were executed by on-line solid phase extraction (on-line SPE). The validated method presents several advantages: reproducibility, automation, minimum analysis time, reduced logistics and above all, detection limits ranging from 0.10 ng·L-1 to 7.5 ng·L-1 considering the different matrices studied. The second approach proposed herein is based on the development of an analysis method allowing lower detection limits compared to the previous workflow. The same detection method was used, but a modification was made to the sample extraction and purification. Allowing for greater pre-concentration than online SPE, manual SPE (off-line SPE) was used in this method. Depending on the particular matrix, the extraction step allowed to reach adequate detection limits for the analysis of environmental aqueous samples: 0.010 ng·L-1 up vi to 6.0 ng·L-1 from the matrix-free sample to the most complex matrices. The use of an automated system also made it possible to make the extraction step robust and reproducible. The analysis of the dissolved phase of water samples cannot be sufficient to understand and comprehensively assess the contamination of aquatic environments. The particulate phase in suspension in the water column (SPM) was also studied. The extraction method was optimized and validated. Coupled with the previous method of analysis, it was possible to quantify the steroid hormones attached to suspended materials. The obtained detection limits ranged from 0.10 ng/g to 3.0 ng/g dry weight. For each developed method, dissolved phase samples were analyzed for all the studied matrices (tap water, surface water and wastewater). Quantification of steroid hormones allowed the comprehension of concentration levels found in the environment under usual discharge conditions in multiples matrices. A seasonal study of a watercourse was also carried out during the winter, spring, summer and fall seasons to observe possible seasonal variations in terms of occurrence and concentration.

Ongoing development of modern society, based on consumption of goods and services, leads to the increase of compulsoriness of economic agents to face market requirements by increasing the degree of local and regional industrialization. Establishment of new economic activities generates negative pressures on the environment and surface waters, generating increased pollution, manifested by vulnerability of aquatic ecosystems to stressors. Preliminary studies carried out within the doctoral thesis entitled 'Research on the evolution, magnitude and complexity of the impact of economic activities on the East Jiu' include information on characteristic elements of the East Jiu River basin, in accordance with the Water Framework Directive 2000/60/CE. The objectives of the field research aimed to identify economic activities in the eastern Jiu Valley generating an impact on the environment (especially the mining industry, but also timber exploitation and processing, local agriculture, animal husbandry and waste storage), establishing a quarterly monitoring program of the river basin, identification of flora and fauna species and identification of areas vulnerable to potential pollution. Based on observations made in situ and on information obtained from the evolution process of the monitoring program, the appropriate methodologies for assessing physical-chemical and ecological quality of the water were selected. Study of the evolution of the impact generated by economic activities on the East Jiu was carried out by mathematical modelling, with finite volumes, of the East Jiu River basin and plotting of pollutant dispersion maps. The magnitude and complexity of impact generated by economic activities was studied by using a complex system based on fuzzy logic, designed based on interactions between natural and artificial systems, between physical-chemical indicators of water and ecosystem. The research carried out substantiates in development of necessary technical measures to reduce the impact generated by economic activities located in eastern Jiu Valley, without significantly changing the hydrodynamics of the river basin. Following research, during different research stages, methods, techniques and tools were designed and accomplished with the help of which, water and aquatic ecosystems’ quality can be assessed, as well as the impact generated by human activity on the Jiu River, at a given moment and/or continuously.:CONTENT ACKNOWLEDGEMENTS SUMMARY LIST OF FIGURES LIST OF TABLES ABBREVIATIONS INTRODUCTION PURPOSE OF THE THESIS AND RESEARCH METHODOLOGY CHAPTER 1 THE EAST JIUL RIVER HYDROGRAPHIC BASIN 1.1. Soil and subsoil of the Eastern part of Jiu Valley 1.2. Climate description of the Eastern part of Jiu Valley 1.3. Geology particularities of the Eastern part of Jiu Valley 1.4. Groundwater features of the Eastern part of Jiu Valley 1.5. Flora and fauna of the Eastern part of Jiu Valley CHAPTER 2 SOURCES OF IMPACT ON THE QUALITY OF WATER, RIPARIAN, TERRESTRIAL AND AQUATIC ECOSYSTEMS 2.1. Mining industry 2.2. Wood processing industry in the Eastern part of Jiu Valley 2.3. Urban agriculture and local animal husbandry 2.4. Inappropriate urban household waste storage CHAPTER 3 MONITORING PROGRAM AND METHODS OF EVALUATION OF THE QUALITY OF THE EAST JIUL RIVER 3.1. Establishment of monitoring (control) sections 3.2. Monitoring program of the East Jiu River basin 3.3. Sampling, transport and analysis of water samples 3.4. Methodology used to establish the water quality CHAPTER 4 QUALITY ASSESSMENT OF WATER IN THE EASTERN JIU HYDROGRAPHIC BASIN 4.1. Section 1 - Jieț River - upstream of household settlements (blank assay) 4.2. Section 2 - East Jiu River - in the area of