Thesis (M.Sc.)--Memorial University of Newfoundland, 2002. / Restricted until May 2003. Bibliography: leaves 110-115.

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Η παρούσα μελέτη υλοποιήθηκε με σκοπό την μελέτη των περιβαλλοντικών παραμέτρων της λίμνης Παμβώτιδας - Ιωάννινα. Συγκεκριμένα διερευνάται η πιθανή περιβαλλοντική επιβάρυνση του λιμναίου πυθμένα της περιοχής από βαρέα μέταλλα. Στα πλαίσια της μελέτης έγιναν ορυκτολογικές και γεωχημικές αναλύσεις, κοκκομετρία καθώς και στατιστική επεξεργασία των αποτελεσμάτων (R-τύπου Παραγοντική Ανάλυση). Τα Al2O3, Fe2O3, MgO, K2O, Y, V, Rb, Co, Ni και Zn συνδέονται με τα αργιλικά ορυκτά. Η ύπαρξη P2O5 σχετίζεται με φωσφορικά λιπάσματα. Το ίδιο ισχύει και για το Th και U. Βέβαια η σταθερή κατακόρυφη κατανομή αυτών πιθανών σχετίζεται με τροφοδοσία από τα υλικά αποσάθρωσης των φωσφοριτών που υπάρχουν στο Μιτσικέλι. Τα As και Pb σχετίζονται με πιθανή ανθρωπογενή ρύπανση αν και η κατακόρυφη κατανομή του As δεν συμβαδίζει με αυτό. Η ύπαρξη του Cr συνδέεται με απόβλητα από βυρσοδεψεία. / This study was carried out to study environmental issues of lake Pamvotida - Ioannina. It investigates the potential environmental impact of lake bottom area by heavy metals. The study took mineralogical and geochemical analysis, particle size and statistical analysis of results (R-type Factor Analysis). The Al2O3, Fe2O3, MgO, K2O, Y, V, Rb, Co, Ni and Zn associated with clay minerals. Being associated with P2O5 phosphate fertilizers. The same is true for Th and U. Of course, the constant vertical distribution of these probably associated with a supply of materials of weathering phosphorites present in Mitsikeli. The As and Pb associated with possible anthropogenic pollution, although the vertical distribution of As is not consistent with it. The existence of Cr associated with waste from tanneries.

I Brista kraftvärmeverk i Sigtuna förbränns träflis och utsorterat avfall från hushåll och industri för att utvinna och exportera el och fjärrvärme. När rökgasen kyls ner, som en del av återvinningen av energi till fjärrvärmenätet, bildas rökgaskondensat. Direkt efter produktionen har kondensatet en temperatur av cirka 30 °C och innehåller höga halter av bland annat ammoniumkväve och vissa metaller. Efter rening av kondensatvattnet inuti verket efterpoleras det i en nyanlagd våtmark. Syftet med arbetet var främst att undersöka kvävereningen i våtmarken men även om riktvärden för utsläpp uppsatta av miljödomstolen efterlevs med avseende på total- och ammoniumkväve samt As och tungmetallerna Cd, Co, Cr, Cu, Hg, Ni, Pb, Tl och Zn. Arbetet syftade även på att bestämma våtmarkens area, volym och uppehållstid, undersöka eventuella skillnader i vattenföring mellan in- och utlopp samt undersöka vattentemperaturens effekt på kvävereningen. För att undersöka reningen togs veckovisa prover i våtmarkens in- och utlopp under nio veckor under hela oktober och november 2014. Proverna analyserades med jonkromatografi för bestämning av nitrat-, nitrit- och ammoniumhalt. Vidare användes data från Fortum, som driver verket, för att undersöka halter av kväve och olika metaller i våtmarken. Höjdmätningar med avvägningsinstrument användes för att bestämma våtmarkens volym och GPS för att bestämma våtmarkens längd och area. Vattentemperaturmätningar i våtmarkens utlopp genomfördes med hjälp av en logger under en tvåmånadersperiod. Vattenföring ut ur våtmarken räknades ut med hjälp av nivådata från en pumpbrunn vid utloppet. Resultaten visade att halterna av alla de studerade ämnena i både egna prover och från Fortum klarade riktvärdena för utsläpp till recipient. Halterna var även låga i rökgaskondensatet som lämnade Bristaverket vilket tyder på att reningen inuti verket fungerar bra. Våtmarkens area uppmättes till 2300 m2 och volymen till 940 m3. Den beräknade vattenföringen ut var i genomsnitt cirka 100 m3/dygn högre än inflödet. Fel i beräkningsmodellen kunde dock inte uteslutas som orsak till skillnaden. Vid låga lufttemperaturer verkade våtmarken klara av att kyla betydligt högre temperaturer hos rökgaskondensat än vad som vanligtvis skickas ut från verket. Därför rekommenderas att Fortum undersöker möjligheterna för minskad kylning av rökgaskondensatet för att möjliggöra en ökad reningsgrad av temperaturberoende processer i våtmarken, så som kväveavskiljning. / At the Brista combined heat and power plant in Sigtuna, wood chips and municipal and industrial waste are incinerated to generate and export electricity and distric heating. When the flue gas is cooled