Applications of Hot Melt Extrusion (HME) in pharmaceuticals have become increasingly popular over the years but nonetheless a few obstacles still remain before wide scale implementation. In many instances these improvements are related to both processing and product performance. It is observed that HME process optimisation is majorly focused on the active pharmaceutical ingredient's (API) properties. Characterising polymeric properties for their suitability in HME should be equally studied since the impact of excipients on both product and process performance is just as vital. In this work, two well-established cellulose ester derivatives: Hydroxy Propyl Methyl Cellulose Acetate Succinate (HPMCAS) and Hydroxy Propyl Methyl Cellulose Phthalate (HPMCP) are studied for their HME suitability. Their thermal, thermodynamic, rheological, thermo-chemical and degradation kinetic properties were evaluated with model plasticisers and APIs. It was found the thermal properties of HPMCP are severely compromised whereas HPMCAS is more stable in the processing zone of 150 to 200 °C. Thermodynamic properties revealed that both polymers share an important solubility parameter range (20-30 MPa P1/2P) where the majority of plasticisers and BCS class II APIs lie. Thus, greater miscibility/solubility can be expected. Further, the processability of these two polymers investigated by rheometric measurements showed HPMCAS possesses better flow properties than HPMCP because HPMCP forms a weak network of chain interactions at a molecular level. However, adding plasticisers such as PEG and TEC the flow properties of HPMCP can be tailored. The study also showed that plasticisers have a major influence on thermo-chemical and kinetic properties of polymers. For instance, PEG reduced polymer degradation with reversal in kinetic parameters whereas blends of CA produced detrimental effects and increased polymer degradation with reduction in onset degradation temperatures. Further, both polymers are observed to be chemically reactive with the APIs containing free -OH, -SOR2RN- and -NH2 groups. Finally, these properties prove that suitability of HPMCP is highly debated for HME and demands great care in use while that of HPMCAS is relatively better than HPMCP in many instances.

Os ésteres de ftalato (PAEs) são compostos produzidos em grandes quantidades, amplamente utilizados industrialmente como agentes plastificantes. Seus resíduos são lixiviados pela água tornando-se poluentes orgânicos persistentes (POPs) no meio ambiente aquoso, além de apresentar características de interferência endócrina. O dietil ftalato (DEP) é frequentemente encontrado nas amostras ambientais, pois possui elevada solubilidade na água e pode ser gerado durante a degradação de outros PAEs. Assim, este trabalho teve como objetivo a degradação do dietil ftalato em meio aquoso por método eletroquímico utilizando um ânodo dimensionalmente estável (ADE) comercial representado como Ti/Ru0,3Ti0,7O2 em uma célula do tipo filtro-prensa. As eletrólises foram de 120 minutos contendo uma concentração inicial de 100,3 mg L-1 de DEP, pH inicial igual a 3, a temperatura em 25 °C e vazão em 250 mL min-1. Os experimentos foram feitos utilizando planejamento fatorial do tipo 32 com duas réplicas no ponto central, apresentando como variáveis independentes a densidade de corrente (10, 25 e 40 mA cm-2) e o logaritmo em base 10 da forca iônica do eletrólito suporte, NaCl e Na2SO4 (µ = 0,05, 0,15 e 0,5 mol L-1), com o intuito de estudar o efeito da densidade de corrente, concentração e natureza do eletrólito para determinar a melhor condição de degradação do dietil ftalato. O monitoramento da concentração do DEP foi feito com cromatografia líquida de alta eficiência (CLAE) e a mineralização foi acompanhada pelas análises de carbono orgânico total (COT). Foram obtidas maiores porcentagens de remoção e mineralização com uso das maiores densidades de corrente e na presença de altas concentrações de NaCl em comparação com Na2SO4. Dessa maneira, se obteve remoção de 63,2 % e mineralização de 63,9 % em solução 0,5 mol L-1 NaCl e densidade de corrente de 40 mA cm-2, enquanto que para Na2SO4 (µ = 0,5 mol L-1) e 40 mA cm-2 foi removido 51,3 % e mineralizado 53,0 % de DEP. O mecanismo de degradação de DEP foi determinado em meio de NaCl e Na2SO4, através de CLAE-MS nas condições citadas anteriormente, identificando-se os íons moleculares de m/z 149 e 177 em ambos eletrólitos, correspondentes ao anidrido ftálico protonado e ao aduto do anidrido ftálico com C(2)H(5)(+) respectivamente, íons característicos