京都大学 / 0048 / 新制・課程博士 / 博士(地球環境学) / 甲第19348号 / 地環博第141号 / 新制||地環||28(附属図書館) / 32350 / 京都大学大学院地球環境学舎環境マネジメント専攻 / (主査)教授 藤井 滋穂, 教授 高岡 昌輝, 准教授 田中 周平 / 学位規則第4条第1項該当 / Doctor of Global Environmental Studies / Kyoto University / DFAM

The biological treatment of wastewaters from an industry was studied. Among the more important wastewater constituents of concern were high levels of suspended solids, due to graphite and nitrocellulose, the solvents, ethanol and acetone, and nitroglycerine (NG). The goal of this project was divided into four objectives. The impacts of graphite on a microbial population were evaluated. Sequencing batch reactors (SBRs) were used to monitor the effects of graphite on mixed liquor suspended solids (MLSS), removal of soluble chemical oxygen demand (sCOD), and specific oxygen uptake rates (sOUR). Graphite appeared to have no adverse effect on the microbes. The potential benefits of adding sucrose, nitrogen, and phosphorus to SBRs were evaluated. The MLSS was maintained at 1,250 mg/L, similar to the microbial population in the suspended growth system at the industry. Sucrose addition increased the sCOD removals and sOUR. No direct effect was observed with the addition of nitrogen and phosphorus. The treatability of acetone and ethanol was studied through sOUR and batch testing to determine bacterial response to solvents. Both solvents were utilized by the microbes. The concentrations tested proved to be beneficial, not inhibitory. Ethanol and a 50/50 mixture of acetone and ethanol were more viable substrates than acetone. NG treatability was examined under anoxic and aerobic conditions in SBRs and batch biological reactors. NG degradation occurred under anoxic conditions, but was more favorable in aerobic environments. NG was degraded in all SBR tests to below detection limit (0.5 mg/L); therefore, the optimal treatment could not be determined. / Master of Science

In 2012, mandatory effluent quality standards were established in Canada as part of the Wastewater Systems Effluent Regulations (WSER) with compliance deadlines starting in 2020. Maintaining the treatment process efficacy to meet these new stringent discharge regulations is extremely challenging at treatment facilities that treat wastewater from multiple industries due to the high variation in the composition of the incoming feed to the process. In this work, application of two new analytical tools, PeCOD® and Liquid Chromatography-Organic Carbon Detection (LC-OCD), for measurement and characterization of industrial wastewater organic pollution respectively, has been investigated. Organic pollution is commonly measured as Chemical Oxygen Demand via the dichromate method (CODCr) which requires 2-3 hours to complete. Thus this method is not suitable for applications that require rapid and frequent pollution monitoring. The Photoelectrochemical Oxygen Demand (peCOD) is an alternative parameter of organic pollution that can be measured in approximately 15 minutes via a method that utilizes the high oxidation potential of UV-irradiated TiO2 nano-particulates. Herein peCOD suitability to replace CODCr for analysis of industrial wastewater was investigated. The results indicated that for both untreated (i.e. incoming) and treated (i.e. effluent) industrial wastewater samples, peCOD results are lower than CODCr results. However, for the effluent samples, the two methods’ results are strongly correlated. Containing hard to oxidize materials (i.e. macromolecules) and high concentrations of chloride and nitrogenous compounds were identified as potential causes of difference between the results of the two methods. When there is variation in the composition of the incoming wastewater to a treatment process, information about the wastewater composition is required for process optimization. Thus optimization cannot be based solely on bulk measurements of organic pollution (e.g. COD). In this study, a novel combination of LC-OCD analysis with Design-Of-Experiments (DOE) methods was used to optimize the Fenton Advanced Oxidation (AO) treatment conditions in terms of chemical reagent concentrations, to develop statistical models of the process, and to identify potential mechanisms of COD removal. / Thesis / Master of Applied Science (MASc) / Many industrial facilities do not treat their wastewater on-site and instead ship it to specialized treatment facilities. Ensuring that the treated effluent meets the stringent discharge regulations is a challenging task for such facilities as the composition of the incoming feed to the treatment process changes with each shipment. In this work, application of two new analytical tools, PeCOD® and Liquid Chromatography-Organic Carbon Detection (LC-OCD), for measurement and characterization of industrial wastewater organic pollution respectively, has been investigated. The conventional method of measuring organic pollution, Chemical Oxygen Demand (COD), requires 2-3 hours to complete. Herein the suitability of an alternative parameter, Photoelectrochemical Oxygen Demand (peCOD), that can be measured in approximately 15 minutes for replacing COD analysis in industrial wastewater plants was investigated. Implementation of effective treatment processes that are operated at their optimum conditions is required to meet the stringent discharge regulations. Advanced Oxidation (AO) is an effective method of industrial wastewater treatment. Herein, optimum AO treatment conditions were studied via application of the LC-OCD analysis for organic pollution characterization.

