Thesis (M.E.S.)--Evergreen State College, 2009. / "June 2009." Title from title screen (viewed 4/8/2010). Includes bibliographical references (leaves 54-56).

Thesis (M. Sc.)--University of Canterbury, 2009. / Typescript (photocopy). Includes bibliographical references (p. 115-130). Also available via the World Wide Web.

Diploma thesis Effect of emergent micropolutants on the denitrification process through activated sludge is focused on three specific substances. The substances under investigation are atrazine, terbutylazine and sulfametaxazole. Atrazine and terbutylazine are pesticides, particularly herbicides. Sulfametaxazole was chosen as a common antibiotic. The thesis is summarized into 10 chapters and conclusion. The work consists essentially of theoretical and practical part. Part of the theoretical part of the thesis is legislation that deals with the matters of the problem with micropolutants. The next chapter is an introduction to the issue, where we want to familiarize the reader with the current situation. There are also chapters on emergent micropolutants, denitrification and investigated substances. If we look at the practical part, there are chapters on sampling, evaluation of BATCH tests and evaluation of inhibition tests. There are also chapters on BATCH tests and respiratory inhibition test, which describe procedures of how we performed this test. Laboratory test reports are included in the Annex.

An understanding of solute-solute interactions is essential for aquatic systems as this can affect the fate and behaviour of micropollutants in the environment and engineered systems. Despite the importance of solute-solute interactions there is a general lack of understanding which may be attributed to the fact that many engineering models overlook solute-solute interactions and that the quantification of such interactions is inherently difficult. When solute-solute interactions are considered, they are often studied at unrepresentative concentrations and do not consider the influence of organic matter type or solution chemistry. Steroidal hormones, such as estradiol and estrone, were selected as model micropollutants as they are ubiquitous in the aquatic environment due to constant introduction of wastewater effluent, and can have implications for growth and development of organisms including impaired fertility and behavioural abnormalities. The purpose of this study was to develop a methodology to quantify solute-solute interactions at environmental concentrations, and to determine the implications of such interactions in membrane filtration. A solid-phase microextraction (SPME) technique was developed to quantify solutesolute interactions at environmental (low) concentrations. Using SPME, organic matter-water partition coefficients (log KOM) were measured for a range of steroidal hormones including estradiol, estrone, progesterone and testosterone with different organic matter types such as humic acid. The dominant mechanism of hormoneorganic matter interactions was identified as hydrogen bonding. In the case of estrone and progesterone the log KOM values were significantly influenced by organic matter type and concentration, as well as solution chemistry. No difference was observed for estradiol and testosterone due to generally weaker sorption to organic matter. Previous studies have indicated that the presence of organic matter can alter micropollutant retention in membrane filtration. Much of the current literature focuses on solute-membrane interactions, as the influence of solute-solute interactions are typically difficult to determine in membrane filtration. Therefore, hormone-organic matter interactions were studied to determine if this interaction had an influence on hormone removal by ultrafiltration (UF) using a range of molecular weight cut-off (MWCO) membranes. The results indicated increased retention of estrone in the presence of humic acid, while organic matter concentration and solution chemistry influenced retention by affecting solute-solute interactions. The findings of this study indicate the importance of solute-solute interactions in membrane filtration and experimental log KOM results were used to quantify the findings and elucidate the influences of 1) membrane sorption, 2) solute-solute interactions and 3) solute-foulant interactions. Further, the removal of steroidal hormones using a magnetic ion exchange (MIEX®) resin with a range of MWCO UF membranes was studied as such sorbents can be used to improve micropollutant removal in wastewater treatment. Greater removal with IX-UF was observed compared to UF alone and the main hormone removal mechanisms were sorption to MIEX® and solute-fouling interactions. The findings of this study indicate that it is indeed possible to quantify solute-solute interactions at environmental concentrations using SPME, with hydrogen bonding being the main mechanism of interaction for steroidal hormones and organic matter. Further, micropollutant retention by membrane filtration can be influenced by solutesolute interactions.