da fragmentação do DEP, além do íon m/z 239 em Na2SO4 correspondente ao dietil 3-hidroxiftalato. A degradação do DEP acontece através da cadeia alifática. / Phthalate esters (PAEs) are compounds produced in large amounts industrially widely used as plasticizers. Their waste are leached by water becoming persistent organic pollutants (POPs) in the aqueous environment, besides having endocrine disrupting characteristics. Diethyl phthalate (DEP) is frequently found in environmental samples, it has high solubility in water and can be generated during the degradation of other PAEs. This work studied the degradation of diethyl phthalate in aqueous media by electrochemical method using a commercial dimensionally stable anode (ADE) represented as Ti/Ru0,3Ti0,7O2 in a filter-press flow cell. The electrolysis were carried out during 120 minutes containing an initial concentration of 100.3 mg L-1 DEP, initial pH = 3, temperature at 25 °C and flow rate of 250 ml min-1. The experiments were performed using factorial design 32 with two replicas at the midpoint, with as independent variables the current density (10, 25 and 40 mA cm-2) and the logarithm base 10 of the ionic strength of the electrolyte, NaCl and Na2SO4 (µ = 0.05, 0.15 and 0.5 mol L-1), in order to study the effect of current density, concentration and nature of the electrolyte to determine the best diethyl phthalate degradation condition. The monitoring of DEP concentration was made by high-performance liquid chromatography (HPLC) and the mineralization was accompanied by total organic carbon (TOC) analysis. They obtained higher percentages of removal and mineralization with the use of higher current densities and in the presence of high concentrations of NaCl in comparison with Na2SO4. Thus, there was obtained the removal of 63.2 % and 63.9 % mineralization in 0.5 mol L-1 NaCl and current density of 40 mA cm-2, whereas for Na2SO4 (µ = 0.5 mol L-1) and 40 mA cm-2 was removed 51.3 % and 53.0% mineralized DEP. The DEP degradation mechanism was determined in NaCl and Na2SO4, by HPLC-MS under the conditions mentioned above, identifying the molecular ion of m/z 149 and 177 on both electrolytes, corresponding to protonated phthalic anhydride and an adduct of phthalic anhydride with C(2)H(5)(+), respectively, characteristic ions of DEP fragmentation, besides the ion m/z 239 over Na2SO4 corresponding to diethyl 3-hydroxyphthalate. The DEP degradation takes place through the aliphatic chain.

Today, assessment of the health of coastal waters is recognized as being important for both the conservation of nature and well-being of humans. Anthropogenic pollution has been the focus of extensive research for some time and a variety of programs for the monitoring and assessment of environmental pollution have been developed. Determination of the levels of pollution in sensitive ‘sentinels’ such as mussels, allows monitoring of these levels in a given area over a prolonged period of time. Furthermore, the biological effects of pollution are reflected in a series of biomarkers, none of which provides a general picture of the sentinel’s state of health and all of which are individually specific for certain pollutants and influenced by both biotic and abiotic factors. In an attempt to improve biomonitoring of marine pollution, we have developed two proteomic approaches here. In the first portion of the thesis, a proteomic analysis was performed on peroxisomes isolated from mussels exposed either to one of three model anthropogenic pollutants, or two different types of crude oil, or from mussels exposed to the Prestige oil spill. Application of two-dimensional electrophoresis (2-DE) provided protein expression signatures (PES) for exposure to these different pollutants.Furthermore, several individual protein components of these PES could be putatively identified. In the second portion of this work, such analysis of subproteomes was developed further in order to improve the applicability of this approach to biomonitoring. A simple fractionation procedure in combination with liquid chromatography and 2-DE provided samples from mussels residing in different regions of a pollution gradient around the harbor of Gothenburg, as well as from mussels exposed to two types of fuel oil similar to that of the Prestige that were suitable for environmental proteomics. In addition, we constructed a model for this approach that can be cross-validated in the future and applied to assess sources of fuel oil pollution in connection with biomonitoring programs.

No description available.