M. Tech. (Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology| / The co-existence of organic acids and toxic heavy metals in natural water creates harmful effects on human, plants and animals. Therefore, it is necessary to treat organic acids and toxic heavy metal contaminated wastewater prior to its discharge to the environment. The aim of this study was to apply co-treatment of industrial wastewater containing citric acid and toxic heavy metals in single and binary systems using photocatalysis process. The hydrothermal method was used to synthesise dandelion-like TiO2 structures. Modifications of the dandelion-like TiO2 by deposition of gold nanoparticles and immobilisation on calcium alginate were done using deposition precipitation and one-step encapsulation methods, respectively. Dandelion-like TiO2 and dandelion-like TiO2 immobilised on calcium alginate (Alg/TiO2) were used as photocatalysts for Cr(VI), Hg(II) and citric acid removal from water. The results showed that the production of dandelion-like TiO2 structures strongly depends on the reaction time and synthesis temperature as key process parameters. The characterisation of the dandelion-like TiO2 by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and Brunauer-Emmett-Teller (BET) revealed the crystal structure, morphology, chemical composition and surface area. It was found that the efficiency of photocatalytic process depends on the type of pollutants, initial pH of the solution, photocatalyst dosage, contact time, substrate initial concentration, UV wavelength and light intensity. The reduction efficiency of Cr(VI) ion and citric acid increased with decreasing the initial pH values and initial concentration. On the other hand, Hg(II) reduction efficiency increased with increasing the initial pH values and initial concentration. In a binary system, the reduction of Cr(VI) and Hg(II) was found to be faster than in the single and ternary systems. The relationship of the chemical reaction rate of Cr(VI), Hg(II) and citric acid were expressed by the pseudo-first-order kinetic equation. Addition of ferric ions to Cr(VI)-citric acid complex and Hg(II)-citric acid complex enhanced the reduction of Cr(VI) and Hg(II), a complete reduction was accomplished within 30 and 60 minutes (min) of irradiation time, respectively. The reduction efficiency of both Cr(VI) and Hg(II) in the presence of citric acid in a solution was still significant after four times of Alg/TiO2 reuse. These results indicated that the UV/TiO2 photocatalysis process can be considered as a suitable method to reach a complete reduction of Cr(VI) and Hg(II) in the presence of citric acid in a solution.

Οι βιοαντιδραστήρες μεμβρανών αποτελούν μια καινοτόμο τεχνολογία, ιδανική για την αποκατάσταση προηγμένων αστικών και βιομηχανικών λυμάτων, τα οποία περιέχουν υψηλά ποσοστά βιοαποικοδομήσιμων οργανικών ενώσεων. Η παρούσα εργασία αποτελεί ένα μέρος μιας ευρύτερης προσπάθειας ανάπτυξης μιας νέας κατηγορίας λειτουργικών μεμβρανών τεχνολογίας “Βιοαντιδραστήρα Μεμβρανών” (Membrane Bioreactors, MBRs) ή/και βελτίωσης των ήδη χρησιμοποιούμενων μεμβρανών τεχνολογίας MBR με την ενσωμάτωση στο ενεργό πορώδες τους νανοσωλήνες άνθρακα. Οι νανοσωλήνες άνθρακα δυνητικά θα προσέφεραν ταυτόχρονα υψηλότερες ταχύτητες ροής νερού, υψηλότερο ποσοστό απόρριψης οργανικών ενώσεων και ανόργανων αλάτων χαμηλού μοριακού βάρους, καθώς και υψηλότερη αντοχή της μεμβράνης στην εναπόθεση διαφόρων μικροοργανισμών. Η πρόκληση στην περίπτωση αυτή είναι η αποτελεσματική ενθυλάκωση τους στην ενεργή εκλεκτική στοιβάδα των μεμβρανών αυτών. Οι νανοσωλήνες άνθρακα από την πρώτη στιγμή της ανακάλυψης τους, έχουν προσελκύσει το ενδιαφέρον της επιστημονικής κοινότητας, λόγω της ευρείας εφαρμογής τους σε πολλά επιστημονικά και τεχνολογικά πεδία, ως συνέπεια των μοναδικών ιδιοτήτων τους. Οι χημικές, οπτικές, ηλεκτρικές και μηχανικές ιδιότητές τους, τους καθιστούν δυνητικά χρήσιμους σε πάρα πολλές εφαρμογές. Στη συγκεκριμένη περίπτωση, τα τελευταία 5-7 έτη, οι νανοσωλήνες άνθρακα έχουν ταυτοποιηθεί ως μια καινούργια γενιά νανο-πορωδών υλικών με τρομερό δυναμικό για εφαρμογές ως φίλτρα σε υλικά μεμβρανών που θα μπορούσε να φέρει πραγματική επανάσταση στο σχετικό χώρο. H δυνατότητα ελέγχου της διαμέτρου τους και κατά συνέπεια του μεγέθους των πόρων τους μέσω των οποίων λαμβάνει χώρα το φαινόμενο της διάχυσης ή ροής (από τα 4 Angstroms έως τα 15 nm), σε συνδυασμό με τα σχεδόν άτριβου χαρακτήρα