Dissertations / Theses on the topic 'Emerging contaminants'

Aquesta Tesi Doctoral se centra en el desenvolupament de nous mètodes analítics per determinar diferents contaminants orgànics emergents, com ara productes farmacèutics de consum generalitzat, els medis iodat de contrast per a raigs-X (un altre grup de productes farmacèutics emprats en la medicina de diagnòstic), i un grup d'edulcorants d'alta intensitat en organismes aquàtics. Dues tècniques d'extracció (extracció mitjançant líquids pressuritzats i QuEChERS) van ser avaluades per extreure els compostos seleccionats i diferents neteges també van ser provades. La determinació es va realitzar mitjançant cromatografia de líquids acoblada a espectrometria de masses.D'altra banda, també es va dur a terme un estudi ecotoxicològic en l'espècie Gammarus pulex, on s' avaluà la toxicitat del triclosan en aquesta espècie i, a més a més, es van estudiar poblacions procedents de diferents ambients amb diferents graus de contaminació per determinar si la seva resistència era similar o no.
Esta tesis doctoral se centra en el desarrollo de nuevos métodos analíticos para determinar diferentes contaminantes orgánicos emergentes, como productos farmacéuticos de consumo generalizado, medios yodados de contraste para rayos-X (otro grupo de productos farmacéuticos empleados en medicina de diagnóstico) y un grupo de edulcorantes de alta intensidad en organismos acuáticos. Para ello se evaluaron dos técnicas de extracción (extracción con líquidos presurizados y QuEChERS) para extraer los compuestos seleccionados y también se ensayaron diferentes limpiezas. La determinación se realizó mediante cromatografía de líquidos acoplada a espectrometría de masas. Además, se realizó un estudio ecotoxicológico en la especie Gammarus pulex, donde se evaluó la toxicidad del triclosán para esta especie y, además, se estudiaron poblaciones procedentes de diferentes ambientes con diferentes grados de contaminación para determinar si su resistencia era similar o no.
This Doctoral Thesis focuses on the development of new analytical methods to determine different emerging organic contaminants such as pharmaceuticals of widespread consumption, iodinated X-ray contrast media (another group of pharmaceuticals employed in diagnostic medicine), and a group of high-intensity sweeteners, in aquatic organisms. To do so two extraction techniques (pressurised liquid extraction and QuEChERS) were evaluated to extract the selected compounds and different clean-ups were also tested. The determination was perfomed with liquid chromatography coupled with mass spectrometry. Moreover, another objective is to conduct an ecotoxicological study in the amphipod species Gammarus pulex, where the toxicity of triclosan to this species was evaluated. Moreover, populations that come from different environments with different degrees of pollution were evaluated in order to establish whether their resistance was similar or not.

El objetivo de esta tesis es el desarrollo de métodos analíticos para la determinación de un grupo de contaminantes emergentes entre los cuales se incluyen los fármacos y los compuestos de cuidado personal en lodos de depuradora.
Los métodos desarrollados se basan en la extracción presurizada con solventes (PLE) y, debido a la polaridad de estos contaminantes, la cromatografia de líquidos. Como técnicas de detección se han utilizado la espectrometría de masas (con quadrupolo y tiempo de vuelo como analizadores) y la espectrometría de masas en tandem (con triple quadrupolo como analizador) utilizando la interfase de electrospray.
A parte del desarrollo de los métodos para la determinación de fármacos, hormonas y compuestos de cuidado personal, se han analizado muestras de dos plantas de tratamiento de aguas residuales de la zona de Tarragona. Se han obtenido resultados de la presencia de estos compuestos en lodos de depuradora que hasta la fecha no existían sobre las muestras de esta zona.
The scope of this thesis is to develop analytical methods to determine a group of pharmaceuticals and personal care products included in the list of so called "emerging organic contaminants".
The methods are based on pressurized liquid extraction as extraction technique and due to the polarities of these contaminants, liquid chromatography was the selected separation technique. Because the low concentration of these contaminants in sewage sludge, sensitive and selective detection technique have to be used such as mass spectrometry (with quadruople or time of flight analyzers) and tandem mass spectrometry (with triple quadrupole analyzer) using in all cases the electrospray interface.
The methods developed have been used to monitor several groups of pharmaceuticals and personal care products from sewage sludge from two different sewage treatment plants. The samples have been collected in Tarragona, where no studies related to the control of these compounds have been done.

Civil Engineering
Ph.D.
There are many reports indicating the presence of emerging contaminants such as: estrogen hormones, 1,4-dioxane and perfluoro-octanoic acids in the natural environment. Estrogen hormones are considered important emerging class of contaminants due to their endocrine disrupting effects. These compounds are invariably found in the environment originating mostly from natural sources. Trace concentrations of estrogen hormones (low µg/L concentrations) have been detected in municipal wastewater treatment plants and observed in receiving water bodies. 1,4-Dioxane (C4H8O2) is used as an organic solvent and solvent stabilizer numerous in chemical processes. The United States Environmental Protection Agency (US-EPA) has recognized 1,4-dioxane as a toxic chemical and a possible human carcinogen. 1,4-dioxane has been detected as a contaminant in the natural environment, drinking water supplies, superfund sites, public groundwater sources in the United States, Canada and Japan at concentrations greater than the permissible standards. Perfluorinated chemicals such as perfluoro-octanoic acid (PFOA) and perfluorooctane-sulfonate (PFOS) have been manufactured for use in a variety of industrial and consumer applications. Due to their environmental persistence, PFOAs have been detected in surface waters at a number of locations at concentrations ranging from pg/L to ng/L. Elevated concentrations of PFOAs have been measured in surface and ground waters near specific point sources. Through this project, successful attempts have been made for the destruction of emerging contaminants using ultrasound. This study deals with the optimization of various process parameters for the destruction of estrogen hormones. The influence of process parameters such as power density, reactor geometry, power intensity, ultrasound amplitude, and external mixing was investigated. Artificial neural network (ANN) approach was used to describe the interactions between optimized parameters. The important findings obtained in the present work for the optimized estrogen degradation can help tackle the challenges of scale up such as operational optimization and energy consumption. The effect of process conditions such as pH and presence of oxidizing agents on the ultrasonic destruction of 1,4-dioxane and PFOA was studied. Acidic conditions favored the destruction of both the compounds. The presence of activated sulfate radicals enhanced the reaction rate kinetics. An innovative technology using electric potential and ultrasound for the removal organic contaminants was developed. The existence of organic contaminants in ionic form under certain process conditions has led to the development of this technology. Applying a low electric potential across the probe enhances the mass transfer of the contaminants into effective reaction zone, thereby enhancing the total destruction. A two-fold increase in the reaction rates was observed. This study shows ultrasound as an efficient and effective treatment technology for the destruction of emerging contaminants.
Temple University--Theses

Els contaminants orgànics són substàncies químiques amb el potencial de causar efectes adversos al medi ambient i/o a la salut humana. Degut a l’ús cada cop més elevat de substàncies químiques i la seva emissió continuada al medi ambient, aquestes es poden considerar com a pseudo-persistents, convertint en una prioritat el monitoratge de la seva presència al medi ambient. Un dels aspectes que està suscitant una major preocupació es el control dels contaminants orgànics al medi aquàtic, ja que pot afectar de manera significativa a la seva qualitat. En aquest sentit, l'objectiu principal d'aquesta Tesi es el desenvolupament de metodologia analítica basada en la cromatografía líquida acoblada a l'espectrometría de masses en tandem, utilitzant un analitzador de triple quadrupol, per a la determinació de certs contaminants orgànics, tant prioritàris com emergents, en mostres d'aigua. Un cop la metodologia ha estat desenvolupada i validada, ha estat aplicada a l'analisi de mostres d'aigua del riu Ebre i a mostres recollides en una ETAP. D'aquesta manera s'ha pogut avaluar la presència d'aquests contaminants en aquestes aigües, així com l'efectivitat dels diferents tractaments aplicats en aquesta ETAP per a l'eliminació d'aquests contaminants.
Los contaminantes orgánicos son sustancias químicas con el potencial de causar efectos adversos al medio ambiente y / o la salud humana. Debido al uso cada vez más elevado de sustancias químicas y su emisión continuada al medio ambiente, estas se pueden considerar como pseudo-persistentes, convirtiendo en una prioridad el monitoreo de su presencia en el medio ambiente. Uno de los aspectos que está suscitando una mayor preocupación es el control de los contaminantes orgánicos en el medio acuático, ya que puede afectar de manera significativa a su calidad. En este sentido, el objetivo principal de esta Tesis es el desarrollo de metodología analítica basada en la cromatografía líquida acoplada a la espectrometría de masas en tándem, utilizando un analizador de triple cuadrupolo, para la determinación de ciertos contaminantes orgánicos, tanto prioritarios como emergentes, en muestras de agua. Una vez la metodología ha sido desarrollada y validada, ha sido aplicada al análisis de muestras de agua del río Ebro y en muestras recogidas en una ETAP. De esta manera se ha podido evaluar la presencia de estos contaminantes en estas aguas, así como la efectividad de los diferentes tratamientos aplicados en esta ETAP para la eliminación de estos contaminantes.
Organic pollutants are chemicals with the potential to cause adverse effects to the environment and / or human health. Due to the increasing use of chemical substances and their continuous release into the environment, these can be considered as pseudo-persistent, making monitoring their presence in the environment a priority. One of the aspects that is causing the greatest concern is the control of organic pollutants in the aquatic environment, as it can significantly affect its quality. In this sense, the main objective of this Thesis is the development of analytical methodology based on liquid chromatography coupled to tandem mass spectrometry, using a triple quadrupole analyzer, for the determination of certain organic pollutants, both priority and emerging, in water samples. Once the methodology has been developed and validated, it has been applied to the analysis of water samples from the Ebro river and in samples collected in an ETAP. In this way, the presence of these pollutants in these waters has been evaluated, as well as the effectiveness of the different treatments applied in this ETAP for the elimination of these pollutants.

Over the past decade, the occurrence and removal of emerging contaminants in the environment has received much attention. Both natural and synthetic progestogens, which are hormones, and also benzotriazoles are two examples of such emerging contaminants. Sewage treatment works are recognised as one of the main routes of these compounds to the environment. Low concentrations (nanograms per litre) of biologically active chemicals may exhibit an impact on aquatic organisms and human health. This study was undertaken to determine the occurrence and removal of these two classes of chemicals at sewage treatment works, along with an evaluation of the performance of advanced treatment and also to investigate their fate in the aquatic environment. Therefore, field-based sampling campaigns were undertaken at a sewage treatment works, rivers and potable water to achieve these aims. Solid phase extraction and LC/MS/MS were used in order to analyse the samples from these different locations, along with catchment modelling and assessment of how the use of benzotriazoles may contribute to their presence in the environment. The results have demonstrated that progestogens and benzotriazoles are in the sewage system; the natural hormone (progesterone) was the most predominant compound entering the sewage treatment work (46.9 ng/l) among the progestogens while concentrations of the benzotriazoles were two orders of magnitude higher than the progestogens. The conventional sewage treatment works were, to some extent, able to remove these compounds from wastewaters. However, this may not be adequate to afford protection to the environment. The investigation of advanced treatments, ozone, granular activated carbon and chlorine dioxide, indicated no further significant removal of progestogens, probably as a result of concentrations being close to method detection limits. However, there were indications that benzotriazoles were removed. A degradation study demonstrated that the natural hormone (progesterone) was degraded rapidly while benzotriazoles were not degraded. Catchment modelling indicated that high (up to 2,000 ng/l) concentrations of benzotriazoles would be present in surface waters used for potable supply, and consequently benzotriazoles were found in the tap water with mean concentrations of 30.9 ng/l (benzotriazole) and 15.1 ng/l for tolyltriazole. It is therefore apparent that although conventional treatment may be seen as effective, achieving over 90% removal, this may not be good enough. However, before investing in tertiary treatment, a number of factors, such as the effectiveness at different sites, the presence of degradation products and costs, both financial and in relation to energy use, need to be considered.