Phthalate esters (PEs) belong to a class of organic compounds used as plasticisers in plastic materials such as polyvinyl chloride (PVC), polypropylene (PP), polyethylene terephthalate (PET) and so on, including those used in the food packaging industry. Phthalate plasticisers are not chemically bound to plastic materials and hence, migrate into items such as foodstuffs they house. The study aimed at investigating the prevalence of selected phthalate esters from plastic wrappers into food as well as the presence of food and/or pathogenic microorganisms. Plastic-wrapped cheese, vienna sausages and polony samples purchased from commercial stores in the four regions of Pretoria (Tswane), South Africa, were analysed for the presence of plasticisers; di-2-ethylhexyl adipate (DEHA), di-n-butyl phthalate (DnBP), benzyl-butyl phthalate (BBP), di-butyl phthalate (DBP) and dimethyl phthalate (DMP). Soxhlet extraction using hexane with florisil column cleanup was carried out. Analysis of PEs was by Gas Chromatography-Flame Ionization Detection (GC-FID). Microbiological investigations were performed using standard methods. The concentrations of PEs detected in food samples ranged from below detection limit (bdl) to 4.7003 μg/kg. However, DBP, DMP and BBP were predominantly present with more PEs detected in cheese compared to polony and vienna. In polony samples, DBP levels ranged from 0.0412 to 0.611μg/kg, in cheese, ranged from 0.049 to 0.256 μg/kg and in vienna DBP ranged from 0.074 to 0.209 μg/kg. The phthalate DMP ranged from 0.072 to 4.700 μg/kg in cheese, 0.056 to 0.241 μg/kg in polony and 0.092 to 0.816 μg/kg in vienna. The DEHA detected in cheese and polony was 0.120 μg/kg and 0.075 μg/kg respectively and no DEHA was detected in vienna sausages. For microbiological analysis, the total microbial activity (TMA) ranged from 6.8 x 104 to 1.03 x 108 cfu/g; coliforms ranged from no growth to 2.62 x 106 cfu/g; yeast ranged from no growth to 1.49 x 107 cfu/g; and mould ranged from no growth to 9.2 x 104 cfu/g. The results revealed that microbial activity was high in each sample type but revealed the absence of pathogens. Results revealed incidences of PEs in foods wrapped or packaged in plastics, which gave cause for concern and showed the need for proper monitoring and inspection of the levels of organo-microbial entities in the South African food wrapped in plastic wrappers. / Environmental Sciences / M.Sc. (Environmental Science)

Depuis plusieurs années, un nombre conséquent d’études décrivent une augmentation de l’incidence de pathologies liées à la fonction de reproduction masculine. Ces anomalies ont été regroupées sous le terme de « syndrome de dysgénésie testiculaire ». Ce syndrome aurait pour origine les effets délétères de polluants environnementaux sur le développement du testicule en période fœtale. Parmi ces polluants environnementaux, les phtalates et le bisphénol A (BPA) sont les plastifiants les plus produits et les plus répandus dans les objets de consommation courante. De nombreuses études leur sont consacrées et ont permis de les classer au rang de perturbateurs endocriniens en mettant notamment en cause leurs effets reprotoxiques. Mon travail de thèse est une étude des effets de ces deux perturbateurs endocriniens sur le développement du testicule fœtal.Nous avons réalisé une première étude concernant les effets du BPA sur le développement du testicule fœtal. Grâce au modèle de culture organotypique, nous avons développé notre étude dans trois espèces : le rat, la souris et l’Homme. Nous démontrons que le BPA diminue la sécrétion de testostérone dans le testicule fœtal humain à partir d’une concentration de 10-8M, alors que chez le rat et la souris, la sécrétion de testostérone n’est affectée qu’à partir de 10-5M de BPA. Nous avons également démontré une diminution de l’expression du gène de l’Insl-3, dans ces mêmes conditions. Ceci nous a permis de mettre en évidence une différence de sensibilité entre les espèces. Pour tenter de comprendre les mécanismes par lesquels le BPA exerce son effet toxique, nous avons comparé ses effets à ceux du DES, autre perturbateur endocrinien œstrogénomimétique. Contrairement au BPA, le DES diminue la sécrétion de