as a part of recycling its energy for distric heating, condensate is formed. Directly after production, the flue gas condensate has a temperature of approximately 30°C and contains relatively high levels of ammonia and certain heavy metals. After treatment inside the plant, the condensate is post-treated in a newly constructed wetland. The main aim of the study was to investigate the nitrogen removal in the wetland but also if current guideline values for effluents established by the environmental court are fulfilled in regard to levels of total and ammonia nitrogen as well as As and heavy metals Cd, Co, Cr, Cu, Hg , Ni, Pb, Tl  and Zn. The study also aimed to measure the wetland area, volume and retention time, investigate differences in water flow between the inlet and outlet as well as study the effect of water temperature on nitrogen removal. Water samples were taken weekly for nine weeks in October and November 2014 in the inlet and outlet of the wetland. The samples were analysed for nitrate, nitrite and ammonium ions using ion chromatography. Data from Fortum, the company that runs the heat and power plant, were also used to study levels of nitrogen and metals in the wetland. An optical leveling instrument was used to calculate the wetland volume and GPS was used to calculate its length and area. Measurements of water temperature in the outlet of the wetland were conducted using a logger during a two-month period. Water flow out of the wetland was calculated using water level data from a pump well connected to the outlet. The results showed that the levels of the studied compounds in samples collected in this study and by Fortum were all below guideline values. The levels were also low in the flue gas condensate leaving the combined heat and power plant, indicating that the treatment inside the plant is working well. The area of the wetland was measured to 2300 m2 and the volume 940 m3. The calculated water flow out of the wetland was at an average approximately 100 m3/day higher than the inflow, but an error in the calculation model is a possible cause of the difference. At low air temperatures, the wetland showed a capacity of cooling significantly higher temperatures of the flue gas condensate than what is usually released from the plant. Because of this, Fortum is recommended to investigate the possibility of reducing the cooling of the flue gas condensate and thus enabling a higher efficiency of temperature dependent treatment processes in the wetland such as nitrogen removal.

Avloppsvatten innehåller näring, bland annat kväve och fosfor som kan orsaka övergödningom det kommer ut i sjöar och vattendrag. Samtidigt behöver stora mängder näringsämnen tillföras i jordbruket för att producera mat. Ett sätt att effektivt ta till vara på näringen i avlopp och återföra den till jordbruket skulle kunna vara källsortering av avlopp. På så sätt samlas näringsämnena i en mindre volym och blandas inte med bad-, disk-, och tvättvatten. Examensarbetet syftade till att undersöka rötning som behandlingsmetod och teknik för att utnyttja energin i latrin. I rötning bryter mikroorganismer ner organiskt material anaerobt och producerar energirik biogas som kan användas till värme, el eller fordonsbränsle. Rötresten som blir kvar efter rötningen innehåller näringsämnen men också föroreningar. I studien undersöktes latrinens innehåll av tungmetaller och läkemedelsrester och hur läkemedelshalten påverkades under rötningsprocessen. För att utvärdera rötning som behandlingsmetod av latrin gjordes 44 satsvisa utrötningsför-sök i laboratorium. Latrinen hämtades från en latrininsamling i Norrtälje. Ymp från två aktiva rötningsanläggningar blandades med latrinen i gastäta glasflaskor vilka sattes på skakbord i ca 60 dagar. En del flaskor innehöll en tillsats av läkemedel lösta i metanol. Två parallella försök utfördes i olika temperaturer, i mesofil temperatur (37ºC) och i termofil temperatur (52ºC). Gasproduktion och gasens metanhalt mättes under försöksperioden för att beräkna latrinens biogaspotential. Efter avslutad rötningsperiod separerades vätskan och det fasta materialet i rötresten och frystes in i väntan på analys av läkemedelsrester. Biogasproduktionen var drygt 250 Nml CH4/g VS (ml metan per gram organiskt material vid tryck 1 atm och 0ºC) efter 60 dagar, vilket antas vara biogaspotentialen hos latrin. Det är i samma nivå som biogaspotentialen från hönsgödsel och svinkletgödsel. Gasproduktionen i flaskorna med tillsats av läkemedel var något högre och någon inhibering av