L'objectif de cette thèse est d'évaluer le concept d'un dispositif intégré comprenant un bioréacteur à biofilm fluidisé bio-augmenté, couplé à une membrane de nanofiltration de type polyelectrolyte multicouche, destiné à éliminer les micropolluants en traitement tertiaire des eaux usées domestiques, traitées conventionnellement. Les résultats montrent que, pour des micropolluants ciblés, chacun des procédés est efficace comme traitement tertiaire. Les mécanismes biologiques et de rétention membranaires sont explicités. Cependant des challenges restent à relever en particulier pour l'étape de bio augmentation (survie et implantation de la souche apportée) pour une exploitation de cette étape. D'autre part, des investigations plus poussées sont nécessaires à l'élaboration d'une membrane fiable et robuste. Un tel procédé couplé MBBR-NF pourra alors être entièrement justifié dans le contexte d'une élimination performante de micropolluants ciblés. Il aura toute sa place dans le panel des technologies vertes pour la préservation de l'environnement. / This thesis aims at answering whether the concept of an integrated layout comprised of a coupled "bioaugmented moving bed biofilm reactors (bMBBRs) - polyelectrolyte multilayer (PEM)-based nanofiltration (NF) membrane" can be considered as a promising technology to eliminate target MPs from conventionally-treated municipal wastewater. Results presented herein indicate that each given component of the layout is efficient in the tertiary removal of MPs. Still, several challenges ahead of the process bioaugmentation (such as the survival and maintenance of inoculated strains) must be in-depth studied to find convenient operating solutions. On the other hand, further investigations are definitely needed to achieve a robust PEM-based membrane as a long-lasting technology. Even though a coupled bMBBR-NF system for enhanced MPs removal can be experimentally justified is, however, practically questionable. "The tale of bMBBR-NF" deserves much more scientific endeavors as plenty of environmental considerations are placed in, whereby achieving a future Green technology will not be far from our expectation.

Runoff from paved surfaces in the urban environment is recognised as a major contributing source to deteriorated water quality. In stormwater, both various metals and organic compounds can be present and the quality of stormwater is dependent on e.g. the characteristics of the surfaces that the runoff encounters. Diffuse pollution sources, i.e. anthropogenic emissions from e.g. traffic or constructions, has been pointed out by the European Water Framework Directive to significantly contribute to pollution of stormwater receivers. In order to create and obtain a sustainable, liveable and aesthetical urban environment it is critical to be able to mitigate stormwater pollution, not least considering the increasing amount of stormwater due to climate change.The aim of this master’s thesis was to evaluate the potential release of inorganic- and organic stormwater pollutants from conventional roofing materials by laboratory leaching experiments. The study was mainly aimed to serve as a first screening on the roofing materials, in order to be able to select a number of materials for further investigation later on. The organic compounds included in this study were polycyclic aromatic hydrocarbons, nonylphenols and -ethoxylates, phthalates and herbicides. Previous research on stormwater pollution has mainly focused on metals and there is therefore a knowledge gap on organic compounds in urban runoff. The leaching experiments were designed considering previous similar studies. Synthetic rainwater was prepared based on measurements of rainwater quality in Sweden. Duplicates of 16 commonly used roofing materials were prepared and immersed in beakers of synthetic rainwater. The beakers were agitated on an orbital shaking device for 24 hours and pH as well as conductivity was recorded in the leachates before sending the samples to the contracted laboratory for analysis. Metals were analysed on all materials and the organic compound analyses were performed on selected materials based on each material’s composition and was limited with the substance’s probability to release from each material.From the analysis results, mean values for the leached concentrations of all duplicates were calculated. The annual potential release of substances from materials was estimated based on the leached concentrations and data on the average annual precipitation in Sweden, in order to get an indication of the order of magnitude of the pollutant release. The results showed a potential release of a number of the included substances from many of the studied roofing materials, in varying order of magnitude. The shingle roofing was the material that showed the ability to release the largest number of pollutants. Some materials e.g. the clay tile also showed potential to adsorb substances on the material surface. Metals were mainly released in dissolved form from most materials. Phthalates were not present in concentrations above report limits in the leachates from any of the studied materials. The results also indicate a significant different in the release potential from materials that were considered similar in their composition and expected to have similar leaching behaviour prior to the laboratory experiments, e.g. two similar felt roof materials from different manufacturers. / <p>Validerat; 20150715 (global_studentproject_submitter)</p>