Environmental contamination of legacy contaminants has been of great concern worldwide because of their persistence and toxicity to humans and marine species. Only in the last decade, the presence and accumulation of emerging contaminants, and, consequently, their adverse effects in marine biota have been considered. The present research was performed to compare the different distribution of legacy contaminants (Pesticides, PCBs and PAHs) and emerging contaminants (UV filters and Fragrances) in the liver and muscle tissues of three tuna species living in different locations and with different behaviour and feed habits: Sarda sarda, Katsuwonus pelamis from the Atlantic Ocean (Gulf of Càdiz) and Thunnus thynnus from the Strait of Gibraltar. The extraction and quantitative determination of these contaminants from liver and muscle samples have been carried out by Accelerate Solvent Extraction and GC-MS/MS techniques, respectively. From the statistical analysis, significant differences have been found for Fragrances, Pesticides, PCBs and PAHs both among the three tuna species and between the two tissues. Post-hoc analysis showed significant differences between the three tuna species and the tissues, revealing that K. pelamis species differs significantly from the other two species, both in liver and muscle, and that legacy contaminants are responsible for significant differences between and within species. We also explored the similarities between concentrations of PCBs and DDTs in liver and muscle tissue found in samples of T. thynnus and K. pelamis in this study, compared to concentrations of PCBs and DDTs found in specimens of tuna collected in different geographical areas. As a result of the continuous exposure of the marine top predators, such as tuna species, to variable concentrations of emerging and legacy contaminants, their concentration in the marine environment must be constantly monitored.

Potential risk and toxicity of emerging contaminants (ECs) on the human population and the surrounding ecosystem have led to growing concern in the scientific world. This class of contaminants includes a variety of commonly used compounds such as pharmaceuticals and personal care products, as well as industry-based compounds such as surfactants and plasticizers. There are many challenges involved when studying these contaminants with the most apparent one relating to the lack of a standardized analytical method. As a result, this research investigated and optimized an analytical method for the determination of selected EC compounds in the soluble and particulate fractions of samples collected from the wastewater treatment pilot plant located at the University of British Columbia, Vancouver, Canada. Once the method was optimized, the effects of hydraulic retention time (HRT) and solids retention time (SRT) on the fate of ECs through the wastewater treatment process were studied using the UBC membrane biological nutrient removal pilot plant. The study involving the HRT failed to provide sufficient evidence to adequately assess the observed effects, since an inadequate quantity of each contaminant was spiked into the pilot plant. However, the spiking quantity was adjusted for the individual contaminants based on these observations, enabling the effect of the SRT to be studied. All analytes exhibited one of two trends during the mass balance analysis. For all of the EC compounds that were studied, sorption to the mixed liquor particulates and washout in the effluent were not the only removal mechanisms in the experimental system of the UBC pilot plant.

Silver nanoparticles (AgNPs) are tiny particles of silver with nanoscale dimensions (between 1 and 100 nm) and unique antimicrobial properties. AgNPs are potential environmental contaminants increasingly applied in consumer products. The effects on nontarget biological systems are not clearly defined. Research has shown that AgNPs may inhibit the function of bacteria responsible for organic matter decomposition, nutrient cycling, and control of pathogens population in the aquatic system. AgNPs have recently been detected in a treated municipal wastewater raising concerns about their potential risk to aquatic organisms. The microbial community in the sediment has a greater risk of AgNPs exposure, as metals in aquatic systems settle in the sediment. Studies have shown that microbial community growth and carbon sources utilization patterns were altered in response to AgNPs exposure in marine estuarine sediments. The antimicrobial activity of AgNPs in freshwater sediments may be different due to the water chemistry. Few studies have evaluated the toxicity of AgNPs in freshwater sediments due to the complex nature of their water chemistry. The current study investigated microbial community’s responses to AgNPs in sediments collected from a local stream. Microbial growth and activity assays were performed to determine whether AgNPs pose a risk to the microbial community in freshwater sediments. We found that AgNPs inhibited microbial growth, enzyme activity, and catabolic capabilities (P < 0.05). The number of viable bacterial cells and the ability of the microbial community to utilize different carbon sources decreased at 0.431 and 0.538 mg AgNPs kg-1 sediment, which are found within the estimated AgNPs concentration range in sediments. AgNPs inhibited the activity of glucosidase, an enzyme responsible for carbohydrate metabolism, but the activity of alkaline phosphatase was not affected. The current study demonstrates that AgNPs can inhibit the growth and functional diversity of beneficial microorganisms, which may affect the quality of surface waters and their designated uses. These adverse effects are expected due to the demonstrated antimicrobial properties of AgNPs incorporated in several commercial products. Toxicological data generated from this study could be incorporated in ecological risk assessment by regulatory agencies to assess the impacts of AgNPs on ecosystem systems.

In recent years there has been a growing interest from the scientific community in contaminants of emerging concern which include a large group of currently unmonitored chemicals, such as PFAS and DRCs, which are released from human activities and accumulate in the environment and in the food chain causing potentially dangerous damage to health. The aim of this thesis was to determining the levels of PFAS in commercial and domestic Italian eggs, and DRCs in different food samples purchased from Italian and French large-scale retailers. The results show PFAS contamination at much higher levels in domestic eggs then commercial eggs. This can be explained by the fact that hens that live outdoors and have the possibility to scratch in the soil, are more exposed to these substances compared to hens raised in industrial systems. Regarding DRCs contamination the procedural contamination encountered during the analysis of the samples led to an underestimation of the real values of contamination. Despite this, for both France and Italy, the food category most contaminated by DRCs was that of fish and seafood. The Italian samples showed DP contamination also in meat and eggs, and in eggs at levels higher than all other food categories considered. From the comparison with the reported works, it emerged that eggs, after fish, have the highest average levels of DP. This, added to the results obtained for PFAS on eggs, highlights how eggs are also an important source of food exposure to emerging contaminants. In conclusion, the general trend also confirmed by the available literature, shows that one of the main sources of dietary exposure for humans to some classes of emerging contaminants are fish products, to which the category of eggs is also added, as has been shown a source of exposure not to be underestimate.

Il progetto ha come scopo generale l’incremento delle conoscenze scientifiche relative al destino ambientale di alcuni contaminati emergenti e tradizionali. Lo studio si è concentrato sulla distribuzione e sugli effetti degli inquinanti a diversi livelli della scala gerarchica ecologica. In particolare è stato studiato il potenziale rilascio dei POP e degli inquinanti emergenti (EC, Emerging Contaminants) dovuto alla fusione dei ghiacciai alpini italiani per evidenziare la presenza di questi composti in un ambiente freddo ad alta quota a seguito dei processi di trasporto atmosferico a scala regionale. L’analisi di campioni di acqua di fusione glaciale raccolti sui ghiacciai alpini ha permesso di notare che la contaminazione degli stessi è dovuta a due processi opposti: da un lato è stata infatti registrata una tendente diminuzione delle concentrazioni dei POP, contrastata però dai processi di accumulo dei EC. Sulla base di questi risultati è stato condotto uno studio sul potenziale di degradazione ad alta quota del clorpirifos (CPF). L'obiettivo è stato quello di descrivere il ruolo della crioconite nell'accumulo di inquinanti organici al fine di includerne il contributo tra i processi di rimozione nei modelli di previsione del destino ambientale di questi composti nelle zone fredde. A tale scopo, è stato condotto un esperimento in situ sul Ghiacciaio dei Forni testando la degradazione del CPF in condizioni di luce e di buio, in ambienti abiotici e biotici. I risultati evidenziano che la biodegradazione contribuisce alla rimozione del CPF dalla superficie del ghiacciaio più significativamente della degradazione fotochimica. Pertanto, la degradazione microbica può contrastare l'accumulo di inquinanti trasportati sui ghiacciai e la loro possibile remissione in ambiente. Sono stati inoltre studiati i potenziali effetti sub-letali indotti sugli invertebrati acquatici dalle concentrazioni ambientali di ECs. Infatti, attualmente gli effetti ecotossicologici dei composti chimici vengono valutati mediante test di tossicità standardizzati, che trascurano molti processi biochimici e fisiologici in quanto non consentono agli organismi di far fronte ai contaminanti come farebbero in ambiente. Ciò è particolarmente vero a concentrazioni sub-letali poiché questi meccanismi sono funzionali e molti di essi rispondono su scala di giorni. Soprattutto gli effetti non letali, compresi i cambiamenti nel comportamento, potrebbero influenzare la fitness individuale e di conseguenza le dinamiche della popolazione. Evidenze di laboratorio mostrano che l'esposizione a concentrazioni ambientali di diversi EC può causare effetti negativi sugli organismi. Tuttavia è in gran parte sconosciuto come le risposte allo stress chimico si diffondano attraverso i diversi livelli della gerarchia ecologica. Ottenere questo tipo di informazioni sarebbe molto utile per promuovere l'uso dei biomarcatori come indicatori di rischio precoce. Al fine di comprendere come e se i segnali di stress vengono trasmessi attraverso i livelli gerarchici e la capacità degli endpoint sub-individuali di predire effetti ecologicamente rilevanti, individui di Daphnia magna sono stati esposti a concentrazioni ambientali di CPF e benzoilecgonina (BE). I risultati mostrano che le dafnie esposte a BE e CPF erano in una condizione di stress. È stato inoltre notato che l'attivazione o la non attivazione di alcune attività enzimatiche può portare a diverse modifiche del comportamento del nuoto in D. magna, suggerendo l'esistenza di un legame tra i livelli sub- e sovra-organismo. Infine, sono state confrontate le risposte comportamentali di dafnia e Diamesa zernyi indotte da diverse diluizioni degli effluenti di depurazione. I risultati ottenuti evidenziano che i campioni di acqua raccolti inducono alterazioni sul comportamento di entrambe le specie.
In the present work, the environmental fate of some chemicals in temperate-zone mountain regions and their sub-lethal effects on no-target organisms have been studied to improve knowledge and propose new approaches that would be useful in the risk assessment procedures. In particular, the potential release of legacy POPs and emerging pollutants from the melting of Italian Alpine glaciers is described with the aim of highlighting the presence of these compounds in a remote high-altitude cold site because of Medium Range Atmospheric Transport (MRAT) processes. Two contrasting processes leading to glaciers contamination have been underlined: on one hand, the results suggest a declining trend of POPs while the accumulation of Emerging Contaminants (ECs) in glaciers has been highlighted. Based on these results, a study of the potential degradation of chlorpyrifos (CPF) in a remote high-altitude cold site was performed. The aim is to describe the role of cryoconite in the accumulation of organic pollutants to include its contribution to the removal of organic pollutants in models predicting the environmental fate of these compounds in cold areas. For this purpose, in situ microcosm experiment was carried out on Forni Glacier by testing the degradation of CPF in light and dark conditions, in abiotic and biotic environments. The results highlight that biodegradation contributes to the removal of CPF from the glacier surface more than photochemical degradation. Therefore, microbial degradation can contrast the accumulation of pollutants transported on glaciers and their possible re-emission. The potential sub-lethal effects induced on aquatic invertebrates by environmental concentrations of widespread ECs were investigated. Indeed, currently the ecotoxicological effects of chemical compounds are evaluated by means of standardised toxicity tests, which overcome many biochemical and physiological processes because they do not allow organisms to cope with contaminants as they do in the field. This should be particularly true at sub-lethal concentrations since these mechanisms are functional, and many of them respond on the scale of days. Especially not lethal effects, including changes in behaviour, could affect fitness and consequently population dynamics. These criticalities are particularly true for the ECs, whose adverse effects towards non-target organisms have been only recently highlighted. Moreover, increasing laboratory evidences show that the exposure to environmental concentrations of different ECs may induce several adverse effects to organisms. Nevertheless, it is largely unknown how the responses to chemical stress are spread through the different levels of the ecological hierarchy. Unveiling this kind of information would be very effective for improving the use of biomarkers as early warning indicators of risk. In order to understand how and if the stress signals measured at a given ecological level are transmitted through the other hierarchical levels and the capability of sub-individual endpoints to predict ecologically relevant effects, Daphnia magna individuals were exposed to environmentally relevant concentrations of CPF and benzoylecgonine (BE). The results show that daphnids exposed to environmental levels of BE and CPF were in a condition of stress. In addition, it was noticed that the activation or non-activation in some enzymes activities can lead to different modifications of the swimming behaviour in D. magna, suggesting the existence of a link between sub- and supra-organismal levels. Eventually, the behavioural responses of daphnids and Diamesa zernyi induced by different dilutions of treated sewage effluents were compared. The results obtained highlight that water samples collected induced significant alteration on different swimming behavioural parameters in both species.