processen kunde alltså ej påvisas. Kvävehalten i latrinen var 3,7 g/l, fosforhalten 1,0 g/l, kaliumhalten 1,0 g/l. Latrinens tungmetallhalter var under Naturvårdsverkets föreslagna gränsvärden för avloppsfraktioner som tillförs åkermark och skulle därför kunna användas som gödsel med dagens regelverk. Kadmiumfosforkvoten var 25 mg Cd/kg P vilket är lika mycket som medelvärde av Revaq-certifierat avloppsslam. Flera saker tyder på att latrinen som användes innehöll mer fekalier än urin i förhållande till vad som borde produceras och därmed inte fullt ut representerar ett komplett toalettavfall. Analyser gjordes av läkemedelskoncentrationer i vätskefasen av rötningsmaterialet före och efter olika långa perioder av rötning. Rötning visade sig inte vara någon effektiv metod för att rena latrin från läkemedel. Det var i fler fall som koncentrationen av läkemedel ökade än minskade under rötning. Ökningen kan bland annat ha att göra med att adsorptionsegen-skaper hos materialet förändras under rötningen och därmed frigörs substanserna och syns bättre i analysen av vätskefasen. Förekomsten av läkemedel i miljön är relativt väl undersöktmen däremot behövs mer förståelse för riskerna med läkemedel i vattenmiljö men framför-allt i jordbruksmiljö där kunskapsluckorna är stora / Wastewater contains nutrients such as nitrogen and phosphorous which can cause eutrophi-cation in lakes and streams. Meanwhile, large quantities of nutrients are used in agriculture in order to produce food. One way to utilize nutrients in wastewater and return them to agriculture could be source separation of sewage. This way, nutrients are collected in smallvolumes and are not mixed with bathing, washing, and cleaning water. This thesis aimed at investigating anaerobic digestion as a treatment method and technology to make use of the energy in latrine. In anaerobic digestion, microorganisms degrade organic material and produce energy rich biogas that can be used for heating, electricity, or vehicle fuel. The residue remaining after digestion contains nutrients but also pollutants. The study examined the content of heavy metals and drug residues in latrine, and to what extent the digestion process affected the pharmaceutical content. To evaluate the anaerobic digestion as treatment of latrines, 44 batch experiments wereperformed at laboratory scale. Latrine was taken from a collection basin in Norrtälje. Inoculum from two active anaerobic digestion plants were mixed with latrine in sealed glass bottles and put on shaking tables for approximately 60 days. Some bottles contained an addition of eight drugs dissolved in methanol. Two parallel experiments were performed one at mesophilic temperature (37ºC) and one at thermophilic temperature (52ºC). The volume of gas produced and methane content was measured for calculation of the biogas potential. After completion of the digestion period, the liquid and solids were separated and frozen pending analysis of drug residues. The biogas produced was a little over 250 Nml CH4/gVS after 60 days being comparable to production from pig and chicken manure. The bottles containing added substances showed no inhibition of the biogas process since the gas production was slightly greater in these. The nitrogen content of latrine was 3.7 g/L, the phosphorus content 1.0 g/L and potassium content of 1.0 g/L. The cadmium-phosphorus ratio was 25 mg Cd/kg P, same as the average of Revaq certified sewage sludge. The heavy metal concentrations were below the limits allowed for sewage fractions applied on arable land as proposed by the Swedish Environ-mental Protection Agency. The latrine could be used as fertilizer with current and proposed regulations. Several things indicate that the latrine used contained a higher feces-urine ratio than expected and therefore does not fully represent a complete blackwater. Analyses on drug concentrations were preformed on the liquid phase of the material before and after various periods of anaerobic digestion. Anaerobic digestion proved not to be an effective method to reduce pharmaceuticals in latrine. There were more cases where the concentration of the drug increased rather than decreased during digestion. The increase could be due to changes in adsorption properties of the material during digestion, making them more observable in the analysis. The presence of pharmaceuticals in the environment is relatively well known but more understanding is needed on the hazards of pharmaceutical residues in aquatic and especially agricultural environment.