The study examined the removal mechanism of non-acclimated and acclimated aerobic activated sludge for 29 target organic micropollutants (OMPs) at low concentration. The selection of the target OMPs represents a wide range of physical-chemical properties such as hydrophobicity, charge state as well as a diverse range of classes, including pharmaceuticals, personal care products and household chemicals. The removal mechanisms of OMPs include adsorption, biodegradation, hydrolysis, and vaporization. Adsorption and biodegradation were found to be the main routes for OMPs removal for all target OMPs. Target OMPs responded to the two dominant removal routes in different ways: (1) complete adsorption, (2) strong biodegradation and weak adsorption, (3) medium biodegradation and adsorption, and (4) weak sorption and weak biodegradatio. Kinetic study showed that adsorption of atenolol, mathylparaben and propylparaben well followed first-order model (R2: 0.939 to 0.999) with the rate constants ranging from 0.519-7.092 h-1. For biodegradation kinetics, it was found that benzafibrate, bisphenol A, diclofenac, gemfibrozil, ibuprofen, caffeine and DEET followed zero-order model (K0:1.15E-4 to 0.0142 μg/Lh-1, R2: 0.991 to 0.999), while TCEP, naproxen, dipehydramine, oxybenzone and sulfamethoxazole followed first-order model (K1:1.96E-4 to 0.101 h-1, R2: 0.912 to 0.996). 4 Inhibition by sodium azide (NaN3)and high temperature sterilization was compared, and it was found that high temperature sterilization will damage cells and change the sludge charge state. For the OMPs adaptation removal study, it was found that some of OMPs effluent concentration decreased, which may be due to the slow adaptation of the sludge or the increase of certain bacteria culture; some increased due to chromic toxicity of the chemicals; most of the OMPs had stable effluent concentration trend, it was explained that some of the OMPs were too difficutl to remove while other showed strong quick adaptation. A new module combined of sequencing batch reactor (SBR) and nanofiltration membrane filtration (NF-MBR) was developed to further study the OMPs removal and to exam the concept of compounds (CRT). The NF-MBR was proved to be a promising bioreactor, as OMPs were rejected by NF membrane which leaded to a low OMPs concentration in permeate water, the apparent removal rate was over 80% for most of the OMPs.

Efficient reuse of waste water requires removal of micro-pollutants from waste water streams by affordable and sustainable methods. Activated carbon is considered a powerful adsorbent due to its high surface area and low cost of treatment, compared to other expensive methods such as membrane filtration. Producing activated carbon with larger mesoporosity (>2nm) is of particular interest in industry in the removal of larger molecular sized pollutants. This study reports the synthesis of mesoporous activated carbons from a nonsoluble biomass precursor (date-pits) along with chemical activation using ZnCl2. Thus, produced activated carbon showed high surface area and large mesopore volume up to 1571 m2/g and 2.00 cm3/g respectively. In addition, the pore size of the product was as high as 9.30 nm. As a method of verification, HRTEM (Highresolution transmission electron microscopy) was used to directly authenticate the pore size of the synthesized activated carbons. Tannic acid and atrazine were used as model waste water pollutants and the adsorption capability of the produced activated carbon for these pollutants were evaluated and compared to a commercial mesoporous carbon: G60 from Norit. The results showed that the sorption capacity of produced activated carbon for tannic acid was 2 times that of G60 while the sorption capacity of produced activated carbon for atrazine was lower than that of G60. The activated carbon was also evaluated for adsorption of real secondary effluent municipal wastewater and the results suggest that the produced activated carbon was able to sorb a greater amount of biopolymers than G60. These results demonstrate that the thus-produced activated carbon may be a promising sorbent for waste water treatment.