testostérone fœtale chez les rongeurs, et non chez l’Homme. Ce résultat suggère l’implication de deux voies de signalisation différentes pour ces deux xéno-œstrogènes. Cette hypothèse est d’ailleurs renforcée par l’étude que nous avons SourceMécanismes d’action des perturbateurs endocriniens bisphénol A et phtalates sur le développement du testicule fœtal / par Thierry N’Tumba-Byn ; sous la direction de Virginie Rouiller-Fabre, Université Paris Sud, 2013 [Thèse de Biologie de la Reproduction et du Développement]réalisée sur des souris invalidées pour le récepteur des œstrogènes ERα, dans lesquelles l’effet anti-androgénique du BPA persiste, contrairement à celui du DES.Parallèlement, nous avons recherché les mécanismes d’action des phtalates et de leur métabolite actif le plus répandu, le MEHP (mono-2-éthyl-hexyl phtalate). Dans la continuité de plusieurs travaux réalisés dans notre laboratoire sur les effets du MEHP, nous avons tenté de comprendre les mécanismes par lesquels le MEHP induit un effet pro-apoptotique dans les cellules germinales mâles. Nous avons mis en évidence une augmentation de l’expression du gène Stra8 dans les cellules germinales traitées au MEHP. Ce résultat nous suggère que le MEHP pourrait induire une différenciation erronée des cellules germinales mâles. De plus, nous avons recherché les récepteurs et la voie de signalisation activée par le MEHP. Nous observons que les agonistes des récepteurs PPARα et de PPARγ entrainent dans les cellules germinales les mêmes phénotypes que le MEHP, à savoir une augmentation du taux d’apoptose et de l’expression du gène Stra8. / For several years, an increase in the incidence of pathologies connected to the male reproductive functions has been described in numerous studies. These anomalies are classified under the term “testicular dysgenesis syndrome”. This syndrome might find its origins in the deleterious effects of environmental pollutants on the testis development in fetal period. Among theses environmental pollutants, phthalates and bisphenol A (BPA) are the most produced plasticizers found in products of common use. Many studies were performed in order to determine their effects, and allowed to classify them as endocrine disruptors because of their reprotoxic effects. My thesis work is a study of the effects of these two endocrine disruptors on the fetal testis development.Our first study focuses on the effects of BPA on the fetal testis development. Using the organotypic culture model, we developed our study in three species: rat, mouse and human. We demonstrated that BPA decreases the testosterone secretion in the human fetal testis from a 10-8M concentration, while in rat and mouse the testosterone secretion is only affected by 10-5M BPA. We also demonstrated a decreased Insl-3 gene expression, in the same conditions. These results allowed us to evidence a difference of sensibility between species. To understand the mechanisms involved in the BPA toxic effect, we compared it with the effect of DES, another endocrine disruptor with estrogenic activity. Unlike BPA, DES decreases the fetal testosterone secretion in rodents and not in human. This result suggests the involvement of two different signalisation pathways for these two xenoestrogens. This hypothesis is reinforced by the study that we performed in mice invalidated for the estrogen receptor ERα. In those mice, the anti-androgenic effect of BPA is maintained, unlike DES effect.In parallel, we investigated the mechanisms of action of phtalates and particularly of their most prevalent active metabolite, the MEHP (mono-2-ethyl-hexyl phthalate). Following previous studies performed in our laboratory concerning the effects of MEHP, we intended to understand the mechanisms by which MEHP induces the apoptosis in male germ cells. We evidenced an increase in Stra8 gene expression in MEHP treated germ cells. This result suggests that MEHP might induce a wrong differentiation in male germ cells. Furthermore, we investigated the receptors and the signalisation pathway activated by MEHP. We observe that PPARα and PPARγ receptors agonists induce the same phenotypes as MEHP, namely an increase in the apoptosis and in Stra8 gene expression in germ cells.