Orientador: Gustavo Rocha de Castro / Resumo: O desenvolvimento de materiais adsorventes e posterior utilização em procedimentos de extração em fase sólida (remoção/ pré-concentração) de espécies metálicas é uma área da Química/ Engenharia Química, que sempre se manteve em destaque devido à necessidade, seja de monitorar, realizar a remoção da matriz antes da análise ou de remover o contaminante da amostra. A determinação direta de metais presentes em baixas concentrações em amostras de águas naturais é geralmente dificultada devido à presença de espécies interferentes e à necessidade do uso de técnicas sofisticadas para quantificá-los. Os metais determinados: Cu(II), Cd(II), e Pb(II); são de interesse ambiental em razão de seu uso intensivo, distribuição e por serem não-degradáveis, podendo acumular-se em matrizes ambientais manifestando toxicidade. Desta forma, o projeto teve como objetivo a utilização do PVC como suporte sólido para o ancoramento da molécula 4-amino-3-hidrazino-5-mercapto-1,2,4-triazol (AHMT) e aplicação em sistema de pré-concentração e remoção de espécies metálicas em amostras aquosas. O material foi caracterizado por Análise Elementar, a qual determinou a concentração do ligante por meio da porcentagem de nitrogênio, que foi de 3,88%. Espectroscopia de infravermelho por transformada de Fourier (FTIR) que constou a presença de bandas em 3200 cm-1 e entre 3300 e 3500 cm-1 que podem ser atribuídas ao grupamento amina, presente na molécula do ligante, cujos resultados podem ser indicativos de que a func... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The development of adsorbent materials and subsequent use in the phase extraction processes (preconcentration) of metallic species is an area of Chemistry / Chemical Engineering that has always attracted great attention in virtue of the need to monitor contamination and to perform matrice-analyte separation prior to analysis. The direct determination of metals present at low concentrations in samples of natural waters is difficult due to the presence of interfering species and to the need of sophisticated techniques to quantify them. The metals, Cu(II), Cd(II) and Pb(II) have environmental interest because of their intensive use, distribution and because they are non-degradable, thus accumulating in the environment and manifesting toxicity. Thus, the objective of the project was to use PVC as a solid support for the anchoring of the molecule 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (AHMT) and its application in a system for the preconcentration and removal of metal species from aqueous samples. The material was characterized by Elemental Analysis, Fourier-transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy, specific surface measurements according to BET method, Scanning Electron Microscopy (SEM) and Point of Zero Charge (pHpzc) to verify the occurrence of the modification reaction and to enable the construction of a model.The material was applied in adsorption studies to determine the minimum contact time, the optimum adsorption pH and its maximum ad... (Complete abstract click electronic access below) / Mestre

Made available in DSpace on 2015-04-17T14:55:30Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 4168210 bytes, checksum: a11f3130727a4c7d1cce532dea7a0d13 (MD5) Previous issue date: 2013-06-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The objective of this study was to determine the fish diversity and the bioaccumulation of heavy metals in the trophic chain of River Gramame in the hydrographic basin of River Gramame, Paraíba. The fish composition was determined by collecting fish from 10 specific areas along the River Gramame, utilizing diversified fishery techniques, during the dry and rainy seasons of 2010 to 2011. The fish collected was transported to the Laboratory of Aquatic Ecology (DSE/CCEN/UFPB), where biometry of fish was carried out (total weight and standard length), to determine the type of growth and condition factor, with a view to compare these parameters in contaminated fish. The food habits of the fish were determined by analyzing the stomach contents using the frequency of occurrence method. This was useful to understand the food chain which served as a base for the study of bioaccumulation of heavy metals in fish. The ecological diversity was determined from the indices of diversity (Shannon-Wiener), equitability (Simpson), similarity (Jaccard) and species richness. The concentrations of heavy metals (Pb, Zn, Cd, Cu) in the fish muscle were quantified by square wave voltammetry (VOQ) in a potentiostat/galvanostat in the Laboratory of Environmental Chemical Studies (DQ/CCEN/UFPB), and total mercury (Hg) by atomic absorption spectrometry with cold vapor (CV AAS) in IPEN/USP/SP. The fish composition of the upstream area showed lower taxa than the downstream area (16 to 26 genera and 17 to 27 species, respectively). The abundant species were, Cichla ocellaris (55.39%±28.96), Metynnis lippincottiannus (20.34%±13.4), Prochilodus brevis (16.63%±11.36) and Hoplias malabaricus (13.33%±7.57), during both seasons of the year. The indices of diversity showed differences between the rainy and dry seasons and the upstream and the downstream areas of the reservoir (H =1.3075; H =1.538), (H =1.6497; H =1.3553), with richness represented (17 to 26 and 18 to 22 species respectively) and a heterogeneous distribution of species (J =0.52269 and J =0.38618 respectively), due to the dominance of C. ocellaris in upstream and of M. lippincottianus in downstream of the reservoir. The growth rate of most of the species analyzed showed young individuals, indicating negative allometric growth. The diet of the species showed little difference, indicating mostly generalist food habits of fish along River Gramame. The principal component analysis (PCA) expressed a tendency in upstream and downstream areas of the reservoir to differ in terms of heavy metal accumulation in the trophic chain. A major contamination of total mercury was registered in the upstream area, while there was lead and zinc contamination in the downstream area of the reservoir. It could be concluded that along River Gramame there is major dominance of exotic species with a low diversity of native species. The feeding habits of the fish species showed a generalist tendency, with more omnivores. High heavy metal concentration was registered in the omnivores, indicating biomagnifications of toxic elements among the studied species. / O presente trabalho teve por objetivo, determinar a diversidade da ictiofauna e a bioacumulação de metais pesados na cadeia trófica do Rio Gramame, Bacia do Rio Gramame, Paraíba. Para isso foi realizada análise da ictiofauna presente, com coletas dos espécimes realizadas em 10 pontos ao longo do Rio Gramame, utilizando diversas artes de pesca, durante as estações de chuva e estiagem de 2010 a 2011. O material coletado foi transportado para o Laboratório de Ecologia Aquática (DSE/CCEN/UFPB), onde foram feitas as análises biométricas dos indivíduos (peso total e comprimento padrão), para determinar o tipo de crescimento e o fator de condição, objetivando a comparação desses parâmetros com a contaminação dos peixes. A dieta alimentar das espécies foi conhecida a partir de análises do conteúdo estomacal pelo método de freqüência de ocorrência, com finalidade de conhecer a teia alimentar, que serviu de base para o estudo da biomagnificação dos metais pesados na ictiofauna. Posteriormente, a diversidade ecológica foi determinada a partir dos índices de diversidade (Shannon-Wiener), Equitabilidade (Simpson), similaridade (Jaccard) e riqueza de espécies. As concentrações dos metais pesados (Pb, Zn, Cd, Cu) no tecido muscular das espécies foram quantificados por voltametria de onda quadrada (VOQ) em um potenciostato/galvanostato no Laboratório de Estudos Químicos Ambientais (DQ/CCEN/UFPB), e o mercúrio total (Hg) por espectrometria de absorção atômica com geração de vapor frio (CV AAS) no IPEN/USP/SP. A composição da ictiofauna a montante apresentou um número de taxa menor do que a jusante do reservatório (16 e 26 gêneros e 17 e 27 espécies, respectivamente), sendo as espécies mais abundantes, Cichla ocellaris (55,39%±28,96), Metynnis lippincottiannus (20,34%±13,4), Prochilodus brevis (16,63%±11,36) e Hoplias malabaricus (13,33%±7,57), em ambas as estações do ano. Os índices de diversidade apresentaram diferenças entre as estações de chuva e estiagem e as áreas a montante e a jusante do reservatório (H =1,3075; H =1,538), (H =1,6497; H =1,3553), como uma riqueza representada (17 e 26 e 18 e 22 espécies respectivamente) e uma distribuição heterogênea das espécies (J =0,52269 e J =0,38618 respectivamente), devido à dominância de C. ocellaris a montante e de M. lippincottianus a jusante do reservatório. A estrutura de crescimento da maioria das espécies analisadas foi representada por indivíduos jovens, revelando um crescimento do tipo alométrico negativo na população. A dieta alimentar das espécies apresentou-se pouco diferenciada, levando a uma maior incidência de hábitos alimentares generalistas ao longo do Rio Gramame. A análise de componentes principais (PCA) expressou uma tendência das áreas a montante e a jusante do reservatório diferir quanto à acumulação por metais pesados na cadeia trófica. A maior contaminação por mercúrio total foi registrada a montante, enquanto que, chumbo e zinco a jusante do reservatório. Concluí-se que, ao longo do Rio Gramame a ictiofauna apresentou uma maior dominância de espécies exóticas, levando a uma menor representação na diversidade das espécies nativas. A dieta alimentar das espécies revelou hábitos alimentares generalistas, com a categoria trófica onívora mais abundante. As maiores concentrações dos metais pesados foram registradas entre espécies de hábitos onívoros, indicando uma biomagnificação dos elementos tóxicos entre as espécies estudadas.

