Mathematical models elaborated for removal of microconstituents (MCs) in activated sludge (AS) system have not incorporated developments in International Water Association (IWA) models. In this thesis, sorption and biodegradation kinetic models that can be applied to describe transformation of MCs in an AS process were evaluated (volatilization and photodegradation were considered negligible). Bisphenol-A (BPA), 17α-ethinylestradiol (EE2), and triclosan (TCS) have been selected as target compounds in this thesis. Sorption batch tests were conducted to retrieve kinetic and equilibrium data. Nine lab-scale continuous flow porous-pot bioreactors operating at various solids retention times (SRTs) and hydraulic retention times (HRTs) were studied for biodegradation of MCs. The effects of SRT, HRT and the biomass concentration on sorption and removal of MCs were also investigated and the results of each phase were incorporated into MCs fate models. Freundlich and linear sorption isotherms and pseudo-second-order kinetic models with different kinetic rates were found to best fit the sorption and desorption results. The result of biodegradation study in the presence of 20 µg/L of MCs demonstrated 90-98, 63-91 and 97-98% mean removal rates of BPA, EE2 and TCS, respectively, in systems operating at SRT of 5–15 d and HRT of 4-10 h. Calculation of mass fluxes of selected MCs in the dissolved and particulate phases showed that biotransformation was the principal removal mechanism of targeted MCs. The fate models for the degradation mechanism of selected MCs were evaluated by applying various mathematical models. The pseudo-second-order model was found to best fit the results when active MCs degraders (XC) were used in the model. It was found that biodegradation studies should incorporate XC and not mixed liquor suspended solids concentration in their kinetic formulations. Therefore, the result of this study could be seen in the context, where the active MCs degraders are proposed to reduce the variability of biodegradation kinetic rates in AS systems operating at different operational conditions. Finally nitrification inhibitors, allylthiourea (ATU) were added to reactors and it was found that although nitrification process affects the fate of MCs in AS system, heterotrophs were most likely responsible for the biotransformation of the targeted MCs.

The treatability of a high strength industrial wastewater, 9,000 mg/L as chemical oxygen demand (COD), by three sequencing batch reactor (SBRs) systems operated under alternating redox environments: anaerobic/aerobic (ANA), anoxic/aerobic (ANX), and aerobic was investigated. A synthetic wastewater was modeled after a wastewater from an existing chemical processing facility. The largest component, hydroxypivaldehyde, was unavailable for the use in this research and was substituted by pivalic acid, both of which have a tertiary carbon. No significant degradation occurred in the anaerobic phase of operation; however, 55-65% of the COD was removed during anoxic operation. Simultaneous removal of pivalic acid and acetic acid was seen in both the anoxic and aerobic reaction phases. The anoxic/aerobic SBR provided the best overall treatability of the synthetic wastewater based on: effluent quality, sludge characteristics and settling properties. The results suggested that anoxic/aerobic treatment schemes are a viable treatment alternative for industrial wastewaters containing high concentrations of organic acids, including acids with tertiary carbons. The treatability of the three alternating redox environments on the Industry's wastewater was also investigated. Again, no significant degradation of the industrial wastewater occurred during the anaerobic reaction phase. During the anoxic reaction phase, 15-20% of the COD was removed from the industrial wastewater in contrast to the high removals seen with the synthetic wastewater. The aerobic SBR provided the best COD removal for the industrial wastewater. The performance differences between the synthetic and industrial wastewaters stress the importance of treatability studies on the actual industrial wastewater. Biological treatment of the synthetic and Industry wastewaters was unable to achieve the effluent goal of 100 mg/L as COD. Sand filtration followed by granular activated carbon adsorption treatment of the effluent from the synthetic wastewater-fed ANA SBR provided the COD removal necessary to achieve the effluent goal. / Master of Science