There has been increasing concern about the widespread occurrence of emerging organic contaminants (EOCs) in the aquatic environment which could pose potential risks to humans and ecosystems. Wastewater treatment plants (WWTPs) are significant sources and major routes of EOCs entering the environment. There is therefore a need to study the fate of EOCs in WWTPs to improve the risk assessment for these EOCs. In this thesis, the passive sampling technique of diffusive gradients in thin-films (DGT) for in situ measurement of selected EOCs in water was developed in the laboratory and validated under the real world condition-a WWTP. This sampler was then employed to study the occurrence and removal efficiencies of EOCs in Chinese WWTPs, as China represents a significant and growing market for many of these chemicals. A novel DGT technique was developed for in situ measurement of EOCs in water, with hydrophilic-lipophilic-balanced (HLB) resin as the binding agent and agarose gel as the diffusion layer. The performance of DGT sampler (indicated by ratio of DGT-measured concentrations (CDGT) to the directly-measured concentration (Cb), the ratio of CDGT/Cb ranged from 0.9 to 1.1 indicating the excellent performance of DGT) in different pH, ionic strength and dissolved organic matter contents was tested with 11 chemicals and found to be relatively independent of pH (3.5-9.5), ionic strength (0.001-0.1 M) and dissolved organic matter (0-20 mg L-1). Time and diffusion layer thickness dependence experiments confirmed the principle of DGT for accumulated chemicals consistent with theoretical predictions. The performance comparison of three types of resins (HLB, XAD18 and Strata-XL-A) was undertaken. Resin properties and the interactions of functional groups between the resin and chemicals controlling the uptake of EOCs for DGT sampler were evaluated by comparing the uptake capacities and the kinetics of the test chemicals among three resins. The study in the laboratory, which is similar to above section for three types of DGT devices with HLB, XAD18 and Strata-XL-A resins as the binding gels, confirmed the potential application of DGT principle for in situ measurement of EOCs in water. This DGT sampler was then compared with active sampling approaches, auto-sampling and grab-sampling in a WWTP. This study showed that the DGT sampler can continuously uptake the majority of detected EOCs in wastewater for 7-18 days. The time-weighted average concentrations measured by DGT were found to be comparable with the results delivered from the auto-samplers, showing similar concentrations and patterns. The effect of diffusive boundary layer was estimated, and was found to be relatively limited and much less compared with other passive samplers, demonstrating the advantage of DGT sampler. The field validation confirmed applicability of DGT sampler for studying the fate of EOCs in the wastewater. Before application of the DGT sampler into a large scale of fate study in Chinese WWTP, a sensitive analytical method was developed for simultaneous determination of target EOCs in surface water and wastewater. This method was optimised from solid-phase extraction (SPE) procedures to liquid chromatography-mass spectrometer (LC-MS) analysis, and was demonstrated to provide reliable data for the samples with complex matrix and low enough detection limits for EOCs in the water. This analytical method could perform similarly or even better to some related studies for detection of the EOCs in wastewater. DGT devices with HLB resin gels were then applied to 10 WWTPs in China for studying the occurrence and removal of EOCs. All target EOCs could be found in the raw influent and majority of them (18 of 20) could still be detected in the final effluent. Removal efficiency of the EOCs varied, showing the performance of different treatment technology/processes on the EOCs removal in wastewater. The primary and secondary treatment units contributed to the most removal of the EOCs. This demonstrated that DGT sampler can be an effective and simple tool to study in fate of EOCs in wastewater. This research programme has shown that DGT sampler is an effective tool for studying the fate of wide range of emerging organic chemicals in the aquatic environment and assessing their risk/ toxicity of EOCs to the human and ecosystem.

Les usines de traitement des eaux usées ne sont pas prévues pour traiter les polluants émergeants, substances organiques, tels des résidus de médicament, des produits phytosanitaires ou des hormones. Par conséquent, elles sont la source principale d’émission de micropolluants récalcitrants dans l’environnement. La Directive DCE 2000/60/CE demande un "bon statu chimique et biologique” de tous les plans d'eau d'ici 2015. L’objectif principal de cette thèse de doctorat a été d’adopter une méthode respectueuse de l’environnement pour traiter ces polluants. La méthode choisie est basée sur le processus d’oxydation avancée (POA). Elle se base sur la génération par voie solaire, et in situ, d’espèces radicalisées hautement réactives (HO● et/ou SO4-), en se focalisant sur la photocatalyse hétérogène et homogène. Les performances de l'POA ont été évaluées en comparant les taux de dégradation et/ou reminéralisassions des micropolluants. Ce critère a été complété par l'identification des sous-produits, de ses transformations associés et de mesures de toxicité. A cet effet, des tests standards d'écotoxicité ainsi que d'activité oestrogénique ont été réalisés, par la méthode toxicologique ISO ou par le test spécifique inhérent au contrôle de l’activité oestrogénique des eaux usées. Les technologies basées sur les processus d’oxydation avancée par voie solaire peuvent être des méthodes prometteuses de traitement des eaux usées. Toutes les molécules testées sont systématiquement dégradées, même celles présentes à de basses concentrations. La compatibilité environnementale a systématiquement été améliorée. L’irrigation des cultures en réutilisant des eaux usées devient possible
Wastewater effluents are the major source of micropollutants in the environment. These recalcitrant compounds that can be escape from wastewater treatment plant (WWTP) are called emerging contaminants. It is necessary to improve the efficiency of wastewater treatment plants. In fact, Water Framework Directive required a “good chemical and biological status” of all water bodies until 2015. The major aim of the dissertation was to contribute to improve the evaluation of solar advanced oxidation processes, and more specifically heterogeneous and homogeneous photocatalysis, for removing emerging contaminants from wastewater effluents. In this objective, the efficiency of AOPS was not only evaluated with the degradation and/or mineralization rates of the micropollutants. This necessary criterion was completed with the identification of the by-products and the associated transformation pathways, but also with toxicity measurements. This last point was explored with standard ecotoxicity tests and also estrogenic activity that represent a specific test relevant to characterize an identified risk associated to the discharge of effluents into the environment.All the experimental results obtained during this dissertation tends to demonstrate that solar advanced oxidation processes has the potential to open new feasible remediation strategies for WWTPs effluent tertiary treatment before wastewater reuse in irrigation for instance. All the tested molecules have systematically been degraded, high number of micro-organic pollutants initially presented in a mixture were removed even at very low concentration, environmental compatibility is systematically improved

In recent years, the increasing release of trace organic chemicals to the aquatic environment have been problematic to both the ecosystem and the human society. These trace organic chemicals, regarded as emerging contaminants, include different categories of chemicals, which are either deemed to be safe for human consumption or they are naturally occurring compounds. As a newly recognized class of emerging contaminant, artificial sweeteners are proven to be one of the most ubiquitous classes of emerging contaminants in environmental waters. Its transformation to different suite of TPs during water treatment processes generated more toxic influence than the parent compound is problematic. The realization of the widespread of emerging contaminants, together with their ambiguous fate and impact to the environment have led to the development of advanced oxidation processes that can effectively attenuate this wide range of contaminants. In this work, several catalytic advanced oxidation processes were studied. On one hand, it aimed to evaluate their effectiveness on the removal of the artificial sweetener - acesulfame; and on the other hand, to shed lights on the future development of catalytic advanced oxidation processes. In the first part of this thesis, the photo-Fenton treatment was evaluated on its potential to effectively remove acesulfame together with the produced transformation products, and the post-treatment toxicity screening. The photo-Fenton treatment was found to be effective in removing both the parent compound and the transformation products, without leading to an increase in toxicity, which is largely related to the effective removal of the transformation products. In attempt to reduce the reliance on UV irradiation, newly synthesized carbon and nitrogen co-doped TiO2-based photocatalyst was applied to capture the simulated sunlight for the degradation of acesulfame. The heterogenous photocatalytic treatment was found to involve several different oxidative reactive species for both degradation and transformation by using several scavengers to alter the degradation profile. Unexpected transformation product was also formed upon treatment in actual water matrix, suggesting the impact of water constituents to the transformation of emerging contaminants. Toxicity results indicated the inability to achieve detoxification, suggesting that a more effective degradation process was needed. To accelerate the degradation process, and enhance the performance at neutral pH, the use of redox mediators for Fenton/Fenton-like system was evaluated. Developed novel Fenton-like system involving copper(II) as transition metal ion, persulfate as oxidant and mercaptosuccinic acid as redox mediator led to effective removal of different contaminants. Elucidation of the proposed oxidation mechanism suggested the role of each components of the system, and the generation of different reactive species for degradation as indicated by the different acesulfame transformation profile obtained. The implementation of redox mediators to Fenton/Fenton-like system was beneficial and an effective approach. In short, this work presents several kinds of catalytic advanced oxidation process and shed lights on improving the degradation performance with directions for the future development of better and more effective water treatment processes.