γραφιτικά τους τοιχώματα, εξασφαλίζει εξαιρετικά ταχεία ροή μικρών μορίων με ταυτόχρονη καταπληκτική εκλεκτικότητα στη διαπερατότητα μορίων με βάση το μέγεθός τους. Η ροή υγρών μέσα από αυτές των νανοσωλήνων άνθρακα προβλέπεται να είναι 3-5 τάξεις μεγέθους πάνω απ’ ότι αναμένεται με βάση υπολογισμούς βασισμένους σε απλές αρχές της υδροδυναμικής. Στο πλαίσιο αυτό, μελετήθηκε ο εμβολισμός νανοπορωδών εμπορικών μεμβρανών με διάφορα είδη νανοσωλήνων άνθρακα (CNTs): μονοφλοιϊκών (με ένα τοίχωμα) (Single Wall CNT: SWCNT), διπλοφλοιϊκών (με δύο τοιχώματα) (Double Wall CNT: DWCNT), πολυφλοιϊκών (με πολλαπλά (~15) τοιχώματα) (Multi Wall CNT: MWCNT), λεπτών “πολλαπλού” τοιχώματος (με λίγα (~6-7 ) τοιχώματα) (thin MWCNT), αλλά και τροποποιημένων νανοσωλήνων άνθρακα πολλαπλού τοιχώματος με υδρόξυ-ομάδες (-OH) και καρβόξυ-ομάδες (-COOH) καθώς επίσης και νανοσωλήνων άνθρακα τροποποιημένων με διάφορα πολυμερή όπως πολυβινυλοπυρολιδόνη (PVP), πολυμεθακρυλικό γλυκιδιλεστέρα (PGMA), (PSSPC16). Οι νανοσωλήνες άνθρακα, αρχικά, χαρακτηρίσθηκαν με τη βοήθεια της φασματοσκοπίας Raman και της Ηλεκτρονικής Μικροσκοπίας Σάρωσης και μελετήθηκε η διασπορά τους σε νερό (H2O) και αιθανόλη (EtOH). Κατόπιν, εμβολίσθηκαν σε διαφόρων τύπων πορώδεις ανισοτροπικές μεμβράνες (πόρων κωνικού τύπου), αλλά και σε μεμβράνες καθορισμένου μεγέθους πόρων κυλινδρικού τύπου (track etched), στην προσπάθεια ανάδειξης μιας βέλτιστης ενθυλάκωσής τους στο ενεργό/εκλεκτικό τμήμα των μεμβρανών αυτών, κάτι που δεν είναι καθόλου προφανές. Αναπτύχθηκε μια πειραματική διάταξη εμβολισμού νανοσωλήνων άνθρακα, βασιζόμενη στην αρχή της διήθησης/φιλτραρίσματος, η οποία επέτρεψε ένα βαθμό εμβολισμού τους στις μεμβράνες και μια τάση βελτίωσης του χρόνου/των ρυθμών διέλευσης του νερού από αυτές. Στην προσπάθεια αυτή αρωγός σ’ ένα μεγάλο βαθμό αποδείχθηκε η Ηλεκτρονική Μικροσκοπία Σάρωσης. / Membrane Bioreactors are an innovative technology, ideal for the treatment and rehabilitation of advanced municipal and industrial wastewater which contain high biodegradable organic compounds. A new category of functional membranes for technology MBR, which offer higher water flow, higher rejection rate of organic compounds and inorganic salts of low molecular weight, and greater resistance to the deposition of the membrane of microorganisms may be ensured by the inclusion of various types of carbon nanotubes (CNT’s) into porous polymeric membranes and its basic principle is the efficient binding of modified carbon nanotubes in these membranes. Carbon nanotubes, from the first moment of their discovery, have attracted the interest of the scientific community, due to their wide application in many scientific and technological fields, as a result of their unique properties. More specifically, the chemical, optical, electrical and mechanical properties make them potentially useful in many applications. Important is the use of carbon nanotubes for the development of an innovative high performance membrane for use in Membrane Bioreactors Technology (Membrane Bioreactors, MBR’s). In the present study different types of carbon nanotubes were examined, such as single-wall carbon nanotubes (SWCNT’s), double-wall carbon nanotubes (DWCNT’s), multi-wall carbon nanotubes (MWCNT’s), thin multi-wall carbon nanotubes (thin MWCNT’s), and modified carbon nanotubes with hydroxy groups (-OH), carboxyl groups (-COOH) as well as carbon nanotubes modified with various polymers such as polyvinylpyrrolidone (PVP), phosphonium salt of polystyrene sulfonate (PSSPC16) and polyglycidyl methacrylate (PGMA). Initially, the different types of carbon nanotubes were characterized, using Raman Spectroscopy and Scanning Electron Microscopy. Their dispersion in H2O and ethanol was also examined. Then, they were infiltrated into various types of porous anisotropic membranes with conical porous and into defined pore size membranes (track etched), to find the most suitable combination, which would result to the best water flow through the infiltrated membrane. For this purpose, an experimental device was developed, based on the principle of filtration, which allowed both the filtration of the nanotubes in the films, and the measuring of the water flow through them. Furthermore, the optimal conditions of the system were studied that could both bring about the greater coverage of the membrane pores from nanotube suspensions, (probed by SEM), and result to the optimum water flow rate.