Applications of Hot Melt Extrusion (HME) in pharmaceuticals have become increasingly popular over the years but nonetheless a few obstacles still remain before wide scale implementation. In many instances these improvements are related to both processing and product performance. It is observed that HME process optimisation is majorly focused on the active pharmaceutical ingredient's (API) properties. Characterising polymeric properties for their suitability in HME should be equally studied since the impact of excipients on both product and process performance is just as vital. In this work, two well-established cellulose ester derivatives: Hydroxy Propyl Methyl Cellulose Acetate Succinate (HPMCAS) and Hydroxy Propyl Methyl Cellulose Phthalate (HPMCP) are studied for their HME suitability. Their thermal, thermodynamic, rheological, thermo-chemical and degradation kinetic properties were evaluated with model plasticisers and APIs. It was found the thermal properties of HPMCP are severely compromised whereas HPMCAS is more stable in the processing zone of 150 to 200 °C. Thermodynamic properties revealed that both polymers share an important solubility parameter range (20-30 MPa P1/2P) where the majority of plasticisers and BCS class II APIs lie. Thus, greater miscibility/solubility can be expected. Further, the processability of these two polymers investigated by rheometric measurements showed HPMCAS possesses better flow properties than HPMCP because HPMCP forms a weak network of chain interactions at a molecular level. However, adding plasticisers such as PEG and TEC the flow properties of HPMCP can be tailored. The study also showed that plasticisers have a major influence on thermo-chemical and kinetic properties of polymers. For instance, PEG reduced polymer degradation with reversal in kinetic parameters whereas blends of CA produced detrimental effects and increased polymer degradation with reduction in onset degradation temperatures. Further, both polymers are observed to be chemically reactive with the APIs containing free -OH, -SOR2RN- and -NH2 groups. Finally, these properties prove that suitability of HPMCP is highly debated for HME and demands great care in use while that of HPMCAS is relatively better than HPMCP in many instances.

Food is one of the main routes by which xenobiotic (synthetic) chemicals enter the body of man and wildlife. The routes could be from wrappers in which the foods are presented with possible transfer of the compounds to consumers, hence need for regular screening. The research work is aimed at investigating possible prevalence of phthalate esters in selected foods (cheese, polony and vienna) and their plastic wrappers from commercial stores in Tshwane metropolis. Food samples were purchased from selected stores, taken to the laboratory and stored at 4oC until analysed. Analysis was done by soxhlet extraction while determination and quantification of phthalates was carried out using Gas Chromatography-Flame Ionization Detection (GC-FID). Quality assurance of the process was by standard addition of the phthalate ester standards. Results obtained revealed good chromatographic separation of the analysed esters which ranged from 5.55 min for Dimethyl phthalate (DMP) to 8.96 min for Benzylbutyl phthalate (BBP). Instrumental detection limit of the esters varied from 0.03 - 0.05 μg/kg. The percentage recovery of the phthalate esters ranged from 75 – 90% from spiked cheese samples; 33 – 66% from spiked polony samples and 69 – 99% from spiked vienna samples. These recoveries are quite acceptable and applicable to the analysis and quantification of the compounds in the samples with the exception of Dibutyl phthalate (DBP) (33%); DMP (34%) and BBP (46 %) in polony samples. Results from chromatographic quantification revealed the absence of or non-detection of most of the analysed phthalate esters in the selected food samples. However, level of 0.031 μg/kg of BBP - 0.816 μg/kg of DMP were obtained in some of the analysed samples. / Environmental Sciences / M.Sc. (Environmental Science)