Made available in DSpace on 2015-04-17T14:55:30Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 4168210 bytes, checksum: a11f3130727a4c7d1cce532dea7a0d13 (MD5) Previous issue date: 2013-06-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The objective of this study was to determine the fish diversity and the bioaccumulation of heavy metals in the trophic chain of River Gramame in the hydrographic basin of River Gramame, Paraíba. The fish composition was determined by collecting fish from 10 specific areas along the River Gramame, utilizing diversified fishery techniques, during the dry and rainy seasons of 2010 to 2011. The fish collected was transported to the Laboratory of Aquatic Ecology (DSE/CCEN/UFPB), where biometry of fish was carried out (total weight and standard length), to determine the type of growth and condition factor, with a view to compare these parameters in contaminated fish. The food habits of the fish were determined by analyzing the stomach contents using the frequency of occurrence method. This was useful to understand the food chain which served as a base for the study of bioaccumulation of heavy metals in fish. The ecological diversity was determined from the indices of diversity (Shannon-Wiener), equitability (Simpson), similarity (Jaccard) and species richness. The concentrations of heavy metals (Pb, Zn, Cd, Cu) in the fish muscle were quantified by square wave voltammetry (VOQ) in a potentiostat/galvanostat in the Laboratory of Environmental Chemical Studies (DQ/CCEN/UFPB), and total mercury (Hg) by atomic absorption spectrometry with cold vapor (CV AAS) in IPEN/USP/SP. The fish composition of the upstream area showed lower taxa than the downstream area (16 to 26 genera and 17 to 27 species, respectively). The abundant species were, Cichla ocellaris (55.39%±28.96), Metynnis lippincottiannus (20.34%±13.4), Prochilodus brevis (16.63%±11.36) and Hoplias malabaricus (13.33%±7.57), during both seasons of the year. The indices of diversity showed differences between the rainy and dry seasons and the upstream and the downstream areas of the reservoir (H =1.3075; H =1.538), (H =1.6497; H =1.3553), with richness represented (17 to 26 and 18 to 22 species respectively) and a heterogeneous distribution of species (J =0.52269 and J =0.38618 respectively), due to the dominance of C. ocellaris in upstream and of M. lippincottianus in downstream of the reservoir. The growth rate of most of the species analyzed showed young individuals, indicating negative allometric growth. The diet of the species showed little difference, indicating mostly generalist food habits of fish along River Gramame. The principal component analysis (PCA) expressed a tendency in upstream and downstream areas of the reservoir to differ in terms of heavy metal accumulation in the trophic chain. A major contamination of total mercury was registered in the upstream area, while there was lead and zinc contamination in the downstream area of the reservoir. It could be concluded that along River Gramame there is major dominance of exotic species with a low diversity of native species. The feeding habits of the fish species showed a generalist tendency, with more omnivores. High heavy metal concentration was registered in the omnivores, indicating biomagnifications of toxic elements among the studied species. / O presente trabalho teve por objetivo, determinar a diversidade da ictiofauna e a bioacumulação de metais pesados na cadeia trófica do Rio Gramame, Bacia do Rio Gramame, Paraíba. Para isso foi realizada análise da ictiofauna presente, com coletas dos espécimes realizadas em 10 pontos ao longo do Rio Gramame, utilizando diversas artes de pesca, durante as estações de chuva e estiagem de 2010 a 2011. O material coletado foi transportado para o Laboratório de Ecologia Aquática (DSE/CCEN/UFPB), onde foram feitas as análises biométricas dos indivíduos (peso total e comprimento padrão), para determinar o tipo de crescimento e o fator de condição, objetivando a comparação desses parâmetros com a contaminação dos peixes. A dieta alimentar das espécies foi conhecida a partir de análises do conteúdo estomacal pelo método de freqüência de ocorrência, com finalidade de conhecer a teia alimentar, que