<p>År 2000 startades ett samarbete mellan Wuhan i Kina och Borlänge Energi i Sverige. De två parterna bestämde år 2005 tillsammans med IVL, Svenska Miljöinstitutet, att samarbeta inom följande områden; hållbar energiproduktion, hållbar avfallsproduktion samt grundandet av ett miljöteknikcentrum i Wuhan. Miljöteknikcentrumet är till för att vara en plattform för svensk miljöteknik och expertis. Som ett första steg inför grundandet av ett miljöteknikcentrum gjordes en undersökning för att se inom vilka sektorer svensk miljöteknik kan etableras.</p><p>Undersökningen var inriktat på industriell avloppsvattenrening i Wuhan; bedömning av vilka typer av industrier/företag som har problem med avloppsvattenreningen och i vilken utsträckning det finns svenska tekniklösningar på problemen. Undersökningen genomfördes genom intervjuer med myndigheter och en del utvalda företag. Det var svårt att få fram information om vilka företag som inte följer de kinesiska gränsvärdena, varför en del besök gjordes till företag som lever upp till gränsvärdena. På grund av detta togs även andra problem med miljön som företagen hade upp. Några kommunala reningsverk besöktes och intervjuades också för att få en bättre bild av den kommunala vattenreningssituationen. En generell beskrivning av Wuhans miljösituation utfördes också samt en beskrivning av de viktigaste miljömyndigheterna och institutionerna.</p><p>Wuhans största utmaning är att konstruera reningsverk till alla de 3.5 miljoner som fortfarande släpper sitt avloppsvatten rätt ut till sjöar och floder, snarare än att ytterligare rena det industriella avloppsvattnet. Behandlingsgraden av det industriella avloppsvattnet har nått 97 % medan behandlingsgraden av det kommunala avloppsvattnet endast nått 70 %.</p><p>Besök vid de utvalda företagen och kommunala reningsverk ledde till slutsatsen att svensk teknik och expertis kan införas i följande områden: hantering av slam från reningsverk, byggandet av förbränningsanläggningar för sopor och hur man löser problemet med att rena luften från gaser som SO2 och dioxiner. De flesta företagen kunde följa de kinesiska gränsvärdena för utsläpp av avloppsvatten men mycket kan göras för att förbättra företagens tekniker ytterligare. Detta utförs dock nästan aldrig eftersom det är en ekonomisk fråga. Det är möjligt för Wuhan att sätta lokala, hårdare gränsvärlden för att tvinga företagen att förbättra sina reningstekniker ytterligare.</p> / <p>In 2000 a co-operation between Wuhan in China and Borlänge Energi in Sweden started. The two parts decided in 2005 together with IVL, the Swedish Research Institute, to co-operate in the fields of sustainable energy production, sustainable waste management and the establishment of an Environmental Technology Centre, supplying Swedish environmental expertise to companies in Wuhan. As a first step for the establishment of an Environmental Technology Centre in Wuhan, an investigation was made to find out in which sectors Swedish environmental technology could be established.</p><p>The investigation took aim at observing the industrial wastewater treatment in Wuhan and to see which types of companies that have problems with the wastewater treatment and if there existed Swedish technology that could solve the problems. The investigation was performed through interviews with the authorities and some selected companies. It was difficult to get information about companies that did not comply with the National Chinese wastewater standards. This meant that some of the visits were made to companies that comply with the standards, also taking into consideration other problems with the environment that the companies might have. Visits were also paid to municipal wastewater treatment plants to get an overview over the municipal wastewater treatment situation. An overall survey of the environmental situation in Wuhan was also made and a presentation of the most important environmental departments and institutions is given.</p><p>The greatest challenge for Wuhan is to construct wastewater treatment plants for the around 3.5 million people that still discharge their wastewater directly to rivers and lakes, rather than to improve the industrial wastewater treatment further. The treatment rate of the industrial wastewater has reached 97%, but the municipal wastewater treatment rate has only reached 70%.</p><p>After the visits to the selected companies and municipal wastewater treatment plants the conclusion was made that Swedish technologies and expertise can be applied to the following areas; handling sludge from the wastewater treatment plants, construction of waste incineration plants and handling flue gas and dioxins. Most of the visited companies could follow the wastewater standards. Although much can be done to improve their technologies further, this is not done since it is too expensive. It is possible for Wuhan to apply stricter local wastewater treatment standards. This could be used as a tool to make companies invest more money in improvements of their technologies.</p>