The aim of this PhD study was to assess the occurrence, behavior and fate of Contaminants of Emerging Concern, and more specifically Endocrine Disrupting Compounds (EDCs) in natural freshwater and saltwater environments. To this purpose, estrogens, perfluorinated compounds (PFCs) and phenolic compounds were analysed in the freshwater environment of the Romagna area (Italy). Two sampling campaigns were carried out in two following years during summer. Wastewater treatment plant effluents were the main source of introduction of PFCs in the water compartment, whereas phenolic compounds occurrence was likely related to the presence of industrial activities. Both PFCs and phenolic compounds were persistent in the aquatic compartment during the monitoring periods. On the contrary, estrogens occurrence was not constant over time, suggesting local sporadic events of contamination. Sediments were mainly affected by the occurrence of the phenolic group, whose presence was controlled by sediment size and organic carbon content. Analysis on the surrounding transitional environment of the Pialassa Baiona revealed salinity to be a relevant element controlling their partition between water and sediment. PFCs were also analysed in the transitional environment of the Ebro delta (NE Spain) during three sampling campaigns (autumn, winter, spring-summer). PFCs were confirmed to be persistent in the water compartment over the year. On the contrary, concentrations in sediments were highly influenced by seasonality. Nevertheless, a greater partition of PFCs between water and sediment was registered in the Ebro delta, in contrast with their almost absence in riverine sediments of the Romagna area, as a consequence of PFCs lower solubility in saline environments. Analyses of PFCs in both seawater and freshwater fish pointed out a higher PFCs accumulation in the freshwater species, with perfluorocarboxylic acids being more concentrated than sulfonates.

I prodotti farmaceutici e per la cura personale (PPCP) costituiscono un gruppo eterogeneo di contaminanti ambientali emergenti (CE). Negli ultimi anni, un numero crescente di studi ha confermato la loro presenza in differenti compartimenti ambientali, sollevando delle preoccupazioni circa i loro effetti per l’uomo e la fauna selvatica. Questo diventa particolarmente vero se si considera il problema della presenza delle miscele. In questo contesto il presente studio ha avuto lo scopo di contribuire alla conoscenza scientifica circa i potenziali effetti avversi per l’ambiente posti da differenti classi di CE. Durante il dottorato di ricerca sono state considerate diverse problematiche. In una prima fase dello studio è stato sviluppato e proposto un sistema di prioritizzazione attraverso un indicatore (RANKVET) per la classificazione del rischio ambientale di farmaci veterinari (veterinary medicinal products [VMP]). L’elevato numero di sostanze che potenzialmente può essere ritrovato in un compartimento ambientale mette in evidenza la necessità di strumenti di screening utili alla creazione di liste di priorità di sostanze chimiche potenzialmente dannose. Nello specifico, RANKVET è stato sviluppato sulla base delle specifiche informazioni richieste dalle Direttive e dai Regolamenti Europei per l’autorizzazione al commercio di VMP. In una fase successiva, gli effetti di diversi prodotti farmaceutici (ad uso umano e veterinario) e di composti quaternari di ammonio (QAC) sono stati valutati sia come singoli che come diverse combinazioni binarie e multicomponenti di miscele usando Aliivibrio fischeri come organismo test (Microtox® test system). Sono stati anche applicati i modelli QSAR (Quantitative Structure Activity Relationship) specificatamente sviluppati per A. fischeri allo scopo di indagare il modo di azione (MoA) dei CE selezionati sull’organismo test. Nello specifico, i risultati ottenuti hanno mostrato un simile MoA per i due differenti gruppi di contaminanti: narcotico polare per la maggior parte dei composti farmaceutici e un MoA reattivo aspecifico per la maggior parte dei QAC. Valutati come singoli composti chimici, i prodotti farmaceutici hanno mostrato una tossicità moderata, mentre i QAC hanno prodotto una rilevante inibizione di bioluminescenza in A. fischeri. Infine, sono stati utilizzati i principali parametri delle curve concentrazione-risposta dei singoli contaminanti allo scopo di studiare l’applicabilità di due modelli predittivi di tossicità di miscela ampiamente impiegati in eco-tossicologia: Concentration Addition (CA) e Independent Action (IA). Rispetto a quanto concettualmente atteso, i risultati ottenuti hanno mostrato delle deviazioni in direzione di effetti sinergici e antagonistici per la maggior parte delle miscele di farmaci testata. L’ipotesi della presenza di interazioni tossicologiche tra i componenti è stata confermata e quantificata mediante l’applicazione del metodo della Combination Index (CI). In un caso, per le miscele di QAC, sono state osservate interazioni sinergiche a concentrazioni rilevanti per l’ambiente. Da questi studi sono state elaborate alcune conclusioni principali: (i) la conoscenza dei singoli parametri delle curve concentrazione-risposta non sempre è sufficiente per una buona predizione degli effetti di tossicità di miscela soprattutto nel caso di miscele di prodotti farmaceutici; (ii) gli effetti sinergici e antagonistici sembrano essere confinati a miscele di pochi composti; (iii) le deviazioni dal concetto di additività sono principalmente dipendenti dalla specifica combinazione di sostanze chimiche testata e dal livello di effetto considerato, mentre sembrano essere indipendenti dallo specifico modo di azione dei contaminanti verso l’organismo test.
Pharmaceuticals and personal care products (PPCPs) constitute a heterogeneous group of emerging environmental contaminants (ECs). In the last years, an increasing number of studies has confirmed the presence of various PPCPs in different environmental compartments, and this raises concerns about the their potential effects to humans and wildlife. This is particularly true if the problem of the presence of mixtures in the environment is considered. In this framework, the present study aimed to contribute to the scientific knowledge about the potential environmental adverse effects of different classes of emerging contaminants. During the PhD, different issues were considered. In a first phase of the study, a prioritization method (RANKVET indicator) was developed and proposed for ranking the environmental risks of veterinary medicinal products (VMPs). As previously stated, the high number of substances that are likely to be found in an environmental compartment enlightens the need for screening tools useful to produce lists of priority substances. Particularly, RANKVET was developed on the basis of the specific requirements of the EU Directives and Regulations for placing VMPs on the market. In a further step, the toxic effects of pharmaceuticals (for veterinary and human use) and quaternary ammonium compounds (QACs) were assessed as single toxicants and as different combinations of binary and multicomponent mixtures by using Aliivibrio fischeri as test organism (Microtox® test system). In order to acquire knowledge about their mode of action (MoA), QSAR models, specifically developed for A. fischeri, were applied. Results showed a similar MoA for the two separate groups of toxicants: polar narcotic type behaviour for the majority of pharmaceuticals and a-specific reactive MoA for almost all the QACs. Assessed as single chemicals the toxic effects of pharmaceuticals were moderate, whereas a relevant bioluminescent inhibition was obtained for QACs. Single toxicity parameters were used in order to investigate the predictability of mixtures toxicity by using the two widely used eco-toxicological predictive models: Concentration Addition (CA) and Independent Action (IA). Results showed deviations from conceptual expectations in direction of synergistic and antagonistic effects for the majority of tested binary mixture of PhACs. The hypothesis of interactions among components were confirmed and quantified by the application of the Combination Index method. Synergistic interactions were observed at environmentally relevant concentrations in one case for QACs. From this study some main conclusions were drawn: (i) the knowledge of single toxicity parameters is not always sufficient for a good prediction of mixture effects, especially in the case of pharmaceutical active compounds; (ii) synergistic and antagonistic deviations seem to be confined to mixture of few compounds, (iii) deviations from additivity are mainly dependent of the specific tested combinations of chemicals and on the effect levels under consideration, whereas seem to be independent from the specific mode of action of toxicants towards the organism.

Emerging contaminants (ECs) are chemicals such as pharmaceuticals and personal care products that have been detected in various environmental matrices, including drinking water supplies at trace concentrations (ng/L-ug/L or ng/kg-ug/kg). Current wastewater treatment plant technology is largely ineffective at removing ECs. The objectives of this investigation were to: 1) determine the occurrence of ECs in private well water supplies in Montgomery and Roanoke County, VA 2) quantify the concentrations of three ECs in selected private water supplies; 3) examine the relationship between water quality constituents (nitrate, bacteria, pH and total dissolved solids) to EC occurrence in private water supplies; and 4) determine the ability of the MicroEvapTM, a novel wastewater treatment technology, to remove ECs from secondary wastewater effluent. In partnership with the Virginia Household Water Quality Program, 57 private water supplies were sampled and tested for the occurrence of 142 ECs and 43 other water quality constituents. Up to 73 ECs were detected in the sampled private water supplies. Higher numbers of ECs detected in the tested private water supplies were related with nitrate >1 mg/L, total dissolved solids >250 mg/L, and the presence of total coliform bacteria. Results indicate the MicroEvapTM technology had >99% removal effectiveness for all 26 tested ECs from three secondary wastewater effluent. With the increasing detection of ECs in water bodies, it is essential to understand the occurrence of ECs and environmental predictors of EC presence in different water matrices and continue to develop water treatment technology capable of treating wastewater for EC removal.
Master of Science

Advanced water treatment processes are necessary for the treatment of emerging organic contaminants. Traditional treatment processes do not filter or treat these contaminants causing humans and animals to come into contact and ingest them, both causing illness. Advanced oxidation processes are a good alternative method, but are cost and time intensive. Previous research on ozone and hydroxyl radicals leads to the conclusion that they might be a vial option for advanced water treatment processes. To test the effects of ozone and hydroxyl radicals on the destruction of algae, ozonated phosphate buffer was mixed with Anabaena and modified BG11 culture media and placed in a culturing apparatus to regrow the destructed Anabaena. The biomass density was measured via the optical density for five days and compared to controls. Exposure to ozone killed most of the algae in each batch, as expected. The higher the concentration of ozone, the higher amount of algal destruction. The Ozone Plus generator was more powerful at initial algal destruction than the Standard ozone generator, as indicated by the comparison between the results at 2 ppm ozone concentration. ! To test the effects of ozone and hydroxyl radicals on the treatment of carbamazepine (CMZ) and phenytoin (PHT) in controlled water systems, ozonated phosphate buffer was mixed with CMZ stock solution to make a 0.25 uM CMZ solution or PHT stock solution to form a 0.25 PHT solution. The dissolved organic carbon was measured through a total organic carbon (TOC) analyzer to determine degradation of organic compounds after exposure to ozone. With the same goal in mind, other experiments were performed using ozonated carbon nanotubes to treat CMZ and PHT in a series of increasingly complex water systems. To test the effects of ozonated carbon nanotubes (CNTs) on the treatment of CMZ and PHT, mixtures of 5.0 mM CMZ or PHT and tert-butonal were treated with ozonated phosphate buffer or treated effluent wastewater and 10 ppm or 20 ppm carbon nanotube solid loading. A high-performance liquid chromatography analyzer was used to measure the treated CMZ and PHT in the mixtures and compared to controls. The TOC test was used to determine the pharmaceutical destruction to ozone dose relationship was expected to be linear, but these results were inconclusive due to the maximum reduction of less than 10% for any level of ozone. In the simple media tests, CMZ was seemed to be completely when exposed to ozone, but a suspected breakdown product was measured. PHT had the most degradation with a CNT loading of 10 ppm and no ozone. This test suggests sorption had a greater effect on the pharmaceuticals than ozone or ·OH did. In more complex systems involving a mixture of the two pharmaceuticals in both a phosphate buffer, PHT with a CNT loading of 10 ppm had a degradation of 14% and 4% for a CNT loading of 20 ppm. The low degradation rate is most likely due to ozone reacting with other organic matter in the reactor and not the PHT. This was the same in the more complex systems involving a mixture of the two pharmaceuticals in both a phosphate buffer and a wastewater effluent system PHT with a CNT loading of 10 ppm had a degradation of 12% and 6% for a CNT loading of 20 ppm. In all three Chapters, the ozone and hydroxyl radicals showed moderate reduction in emerging organic contaminants. These results suggest that ozone and hydroxyl radicals generated from ozonated CNTs have potential to be an effective alternative to current AOPs, and that further study to refine the process is merited.