serviu de base para o estudo da biomagnificação dos metais pesados na ictiofauna. Posteriormente, a diversidade ecológica foi determinada a partir dos índices de diversidade (Shannon-Wiener), Equitabilidade (Simpson), similaridade (Jaccard) e riqueza de espécies. As concentrações dos metais pesados (Pb, Zn, Cd, Cu) no tecido muscular das espécies foram quantificados por voltametria de onda quadrada (VOQ) em um potenciostato/galvanostato no Laboratório de Estudos Químicos Ambientais (DQ/CCEN/UFPB), e o mercúrio total (Hg) por espectrometria de absorção atômica com geração de vapor frio (CV AAS) no IPEN/USP/SP. A composição da ictiofauna a montante apresentou um número de taxa menor do que a jusante do reservatório (16 e 26 gêneros e 17 e 27 espécies, respectivamente), sendo as espécies mais abundantes, Cichla ocellaris (55,39%±28,96), Metynnis lippincottiannus (20,34%±13,4), Prochilodus brevis (16,63%±11,36) e Hoplias malabaricus (13,33%±7,57), em ambas as estações do ano. Os índices de diversidade apresentaram diferenças entre as estações de chuva e estiagem e as áreas a montante e a jusante do reservatório (H =1,3075; H =1,538), (H =1,6497; H =1,3553), como uma riqueza representada (17 e 26 e 18 e 22 espécies respectivamente) e uma distribuição heterogênea das espécies (J =0,52269 e J =0,38618 respectivamente), devido à dominância de C. ocellaris a montante e de M. lippincottianus a jusante do reservatório. A estrutura de crescimento da maioria das espécies analisadas foi representada por indivíduos jovens, revelando um crescimento do tipo alométrico negativo na população. A dieta alimentar das espécies apresentou-se pouco diferenciada, levando a uma maior incidência de hábitos alimentares generalistas ao longo do Rio Gramame. A análise de componentes principais (PCA) expressou uma tendência das áreas a montante e a jusante do reservatório diferir quanto à acumulação por metais pesados na cadeia trófica. A maior contaminação por mercúrio total foi registrada a montante, enquanto que, chumbo e zinco a jusante do reservatório. Concluí-se que, ao longo do Rio Gramame a ictiofauna apresentou uma maior dominância de espécies exóticas, levando a uma menor representação na diversidade das espécies nativas. A dieta alimentar das espécies revelou hábitos alimentares generalistas, com a categoria trófica onívora mais abundante. As maiores concentrações dos metais pesados foram registradas entre espécies de hábitos onívoros, indicando uma biomagnificação dos elementos tóxicos entre as espécies estudadas.

Submitted by CLAUDEMIR OLIVEIRA SOUZA null (clau_souza10@hotmail.com) on 2018-04-05T00:34:55Z No. of bitstreams: 1 Dissertação Claudemir final.pdf: 2598018 bytes, checksum: 6a02fac38da72d304450321a6bebe674 (MD5) / Approved for entry into archive by Ana Carolina Gonçalves Bet null (abet@iq.unesp.br) on 2018-04-05T20:46:17Z (GMT) No. of bitstreams: 1 souza_co_me_araiq_int.pdf: 2522583 bytes, checksum: 763389bef408c84daca17f39d0af0cd5 (MD5) / Made available in DSpace on 2018-04-05T20:46:17Z (GMT). No. of bitstreams: 1 souza_co_me_araiq_int.pdf: 2522583 bytes, checksum: 763389bef408c84daca17f39d0af0cd5 (MD5) Previous issue date: 2018-03-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / As hemoproteínas desempenham um papel vital nos organismos. Dentre elas, as hemoglobinas extracelulares gigantes (Hbs) se destacam por sua alta cooperatividade, alta estabilidade oligomérica, grande afinidade para ligação com oxigênio e resistência à oxidação. Devido estas propriedades, as Hbs apresentam um grande potencial biotecnológico, como é o caso de estudos buscando protótipos de substituição sanguínea e elaboração de biossensores. Porém, o uso das hemoglobinas gigantes em biossensores para detecção de metais pesados ainda não é encontrado na literatura, este tipo de biossensor agiliza e diminui o custo das análises de empresas e agências de fiscalização ambiental, obtendo o resultado in loco. Diante do exposto, o objetivo deste trabalho foi verificar a sensibilidade da hemoglobina de Amynthas gracilis (HbAg) com os metais cobre e cádmio em diferentes valores de pH e imobilizá-la em substrato sólido com o auxílio dos seguintes polímeros: o catiônico polietilenoimina (PEI) e o aniônico hidrocloreto de