<p>Chile and Santiago are struggling with heavy environmental problems as a consequence of urbanisation and industrialisation. In the Santiago region the air is seriously contaminated and most of the rivers are classified as heavily polluted.</p><p>The aim of this thesis is to survey the industrial fluid waste situation in the Santiago region and to make suggestions on technological improvements or process changes. The purpose is also to study five different enterprises more closely and to give more detailed suggestions for improvement. Another purpose is to summarize relevant Chilean legislation.</p><p>Information, provided by the supervisory authority, about the release of industrial wastewater to rivers has been analysed. Deep interviews have been made with authorities and consultants. Five enterprises have been visited; a brewery, a dairy, a bakery, a producer of cooked meat and a surface treatment industry. The present treatment of the wastewater was studied at the plants and the information was completed with a questionnaire to the responsible at each company.</p><p>The contamination load released to the Chilean rivers is heavy. The rivers in southern Chile receive the biggest loads of BOD and SS and the rivers in central Chile were the most exposed to discharges of the metals Cr, Cu, Zn and CN as well as phenols.</p><p>The industrial discharge into the rivers of Santiago RM and Region VII is also to a large extent characterized by high concentrations of BOD and SS. Large releases of oils and greases, nitrogen and phosphorus are also fairly common, as are too high or too low pH levels. The food industry is the most contaminating sector, but also tanneries have great problems with effluents exceeding limits.</p><p>All five companies visited share the need to take measures towards more water saving technologies. The brewery, the producer of cooked meat and the surface treatment company also need end-of-pipe-treatment of their wastewater. In many cases, the recommended and most economic alternative is to separate the flows with the highest concentration of polluting substances for internal treatment, while releasing the rest of the wastewater to the outside sewage system. The costs of the suggested changes must be balanced against the present costs for treatment of wastewater and remaining solid waste as well as the costs for alternative treatments.</p><p>The economic incentives for Chilean companies to invest in wastewater treatment plants or to optimize the processes until today have been few. Cost reductions may be achieved by savings in water consumption and reuse of raw material. Another motive could be to keep “one step ahead” if the discharge limits in the future are tightened up leading to rising costs.</p> / <p>Chile och Santiago brottas med omfattande miljöproblem till följd av urbanisering och industrialisering. I santiagoregionen är luftföroreningarna svåra och de flesta floderna klassas som gravt förorenade av CONAMA, det chilenska naturvårdsverket.</p><p>Syftet med examensarbetet är att kartlägga situationen i santiagoregionen med avseende på industriell avloppsrening samt att ge förslag på förbättring av teknik eller förändring av processer. Dessutom är syftet att studera fem industrier närmare och att ge mer detaljerade förslag på åtgärder. Syftet är också att ge rekommendationer för fortsatt utveckling av relevant chilensk lagstiftning.</p><p>Uppgifter från tillsynsmyndigheten för utsläpp till ytvattendrag har studerats och djupintervjuer har gjorts med myndigheter och konsulter. Fem olika industrier besöktes; ett bryggeri, ett mejeri, ett bageri, ett charkuteri samt en ytbehandlingsindustri. Nuvarande hantering av processvattnet studerades på plats och med hjälp av ett frågeformulär kompletterades uppgifterna av ansvariga på företagen.</p><p>Föroreningsbelastningen på Chiles floder är stor. Floderna i södra delen av landet tar emot störst mängder organiskt material och suspenderat material medan centrala Chiles floder är värst drabbade av utsläpp av metallerna Cr, Cu, Zn och CN samt utsläpp av fenoler. Utsläppen från industrin till floderna i Region Metropolitana och Region VII kännetecknas också i stor utsträckning av höga halter BOD och suspenderat material. Relativt vanligt är också stora utsläpp av oljor och fetter, kväve, fosfor samt för höga eller låga för pH-värden. Det är främst flera olika typer av livsmedelsindustri, som har de största utsläppen till floderna, men även garverierna har stora problem med överskridande av gränsvärden.</p><p>Gemensamt för de fem besökta företagen är att vattenbesparande åtgärder bör vidtas för att minska volymen avloppsvatten som går till extern eller intern behandling. Bryggeriet, charkuterifabriken och ytbehandlaren behöver även end-of-pipe-rening. Det kan ofta vara lämpligt och mer ekonomiskt att avskilja de flöden som har högst halt av föroreningar till den interna reningsanläggningen. Resten av avloppet kan i vissa fall släppas ut på avloppsnätet. Kostnader för föreslagna åtgärder måste vägas mot aktuella kostnader för behandling av avlopp och restprodukter, samt kostnader för alternativa behandlingar.</p><p>Incitamenten, bl a de ekonomiska, för chilenska företag att skaffa eget reningsverk eller att resurseffektivisera produktionen har hittills varit små. Kostnadsminskningar kan uppnås genom sänkt vattenförbrukning samt återanvändning av råmaterial. Ytterligare en drivkraft kan vara att ”ligga steget före” om utsläppskraven i framtiden skärps och kostnaderna därmed ökar.</p>