Τις τελευταίες δεκαετίες η συνεχώς αυξανόμενη παγκόσμια δραστηριότητα, λόγω της έντονης αστικοποίησης και βιομηχανοποίησης, έχει σαν αποτέλεσμα την παραγωγή σημαντικών ποσοτήτων αποβλήτων. Μεταξύ αυτών είναι και η ιλύς, δηλαδή το ημιστερεό υπόλειμμα που παράγεται από τις μονάδες επεξεργασίας αστικών και βιομηχανικών αποβλήτων. Μολονότι η ιλύς αντιμετωπίζεται ως απόβλητο που πρέπει να διατεθεί, είναι στην πραγματικότητα ένας σοβαρά υποτιμημένος πόρος. Πιο συγκεκριμένα, η ιλύς διαθέτει πολύτιμα θρεπτικά συστατικά, ενώ παράλληλα έχει και υψηλή θερμική αξία, ιδιότητες που την καθιστούν κατάλληλη για ένα μεγάλο εύρος χρήσεων. Ωστόσο, η ιλύς είναι φορέας ρύπων, όπως οι παθογόνοι μικροοργανισμοί και οι ξενοβιοτικές ουσίες, η ύπαρξη των οποίων βρίσκεται στο επίκεντρο των ενδιαφερόντων των ερευνητών. Ανάμεσα στις διάφορες διεργασίες που έχουν εφαρμοσθεί μέχρι σήμερα τόσο για την επεξεργασία της ιλύος, όσο και για την απομάκρυνση των ξενοβιοτικών παραγόντων από το περιβάλλον, οι βιολογικές διεργασίες φαίνεται να υπερτερούν αισθητά έναντι των άλλων. Στόχος της παρούσας διατριβής ήταν η εφαρμογή μιας βιολογικής μεθόδου, της βιοσταθεροποίησης, για την επεξεργασία της ιλύος. Η ολοκλήρωση της μελέτης της βιοσταθεροποίησης έγινε με την ανάπτυξη ενός μαθηματικού μοντέλου ικανό να περιγράφει τη διεργασία. Παράλληλα, ερευνήθηκε η δυναμικότητα της διεργασίας αυτής στη βιοαποκατάσταση της ιλύος από το ξενοβιοτικό περιεχόμενό της. Επιπρόσθετα, μελετήθηκε η απομάκρυνση των ξενοβιοτικών ουσιών, μέσω της βιοαποδόμησής τους από αυτόχθονες μικροβιακούς πληθυσμούς της ιλύος, σε άλλα αερόβια περιβάλλοντα. Η εφαρμογή της διεργασίας της βιοσταθεροποίησης πραγματοποιήθηκε σε κατάλληλη πειραματική διάταξη που σχεδιάστηκε και υλοποιήθηκε για το σκοπό αυτό. Η διάταξη αυτή επέτρεπε τον πλήρη έλεγχο και τη σωστή ρύθμιση της διεργασίας. Η ολοκλήρωση των πειραμάτων της λιπασματοποίησης έδειξε ότι η διεργασία αυτή μπορεί να εφαρμοσθεί ως μέθοδος επεξεργασίας και σταθεροποίησης της ιλύος, αρκεί να ρυθμιστούν κατάλληλα καθοριστικές φυσικές και χημικές παράμετροι. Τα αποτελέσματα έδειξαν, επίσης, ότι η διεργασία δεν παρεμποδίζεται από την παρουσία υψηλών αρχικών συγκεντρώσεων ξενοβιοτικών ουσιών στην ιλύ, ενώ αντίθετα οδηγεί στην απομάκρυνσή τους. Τα ποσοστά απομάκρυνσης ήταν ιδιαίτερα υψηλά προκειμένου για τις επιφανειοδραστικές ενώσεις και αρκετά σημαντικά για το φθαλικό εστέρα και τους πολυκυκλικούς αρωματικούς υδρογονάνθρακες. Φαίνεται, λοιπόν, ο πολυποίκιλος μικροβιακός πληθυσμός της βιοσταθεροποίησης να συμβάλλει στην ουσιαστική, αν όχι πλήρη, απομάκρυνση των ξενοβιοτικών ουσιών κατά τη διάρκεια της διεργασίας και να οδηγεί στην παραγωγή σταθερού και ασφαλούς τελικού προϊόντος. Ωστόσο, υψηλά ποσοστά απομάκρυνσης των παραπάνω ξενοβιοτικών ουσιών κατέδειξαν και τα πειράματα που πραγματοποιήθηκαν σε αερόβιες υγρές μικτές καλλιέργειες. Ενδεχομένως, η μικροβιακή συνεργασία να παίζει τον καθοριστικό ρόλο στη βιοαποδόμηση αυτών των ουσιών. Η παρούσα μελέτη θα μπορούσε να συνεισφέρει αποτελεσματικά στην ανάπτυξη μιας αξιόπιστης μεθόδου για τη διαχείριση της ιλύος. Συνολικά, η λιπασματοποίηση μπορεί να αποδειχθεί ένα χρήσιμο εργαλείο για την επιθυμητή βιώσιμη ανάπτυξη της κοινωνίας μας, αφού αφ’ ενός μπορεί να συμβάλλει στη λύση του περιβαλλοντικού προβλήματος της διαχείρισης της ιλύος που παράγεται από τις εγκαταστάσεις επεξεργασίας λυμάτων, που την απασχολεί έντονα, και αφ’ ετέρου μπορεί να εξουδετερώσει το παθογόνο περιεχόμενο και να εξαλείψει τις τοξικές ξενοβιοτικές ουσίες. / The continuously increased human activity of the last few decades, because of the intense urbanization and industrialization, has resulted in the production of a serious amount of wastes. Among these is sewage sludge, which is the semi-solid residue produced by municipal and industrial waste treatment plants. Although sludge is considered as a waste product which must be disposed, it is actually an underestimated resource. Specifically, sludge contains valuable nutrients and high thermal value making sludge appropriate for a wide range of uses. Nevertheless, the existence of pathogens and xenobiotics in sludge has attracted the interest of scientific community. Among various methods that have been used for sludge treatment, as well as the removal of xenobiotics from environmental systems, biological methods are advantageous. The aim of the present work was to assess the sewage sludge treatment by a biological process, which is closed-vessel composting. This study involved also the development of a mathematical model capable of describing the composting process. The efficiency of bioremediation of xenobiotics content during sludge composting was also studied. Finally, the xenobiotics removal was investigated through biodegradation using sludge indigenous microbial populations in other aerobic environments. A suitable experimental configuration was designed and constructed in order to study the