Das grundsätzliche Verständnis von Karstgrundwasserleitern ist essentiell für das nachhaltige Management der Rohwasserqualität und letztendlich für sauberes Trinkwasser für bis zu 25 Prozent der Weltbevölkerung. Um dieses Verständnis zu verbessern, wird in der vorliegenden Arbeit das Speicher- und Attenuationspotential eines Karstgrundwasserleiters untersucht. Hierbei werden organische Spurenstoffe als Indikatoren für Transportpfade, Attenuation und Attenuationsprozessen eingesetzt. Als Voraussetzung für die Erfassung belastbarer Daten, wurden geeignete Stabilisierungsstrategien für organische Spurenstoffe in Wasserproben bewertet: Zugabe der Biozide (i) Kupfersulphat und (ii) Natriumazid zu Wasserproben nach der Probenahme und anschließende Lagerung der Proben in flüssiger Form sowie (iii) sofortige Festphasenextraktion (SPE), was zu einer Stabilisierung der Proben durch eine Reduktion des Wassergehaltes führt. Es wurden Fluss- und behandeltes Abwasser untersucht. Diese zeichnen sich üblicherweise durch ein hohes Potential für biologische Aktivität und demnach hohe Biotransformationsraten aus. Analysiert wurde der Einfluss der Lagerungstemperatur von 4 und 28° C für die Proben, die in flüssiger Form gelagert wurden und von 4, 20 und 40° C für die Lagerung der SPE-Kartuschen. Kühlen der Wasserproben allein reichte nicht aus, um die Proben für längere Zeit (> 24 h) zu stabilisieren. Die Zugabe von Kupfersulphat führte zu Problemen mit Azol- und Imidazol-ähnlichen Verbindungen. Natriumazid erwies sich als geeigneter Stabilisierungszusatz. Die besten Ergebnisse konnten für kühl gelagerte SPE-Kartuschen beobachtet werden. Im darauffolgenden Kapitel wird das Langzeitspeicherpotential von Karstgrundwasserleitern untersucht. Um eine nachhaltige Rohwasserqualität zu gewährleisten ist das Verständnis dieses Potentials essentiell. Die Transportdynamik der zwei Herbizide Metazachlor und Atrazin sowie dessen Abbauprodukt (Desethylatrazin) wurde an einer Karstquelle untersucht. Sogar 20 Jahre nach dessen Anwendungsverbot konnten Atrazin und dessen Abbauprodukt nahezu immer im Quellwasser in geringen Konzentrationen (wenige ng L‒1) nachgewiesen werden. Metazachlor dagegen tritt nur nach Niederschlagsereignissen auf und die beobachteten Konzentrationen sind deutlich höher. Ein Vergleich der Dynamik der zwei Herbizide mit der der anorganischen Kationen Ca2+, Mg2+ und der elektrischen Leitfähigkeit zeigte, dass Atrazin mit diesen Parametern korreliert. Aus dieser Beobachtung konnte abgeleitet werden, dass Atrazin innerhalb der Gesteinsmatrix vorliegt und die Rohwasserqualität für Jahrzehnte beeinflusst. Um das in-situ Attenuationspotential innerhalb des Röhrensystems eines Karstgrundwasserleiters zu identifizieren und das Risiko, das von organischen Spurenstoffen ausgeht, abzuschätzen, wurde ein Doppeltracer-Experiment durchgeführt: Der reaktive Stoff Coffein wurde als Markierungsstoff genutzt um das in-situ Attenuationspotential des untersuchten Grundwasserleiters zu bewerten. Aufgrund der niedrigen Bestimmungsgrenze konnten sehr geringe Mengen eingesetzt werden. Um ein Modell zu kalibrieren und die Attenuation des Coffeins zu visualisieren wurde der konservative Markierungsstoff Uranin simultan eingegeben. Diese Methodik wurde in einem gut charakterisierten Karstgrundwasserleiter in Baden-Württemberg getestet. Die Ergebnisse zeigten eine deutlich höhere Attenuationsrate als für einen Karstgrundwasserleiter erwartet wurde. Die Attenuation wurde als Prozess erster Ordnung beschrieben; die bestimmte Halbwertszeit betrug 104 h. Diese geringe Halbwertszeit deutet darauf hin, dass das generell angenommene geringe Attenuationspotential nicht gerechtfertigt ist. Der beobachtete Massenverlust des Coffeins zeigt auf, dass Coffein als reaktiver Markierungsstoff in hydraulisch hochdurchlässigen Systemen, wie Karstgrundwasserleitern, zur Untersuchung des in-situ Attenuationspotentials geeignet ist. Aufgrund der hohen Attenuationsrate des Coffeins, ist nicht mit einer Langzeitkontamination zu rechnen. In der Kombination mit einem konservativen Referenzmarkierungsstoff wird in diesem Kapitel eine ökonomische und ökologisch ungefährliche Methode zur Bestimmung des in-situ Attenuationspotentials vorgestellt. Aufgrund der Ergebnisse des Doppeltracer-Experiments wurde ein Multitracer-Experiment durchgeführt um das ermittelte Attenuationspotential zu verifizieren, dessen