As indústrias lançam diversos poluentes no meio ambiente. Dentre os poluentes destacam-se os elementos tóxicos presentes em efluentes líquidos por acarretarem alto risco potencial à saúde humana e ao meio ambiente. Os efluentes podem ser tratados por materiais adsorventes, os quais podem ser provindos de resíduos industriais. Uma forma de contribuir significativamente na sustentabilidade de uma indústria é a transformação de um de seus resíduos em sub-produto de valor agregado para aplicação no tratamento de seus efluentes líquidos como adsorvente de baixo custo. O objetivo deste trabalho foi sintetizar, e caracterizar zeólitas de cinzas de carvão e avaliar sua aplicação como material adsorvente no tratamento de efluente. Os materiais zeolíticos derivados de três tipos diferentes de cinzas de carvão (cinzas manga, cinzas ciclone e cinzas pesadas) geradas na usina termelétrica de Figueira-PR foram usados para tratar o lixiviado do aterro de cinzas de carvão da mesma usina. As seguintes características das zeólitas foram determinadas: composição mineralógica, composição química, teor de carbono total, análise morfológica, área superficial específica, capacidade de troca catiônica (CTC), perda ao fogo, pH, condutividade e densidade aparente. A fase zeolítica formada foi do tipo sodalita com as três amostras usadas como matéria prima após ativação hidrotérmica alcalina. O material zeolítico de cinzas manga apresentou a menor relação SiO2/Al2O3 (1,46), maior CTC (2,36 meq g-1) e área superficial específica (69,5 m2 g-1) e, consequentemente, maior capacidade de remoção dos íons do efluente. As concentrações de As e Cr estavam acima do padrão de lançamento de efluentes. As três amostras de materiais zeolíticos apresentaram uma remoção significativa de Ni, Cd, Zn e Co na dose de 10 g.L-1. Os materiais zeolíticos das cinzas manga e ciclone foram eficientes para reduzir a concentração de As abaixo do limite imposto pela legislação, enquanto a remoção do Cr não foi efetiva com nenhum dos materiais. Na segunda etapa do trabalho, as zeólitas foram modificadas com o surfactante brometo de hexadeciltrimetilamônio (HTDMA-Br) em concentrações de 1,8 e 20 mmol L-1. A modificação das zeólitas não melhorou a eficiência de remoção do As. A remoção do Cr usando a amostra de zeólita de cinzas manga modificada com HDTMA-Br 20 mmol L-1 resultou em uma concentração final muito próxima ao limite permitido pela legislação. / The industries release various types of pollutants into to the environment. Among these pollutants are the liquid effluents containing toxic elements, they carry a high potential risk to human health and the environment. Some effluents can be treated by adsorbent materials, which can be made from industrial waste. One way to contribute significantly to the sustainability of an industry is to transform one of its residues into a value-added by-product and use in the treatment of its own liquid effluents as a low cost adsorbent. The objective of this estudy was to synthesize and characterize coal ash zeolites and evaluate their application as adsorbent material in the treatment of effluent. Zeolite materials derived from three different types of coal ash (fly ashes, cyclone ashes and heavy ashes) generated at the Figueira-PR thermoelectric plant were used to treat leachate from the coal ash landfill of the same plant. The following zeolite characteristics were determined: mineralogical composition, chemical composition, total carbon content, morphological analysis, specific surface area, cation exchange capacity (CTC), fire loss, pH, conductivity and bulk density. The zeolite phase formed with the three samples used as raw material after alkaline hydrothermal activation was sodalite. The zeolite material from fly ash had the lowest SiO2/Al2O3 ratio (1.46), higher CTC (2.36 meq g-1) and specific surface area (69.5 m2 g-1) and, consequently, greater effluent removal capacity. The As and Cr concentrations were above the effluent discharge standard. The three samples of zeolitic materials showed a significant removal of Ni, Cd, Zn and Co in the dose of 10 g L-1. The zeolite materials from fly and cyclone ash were efficient to reduce As concentrations below the limit imposed by legislation, while removal of Cr was not effective with any of the materials. In the second stage of the study, the zeolites were modified with the surfactant hexadecyltrimethylammonium bromide (HTDMA-Br) in concentrations of 1.8 and 20 mmol.L-1. The zeolite removal efficiency of As did not improve after its modification. Removal of Cr using the 20 mmol.L-1 modified HDTMA-Br modified fly ash zeolite sample resulted in a final concentration very close to the limit allowed by the legislation.