The purpose of this dissertation was to broadly investigate the fate of antibiotic resistance genes (ARGs) and engineered nanomaterials (ENMs) as representative contaminants of emerging concern in wastewater treatment plants (WWTPs). WWTPs may have their performance impacted by ENMs and may also serve as a reservoir and point of release for both ENMs and ARGs into the environment. Of interest were potential adverse effects of ENMs, such as stimulation of antibiotic resistance in the WWTP, toxicity to microbial communities critical for WWTP performance, and toxicity to humans who may be exposed to effluents or aerosols containing ENMs and their transformation products. Response of nine representative ARGs encoding resistance to sulfonamide, erythromycin and tetracycline to various lab-scale sludge digestion processes were examined, and factors that drove the response of ARGs were discussed. Mesophilic anaerobic digestion significantly reduced sulI, sulII, tet(C), tet(G), and tet(X) with longer solids retention time (SRT) exhibiting a greater extent of removal. Thermophilic anaerobic digesters performed similarly to each other and provided more effective reduction of erm(B), erm(F), tet(O), and tet(W) compared to mesophilic digestion. Thermal hydrolysis pretreatment drastically reduced all ARGs, but they generally rebounded during subsequent anaerobic and aerobic digestion treatments. Bacterial community composition of the sludge digestion process, as controlled by the physical operating characteristics, was indicated to drive the distribution of ARGs present in the produced biosolids, more so than the influent ARG composition. Effects of silver (nanoAg), zero-valent iron (NZVI), titanium dioxide (nanoTiO2) and cerium dioxide (nanoCeO2) nanomaterials on nitrification function and microbial communities were examined in duplicate lab-scale nitrifying sequencing batch reactors (SBRs), relative to control SBRs received no materials or ionic/bulk analogs. Nitrification function was only inhibited by high load of 20 mg/L Ag+, but not by other nanomaterials or analogs. However, decrease of nitrifier gene abundances and distinct microbial communities were observed in SBRs receiving nanoAg, Ag+, nanoCeO2, and bulkCeO2. There was no apparent effect of nanoTiO2 or NZVI on nitrification, nitrifier gene abundances, or microbial community structure. A large portion of nanoAg remained dispersed in activated sludge and formed Ag-S complexes, while NZVI, nanoTiO2 and nanoCeO2 were mostly aggregated and chemically unmodified. Thus, the nanomaterials appeared to be generally stable in the activated sludge, which may limit their effect on nitrification function or microbial community structure. Considering an aerosol exposure scenario, cytotoxicity and genotoxicity of aqueous effluent and biosolids from SBRs dosed with nanoAg, NZVI, nanoTiO2 and nanoCeO2 to A549 human lung epithelial cells were examined, and the effects were compared relative to outputs from SBRs dosed with ionic/bulk analogs and undosed SBRs, as well as pristine ENMs. Although the pristine nanomaterials showed varying extents of cytotoxicity to A549 cells, and gentoxicity was observed for nanoAg, no significant cytotoxic or genotoxic effects of the SBR effluents or biosolids containing nanomaterials were observed. Studies presented in this dissertation provided new insights in the fate of ARGs in various sludge digestion processes and ENMs in nitrifying activated sludge system in lab-scale reactors. The study also yielded toxicity data of ENMs to biological wastewater treatment microbial communities and human lung cells indicated by a variety of toxicity markers. The results will aid in identifying appropriate management technologies for sludge containing ARGs and will inform microbial and human toxicity assessments of ENMs entering WWTPs.
Ph. D.

Civil Engineering
M.S.E.
The emerging contaminants (ECs) such as estrogen hormones, perfluorinated compounds (PFCs), bisphenol A (BPA) and 1, 4-dioxane have been detected in natural water bodies at a noticeable level worldwide. The presence of ECs in the aquatic environment can pose potential threats to aquatic organisms as well as human world. Ion-exchange is a highly efficient technology for the removal of heavy metal ions and natural organic materials (NOMs) due to the nature of exchanging similar charged ions. However, this technology has not been explored for removing ECs. In this study, four categories of ECs: estrogen hormones (12), perfluorinated compounds (10), bisphenol A and 1, 4-dioxane were used as model contaminants. The adsorption of each category of ECs onto various types of polymeric resins (MN100, MN200, A530E, A532E and C115) was investigated. The removal of ECs was tested under batch and column mode. The effects of pH, resin dosage, and contact time on the removal of ECs were studied in batch mode; isotherm and kinetics models were applied to fit the experimental data. Column experiments were conducted to verify the practicability of the polymeric resins. Adsorption results have shown that both MN100 and MN200 resins could efficiently remove estrogen hormones mixture (more than 95%), and bisphenol A (more than 80%) with the initial concentration of 100 ìg/L; A532E and A530E could remove perfuorinated compounds mixture (more than 99%) with the initial concentration of 100 ìg/L. As pH increased from 9 to 11, the adsorption capacity onto polymeric resins decreased dramatically for estrogen hormones such as 17á-ethinylestradiol, estriol, 17â-estradiol, 17á-estradiol, estrone, 17á-dihydroequilin and equilin as well as bisphenol A. The adsorption of estrogen hormones and bisphenol A onto MN100 and MN200 resins reached the equilibrium within 24 hours, whereas the adsorption of perfluorinated compounds onto A532E and A530E reached the equilibrium within 8 hours. It was also observed that the adsorption of PFCs largely depends on the C-C chain length. PFCs with longer chain yielded lower adsorption efficiency onto the ion-exchange resins A532E and A530E. Adding salinity decreased the first-order rate constants for the adsorption of bisphenol A onto MN100 and MN200 resins. Fixed-bed column experiment results with estrogen hormones mixtures confirmed that the polymeric resins were good candidates in the removal of estrogen hormones. Trimegestone was the first compound detected in the effluent in the column test while 17â-estradiol, 17á-estradiol were the last. 80% of the exhausted resins (MN100 and MN200) by bisphenol A were regenerated by using pure methanol as regeneration solution. Polymeric resins were not effectively removing 1, 4-dioxane from the aqueous solution.
Temple University--Theses

Civil Engineering
M.S.Env.E.
The presence of emerging contaminants (ECs) in water and wastewater systems has become a subject of significant concern worldwide. These emerging contaminants are complex organic molecules which potentially affect human health and environment. Conventional wastewater treatment plants are unable to completely remove these contaminants from water and therefore can discharge them into environment. The need to develop effective methods for ECs removal is essential. This study assess the potential of ozone based advanced oxidation processes (AOP) to oxidize number of emerging contaminants. Different combinations of ozone with hydrogen peroxide and sodium persulfate were tested. For this study 1-4, dioxane, perfluorinated compounds (PFCs), N,N-Diethyl-metatoluamide, and three pharmaceuticals sulfamethoxazole, trimethoprim and carbamazepine have been selected. The effect of different process parameters such as chemical dosages, ozone weight percent, ozone flow rates, etc. on destruction of ECs were examined. It was observed that 1, 4-dioxane were persistent to direct ozone reaction, however were easily oxidized by hydroxyl radical. However, ozonation was solely very effective (> 99 %) in removing pharmaceuticals such as sulfamethoxaole, trimethoprim and carbamazepine. It was not very efficient for the removal of perfluorinated compound and N,N-Diethylmeta-toluamide. The operational conditions were optimized for maximum removal of every compound and their influence on the degradation process is discussed.
Temple University--Theses