M. Tech. (Civil Engineering, Faculty of Engineering and Technology), Vaal University of Technolog / Textile industry effluents are carcinogenic and highly recalcitrant hence difficult to degrade especially through biological methods. Abattoir effluents are classified under high-strength wastewaters because of their characteristic high organic load hence highly biodegradable. Anaerobic co-digestion is the concept of degrading two effluent streams with complementary characteristics in order to improve the substrate removal rate. The feasibility of co-digesting abattoir and textile wastewater in a UASB reactor was evaluated at mesophilic and ambient temperature conditions. Preliminary experiments were conducted in 500 ml batch reactors to evaluate the optimum abattoir to textile synthetic wastewater ratio. The effect of COD, TVFA, alkalinity and pH on biogas yield was examined at both ambient and mesophilic temperatures. Anaerobic co-digestion of abattoir to textile wastewater in the ratio determined in the batch process was carried out in a 3 L UASB reactor by a continuous process. The continuous biodegradation process was executed at three different HRTs (22, 18 and 14 hrs) over a 60 day operation period. UASB reactor efficiency was achieved at organic loads ranging from 3.0 – 10.8 gCOD L-1 day-1. Continuous mode experiments were carried out at influent flow rates which corresponded to HRTs ranging between 1 to 8 days in order to evaluate the steady state operating parameters for the co-digestion process. The abattoir to textile effluent ratio was found to be 60:40 respectively. The COD, TVFA, alkalinity and pH and biogas yield followed a similar pattern over time at both mesophilic and ambient temperature conditions. Experimental data adequately fit the Grau first order kinetic model and average COD removal efficiencies of 85% and BOD5 of around 96% were achieved. The average biogas yield remained essentially constant, around 0.19 L/g CODremoved. The co-digested mixture was found to be biodegradable judging from the BOD:COD ratio of 0.53. TCOD removal efficiency decreased from 93% to 16% as HRT decreased from 8 days to 1 day. The kinetics of a UASB reactor co-digesting the mixture of synthetic abattoir and textile wastewater was evaluated in this study using Grau second order multicomponent substrate removal kinetic model. The Grau second order kinetic model, whose kinetic coefficient (ks) was 0.389, was found to be suitable for predicting the performance of a lab-scale UASB reactor.

As esculturas de cera do Museu Alpino, no Brasil, compostas por diversos materiais orgânicos e inorgânicos, apresentaram um tipo de degradação da superfície a qual foi investigada cientificamente através de metodologia diversificada baseada no uso de técnicas complementares, com cruzamento dos resultados. As matérias primas assim como os produtos de degradação foram caracterizadas físico-química e analiticamente. Foram empregadas as técnicas: análise térmica (termogravimetria, termogravimetria derivada e calorimetria exploratória diferencial); espectroscopia no infravermelho; análise elementar e microscopia eletrônica de varredura com analisador de dispersão de energia de raios X. A MEV/EDS foi utilizada para inspeção da micro morfologia da superfície e através dela foi possível identificar a presença de microorganismos que estavam causando a degradação físico-química pela forma como se fixaram na superfície através de suas hifas e por utilizarem os ácidos graxos presentes na cera como substrato metabólico. Os resultados de FTIR constataram a diminuição de ácidos graxos na superfície deteriorada em relação à superfície em bom estado. A TG/DTG e DSC permitiram avaliar o comportamento térmico das matérias primas e das amostras retiradas das obras de arte. Foi constatada a teoria da obra de arte como parte do ecossistema e a importância da utilização de políticas de preservação dos bens culturais por meio de ambientes controlados. / The waxy sculptures from Museum Alpino in Brazil, made of different organics and inorganics materials, presented a kind of surface degradation, which was scientifically investigated by multi-step methodology based on the use of complementary techniques with the interconnection of results. The raw materials as well as the degradation products were characterized physical-chemical and analytically. It was applied the following techniques: thermal analysis (thermogravimery, derivated thermogravimetry and differential scanning calorimetry); infrared spectroscopy; elemental analysis and scanning electronic microscopy with X ray energy dispersion system. The scanning electronic microscopy was used for the inspection of the micro morphology of the surface and after that it was possible to identify the presence of microorganisms which were causing the physical-chemical degradation analyzing the way they fixed their hyphae on the surface and the use of fat acids as metabolic substrate. Observing the FTIR results it was possible to notice the reduction of the fat acids on the deteriorated surface compared to the good surface. TG/DTG e DSC allowed to known the thermal behavior of the raw materials and the art works samples. It was possible to realize the theory of the work of art as part of the ecosystem and the importance of the cultural property\'s preservation policy by controlled ambient.