A pesquisa propôs avaliar o desempenho e o comportamento de reatores seqüenciais em batelada com biomassa suspensa e imobilizada, em escala de bancada, na remoção de compostos de nitrogênio. Tais sistemas foram testados como tratamento complementar de reatores sulfetogênico e metanogênico utilizados no tratamento de água residuária industrial com alta concentração de sulfato e amônia. Visou o desenvolvimento de uma estratégia de operação que viabilizasse o uso dos próprios constituintes da água residuária para a maximização da eficiência do tratamento. O estudo foi dividido em 3 etapas principais. Na etapa 1 (181 dias de operação), o reator com biomassa suspensa foi mantido com 4 fases alternadas aeróbio/anóxico e ciclo de 24 horas, e verificou-se a presença da desnitrificação endógena (eficiência de remoção de nitrogênio de 65 \'+ OU -\' 27%). Para a etapa 2 (127 dias de operação), o reator de biomassa suspensa foi submetido ao tempo de ciclo de 12 horas, com uma fase aeróbia (6 horas) e com posterior fase anóxica (6 horas). Nessa etapa adicionou-se efluentes dos reatores metanogênico e sulfetogênico, ricos em ácidos voláteis (ácido acético), com intuito de acelerar o processo desnitrificante. Os resultados obtidos foram baixos em termos de remoção de nitrogênio (42 \'+ OU -\' 21%). Para a etapa 3 (134 dias de operação), foram ensaiados vários meios suportes, através de técnica de microsensores de oxigênio dissolvido, a fim de verificar a formação de biofilme específico (nitrificante/desnitrificante) e optou-se pelo uso do carvão mineral no reator com biomassa imobilizada. Nesta última etapa, foi mantida a estratégia operacional adotada na etapa 2 (ciclo 12 horas), bem como a adição de parcela do afluente na fase anóxica. A remoção de nitrogênio, com períodos aeróbio e anóxico e ciclo de 12 horas, mostrou-se viável no reator com biomassa imobilizada (eficiência de remoção de nitrogênio de 72 \'+ OU -\' 13%). Ao final dos ensaios experimentais, realizaram-se modelagens cinéticas que permitiram a compreensão dos processos convencionais e não convencionais ocorridos nas várias etapas para remoção de nitrogênio, tais como desnitrificação em fase aeróbia e o processo ANAMMOX. / The purpose of this research was to evaluate the performance and the behavior of sequential batch reactors with suspended and immobilized biomass, in benches scale, for the nitrogen composite removal. Such systems had been tested as sulphetogenic and methanogenic reactors complementary treatment, used in an industrial waste water treatment with high sulphate and ammonia concentrations. The research aimed for the development of an operation strategy that could make possible the use of the proper waste water constituent for the improvement of the treatment efficiency. The study was divided into 3 main stages. In stage 1 (181 days of operation), the reactor with suspended biomass was kept with 4 alternating phases aerobic/anoxic and a 24-hour cycle was used, and the endogenous denitrification was verified (nitrogen removal efficiency of 65 \'+ OU -\' 27%). For stage 2 (127 days of operation), the suspended biomass reactor was submitted to a cycle of 12 hours, with an aerobic phase (6 hours) and posterior anoxic phase (6 hours). In this stage effluent of the methanogenic and sulphetogenic reactors, rich in volatile acid (acetic acid), was added to accelerate the denitrify process. The achieved results had been low in terms of nitrogen removal(42 \'+ OU -\' 21%). For stage 3 (134 days of operation), some supports media was tested through dissolved oxygen microsensors technique, in order to check the specific biofilm formation (nitrificant/denitrificant) and the mineral coal was opted to be used in the immobilized biomass reactor. In this last stage it was adopted an operational strategy similar in stage 2 (12 hours cycle), as well as the addition of part of the affluent in the anoxic phase. The nitrogen removal, with aerobic and anoxic periods and 12 hours cycle, revealed feasible in the reactor with immobilized biomass (nitrogen removal efficiency of 72 \'+ OU -\' 13%). In the end of the experimental tests, kinetic modelings were done and had allowed the understanding of conventional and not conventional processes occurred in the stages for nitrogen removal, such as desnitrification in aerobic phase and ANAMMOX process.