Übertragbarkeit auf andere Stoffe zu überprüfen und die Attenuationsprozesse zu spezifizieren. Als Referenzsubstanzen wurden Uranin, Acesulfam und Carbamazepin gemeinsam mit den reaktiven Markierungsstoffen Atenolol, Coffein, Cyclamat, Ibuprofen und Paracetamol in eine Doline eingegeben. Die Durchbruchskurven der reaktiven Markierungsstoffe wurden relativ zu den Referenzsubstanzen ausgewertet. Für keinen der Stoffe konnte eine signifikante Retardation beobachtet werden. Die ermittelten Halbwertszeiten betrugen 38 bis 1400 h (d. h. stabil innerhalb des Beobachtungszeitraums) in der folgenden Reihenfolge (von hoher zu keiner Attenuation absteigend sortiert): Paracetamol > Atenolol ≈ Ibuprofen > Coffein >> Cyclamat. Die Attenuationsraten stimmen generell mit denen aus anderen Studien, die andere Umweltkompartimente untersuchten, und den Ergebnissen des Doppeltracer-Experiments überein. Das Auftreten des Biotransformationsproduktes Atenololsäure diente dem Nachweis von in-situ Biotransformation innerhalb des Karstgrundwasserleitersystems.

De nombreux déchets organiques urbains, industriels et agricoles sont considérés comme des produits résiduaires organiques (PRO). Ils sont potentiellement recyclables en agriculture comme amendement ou fertilisant pour le sol avec selon le type de déchet la mise en œuvre de traitements biologiques (digestion anaérobie, compostage). Du fait de l'utilisation de produits chimiques, les PRO contiennent des micropolluants organiques (µPO) particulièrement quantifiés dans les boues d'épuration. Ces µPO peuvent être toxiques pour les humains et les écosystèmes bien que les concentrations dans les milieux aquatiques soient très faibles (ng-µg.L-1). La plupart de ces µPO ont un fort impact sur l'environnement. Lors des traitements biologiques des boues d'épuration, l'élimination des µPO dépend de deux processus (sorption et biodégradation) eux-mêmes contrôlés par les propriétés physicochimiques de la matière organique et des µPO et les microorganismes présents. La forte sorption et le piégeage des µPO ou leur biodégradation dans la matrice boue lors des traitements minimisent le risque de transfert à l'eau ou à la faune/flore après l'épandage des boues. Cette thèse se propose d'étudier le devenir de différents µPO (hydrocarbures aromatiques polycycliques (HAP), nonylphénols (NP) et produits pharmaceutiques) lors du traitement de boues par digestion anaérobie et compostage en lien avec le devenir de la matière organique et l'affinité des µPO pour certaines fractions de cette matière organique. L'objectif est de mieux comprendre les mécanismes qui régissent l'élimination des µPO et in fine d'estimer comment améliorer le procédé pour limiter les transferts au continuum sol/eau/biote. Dans un premier temps, un protocole de caractérisation de la matière organique a été couplé avec un dosage de µPO au cours d'une incubation anaérobie, sur une matrice modèle (boue) et sur des composés modèles (HAP, NP). Les résultats ont montré que les µPO dissipés se situent dans les compartiments les plus accessibles et les plus dégradables de la matière organique et que cette dissipation est pilotée par la dégradation de la matière ; de plus, un phénomène de vieillissement a été observé pour des molécules dopées. Les résultats démontrent que les µPO étudiés ici ont une affinité pour les matières organiques complexes de type humiques. Lors des incubations, seule la moitié de la matière organique est caractérisée. Le protocole de caractérisation de la matière organique a été modifié pour aller plus loin dans la caractérisation « matière » mais aussi en vue d'une application sur la localisation des µPO tout au long d'un système de traitement comprenant digestion et compostage. Ce protocole a donc été revu afin de pouvoir caractériser des matrices de type lignocellulose. Ce protocole a été appliqué à des échantillons issus de la digestion anaérobie et du compostage de boues en laboratoire. Ces procédés sont capables d'éliminer une partie des µPO ; le couplage des deux augmentant le taux d'élimination. L'évolution des fractions matière reflètent la dégradation de la matière organique lors des traitements. De plus, le devenir des µPO étudiés est piloté par le devenir de la matière organique nous permettant de proposer des stratégies d'optimisation de leur dissipation.Les résultats acquis permettent de déterminer des taux d'abattement des µPO