composting process. The composting system was designed for complete control and regulation of the process. Based on the results of the composting experiments, it can be concluded that composting is an efficient method allowing for treating and stabilization of sewage sludge, provided that critical physicochemical parameters are adjusted. Results revealed also that composting process is not inhibited by the presence of high initial concentration of xenobiotics. On the contrary, composting results in removal of xenobiotics. With reference to surfactants (LAS.NP and NPEO), the removal percentages were particularly high, while the relevant percentages for phthalate ester and polycyclic aromatics hydrocarbons were also significant. It seems, then, that the variable microbial population of the composting mixture contributes to the elimination of xenobiotic compounds and results in a safe and stable final product. The experiments which were conducted in aerobic mixed liquid cultures showed also high xenobiotic removal percentages. Probably, the microbial consortium could play a significant part in biodegradation of xenobiotic compounds. The present study contributes to the development of a reliable method of sewage sludge treatment. The composting process, totally complies with the desirable sustainable growth for our society by the treatment of sludge produced in waste water treatment plants and by the elimination of the xenobiotic compounds that limit its valorisation.

Submitted by Marlene Santos (marlene.bc.ufg@gmail.com) on 2018-07-13T19:29:17Z No. of bitstreams: 2 Dissertação - Maria Carolina de Almeida - 2017.pdf: 6786764 bytes, checksum: 4574a29178a9cb373e63d3280e95024e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-07-17T13:38:02Z (GMT) No. of bitstreams: 2 Dissertação - Maria Carolina de Almeida - 2017.pdf: 6786764 bytes, checksum: 4574a29178a9cb373e63d3280e95024e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-07-17T13:38:02Z (GMT). No. of bitstreams: 2 Dissertação - Maria Carolina de Almeida - 2017.pdf: 6786764 bytes, checksum: 4574a29178a9cb373e63d3280e95024e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-05-05 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / The objective of this work was to compare the efficiency of conventional treatments such as activated carbon (AC) Adsorption and the advanced oxidation process (AOP), UV-C/H2O2, for degradation of diethyl phthalete (DEP) and coupling UV-C/H2O2/AC in laboratory effluent, ultrapure water and faucet water doped with DEP and laboratory effluent with multicomponents (DEP and phenol). The chemical characterization (Boehm method, pHPZC, IRTF, elemental analysis) and physical (volume of micropores and mesopores, mean micropore width by the Dubini-Radushkevich method were used as a predecessor to the kinetic adsorption study, Surface area and microporous specific volume by the alpha method, microporous and total surface, BET surface area by BET method, cumulative mesopore distribution and pore volume, cumulative area and surface area and pore size by BJH method) of AC. The factorial design with eleven tests and three independent variables (AC mass, temperature and pH) was applied, resulting in response surfaces for adsorption capacity, DEP elimination rate and equilibrium time without significant difference between the studied variables. Mathematical modeling of adsorption kinetics using the pseudo-first, pseudo-second order and intraparticle models was performed and the pseudo-second order model was fitted to the experimental kinetic adsorption data. It was followed by the study of the adsorption isotherms for the lower, intermediate and longer equilibrium experimental conditions. It was performed the mathematical modeling of the adsorption isotherms using the Langmuir and Freundlinch models, and adjusted to the Freundlinch model to the experimental data of the adsorption isotherms with higher determination coefficients (R2), confirming the predominant chemorandomization adsorption phenomenon. The treatment of AOP UV-C/H2O2 was then applied alone. The factorial design with eleven tests and three independent variables (H2O2 concentration, temperature and pH) was applied, resulting in surfaces of responses to DEP elimination rate with significant difference between the variables studied for pH, positive effect of H2O2 concentration (p < 0.5). The mathematical modeling of the kinetics of AOP using the first order models was carried out, and the