As esculturas de cera do Museu Alpino, no Brasil, compostas por diversos materiais orgânicos e inorgânicos, apresentaram um tipo de degradação da superfície a qual foi investigada cientificamente através de metodologia diversificada baseada no uso de técnicas complementares, com cruzamento dos resultados. As matérias primas assim como os produtos de degradação foram caracterizadas físico-química e analiticamente. Foram empregadas as técnicas: análise térmica (termogravimetria, termogravimetria derivada e calorimetria exploratória diferencial); espectroscopia no infravermelho; análise elementar e microscopia eletrônica de varredura com analisador de dispersão de energia de raios X. A MEV/EDS foi utilizada para inspeção da micro morfologia da superfície e através dela foi possível identificar a presença de microorganismos que estavam causando a degradação físico-química pela forma como se fixaram na superfície através de suas hifas e por utilizarem os ácidos graxos presentes na cera como substrato metabólico. Os resultados de FTIR constataram a diminuição de ácidos graxos na superfície deteriorada em relação à superfície em bom estado. A TG/DTG e DSC permitiram avaliar o comportamento térmico das matérias primas e das amostras retiradas das obras de arte. Foi constatada a teoria da obra de arte como parte do ecossistema e a importância da utilização de políticas de preservação dos bens culturais por meio de ambientes controlados. / The waxy sculptures from Museum Alpino in Brazil, made of different organics and inorganics materials, presented a kind of surface degradation, which was scientifically investigated by multi-step methodology based on the use of complementary techniques with the interconnection of results. The raw materials as well as the degradation products were characterized physical-chemical and analytically. It was applied the following techniques: thermal analysis (thermogravimery, derivated thermogravimetry and differential scanning calorimetry); infrared spectroscopy; elemental analysis and scanning electronic microscopy with X ray energy dispersion system. The scanning electronic microscopy was used for the inspection of the micro morphology of the surface and after that it was possible to identify the presence of microorganisms which were causing the physical-chemical degradation analyzing the way they fixed their hyphae on the surface and the use of fat acids as metabolic substrate. Observing the FTIR results it was possible to notice the reduction of the fat acids on the deteriorated surface compared to the good surface. TG/DTG e DSC allowed to known the thermal behavior of the raw materials and the art works samples. It was possible to realize the theory of the work of art as part of the ecosystem and the importance of the cultural property\'s preservation policy by controlled ambient.

Norrvatten produces and delivers drinking water to approximately 700 000 people in the northern part of the Stockholm region in Sweden. In their water treatment plant Görvälnverket, water from Lake Mälaren is purified. During the purification, sludge is produced. To be able to use the sludge as landfilling material, it must be dewatered. Polyacrylamide is used as a flocculant for this purpose. However, in the reject water leaving the sludge and discharged into Lake Mälaren, acrylamide monomers are often left as a rest product from the manufacturing of polyacrylamide. The problem is that acrylamide is toxic to living organisms.  The aim of this master thesis was to evaluate proposed water treatment techniques to reduce acrylamide in the reject water leaving Görvälnverket and reach Norrvatten´s goal of an acrylamide concentration below 0.10 µg/l. The water treatment techniques evaluated were ozonation, moving bed biofilm reactor and trickling filter. Along with that, oxidative stress and genotoxicity from the ozone were analysed. Also, the ability of Lake Mälaren to degrade acrylamide was evaluated. The ozone tests were performed in a pilot plant in a laboratory at IVL Swedish Environmental Research Institute (IVL Svenska Miljöinstitutet), the moving bed biofilm reactor- and the trickling filter test were performed in pilot plants at Görvälnverket and the degradation tests in water from Lake Mälaren were performed at Görvälnverket as well.  The results showed that ozonation of the reject water could reduce acrylamide in the reject water and fulfil Norrvatten´s goal of below 0.10 µg/l acrylamide. When an ozone dose of 0.70 mg/l was applied to the reject water with an acrylamide concentration of 2.5 µg/l, more than 98 % of the acrylamide was reduced. Furthermore, no oxidative stress or genotoxicity seemed to be generated from the ozonation. The moving bed biofilm reactor and the trickling filter did reduce the acrylamide by 80.77 % and 94.7 % respectively and the results suggested that they could be used to reach Norrvatten´s goal. Finally, the results indicated that water from Lake Mälaren could degrade acrylamide at a temperature of 15 °C in 4 days and in 8 °C in 13 days and reach the goal. / Norrvatten producerar och levererar dricksvatten till cirka 700 000 människor i norra delen av Region Stockholm i Sverige. I deras vattenverk Görvälnverket renas vatten från Mälaren. När sjövattnet renas produceras slam. För att slammet ska kunna användas som landfyllnadsmaterial måste det avvattnas. Polyakrylamid används som flockningsmedel i det syftet. I rejektvattnet som lämnar slammet och släpps ut i Mälaren finns ofta akrylamid monomerer kvar som en restprodukt från framställning av polyakrylamid. Problemet med detta är att akrylamid är toxiskt för levande organismer.  