Marine organisms are exposed to a wide range of anthropogenic substances, many of them considered as emerging contaminants due to their growing production and not well-known environmental impact. Among emerging contaminants, pharmaceuticals and personal care products are cause for increasing concern, being bioactive substances widely used in both human and veterinary medicine. Climate changes, such as ocean acidification, could have a powerful effect on pharmaceuticals by altering their environmental behaviour and exposure pathways, thus resulting in an increased toxicity. Furthermore, shifts in environmental parameters could alter marine organism susceptibility to these compounds. In this context, the combined effects of seawater acidification, as predicted in climate change scenarios, and emerging contaminants (the non-steroidal anti-inflammatory drug, NSAID, diclofenac and the metabolic activator caffeine) were investigated for the first time in the Mediterranean mussel Mytilus galloprovincialis and the Manila clam Venerupis philippinarum. In adults of both species, we evaluated haemocyte and oxidative stress parameters in order to highlight potential effects due to the combination of seawater acidification and exposure to diclofenac. Other two experiments were carried out to investigate whether the exposure to seawater acidification-diclofenac and acidification–caffeine may affect physiological responses and haemocyte parameters, respectively, in adults of M. galloprovincialis. A flow-through system was used to carry out a three-weeks exposure of the studied bivalves. In the first week, animals were exposed to three pH values (8.1, 7.7, 7.4) only. Thereafter, they were maintained for 7 and 14 days at the three experimental pH values and exposed simultaneously to environmentally relevant concentrations of diclofenac/caffeine (0, 0.05 and 0.5 µg/L). To analyzed haemocyte parameters [total haemocyte count (THC), haemocyte volume and diameter, Neutral Red uptake (NRU), haemocyte proliferation and lysozyme activity) and oxidative stress parameters [superoxide dismutase (SOD), catalase (CAT) and cyclooxygenase (COX) activities, lipid peroxidation (TBARS) and DNA strand-break formation), haemolymph, gills and digestive gland were collected after 7, 14 and 21 days of exposure to differing pH value or pH/diclofenac and pH/caffeine combinations. The same experimental set-up was used to study physiological responses in bivalves. After 7, 14 and 21 days, clearance rate, respiration rate and excretion rate were evaluated in individual mussels. The results obtained showed that cellular, biochemical and physiological parameters measured in both mussels and clams were more influenced by pH than by the contaminants (diclofenac and caffeine). In both species, immune parameters were the most responsive to differing experimental conditions. In V. philippinarum, THC and haemocyte proliferation significantly increased with decreasing pH values, after one week of exposure. Interestingly, NRU decreased significantly at pH 7.4, suggesting that clams were trying to compensate a weak pinocytotic capability, due to damaged cell membranes, by increasing the number of circulating haemocytes to maintain immunesurveillance. Despite COX is involved in inflammatory processes and it should be inhibited by NSAIDs, no significant effects due to diclofenac were revealed in both bivalve species, whereas pH significantly influenced this enzymatic activity. However, an opposite pattern of variation was observed in tissues of clams and mussels kept at low pH. In M. galloprovincialis, differing modulation patterns were found in physiological rates measured after 7, 14 and 21 days of exposure to the experimental conditions tested. Reduction in filtration and nitrogen excretion and increase in oxygen consumption highlighted stressful condition under reduced pH. The combined effects of seawater acidification and diclofenac were also investigated in larvae of the clam V. philippinarum. An experimental flow-through system was used to carry out a 96 hours exposure of clam larvae. Fertilized eggs were exposed to two different levels of pH (8.1 and 7.7) combined with two concentrations of diclofenac (0 and 0.5 µg/L). Throughout the experiment, larval mortality and growth were daily checked and recorded. At the end of the experiment, pools of larvae were constituted to assess oxidative stress (CAT activity) and lipid peroxidation. About 50% mortality was observed in larvae exposed to pH 7.7, both with and without diclofenac, while mortality was lower than 10% in controls kept at pH 8.1. Low pH significantly reduced shell length and height and altered their ratio. Diclofenac significantly decreased shell length only, the reduction being higher at pH 7.7 than at pH 8.1. A strong tissue prolapse outside the shell was observed in larvae kept at pH 7.7. pH significantly increased CAT activity in larvae kept at pH 7.7 for 96 hours, whereas no significant difference in lipid peroxidation was found among treatments. This study demonstrated that seawater acidification negatively influenced susceptibility of V. philippinarum larvae to environmentally relevant concentrations of diclofenac, mostly by altering shell growth.
Gli organismi marini , soprattutto in ambienti costieri ed estuarini, sono continuamente esposti ad una vasta gamma di sostanze di origine antropica, tra cui molte vengono considerate “contaminanti emergenti” a causa della crescente produzione ed immissione in ambiente a fronte di una quasi completa assenza di informazioni relative al loro impatto sul biota. Tra questi composti, una crescente attenzione viene data ai principi attivi contenuti in farmaci per uso medico e veterinario e in prodotti per la cura e l’igiene personale di largo consumo. Le problematiche derivanti dal continuo rilascio di nuovi contaminanti in ambiente si inseriscono in un quadro di cambiamenti climatici, riconducibili all’aumento delle emissioni di anidride carbonica in atmosfera, in particolare all’acidificazione delle acque marine. Una riduzione dei valori di pH in mare potrebbe incidere pesantemente sulle caratteristiche chimico-fisiche dei farmaci rilasciati in ambiente, alterandone distribuzione, biodisponibilità e potenziale tossicità. D’altro canto, variazioni ambientali, come quelle previste in uno scenario di cambiamento climatico, potrebbero modificare la suscettibilità degli organismi marini nei confronti di questi composti. In questo contesto, il presente studio ha voluto indagare gli effetti combinati dell’acidificazione e di contaminanti emergenti (il diclofenac, un antiinfiammatorio non steroideo, e la caffeina, un attivatore metabolico) in due bivalvi marini, il mitilo Mytilus galloprovincialis e la vongola Venerupis philippinarum. In organismi adulti di entrambe le specie, sono stati valutati parametri morfo-funzionali negli emociti e risposte legate allo stress ossidativo in condizioni di esposizione a pH ridotto e a diclofenac . Solo nel mitilo si sono indagati gli effetti delle medesime condizioni sperimentali sulle performance fisiologiche e, in un ulteriore esperimento, gli effetti combinati di acidificazione e caffeina su parametri cellulari negli emociti. Per condurre queste diverse sperimentazioni, ognuna della durata di una settimana, è stato utilizzato un impianto a flusso continuo appositamente allestito. Durante la prima settimana gli animali sono stati esposti a tre diversi valori di pH (8.1, 7.7, 7.4), nelle successive due settimane alle stesse condizioni di pH si è associata un’esposizione a concentrazioni ambientali di diclofenac o caffeina (0, 0.05 and 0.5 µg/L). Dopo 7, 14 e 21 giorni di esposizione alle condizioni sperimentali sopra indicate, sono stati prelevati emolinfa, branchie e ghiandola digestiva e misurati i parametri emocitari [numero di emociti circolanti (THC), volume e diametro degli emociti, saggio di assunzione del Rosso Neutro (NRU), saggio di proliferazione cellulare, attività del lisozima] e i parametri di stress ossidativo [attività della superossido dismutasi (SOD), della catalasi (CAT) e della cicloossigenasi (COX), perossidazione lipidica (TBARS) e rotture al DNA (DNA strand-breaks)]. Analogamente, con la stessa cadenza temporale, sono state misurate nei mitili le risposte fisiologiche (tasso di filtrazione, tasso di respirazione e tasso di escrezione). Nel complesso i risultati ottenuti evidenziano che, sia nei mitili, sia nelle vongole, le risposte risposte biochimiche, cellulari e fisiologiche indagate sono state maggiormente influenzate dalla riduzione di pH che dall’esposizione ai contaminanti (diclofenac e caffeina). In entrambe le specie, i parametri emocitari hanno risposto in maniera più sensibile alle diverse condizioni sperimentali. In V. philippinarum, THC e proliferazione cellulare sono aumentati significativamente al diminuire del pH dopo una settimana di esposizione. I valori di NRU invece hanno mostrato una significativa diminuzione a pH 7.4, suggerendo quindi la messa in atto di meccanismo di compensazione dell’indebolita capacità di pinocitosi, dovuta ad un possibile danno alla membrana cellulare, attraverso un aumento dei valori di THC, in modo da mantenere adeguate condizioni di immunosorveglianza. Nonostante la COX sia coinvolta nei processi infiammatori e venga normalmente inibita dagli antiinfiammatori non steroidei, in nessuna delle due specie la sua attività è risultata significativamente influenzata dall’esposizione a diclofenac. Viceversa si è evidenziato un effetto significativo del pH, anche se con un opposto pattern di variazione in mitili e vongole dopo esposizione a pH ridotto. In M. galloprovincialis sono stati rilevati differenti pattern di modulazione nelle risposte fisiologiche misurate dopo 7, 14 and 21 giorni di esposizione alle condizioni sperimentali saggiate. In particolare, una riduzione della filtrazione e dell’escrezione azotata ed un concomitante aumento del consumo di ossigeno hanno messo in luce condizioni di stress associate ad una riduzione del pH. Gli effetti combinati di acidificazione dell’acqua di mare e di esposizione a diclofenac sono stati indagati anche durante la fase larvale della vongola V. philippinarum. In un impianto sperimentale a flusso continuo, uova fecondate sono state esposte per 96 ore a due diversi valori di (8.1 and 7.7) in combinazione con due concentrazioni di diclofenac (0 and 0.5 µg/L). Durante l’esperimento è stata rilevata ogni giorno la mortalità delle larve ed è stata misurata la crescita della conchiglia. Alla fine dell’esperimento sono stati raccolti campioni di larve per la determinazione dell’attività della CAT e della perossidazione lipidica. Una mortalità intorno al 50% è stata registrata a pH 7.7, sia in presenza che in assenza di diclofenac, ma tale valore è sceso a meno del 10% a pH 8.1. A pH 7.7 si è osservata una riduzione significativa delle dimensioni della conchiglia (lunghezza e altezza) e un’alterazione del loro rapporto. L’esposizione a diclofenac ha portato ad una significativa riduzione della sola lunghezza, più marcata a pH 7.7 che a pH 8.1. A pH ridotto sono state osservate larve anomale con un prolasso dei tessuti molli che fuoriuscivano dalla conchiglia. Nelle larve mantenute a pH ridotto si è riscontrato un aumento significativo dell’attività della CAT, ma nessuna variazione nei livelli di perossidazione lipidica rispetto ai controlli. Questo studio ha fornito i primi risultati sui possibili effetti dell’acidificazione nello sviluppo larvale di V. philippinarum , evidenziando come una riduzione di pH possa influire negativamente sulla sensibilità delle larve di vongola al diclofenac, con ripercussioni soprattutto sulla crescita della conchiglia.

"The simultaneous degradation of five organic contaminants: 1,4 dioxane, n-nitrosodimethylamine, tris-2-chloroethyl phosphate, gemfibrozil, and 17β estradiol, was investigated using a 1 L batch water-jacketed UV photoreactor utilizing titanium dioxide (TiO2) nanoparticles (Degussa P-25) as a photocatalyst. The primary objectives of this research were: (1) to experimentally assess the feasibility of heterogeneous photocatalysis as a promising alternative for the degradation of organic compounds in water; and (2) to model the chemical reactions by the application of two different approaches based on adsorption – surface reactions (Langmuir–Hinshelwood) and its simplification to a first order rate reaction. These objectives were motivated by the lack of information regarding simultaneous degradation of organic compounds in different categories as found in real aqueous matrices, and generation of specific intermediates that could eventually represent a potential risk to the environment. Contaminants were chosen based on their occurrence in water sources, their representativeness of individual sub-categories, and their importance as part of the CCL3 as potential contaminants to be regulated. Contaminant degradation was evaluated over time, and the TiO2 concentration and solution pH were varied under constant UV irradiation, oxygen delivery rate, mixing gradient, and temperature. 

 Specific accomplishments of this study were: (1) reaction kinetics data were obtained from the UV/TiO2 experiments and showed the potential that this UV/TiO2 process has for effectively removing different types of organic compounds from water; (2) a good fit was obtained between photocatalytic reaction kinetics models and the contaminant data using pseudo first-order and Langmuir-Hinshelwood (L-H) models; (3) results of the analytical methods developed in this study were validated by measurements performed by a certified laboratory; (4) the reaction kinetic parameters obtained in this study were normalized to electrical energy per order, reactor volume and surface area of the photocatalyst in order to provide rate constants with wider applicability for scale-up to more complex systems; and (5) degradation intermediates from the oxidation process and from interaction among compounds were identified and possible pathways for their formation suggested. This research has provided a better understanding of the photocatalytic process for the removal of organic contaminants from complex aqueous matrices."

Civil Engineering
M.S.E.
Emerging contaminants (ECs) such as estrogen hormones, perfluoro compounds (PFCs), bisphenol-A (BPA), and 1,4-dioxane have been detected in natural water at many places. The existing conventional wastewater treatment systems are not designed for the removal of these contaminants. This critical issue leads to the need for the development of advanced and effective technologies.β-cyclodextrin (β-CD) is a glucose-based molecule which has high affinity for different organic contaminants by the formation of host/guest inclusion complexes. In this research, water soluble β-CD was reacted with certain crosslinking agents and copolymers to form water insoluble β-CD and to coat β-CD onto silica particles. The development of such novel hybrid adsorbents provides high binding capacity with organic contaminants along with high mechanical strength. Three different approaches were used to develop adsorbents by using two crosslinking agents (epichlorohydrin (EPI) and hexamethylene diisocyanate (HMDI), two copolymers (glycidoxypropyl trimethoxysilane and aminopropyl triethoxysilane) and three solvents (NaOH, dimethyl formamide (DMF), and dimethyl sulfoxide (DMSO). The developed adsorbents were tested for the removal of ECs of interest (estrogens, PFCs, 1,4-dioxane, and BPA) under batch and column conditions from Milli-Q water. The adsorbent prepared by reacting β-CD with HMDI as crosslinking agent with the molar ratio of 1:8 showed best results in removing the target compounds. The adsorbent showed more than 95% removal of 17β-estradiol (in single component) and more than 90% of most of the estrogens (in multicomponent), more than 99% of PFOA, and a maximum of 90% removal in case of BPA. However, the developed adsorbent did not show any removal in case of 1,4-dioxane. The developed adsorbent showed a good regeneration capacity in removing PFOA over three successive cycles. The characterization of the adsorbents using FTIR, TGA, and TEM confirmed the coating of β-CD onto silica particles. The removal of ECs of interest was dependent on the nature of both adsorbents and adsorbates. The nature of adsorbent such as type of crossling agent, molar ratio between β-CD and crosslinking agents affect the removal of the contaminants. Similarly, the nature of adsorbates such as size, shape, and presence of functional groups affect the removal efficiency.
Temple University--Theses