polialilamina (PAH). Os estudos por absorção ótica, espalhamento de luz (LSI), dicroísmo circular (CD) e fluorescência da interação da HbAg em função da concentração do metal pesado cobre no pH 7,0 mostraram que a concentração de 30 μmol.L-1 é uma concentração crítica onde observa-se uma maior oxidação do grupo heme, agregação e dissociação da proteína, além de alteração em suas α- hélices. No pH 5,0 foi observada oxidação do grupo heme mas sem alterações nas estruturas secundárias da HbAg e formação de agregados. As análises dos espectros de absorção ótica, CD, fluorescência e LSI da HbAg na presença de diferentes concentrações do metal pesado cadmio não apresentaram mudanças significativas quando comparadas com o espectro da HbAg nativa. A imobilização da HbAg em PEI no pH 7,0 foi monitorada por absorção ótica e voltametria cíclica, entretanto a HbAg não foi possível imobilizar a HbAg no polímero PAH no mesmo valor de pH, sugerindo que a interação da HbAg com os biopolímeros se deve por interações eletrostáticas. A imobilização da HbAg em PEI manteve as características da hemoglobina em pH 7,0. A hemoglobina apresentou respostas ao cobre nas medidas de voltametria cíclica realizadas em concentrações de até 20 μmol.L-1 do metal, evidenciando o grande potencial de biossensoriamento do sensor fabricado. Assim, nestes estudos foi possível verificar que a HbAg na presença de cobre em pH 7,0 se oxida, agrega e dissocia, enquanto que em pH 5,0 ela apresenta apenas oxidação. Na presença de cádmio, a HbAg não apresentou nenhuma alteração através das técnicas avaliadas. Com isso, sugere-se que a HbAg pode ser utilizada como um biossensor de indicação de presença de concentrações micromolares do metal pesado cobre. / Hemoproteins are a group of proteins that play a vital role in organisms. Among them, giant extracellular hemoglobins (Hbs) stand out for their high cooperativity, high oligomeric stability, high affinity for oxygen binding and resistance to oxidation. Due to these properties, the Hbs show a great biotechnological potential, as is the case of studies searching for prototypes of blood replacement and preparation of biosensors. However, the use of giant hemoglobins in biosensors for heavy metals detection is not yet reported on the literature, this kind of biosensors speeds up and lowers costs of analysis of companies and environmental inspection agencies, obtaining on the spot result. Thus, the aim of this work was verified the sensibility of HbAg with the metals copper and cadmium on different pH values and it's immobilization in solid surfaces with the polymers: the cationic polietilenimine (PEI) and anionic polyallylamine hydrochloride (PAH). Studies of optical absorption (UVVis), light scattering (LSI), circular dichroism (CD) and fluorescence of HbAg interaction with copper at pH 7.0 shown that 30 μmol.L-1 it’s a critical concentration where observed a great oxidation of group heme, aggregation and protein dissociation as well as alteration on your α-hélices. In pH 5.0 was observed oxidation of heme group but without alterations in HbAg secondary structure and no aggregates formation. UV-Vis spectra analysis, CD, fluorescence and LSI of HbAg at different concentrations of cadmium doesn’t shown significant changes on native HbAg spectra. The HbAg immobilization on PEI pH 7,0 has monitored by optical absorption and cyclic voltammetry, however it was not possible to immobilize the HbAg in the PAH polymer at the same pH value, suggesting that HbAg interaction with biopolymers is due to electrostatic ligations. The HbAg Immobilization in PEI maintained the hemoglobin characteristics at pH 7.0. The Hemoglobin shown responses to copper at concentrations of up to 20 μmol.L-1 of the metal in cyclic voltammetry measurements performed, demonstrated the great potential of the fabricated biosensor. Thus, in these studies it was possible to verify that HbAg on copper presence at pH 7.0 oxidizes, to aggregates and dissociates whereas at pH 5.0 it presents only oxidation. In the presence of cadmium, the HbAg showed no change through the techniques evaluated. Thereby, it is suggested that HbAg can be used as a biosensor indicating the presence of micromolar concentrations of copper heavy metal.