Syftet med detta masterexamensarbete var att evaluera föreslagna vattenreningstekniker för att reducera akrylamid i rejektvattnet som lämnar Görvälnverket och inte överstiga en akrylamidkoncentration på 0,10 µg/l som är Norrvattens mål. Vattenreningsteknikerna som evaluerades var ozonering, biofilmreaktor med rörlig bädd och biobädd. Utöver det var oxidativ stress samt genotoxicitet från ozoneringen analyserad. Dessutom var nedbrytningsförmågan av akrylamid i Mälaren testad. Ozonerings försöken utfördes i en pilotanläggning i ett laboratorium hos IVL Svenska Miljöinstitutet, testerna med biofilmreaktor med rörlig bädd och biofilter utfördes i pilotanläggningar på Görvälnverket och nedbrytningstesterna i Mälarvatten utfördes också på Görvälnverket.  Resultaten visade på att ozonering av rejektvattnet kan reducera akrylamid och uppfylla Norrvattens mål om en akrylamidkoncentration på mindre än 0,10  µg/l. När en ozondos på 0,70 mg/l applicerades i rejektvattnet med en akrylamidkoncentration på 2,5 µg/l reducerades mer än 98 % av akrylamiden. Vidare tycktes inte ozoneringen bidra till oxidativ stress eller genotoxicitet. Biofilmreaktorn med rörlig bädd och biofiltret reducerade akrylamid med 80,77 % respektive 94,7 %.  Resultaten visade att dessa tekniker skulle kunna användas för att nå Norrvattens mål. Utöver detta visade studien att vatten från Mälaren kan bryta ner akrylamid i 15 °C på 4 dagar och i 8 °C på 13 dagar och nå målet.

Un protocole inspiré du test de simulation 309 de l’Organisation de coopération et de développement économiques (OCDE) nous a permis de mesurer la dégradation chimique (excluant la photolyse) dans des eaux de surface de même que la dégradation chimique et biologique de neuf contaminants émergents dans l’effluent d’un décanteur primaire d’eau usée municipale. Les données étaient compatibles avec le modèle de cinétique de pseudo ordre un. Les résultats démontrant une persistance de plus d’un an dans les eaux de surface et de 71 jours dans l’effluent du décanteur primaire suggèrent que les dégradations chimique et biologique ne contribuent pas significativement à la diminution de: atrazine, déséthylatrazine, carbamazépine et diclofénac dans la phase aqueuse des systèmes testés. Les autres composés se sont dégradés à différents niveaux. Le 17ß-estradiol ainsi que l’éthinylestradiol, la noréthindrone, la caféine et le sulfaméthoxazole ont tous été sujet à la dégradation biologique dans les effluents du décanteur primaire d’eau usée avec des constantes de dégradation k et des demi-vies t1/2 mesurées allant respectivement de 0.0082 à 0.59 j-1 et de 1.2 à 85 jours. Les paramètres de cinétique mesurés peuvent être combinés aux concentrations typiques des composés à l’étude dans un décanteur primaire d’eau usée pour y calculer leur vitesse de dégradation. Cependant, puisque les décanteurs primaires dans les usines de traitement d’eaux usées ont généralement des temps de résidence de quelques heures seulement, il est improbable que les neufs contaminants émergents à l’étude diminuent significativement par ces processus durant leur passage dans le compartiment. / A protocol inspired by the OECD 309 simulation test allowed us to measure the chemical (excluding photolysis) degradation in surface waters as well as the chemical and biological degradation potential of 9 emerging contaminants in urban primary settling tank (PST) effluents. The data confirmed that a pseudo first order kinetic model provided a good fit. The results suggest that chemical and biological degradation will not significantly contribute to the disappearance of atrazine, desethylatrazine, carbamazepine and sulfamethoxazole in the aqueous phase of the tested systems given the reported persistency of more than a year in surface waters and 71 days in PST effluents. Other compounds were more easily degraded and 17ß-estradiol, ethinylestradiol, norethindrone, caffeine and sulfamethoxazole were all amenable to biological degradation in PST effluents, with measured degradation rate constants k and half-lives ranging respectively from 0.0082-0.59 d-1 and 1.2-85 days. Since PSTs in WWTPs generally have a water residence time of a few hours and considering the typical concentrations of such ECs’ in those compartments, it is unlikely that significant disappearance will occur during their passage through the PST.

