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Este trabalho teve como objetivo determinar as fases de decomposição das frações dos resíduos dispostos no aterro sanitário de São Carlos - SP a partir do estudo das características dos lixiviados gerados. Foram coletadas amostras do lixiviado gerado na parte mais antiga do aterro (encerrada a 10 anos) e nas 1ª, 2ª e 3ª ampliações (esta última em operação). A coleta foi dividida em dois períodos: seco (junho a setembro de 2009) e chuvoso (outubro a dezembro de 2009). As seguintes análises foram realizadas: pH, alcalinidade, ácidos voláteis totais, DQO, sólidos, metais, NTK e \'N\' amoniacal. Em todos pontos os valores de pH encontrados foram superiores a 8. A alcalinidade variou entre 4000 e 12000 mg/L \'CA\'\'CO IND.3\' enquanto os AVT apresentaram concentrações sempre inferiores a 700 mg/L \'CA\'\'CO IND.3\'. A DQO apresentou concentrações entre 3000 e 7000 mg/L durante o período seco, decaindo para 2000 e 4000 mg/L no período chuvoso. Os resultados encontrados sugerem que o lixiviado de todos os pontos encontram-se na fase metanogênica de decomposição da matéria orgânica. A partir dos resultados de NTK e \'N\' amoniacal ficou evidente que a amônia é o poluente presente em maior concentração no lixiviado - corresponde a mais de 70% do NTK. A biodegradabilidade foi investigada através das relações AVT/DQO e STV/ST e resultaram em valores menores que 0,25 e 0,3 respectivamente, indicando que o lixiviado do aterro de São Carlos possui baixa biodegradabilidade. / This work aimed to determine the stages of the decomposition of the waste disposed in São Carlos - SP landfill fractions through the study of the characteristics of the generated leachate. Samples were collected from the older area of the landfill (closed 10 years ago), and also from the first, second and third new built areas (garbage is still being dumped in the third one). The samples were collected in two periods: the dry one (from June to September 2009) and the rainy one (from October to December 2009). The concentration of pH, alkalinity, total volatile acids, COD, solids, metals, sodium and potassium, total nitrogen and ammonium-\'N\' were determined in the study. In all the points sampled the values of pH were higher than 8. The alkalinity ranged from 4000 mg/L to 12000 mg/L \'CA\'\'CO IND.3\', while the total volatile acids concentrations were less than 700 mg/L \'CA\'\'CO IND.3\'. The COD present concentrations between 3000 e 7000 mg/L in the dry period decaying to 2000 and 4000 mg/L in the rainy period. The results found suggest that all the leachate analyzed is in the methanogenic phase of the organic matter. From the total nitrogen and ammonium \'N\' results it turned out to be evident that ammonia is the major pollutant present in the leachate - more than 70% of the total nitrogen. The biodegradability was investigated through the relations VFA/COD and VS/TS and resulted in values lower than 0,25 and 0,3 respectively, indicating that the leachate from São Carlos landfill has low biodegradability.