Tirici village 4.3. Section 3 - Răscoala brook - before the confluence with East Jiu River 4.4. Section 4 - East Jiu River - after the confluence with the Răscoala brook 4.5. Section 5 - Taia River - upstream of the confluence with East Jiu River 4.6. Section 6 - East Jiu River - before the confluence with the Taia River 4.7. Section 7 - East Jiu River - after the confluence with the Taia River 4.8. Section 8 - Jiet River downstream of household settlements 4.9. Section 9 - East Jiu River - after the confluence with the Jieț River 4.10. Section 10 - East Jiu River - before the confluence with Banița River 4.11. Section 11 - Roşia River - upstream of household settlements 4.12. Section 12 - Bănița River - after the confluence with the Roșia River 4.13. Section 13 - East Jiu River - after the confluence with the Banița River 4.14. Section 14 - Maleia River - before the confluence with East Jiu River 4.15. Section 15 - Slătioara River - before the confluence with East Jiu River 4.16. Section 16 – East Jiu River - before the confluence with West Jiu River CHAPTER 5 INFLUENCES OF PHYSICAL-CHEMICAL FACTORS ON AQUATIC ICHTHYOFAUNA IN THE EAST JIU RIVER BASIN 5.1. Total suspended solids and aquatic ecosystems 5.2. Acidity or basicity reaction of surface watercourses 5.3. Aquatic ecosystem requirements for gas oversaturation 5.4. Nitrogenous compounds in watercourse 5.5. Phenols, aquatic ecosystems and water quality CHAPTER 6 ANALYSIS OF THE IMPACT GENERATED BY ECONOMIC ACTIVITIES IN THE EASTERN PART OF JIU VALLEY 6.1. Impact analysis of mining industry in the Eastern Part of Jiu Valley 6.2. The general impact of Eastern Jiu Valley dumps to water quality 6.3. Research on effective infiltration in the Eastern part of Jiu Valley 6.4. Research on groundwater quality in the Eastern part of Jiu Valley 6.5. Analysis of the impact generated by local micro-agriculture 6.6. Analysis of the impact generated by deforestation and wood processing 6.7. Analysis of the impact generated by non-compliant landfilling of waste CHAPTER 7 EVOLUTION OF THE IMPACT GENERATED BY ECONOMIC ACTIVITIES IN THE EASTERN JIU VALLEY 7.1. Analysis of the dynamic elements of the watercourse - RMA2 mode 7.2. Analysis of pollutants concentration evolution in the water course - RMA4 module 7.3. Computational field and composition of the energy model of the East Jiu River 7.4. Extension and evolution of the impact generated by economic activities on the East Jiu River 7.5. Extension and evolution of the impact caused by organic pollution of the East Jiu River CHAPTER 8 MAGNITUDE AND COMPLEXITY OF THE IMPACT GENERATED BY ECONOMIC ACTIVITIES IN THE EASTERN JIU VALLEY 8.1. Definition of input linguistic variables 8.2. Linguistic outputs of the fuzzy interference system 8.3. Defining the Black Box set of rules 8.4. Proficiency testing of complex systems based on fuzzy logic 8.5. While it is all about the wheel do not forget about the cube CONCLUSIONS AND PERSONAL CONTRIBUTIONS REFERENCES

<p>Field-edge buffers are a promising way to address nonpoint source pollution from agricultural runoff, but concentrated runoff flow often renders standard fixed-width linear buffers ineffective. AgBufferBuilder (ABB) is a tool within ESRI ArcMap Geographic Information Systems software that designs and evaluates targeted, nonlinear buffers based on hydrologic modeling and other field-specific parameters. We tested ABB on n=45 Areas of Interest (AOIs) stratified based on estimated sediment loading across three sub-watersheds within Michigan’s Saginaw Bay watershed to evaluate the effectiveness of ABB relative to existing practices across a wide range of landscape conditions. We modeled tractor movement around ABB buffer designs to assess more realistic versions of the likely final designs. ABB regularly failed to deliver the desired 75% sediment capture rate using default 9 m x 9 m output raster resolution, with Proposed buffers capturing from 0% to 68.49% of sediment within a given AOI (mean=37.56%). Differences in sediment capture between Proposed and Existing buffers (measured as Proposed – Existing) ranged from -48% to 66.81% of sediment (mean=24.70%). Proposed buffers were estimated to capture more sediment than Existing buffers in 37 of 45 AOIs, representing potential for real improvements over Existing buffers across the wider landscape. In 13 of 45 AOIs, ABB buffers modified for tractor movement captured more sediment than Existing buffers using less total buffer area. We conducted a collaborative design process with three Saginaw Bay watershed farmers to assess their willingness to implement ABB designs. Feedback indicated farmers may prefer in-field erosion control practices like cover cropping and grassed waterways over field-edge ABB designs. More farmer input is needed to better assess farmer perspectives on ABB buffers and to identify preferred data-based design alternatives. Engineered drainage systems with raised ditch berms and upslope catch basins piped underground directly into ditches were encountered several times during site visits. ABB only models surface flow and does not recognize drain output flow entering waterways. Modified ABB functionality that models buffers around drain inlets would greatly improve its functionality on drained sites. This may be accomplishable through modification of user-entered AOI margins but requires further investigation. Unfortunately, the existing tool is built for outdated software and is not widely accessible to non-expert users. We suggest that an update of this tool with additional functionality and user accessibility would be a useful addition in the toolbox of conservation professionals in agricultural landscapes.</p>