kinetic experimental data of the photodegradation with high coefficients of determination (R2> 0.9) were fitted to the model. The degradation kinetics of DEP by AOP coupling and AC, UV-C/H2O2/AC were followed. The factorial design with eleven tests and three independent variables (H2O2 concentration, temperature and pH) and with 0.4 g of AC, resulting in surfaces of responses to elimination rate of DEP with significant difference between the variables studied for pH, positive effect of H2O2 concentration (p <0.5). The mass of AC was determined in 0.4 g for all eleven tests, because it was the mass applied at the highest rates of elimination of DEP by kinetics of Adsorption, which was confirmed by repeatability at the central points of the factorial design (C9, C10 and C11). The catalytic activity of the carbons for the Adsorption process in the presence of tertbutanol was high, however, after the determination of the kinetic parameters, the contribution was higher for photooxidation of DEP by the action of the AOP (homogeneous system). / O objetivo desse trabalho foi comparar a eficiência de tratamentos convencionais como a adsorção com carvão ativado (CA) e o processo oxidativo avançado (POA), UV-C/H2O2, para degradação de dietil ftlato (DEP) e a acoplagem UV-C/H2O2/CA em efluente de laboratório, água ultrapura e água de torneira dopados com DEP e efluente de laboratório com multicomponentes (DEP e fenol). De modo predecessor ao estudo cinético da adsorção, aplicado isoladamente, realizou-se a caracterização química (método de Boehm, pHPZC, IRTF, análise elementar) e física (volume de microporos e mesoporos, largura média de microporos pelo método de Dubini-Radushkevich, superfície exterior e volume específico microporoso pelo método alfa, superfície microporosa e total, área de superfície de BET pelo método de BET, distribuição dos mesoporos cumulativo e volume do poro, área cumulativa e área superficial e tamanho do poro pelo método BJH) do CA. O delineamento fatorial com onze ensaios e três variáveis independentes (massa de CA, temperatura e pH) foi aplicado, resultando em superfícies de respostas para capacidade de adsorção, taxa de eliminação de DEP e tempo de equilibrio sem diferença significativa entre as variáveis estudadas. Foi realizada a modelagem matemática das cinéticas de adsorção utilizando os modelos de pseudo-primeira, pseudosegunda ordem e intrapartícula, e ajustou-se ao modelo de pseudo-segunda ordem aos dados experimentais cinéticos de adsorção. Seguiu-se com o estudo das isotermas de adsorção paras as condições experimentais de menor, intermediário e de maior tempo de equilíbrio. Foi realizada a modelagem matemática das isotermas de adsorção utilizando os modelos de Langmuir e Freundlinch, e ajustou-se ao modelo de Freundlinch aos dados experimentais das isotermas de adsorção com maior coeficientes de determinação (R2), confirmando o fenômeno de adsorção predominante quimiosorção. Seguiu-se a aplicação do tratamento de POA UVC/ H2O2, isoladamente. O delineamento fatorial com onze ensaios e três variáveis independentes (concentração de H2O2, temperatura e pH) foi aplicado, resultando em superfícies de respostas para taxa de eliminação de DEP com diferença significativa entre as variáveis estudadas para o pH, e efeito positivo da concentração de H2O2 (p<0,5). Foi realizada a modelagem matemática das cinéticas de POA utilizando os modelos de primeira ordem, e ajustaram-se ao modelo os dados experimentais cinéticos da fotodegradação com elevados coeficientes de determinação (R2>0,9). Seguiu-se para o estudo das cinética de degradação de DEP pela acoplagem POA e CA, UV-C/H2O2/CA. O delineamento fatorial com onze ensaios e três variáveis independentes (concentração de H2O2, temperatura e pH) e com 0,4 g de CA, resultando em superfícies de respostas para taxa de eliminação de DEP com diferença significativa entre as variáveis estudadas para o pH, efeito positivo da concentração de H2O2 (p<0,5). A massa de CA foi determinada em 0,4 g para todos os onze ensaios, porque foi a massa aplicada nas maiores taxas de eliminação de DEP pelas cinéticas de adsorção, que se confirmou, pela repetitibilidade, nos pontos centrais do delineamento fatorial (C9, C10 e C11). A atividade catalítica dos carvões para o processo de adsorção em presença de tércio butanol foi elevada, contudo a contribuição, após a determinação das constantes cinéticas, revelou-se maior para foto-oxidaçao de DEP pela ação do POA (sistema homogêneo).