Cianobactérias são micro-organismos procarióticos fotoautotróficos que apresentam ampla variedade morfológica e metabólica, o que favorece sua colonização nos mais diversos tipos de ambientes. Essa versatilidade favorece a sua utilização em inúmeras aplicações biotecnológicas em áreas como agricultura, energia, nutrição e tratamento de efluentes. Com o aumento da demanda energética e de alimentos, as cianobactérias são consideradas alternativas mais sustentáveis para a biossíntese de produtos de interesse industrial. Nesse contexto, o objetivo deste estudo foi avaliar o crescimento de cianobactérias em meios suplementados com vinhaça e seus efeitos na produção de lipídios e na composição de ácidos graxos, visando a produção de biodiesel. Para tanto, onze linhagens de cianobactérias isoladas de amostras de água coletadas em rios da Amazônia foram identificadas morfologicamente e geneticamente como pertencentes à quatro ordens - Nostocales, Chroococciodipsidales, Synecoccocales e Oscillatoriales. Essas linhagens tiveram o seu crescimento avaliado em meios de cultivo suplementados com vinhaça (1, 2,5, 5 e 10% v/v) e em vinhaça diluída em água ultrapura (2,5, 5 e 10% v/v). Todas as linhagens foram capazes de crescer nas concentrações testadas, porém, nas concentrações mais elevadas de vinhaça, observou-se a inibição do crescimento e/ou o aumento da proliferação de contaminantes heterotróficos. Nas diluições de vinhaça em água ultrapura, nenhuma linhagem apresentou crescimento. Duas linhagens foram selecionadas para análises subsequentes devido ao rápido crescimento (Planktothrix mougeotii CMAA1564) e ao perfil de ácidos graxos favoráveis à produção de biodiesel (Amazoninema brasiliense CMAA1602, gênero inédito). Essas linhagens tiveram seu crescimento investigado nos meios BG11, BG11+1% e BG11+2,5% de vinhaça utilizando os métodos gravimétrico (biomassa seca) e espectrofométrico (densidade ótica - DO680nm e DO750nm), para a identificação das fases de crescimento. As maiores taxas de produtividade lipídica e de biomassa foram observadas nas biomassas coletadas na fase log em meio suplementado com vinhaça a 1%, com destaque para P. mougeotii CMAA1564 (3,18 e 35,87 mg L-1 dia-1, respectivamente). A análise do perfil de ácidos graxos das frações lipídicas mostrou a predominância dos ácidos graxos saturados e monoinsaturados nos óleos das biomassas cultivadas em meio com vinhaça, sendo majoritários os ácidos palmítico, palmitoleico, oleico e alfa-linolênico. A partir da composição de ácidos graxos das frações lipídicas foi possível estimar 11 parâmetros de qualidade do biodiesel derivado dessa matéria-prima lipídica. A maioria das propriedades avaliadas estavam de acordo com as especificações de qualidade do biodiesel estabelecidas na legislação nacional e internacional, com exceção para a viscosidade cinemática que apresentou valores inferiores. Esses resultados são promissores visto a oportunidade de exploração da biodiversidade de cianobactérias ainda pouco estudada para fins biotecnológicos. Essa pesquisa demonstra a viabilidade de utilização do conteúdo lipídico desses organismos como matéria-prima lipídica alternativa para a produção de biodiesel / Cyanobacteria are photoautotrophic prokaryotes that show a wide morphological and metabolic variety, which favors the colonization of the most diverse types of environments. This versatility reflects in its numerous biotechnological applications in areas such as agriculture, energy, nutrition and effluent treatment. With the increasing in energy and food demand, cyanobacteria are considered a more sustainable alternative for the biosynthesis of products of industrial interest. In this context, the aim of this study was to evaluate the cyanobacteria growth in media supplemented with vinasse and its effect on lipid production and fatty acid composition, with focus on biodiesel production. So, eleven cyanobacterial strains from water samples from Amazonian rivers were morphologically and genetically identified as belonging to four orders - Nostocales, Chroococciodipsidales, Synecoccocales e Oscillatoriales. These strains had their growth evaluated in culture media supplemented with vinasse (1, 2,5, 5 and 10% v/v) and in vinasse diluted in ultrapure water (2,5, 5 and 10% v/v). All strains were able to grow at the concentrations tested, however, at higher vinasse concentrations, growth inhibition and/or higher heterotrophic contaminants proliferation was observed. In vinasse diluted in ultrapure water, none of them were able to grow. Two cyanobacterial strains were selected for subsequent analysis due to rapid growth (Planktothrix mougeotii CMAA1564) and favorable fatty acid profile for biodiesel production (Amazoninema brasiliense CMAA1602, a new genus). Then, these strains had their gowth investigated in the media BG11, BG11+1% and BG11+2,5% of vinasse using the gravimetric (dry biomass) and spectrophotometric (optical density - OD680nm e OD750nm) methods, for growth phases identification. The highest lipid and biomass productivities were observed in the biomass collected in the log phase in medium supplemented with 1% of vinasse, wtith the highest values observed for the P. mougeotii CMAA1564 (3,18 e 35,87 mg L-1 dia-1, respectively). The fatty acid profile of the lipid fraction showed the predominance of saturated and monounsaturated fatty acids in the oils of biomass grown in vinasse medium, with palmitic, palmitoleic, oleic and alpha-linolenic acids being the majority. From the fatty acid composition of the oils, it was possible to estimate eleven quality parameters of the biodiesel derived from these lipid feedstocks. Most of the properties evaluated werein accordance with the biodiesel quality specification estabilished in the national and international legislation, except for the kinematic viscosity that presented lower values. These results are promising given the opportunity for exploiting the underestimated cyanobacteria diversity for biotechnological purposes. This research shows the feasibility of using the lipid content of these organisms as an alternative lipid feedstock for biodiesel production