lors des traitements des boues mais aucune information n'est donnée quant aux mécanismes précis d'élimination. Les mêmes traitements ont été menés en utilisant des molécules marquées au 14C. Les résultats obtenus sur trois molécules (fluoranthène, NP et sulfaméthoxazole) montrent que les µPO ne sont pas minéralisés lors de la digestion anaérobie. Lors du compostage des boues digérées, une minéralisation du NP apparaît lors de la phase de maturation. Diverses hypothèses peuvent alors expliquer l'élimination constatée au cours des traitements sans molécule marquée : métabolites ou résidus non extractibles sont formés. / Animal manures, urban organic wastes including sewage sludge, food processing and other industrial wastes are considered as organic wastes that are potentially recycled in agriculture as soil amendment or fertilizer after biological treatment like anaerobic digestion and composting.Due to the use of chemicals and industrial activities, these organic wastes contain organic micropollutants, particularly quantified in sewage sludge. These micropollutants are a family of organic compounds which may be toxic for humans or ecosystems even though their concentrations in aquatic environments are usually low (µg to ng.L-1). Most of them have huge impacts on environment (e.g. some of them are endocrine disruptors that can feminize fishes in rivers with concentrations of few ng.L-1).During biological treatments of sewage sludge, micropollutants elimination depends on two processes (sorption and biodegradation) that are driven by physicochemical properties of organic matter and micropollutants and microorganisms. Strong sorption and trapping of organic micropollutants or their biodegradation in sludge matric during anaerobic digestion and composting can minimize their transfer into water or biota after spreading.This thesis aims at studying the fate of organic micropollutants (polycyclic aromatic hydrocarbons (PAHs), nonylphenols (NPs) and pharmaceuticals compounds) during sludge treatment by anaerobic digestion and composting in link with the fate of organic matter and the micropollutants affinity for some organic matter fractions. The objective is to better understand the mechanisms which control the micropollutants elimination and estimate how to improve the process to minimize environmental impact.First, a method for sludge organic matter characterization is coupled to organic micropollutants quantification during a model batch process (anaerobic incubation), on a model matrix (sludge) and model compounds (PAHs, NPs). Results show that dissipated micropollutants are located in more accessible and degradable fraction of organic matter and that dissipation is driven by organic matter degradation; furthermore, ageing phenomenon is observed for spiked compounds. Results show that micropollutants have strong affinity for complex organic matter (humic-like substances).During incubations, the quantity of characterized organic matter corresponds only to 50 % of chemical oxygen demand. A modified protocol for characterizing organic matter is set up to go further on organic matter characterization but also to apply it to localization of organic micropollutants. This protocol is also modified in order to characterize other organic matrices (compost).The new protocol is applied to samples from anaerobic digestion and composting of sludge at lab-scale. Anaerobic digestion and composting are able to eliminate organic micropollutants. Coupling both processes increases micropollutants removal. The fate of organic matter pools during processes mimics the fate of organic matter. A link between the fate of organic matter and the fate of organic micropollutants is determined during anaerobic digestion and composting.The results allow determining organic micropollutants removal during anaerobic digestion and composting of sludge but no information is given about the removal mechanisms. Anaerobic digestion with composting is set up at lab-scale with the use of organic 14C labelled micropollutants. The results with three molecules (fluoranthene, sulfamethoxazole, nonylphenols) show that organic micropollutants are not mineralized during anaerobic digestion. During composting, only nonylphenols are mineralized during the maturation phase. Hypothesis about micropollutants removal are the production of metabolites or the formation of non-extractable residues.