In der Landnutzung stellt die Bewertung der Versorgung mit organischer Bodensubstanz (OBS) eine besondere Herausforderung dar. Dabei wird der Einfluss der Bodenfeuchte aufgrund des globalen Klimawandels an Bedeutung gewinnen, da die Wasserverfügbarkeit Einfluss auf die Aktivität der bodenlebenden Mikroorganismen nimmt. Ziel der Arbeit waren daher Aussagen, inwieweit verschiedene Wassergehalte den biologischen Umsatz bei der Inkubation von Bodenproben mit unterschiedlicher Herkunft sowie organischer Düngung beeinflussen. In einem Modellversuch wurden Bodenproben ungedüngter Parzellen von drei deutschen Dauerfeldversuchen in einer zweifaktoriellen Blockanlage in Abhängigkeit von organischer Düngung (Weizenstroh, Stallmist) und Wassergehalt inkubiert. Die Experimente wurden in vier Feuchtigkeitsstufen mit 10, 40, 65 und 90 % der Feldkapazität über einen Zeitraum von 85 Tagen bei einer Temperatur von 25 °C realisiert. Zusätzlich sind vor und nach der Inkubation Thermogravimetrische Bodenanalysen (TGBA) durchgeführt worden. Die Ergebnisse belegen einen mit dem Wassergehalt steigenden C-Umsatz, da die Aktivität von aeroben Mikroorganismen bis zur Wassersättigung des Bodens zunimmt. Die Steigerung war bei Zugabe von Weizenstroh höher als bei Stallmist, ohne Düngerzusatz signifikant niedriger. Gleichzeitig änderte sich die Dynamik der Abbauprozesse. Durch besonders trockene Verhältnisse wurde die Umsetzung verzögert, zudem sank die Umsatzrate langsamer. Ein dauerhafter Einfluss des Standorts auf den Umsatz der Düngemittel war dagegen nicht nachweisbar. Der biologische Abbau im Inkubationsversuch veränderte darüber hinaus die thermische Zerfallsdynamik. Die größten Veränderungen wurden nach Zugabe von Stroh festgestellt. Nicht geklärt werden konnte, ob in Böden mit höherer Versorgung durch organische Substanz gleiche Ergebnisse erzielt werden können. / In land use, the assessment of the supply of organic soil matter (OBS) is a particular challenge. The influence of soil moisture on global climate change will become increasingly important, as water availability influences the activity of soil-living microorganisms. The aim of the work is therefore to determine the extent to which different water contents influence the biological turnover during the incubation of soil samples with different origins as well as organic fertilisation. In a model experiment, soil samples from unfertilized plots of three German long-time field experiments were incubated in a two-factor block facility depending on organic fertilization (wheat straw, manure) and water content. The experiments were carried out in four humidity levels with 10, 40, 65 and 90 % of the field capacity over a period of 85 days at a temperature of 25 °C. In addition, thermogravimetric soil analyses (TGBA) were performed before and after incubation. The results prove a C turnover increasing with the water content, since the activity of aerobic microorganisms increases until the water saturation of the soil. The increase was higher with the addition of wheat straw than with manure, without fertilizer significantly lower. At the same time, the dynamics of the degradation processes changed. Due to particularly dry conditions, conversion was delayed and the turnover rate fell more slowly. A lasting influence of the site on fertilizer turnover was not proved. In addition, the biological degradation in the incubation experiment changed the thermal decay dynamics. The largest changes were observed after the addition of straw. It could not be clarified whether the same results could be achieved in soils with a higher supply of organic matter.