Este trabalho teve como objetivo determinar as fases de decomposição das frações dos resíduos dispostos no aterro sanitário de São Carlos - SP a partir do estudo das características dos lixiviados gerados. Foram coletadas amostras do lixiviado gerado na parte mais antiga do aterro (encerrada a 10 anos) e nas 1ª, 2ª e 3ª ampliações (esta última em operação). A coleta foi dividida em dois períodos: seco (junho a setembro de 2009) e chuvoso (outubro a dezembro de 2009). As seguintes análises foram realizadas: pH, alcalinidade, ácidos voláteis totais, DQO, sólidos, metais, NTK e \'N\' amoniacal. Em todos pontos os valores de pH encontrados foram superiores a 8. A alcalinidade variou entre 4000 e 12000 mg/L \'CA\'\'CO IND.3\' enquanto os AVT apresentaram concentrações sempre inferiores a 700 mg/L \'CA\'\'CO IND.3\'. A DQO apresentou concentrações entre 3000 e 7000 mg/L durante o período seco, decaindo para 2000 e 4000 mg/L no período chuvoso. Os resultados encontrados sugerem que o lixiviado de todos os pontos encontram-se na fase metanogênica de decomposição da matéria orgânica. A partir dos resultados de NTK e \'N\' amoniacal ficou evidente que a amônia é o poluente presente em maior concentração no lixiviado - corresponde a mais de 70% do NTK. A biodegradabilidade foi investigada através das relações AVT/DQO e STV/ST e resultaram em valores menores que 0,25 e 0,3 respectivamente, indicando que o lixiviado do aterro de São Carlos possui baixa biodegradabilidade. / This work aimed to determine the stages of the decomposition of the waste disposed in São Carlos - SP landfill fractions through the study of the characteristics of the generated leachate. Samples were collected from the older area of the landfill (closed 10 years ago), and also from the first, second and third new built areas (garbage is still being dumped in the third one). The samples were collected in two periods: the dry one (from June to September 2009) and the rainy one (from October to December 2009). The concentration of pH, alkalinity, total volatile acids, COD, solids, metals, sodium and potassium, total nitrogen and ammonium-\'N\' were determined in the study. In all the points sampled the values of pH were higher than 8. The alkalinity ranged from 4000 mg/L to 12000 mg/L \'CA\'\'CO IND.3\', while the total volatile acids concentrations were less than 700 mg/L \'CA\'\'CO IND.3\'. The COD present concentrations between 3000 e 7000 mg/L in the dry period decaying to 2000 and 4000 mg/L in the rainy period. The results found suggest that all the leachate analyzed is in the methanogenic phase of the organic matter. From the total nitrogen and ammonium \'N\' results it turned out to be evident that ammonia is the major pollutant present in the leachate - more than 70% of the total nitrogen. The biodegradability was investigated through the relations VFA/COD and VS/TS and resulted in values lower than 0,25 and 0,3 respectively, indicating that the leachate from São Carlos landfill has low biodegradability.

Landfill leachates and thermal hydrolysis pretreated anaerobic digestion centrate can quench UV light at publicly owned treatment works (POTWs). Increased eutrophication, has led to tightening of nutrient discharge limits in some regions of the country. Biologically recalcitrant organic nitrogen, adds to effluent nitrogen making it difficult to meet these requirements. The study aimed at characterizing landfill leachate and centrate fractions to develop an understanding that might help design on-site treatment methods. Leachates varying in on-site treatment and ages were fractionated on basis of hydrophobic nature. Humic substances were the major UV light quenching fractions. Majority of the humic substances were > 1 kDa molecular weight cut off (MWCO) indicating that membrane treatment might be effective for UV quenching substances removal. UV absorbing substances were found to be more bio-refractory than organic carbon. Significant decrease in humic substances with long term landfilling indicated that age was important in determining the potential for leachates to impact the UV disinfection. Organic nitrogen was observed to be hydrophilic in nature (mostly < 1 kDa). Proteins which are easily biodegradable contributed around one-third of the organic nitrogen. For thermal hydrolysis centrate, the optimum treatment depended on particle size and hydrophobic nature. Biological treatment was observed to be more effective for the removal of organic matter and UV254 quenching substances for fractions < 300 kDa. Biological treatment had little impact on organic nitrogen. Coagulation-flocculation is an effective treatment for higher molecular weight (MW) fractions whereas a membrane bioreactor would be more suitable for smaller MW fractions. / Master of Science