This study examined the interaction of model cationic, neutral and anionic endocrine disrupting compounds, pharmaceuticals and personal care products (EDC/PPCPs) with bulk and fractionated freshwater and waste water dissolved organic matter (DOM). The chemical composition of the freshwater DOM (Suwannee River, GA, SROM) proved to be rich in plant-derived hydrophobic aromatics, while the wastewater DOM (WWOM) contained a greater proportion of microbial biomolecular products, presumably resulting mainly from human waste. Studies focused on the fluorescence quenching of excitation-emission matrices (EEMs) of WWOM indicated that interaction with bis-phenol A (BPA), carbamazepine (CBZ), and ibuprofen (IBU) occurred preferentially with soluble protein-like and fulvic acid-like constituents. However, upon introduction to bulk SROM, BPA and CBZ were observed to quench humic acid-like regions of the EEMs, while negatively charged ibuprofen preferentially quenched the protein-like and fulvic acid components irrespective of DOM source and/or fraction. Despite this evidence of EDC/PPCP interactions with both DOM types, the strength of bonds formed was generally not sufficient to preclude full recovery and quantification of all three contaminants by liquid chromatography tandem mass spectrometry (LC-MSMS). An important exception, however, was for the hydrophilic acid fraction (HiA) of both DOM types, whose apparent bonding to cationic CBZ and anionic IBU significantly diminished LC-MSMS recovery. Thus, water sources rich in HiA character might produce a concentration underestimation of ionized EDC/PPCPs even with the use of sophisticated instruments such as LC-MSMS.The results of this research are consistent with the evolving ""supramolecular"" theory of natural organic matter, which postulates that organic matter itself is comprised of fragments of partially degraded biomolecules that are aggregated into ""supramolecular"" structures of apparent higher molar mass via relatively weak electrostatic, hydrophobic, and van der Waals interaction. Our findings suggest that EDC/PPCP contaminants, which comprise many of the same functional groups as waste water and freshwater DOM, may be incorporated into such DOM supramolecular structures, likely via the same types of intermolecular bonding, when they are present in natural waters under environmentally-relevant conditions.

‘Wastewater treatment’ is not itself a new concept, where global water bodies have been polluted since the evolution of mankind. As a result of human activities including domestic, industrial and commercial practices, levels of water pollution through aqueous contaminants are increasing every day. Moreover, rapid industrialisation and recent human progress has given rise to a new classification of pollution, that of emerging contaminants (ECs). Further, these chemicals are highly resistant to biodegradation and are capable of travelling, where they can penetrate from one part of the world to another. Whilst traditional wastewater treatment techniques, such as adsorption, might be effective in combating these chemicals, their production of sludge is a major drawback that leads to secondary contaminants. Advance oxidation processes (AOPs) have gained much attention within environmental remediation, owing to their ability to completely mineralise organic pollutants into less-toxic mineral caids, CO2 and water. The process efficiency of this mineralisation is further improved when it is coupled with nanotechnology. Accordingly, nanostructured transition metal oxides demonstrate exceptional catalytic activity in AOPs. Hematite (α˗Fe2O3), the most stable form of iron oxide, has been demonstrated as an excellent example of this, where its distinct properties, such as high specific surface area, interfacial charge-transfer properties and lower band gap, have made it a promising candidate for AOPs. Moreover, hematite’s good catalytic stability, non-toxic nature, low cost and chemical inertness have rendered it effective in versatile applications. This thesis presents novel strategies for the preparation and modification of α-Fe2O3 nanostructures. Several techniques, such as metal doping, formation of bimetallic oxides, morphological and facet engineering and integration with carbonaceous structures have been applied to enhance the catalytic and photocatalytic activity of α-Fe2O3. Further, facile hydrothermal, solvothermal and thermal treatment methods have been adopted for the design and formation of desired nanostructures. The physical properties and surface chemistry of these as-prepared nanostructures have been unveiled via several advanced characterisation techniques, for example, XRD, XPS, FT-IR, UV-vis, and PL, amongst others. Following this, these materials were applied in AOPs, where they were shown to successfully activate peroxygens (peroxymonsulfate (PMS) and hydrogen peroxide (H2O2)) for the removal of ECs, such as those in pharmaceutical and personal care products (PPCPs). In this study, level of modification was set as a key performance indicator, whereby optimum modification conditions were determined for preserving the best catalytic characteristics. The influence of reaction parameters including pH, catalyst loading, oxidant loading and reaction temperature were comprehensively investigated to optimise reaction kinetics. Electron paramagnetic resonance (EPR) was used to identify the generation of radical and free radical species, whereby their specific role in degradation kinetics was confirmed by performing quenching experiments. At the end, the mineralisation ability of as-prepared catalytic materials was evaluated by performing total organic carbon analysis, where ultra-high performance liquids spectroscopy (UHPLC) chromatograms were used to propose degradation pathways. In summary, the current work serves as a bridging tool between nano structural engineering and reaction engineering for environmental remediation. The former provides fundamental groundwork for the development of efficient catalysts, where the latter expands pathways for real-world applications.

Els contaminants emergents són un ampli grup de compostos orgànics detectats en diversos compartiments ambientals. Tot i que la seva concentració normalment està compresa entre els ng/L fins a pocs µg/L (força inferior que els contaminants orgànics convencionals), poden representar una amenaça per a la salut humana i el medi ambient. D’entre tots els contaminants emergents, els principis actius dels fàrmacs (PhACs) i els compostos disruptors endocrins (EDCs) generen una especial preocupació. Per altra banda, està àmpliament acceptat que la seva principal font d’entrada al medi ambient són els efluents de les plantes depuradores, on els tractaments convencionals de llots actius no són capaços de degradar-ne la majoria. Per tant, s’han de buscar tractaments alternatius. Una d’aquestes alternatives podria ser l’ús de fongs ligninolítics, aprofitant el seu sistema enzimàtic que els hi confereix l’habilitat de degradar un rang molt ampli de contaminants. Aquesta tesi avalua diferents aspectes relacionats amb la degradació de contaminants emergents per part de fongs. El fong de podridura blanca Trametes versicolor, àmpliament estudiat, és el que s’ha triat per a dur a terme els experiments d’aquesta tesi. Primer de tot s’ha estudiat la degradació individual de determinats contaminants. Tenint en compte que la degradació dels EDCs ha estat menys estudiada que la dels PhACs, es van seleccionar sis EDCs pertanyents als grups dels filtres UV (benzofenona-3 (BP3), benzofenona-1 (BP1) i 3-(4-metilbenzilidè) càmfor (4-MBC)) i dels benzotriazols (1H-benzotriazol (BTZ) i toliltriazol, una mescla de 4-metilbenzotriazol (4-MBTZ) i 5-metilbenzotriazol (5-MBTZ)). S’ha fet, doncs, un seguiment de la seva degradació per part de T. versicolor, la toxicitat aguda i les activitats estrogènica i de tipus dioxina, s’han identificat els metabòlits generats pel fong i s’han suggerit els primers passos de la via de degradació. A més a més, el destí de determinats contaminants (la BP3 i l’analgèsic i antiinflamatori diclofenac) durant la seva degradació per part del fong ha estat avaluada a través de compostos marcats amb l’isòtop estable 13C. La combinació d’anàlisis de la composició isotòpica del C del CO2 i de la biomassa total i el sondeig d’isòtops estables en aminoàcids (aa-SIP) han permès la discriminació entre simple transformació, mineralització oxidativa o incorporació del carboni a la biomassa. Pel que fa als dos compostos estudiats, els dos s’han mineralitzat però s’ha vist que només la BP3 s’utilitza com a font de carboni i és incorporada a la biomassa del fong. Per una altra banda, es van tractar dos efluents reals (l’aigua residual d’un hospital veterinari i el concentrat d’osmosi inversa d’una planta pilot de tractament d’aigües residuals urbanes) en un bioreactor de fongs fluïditzat per polsos d’aire i operat sota diferents condicions operacionals (estèril/no estèril i discontinu/continu) en vistes a una possible implementació futura. Amb aquesta intenció, aquesta tesi apunta a la importància de l’addició externa de nutrients i al control de l’aeració, els quals haurien de ser optimitzats per a obtenir una eliminació eficient de contaminants per part del fong inoculat. En aquesta tesi també es remarca la importància dels processos de conjugació i desconjugació. Per una banda, són una una restricció en l’avaluació de la degradació en efluents reals a causa de la seva absència en els mètodes analítics i, per l’altra, els conjugats representen uns metabòlits intermedis importants durant la degradació per part del fong dels contaminants seleccionats . També es van realitzar anàlisis de biologia molecular (anàlisi dels àcids grassos dels fosfolípids (PLFA), PCR quantitativa (qPCR) i gel d’electroforesis en gradient desnaturalitzant (DGGE)) amb l’objectiu de trobar alguna correlació entre l’operació dels bioreactors i el comportament del fong inoculat i els altres microorganismes que es desenvolupen en els bioreactors no estèrils. Els resultats suggereixen que els paràmetres de seguiment clàssics (com poden ser l’activitat lacasa) podrien no ser uns bons indicadors de la supervivència i predominança del fong inoculat.
Emerging contaminants are a wide group of organic compounds detected in many environmental compartments. Even though their environmental concentration is usually in the range of ng L-1 to low µg L-1 (much lower than conventional organic pollutants), they still represent a threat to human health and the environment. Among emerging contaminants, pharmaceutically active compounds (PhACs) and endocrine disrupting compounds (EDCs) are of special concern. It is widely accepted that the main source to the environment are the effluents of wastewater treatment plants (WWTPs), where conventional activated sludge treatments are not able to degrade most of them. Therefore, alternative treatments should be found. One of those alternatives might be the use of ligninolytic fungi by taking advantage of their enzymatic system, that conferes them the ability to degrade a broad range of contaminants. The present thesis assesses different factors related to the fungal degradation of emerging contaminants. The widely studied white-rot fungus Trametes versicolor has been chosen to carry out all the experiments of this thesis. First of all, individual degradation of selected contaminants was studied. Taking into account that EDCs degradation has been less studied than PhACs, six EDCs belonging to the groups of UV filters (benzophenone-3 (BP3), benzophenone-1 (BP1) and 3-(4-methylbenzylidene) camphor (4-MBC)) and benzotriazoles (1H-benzotriazole (BTZ) and tolyltriazole, a mixture of 4-methylbenzotriazole (4-MBTZ) and 5-methylbenzotriazole (5-MBTZ)) were selected. Their degradation by T. versicolor, acute toxicity, estrogenic and dioxin-like activities were monitored, the fungal metabolites were identified and the first steps of the degradation pathway were suggested. Moreover, the fate during fungal degradation of certain contaminants (BP3 and the analgesic and anti-inflammatory diclofenac) was assessed by means of compounds labelled with the stable isotope 13C. Combination of analyses of carbon isotopic composition of CO2, bulk biomass and amino acids-stable isotope probing (aa-SIP) allowed the distinction between simple transformation, oxidative mineralization or carbon incorporation into the biomass. Regarding the two studied compounds, both of them were mineralized, but only BP3 was found to be used as carbon source and incorporated in the fungal biomass. On the other hand, two real effluents (veterinary hospital wastewater and a reverse osmosis concentrate from a pilot plant treating urban wastewater) were treated in fungal air-pulsed fluidized bioreactors under different operational conditions (sterile/non-sterile and batch/continuous) in view of a possible future implementation. With respect to that, the present thesis points out the importance of an external addition of nutrients and the control of aeration, which should be further optimized for an efficient removal of contaminants by the inoculated fungus. The importance of conjugation and deconjugation processes is also highlighted in this thesis. They are a restriction in the assessment of emerging contaminants degradation in real effluents due to the absence of conjugates in the analytical methods and, at the same time, conjugates are important intermediate metabolites in the fungal degradation of the selected contaminants. Molecular biology analyses (phospholipid fatty acids analysis (PLFA), real-time PCR (qPCR) and denaturing gradient gel electrophoresis (DGGE)) were performed as well with the aim of finding some correlation between the operation of the bioreactors and the performance of the inoculated fungus and the other microorganisms that could develop in the non-sterile bioreactors. Results suggest that the classical parameters monitored (i.e. laccase activity) might not be good indicators of inoculated fungus survival and predominance.