Landfill leachates are often discharged to wastewater treatment plants (WWTPs) but their highly varied composition makes their treatment in WWTPs difficult. Landfill leachates contain bio-refractory organic matter which easily passes the biological treatment processes at WWTPs and increases the organic matter in the effluent. Leachates also interfere with the UV disinfection process at treatment plants. Another concern is the presence of large amounts of bio-refractory organic nitrogen in the leachates which makes it difficult for WWTPs to meet the tightening total nitrogen requirements. Studies were conducted to evaluate the applicability of anion exchange resins to remove organic matter, UV quenching substance and organic nitrogen from landfill leachates. Leachate samples based on varying age and treatment methods were utilized. The anion exchange resins were found to work effectively for all studied leachates. The resins were found to remove more bio-refractory UV absorbing substances as compared to total organic carbon (TOC), suggesting that anion exchange resins could be employed for removal of UV absorbing substances. Multiple regenerations of the resin showed slight loss in the capacity to remove UV and organic carbon. Fractionation of leachate samples showed effective removal of humic acid (HA) fraction which is responsible for most of UV quenching. The resin was also found to effectively remove the bio-refractory hydrophilic (Hpi) fraction which tends to persist even after HA fraction has bio-degraded. Membrane filtration (1000 Da and 3000 Da Molecular weight cut off) in conjunction with ion exchange resins achieved better removal of organic matter and UV254 absorbing substances. In addition, this also significantly improved the performance of resins. Significant removal of organic nitrogen was also observed using anion exchange though it was less than both UV and TOC. Around 80% removal of organic nitrogen associated with bio-refractory Hpi fraction was achieved using anion exchange suggesting ion exchange as a viable alternative for removing organic nitrogen. / Master of Science

Η παρούσα μελέτη στοχεύει στη διερεύνηση των τοξικών επιπτώσεων των στραγγισμάτων που δημιουργούνται σε χώρους υγειονομικής ταφής απορριμμάτων (ΧΥΤΑ) σε υδρόβιους οργανισμούς, όπως τα ανόστρακα καρκινοειδή Thamnocephalus platyurus και Artemia franciscana, το τροχόζωο Brachionus plicatilis, το μικροφύκος Dunaliella tertiolecta και το δίθυρο μαλάκιο Mytilus galloprovincialis, καθώς και τη διερεύνηση των παραμέτρων που θα μπορούσαν να επηρεάσουν την εν δυνάμει τοξικότητά τους. Η μελέτη στραγγισμάτων που συλλέχθηκαν από τον ΧΥΤΑ Αιγείρας (ν. Αχαΐας) κατά τη διάρκεια του έτους 2011, έδειξε σημαντικές ποιοτικές και ποσοτικές εποχιακές διαφορές στην εν δυνάμει τοξικότητα των στραγγισμάτων στους οργανισμούς που ελέγχθηκαν, με τις σημαντικότερες τοξικές επιπτώσεις να εμφανίζονται στα δείγματα που συλλέχθηκαν κατά τη διάρκεια άνυδρων περιόδων, όπως η περίοδος μεταξύ Οκτωβρίου και Δεκεμβρίου. Παρόμοια, έκθεση μυδιών σε δείγμα στραγγίσματος που συλλέχθηκε κατά τη διάρκεια της παραπάνω περιόδου (Νοέμβριος 2011) έδειξε σημαντική αύξηση του ποσοστού θνησιμότητας των ατόμων, σε συγκεντρώσεις μεγαλύτερες από 0.5% v/v, ενώ σε μικρότερες συγκεντρώσεις (0.01 και 0.1% v/v) εμφανίστηκαν σημαντικές κυτταροτοξικές, νευροτοξικές και γενοτοξικές επιπτώσεις, καθώς και φαινόμενα οξειδωτικής καταπόνησης (oxidative stress). Τα αποτελέσματα της παρούσας εργασίας καταδεικνύουν την τοξικότητα των σταγγισμάτων σε υδρόβιους οργανισμούς, η οποία μπορεί επιπλέον να εκτιμηθεί μέσω της ανάλυσης επιλεγμένων παραμέτρων όπως η αγωγιμότητα (Cond), τα παράγωγα του αζώτου (NO3−, και NH4–N), ο λόγος BOD5/NH4–N και οι φαινόλες (T-PH). / The present study investigates seasonal variations of leachate composition and its toxic potency on different species, such as the brine shrimp Artemia franciscana (formerly Artemia salina), the fairy shrimp Thamnocephalus platyurus, the estuarine rotifer Brachionus plicatilis and the microalgal flagellate Dunaliella tertiolecta, as well as its ability to induce lethal and pre-pathological alterations in organisms bioindicators, such as the mussel Mytilus galloprovincialis. In specific, leachate regularly collected from the municipal landfill site of Aigeira (Peloponissos, Greece) during the year 2011, showed significant alterations of almost all its physicochemical parameters, as well as its toxic potency, with time. Samples collected during the dry season (October until December) proved to be more toxic than samples from other sample dates/periods. Further analysis showed significant increase of mortality among mussels exposed to leachate collected during that period (November 2011) (96h LC50 = 0.526%, v/v), while mussels exposed to sub-lethal concentrations (0.01 και 0.1% v/v) showed increased cytotoxic, neurotoxic, genotoxic and oxidative effects. The current study revealed for the first time that the estimation of a battery of leachate physicochemical parameters, such as Cond, TDS, NH4–N, T-PH and the respective BOD5/NH4–N ratio, could be used as a low-cost effective tool in order to estimate leachate strength and toxicity, at least in the case of semi-arid areas, such as the most of the Mediterranean countries.

Esta tesis doctoral está dirigida a la investigación y desarrollo de Procesos de Oxidación Avanzada (POAs), los cuales basan su capacidad en la generación in-situ de radicales hidroxilo (OH·), especie capaz de oxidar muchos compuestos orgánicos. Esta propiedad es aprovechada para conseguir la completa mineralización de los contaminantes o su degradación en sustancias más fácilmente biodegradables.Se plantean dos grandes objetivos:1) Contribuir al conocimiento científico a través del análisis y modelado del proceso UV/H2O2 aplicado a la degradación y mineralización de fenol. Para ello, se ha realizado una planificación experimental dirigida a estudiar la influencia de las variables de operación sobre parámetros globales del proceso, como el contenido total de materia orgánica o la toxicidad.2) Desarrollar una alternativa eficaz para la eliminación de materia orgánica de corrientes residuales de escasa biodegradabilidad mediante la aplicación de POAs. Se ha seleccionado el tratamiento de lixiviados de vertedero de residuos sólidos urbanos (RSU) como caso de estudio y se ha realizado un análisis comparativo de los procesos Fenton y foto-Fenton. Los experimentos se han realizado tanto a escala de laboratorio como a escala de planta piloto. / The aim of this thesis is the research and development of Advanced Oxidation Processes (AOPs). AOPs are based on the in-situ generation of hydroxyl radicals (OH·). These radicals are able to oxidize many organic compounds with high oxidation rates but in a non-selective way. This is useful to achieve the complete mineralization of the pollutants or its degradation into more easily biodegradable compounds.Two main objectives have been pursued in this thesis:1) To contribute to the scientific knowledge of the UV/H2O2 process through its analysis and modelling. Phenol degradation has been selected as a case of study. An experimental planning was established to study the influence of process variables on parameters such as total organic matter concentration and ecotoxicity.2) Research on new alternative treatments for suitable organic matter removal from recalcitrant waste effluents by AOPs. As study case, the leachate remediation from a municipal solid wastes landfill was selected. Fenton and photo-Fenton processes were compared and the operational conditions to achieve the maximum organic matter reduction and colour removal have been determined. Both laboratory scale and pilot plant experiments were carried out.

This thesis results from the collaborative projects between the LEQUIA-UdG group and Cespa (a company in charge of several landfill sites in Spain). The aim of the work was the development of a suitable alternative treatment for nitrogen removal from mature landfill leachates. The thesis presents the application of the anammox (anaerobic ammonium oxidation process) process to treat ammonium rich leachates as the second step of the PANAMMOX® process. The work deals with preliminary studies about the characteristics of the anammox process in a SBR, with special focus on the response of the biomass to nitrite exposure. The application of the anammox process with leachate was first studied in a lab-scale reactor, to test the effect of the leachate matrix on anammox biomass and its progressive adaptation. Finally, a start-up strategy is developed and applied for the successful start-up of a 400L anammox SBR in less than 6 months. / Aquesta tesi és fruit de la col•laboració entre el grup LEQUIA-UdG i Cespa. L'objectiu del treball va ser el desenvolupament d'un tractament alternatiu per a l'eliminació biològica de nitrogen dels lixiviats madurs d'abocador. La tesi presenta l'aplicació del procés anammox (anaerobic ammonium oxidation) per tractar elevades càrregues de nitrogen en el segon pas del procés PANAMMOX ®. El treball inclou estudis preliminars sobre les característiques del procés de anammox en un SBR, amb especial atenció a la resposta de la biomassa a l'exposició de nitrit. L'aplicació del procés anammox amb lixiviat es va estudiar inicialment en un reactor a escala de laboratori, per provar l'efecte de la matriu del lixiviat sobre la biomassa anammox i la seva adaptació progressiva. Finalment, es va desenvolupar una estratègia de posada en marxa que va ser aplicada amb èxit per a la posada en marxa d'un SBR anammox de 400L en menys de 6 mesos.