Étant donné que d'innombrables composés xénobiotiques se retrouvent dans l'environnement, l'écotoxicologie doit relever un défi stupéfiant pour identifier les substances toxiques. La combinaison de bioessais in vivo/in vitro à haut débit et d'analyses chimiques à haute résolution est un moyen efficace d'élucider la relation de cause à effet. Cependant, ces stratégies combinées impliquent une énorme charge de travail qui peut entraver leur mise en œuvre dans les analyses de routine. Le premier objectif de cette thèse était de développer une nouvelle méthode de criblage à haut débit pour mettre en œuvre le test de l'embryon d'oursin dans l'analyse dirigée par les effets. Nous avons ainsi développé un nouveau système expert prédictif, le SETApp, qui peut être utilisé pour quantifier automatiquement les deux paramètres du test de l'embryon d'oursin à partir d'un ensemble d'images donné. Nous avons démontré que la chimiométrie, et en particulier les modèles de classification linéaire multivariée, peuvent être mis en œuvre avec succès dans l'automatisation des essais biologiques pour éviter la mesure fastidieuse de la taille des embryons et des niveaux de malformation. En outre, nous avons également démontré l'efficacité de ce SET dans un scénario très exigeant, l'EDA de l'effluent de la STEP du Pont de l′aveugle de Bayonne (Pays Basque, France). Cette étude sur l'EDA a conclu que la SETApp est un outil efficace, rapide, rentable et reproductible qui peut approcher l'EDA de l'analyse de routine.D'autre part, la présence de ces contaminants de préoccupation émergente (CEC) dans l'environnement aquatique a un impact direct sur les organismes vivant dans l'eau et peut altérer leurs fonctions vivantes. Ces composés sont souvent métabolisés et excrétés, mais ils peuvent aussi s'accumuler et se propager dans la chaîne alimentaire. Les contaminants métabolisés peuvent également conduire à la formation de nouveaux composés dont la toxicité et le potentiel de bioaccumulation sont inconnus. Dans la deuxième étude de ce travail, nous avons étudié l'occurrence, la bioconcentration et la biotransformation des CECs dans les civelles (Anguilla anguilla) en utilisant la UHPLC-HRMS.Enfin, dans notre troisième étude, nous nous sommes concentrés sur l'évaluation de l'impact des contaminants émergents sélectionnés chez les civelles au moyen de la métabolomique. Cette approche nous a permis non seulement d'évaluer la toxicité de ces contaminants mais aussi de mieux comprendre les différences métaboliques entre les civelles migrantes et non migrantes
Since countless xenobiotic compounds are being found in the environment, ecotoxicology faces an astounding challenge in identifying toxicants. The combination of high-throughput in vivo/in vitro bioassays with high-resolution chemical analysis is an effective way to elucidate the cause-effect relationship. However, these combined strategies imply an enormous workload that can hinder their implementation in routine analysis. The first aim of this thesis was to develop a new high throughput screening method to implement the sea urchin embryo test in effect-directed analysis. This way, we developed a novel predictive expert system, the SETApp, which can be used to automatically quantify the two endpoints of the sea urchin embryo test from a given image set. We demonstrated that chemometrics, and especially multivariate linear classification models, can be successfully implemented in bioassay automation to avoid the cumbersome measurement of embryo sizes and malformation levels. In addition, we have also shown the efficiency of this HTS in a very demanding scenario, the EDA of Bayonne's (Basque Country, France) Pont de l′aveugle WWTP effluent. This EDA study concluded that the SETApp is an efficient, fast, cost-effective, and reproducible tool that can approach EDA to routine analysis.On the other hand, the presence of these contaminants of emerging concern (CECs) in the aquatic environment directly impacts water-living organisms and can alter their living functions. These compounds are often metabolized and excreted, but they can also be accumulated and spread through the food chain. The metabolized contaminants can also lead to the formation of new compounds with unknown toxicity and bioaccumulation potential. In the second study of this work, we studied the occurrence, bioconcentration, and biotransformation of CECs in glass eels (Anguilla anguilla) using UHPLC-HRMS.Finally, in our third study, we focused on the impact assessment of the selected emerging contaminants in glass eels by means of metabolomics. This approach not only allowed us to evaluate the toxicity of these contaminants but also to gain insight into the metabolic differences between migrant and non-migrant glass eels

Ensuring good water quality is becoming a major challenge in urban areas. Urban aquifers may suffer pollution from different recharge sources such as water leakage from sewer and septic systems, seepage from rivers, seawater intrusion, and losses from water supply network among others. As a result, a wide range of organic pollutants are found in urban aquifers. Since these pollutants enter the groundwater environment through the aforementioned sources, their occurrence depends on the transport mechanisms as well as the chemical and biochemical processes that occurred simultaneously. Thus, a proper assessment of groundwater quality requires an understanding of all the processes that affect these pollutants. However, the quantification of these processes is not an easy task. The aims of this thesis are to investigate the occurrence of emerging organic contaminants (EOCs) and the processes that affect them in an urban aquifer. An extensive review including the occurrence and fate of EOCs in Spanish groundwater and the evaluation of potential sources of contamination was carried out. Among organic contaminants found in groundwater, we have analysed pharmaceutically active compounds (PhACs), drugs of abuse (DAs) and personal care products in urban groundwater of Barcelona. The main sources of pollution of EOCs in urban areas are sewer leakage loss and infiltration from waste water treatment plants. Once these contaminants enter the aquifer, their concentrations are affected by numerous processes, including concentration at the source, dilution, adsorption and degradation. Many EOCs are removed from water by transformation or degradation, especially if the water has undergone a broad range of redox states. Therefore, identifying and quantifying the redox processes along a flow line is a key issue. In order to quantify such processes, we have proposed an approach using mixing ratios. The application of environmental isotopes coupled with hydrochemistry data using mixing ratios has provided the isotopic quantification of groundwater recharge sources and the occurrence of redox processes such as sulphate reduction, aerobic respiration and denitrification. The approach enabled us: (1) to quantify the mixing ratios into groundwater (2) to evaluate redox processes.
Garantir una bona qualitat de l'aigua s'està convertint en un seriós problema en les zones urbanes. Els aqüífers urbans poden patir contaminació de diverses fonts de recàrrega, com fuites d'aigua de clavegueram i fosses sèptiques, filtracions des dels rius contaminats, intrusió marina, i pèrdues de la xarxa de proveïment d'aigua, entre d'altres. Per això, en els aqüífers urbans es troben diversos contaminants orgànics. La presència i evolució d'aquests contaminants als aqüífers depèn dels mecanismes de transport, així com dels processos químics i bioquímics. Per tant, una correcta avaluació de la qualitat de l'aigua subterrània requereix un enteniment de tots els processos que afecten aquests contaminants. No obstant això, la quantificació d'aquests processos no és una tasca fàcil. Els objectius d'aquesta tesi són investigar la presència de contaminants orgànics emergents (COEs) i els processos que els afecten en un aqüífer urbà. S'ha dut a terme una extensa revisió bibliogràfica de la presència de COEs en les aigües subterrànies d'Espanya, juntament amb l'avaluació de possibles fonts de contaminació. Entre els contaminants orgànics que es troben en les aigües subterrànies, s'han analitzat nombrosos fàrmacs, drogues d'abús i productes de cura personal en l'aigua subterrània urbana de Barcelona. Les principals fonts de contaminació dels COEs en zones urbanes són la pèrdua de les xarxes de clavegueram i els efluents de les estacions depuradores d'aigües residuals. Una vegada que aquests contaminants són presents a l'aqüífer, les seves concentracions es veuen afectades per nombrosos processos, incloent dilució, adsorció i degradació. Molts COEs poden ser eliminats de l'aigua subterrània per processos de transformació o degradació, especialment si l'aqüífer ha passat per diferents estats redox. Per això, la identificació i quantificació dels processos redox a l'aqüífer és una qüestió clau. Per quantificar aquests processos, s'ha proposat un mètode que utilitza les proporcions de mescla. L'aplicació dels isòtops ambientals juntament amb les dades hidroquímiques ha proporcionat la quantificació isotòpica de fonts de recàrrega d'aigua subterrània i l'ocurrència de processos redox, com la sulfato reducció, la respiració aeròbica i desnitrificació. L'ús d'aquestes metodologies ha permès: (1) quantificar les proporcions de barreja en l'aigua subterrània i (2) avaluar els processos redox.
Garantizar una buena calidad del agua se está convirtiendo en un gran problema en zonas urbanas. Los acuíferos urbanos pueden sufrir contaminación a través de diversas fuentes de recarga, como fugas de agua de alcantarillado y fosas sépticas, las filtraciones desde los ríos contaminados, intrusión marina, y pérdidas de la red de abastecimiento de agua, entre otros. Por ello, en los acuíferos urbanos se encuentran numerosos contaminantes orgánicos. La presencia y evolución de estos contaminantes en los acuíferos depende de los mecanismos de transporte, así como de los procesos químicos y bioquímicos. Por lo tanto, una correcta evaluación de la calidad del agua subterránea requiere la evaluación de todos los procesos que afectan a estos contaminantes. Sin embargo, la cuantificación de estos procesos no es una tarea fácil. Los objetivos de la presente tesis son determinar la presencia de contaminantes orgánicos emergentes (COEs) y los procesos que los afectan en un acuífero urbano. Se ha llevado a cabo una extensa revisión bibliográfica de la presencia de COEs en las aguas subterráneas de España y la identificación de posibles fuentes de contaminación. Entre los contaminantes orgánicos que se encuentran en las aguas subterráneas, se han analizado numerosos fármacos, drogas de abuso y productos de cuidado personal en las aguas subterráneas urbanas de Barcelona. Las principales fuentes de contaminación de los COEs en zonas urbanas suelen ser las pérdidas de las redes de alcantarillado y los efluentes de las estaciones depuradoras de aguas residuales. Una vez que estos contaminantes están presentes en el acuífero, sus concentraciones se ven afectadas por numerosos procesos, incluyendo dilución, adsorción y degradación. Muchos COEs pueden ser eliminados del agua subterránea por procesos de transformación o degradación, especialmente si en el acuífero ha pasado por diferentes estados redox. Por ello, la identificación y cuantificación de los procesos redox en el acuífero es una cuestión clave. Para cuantificar estos procesos, se ha propuesto un método que utiliza las proporciones de mezcla. La aplicación de los isótopos ambientales junto con los datos hidroquímicos ha proporcionado la cuantificación isotópica de fuentes de recarga de agua subterránea y la ocurrencia de procesos redox, como la sulfato reducción, la respiración aeróbica y desnitrificación. El uso de estas metodologías ha permitido: (1) cuantificar las proporciones de mezcla en el agua subterránea y (2) evaluar los procesos redox.

The presence of anthropogenic chemical substances in water resources can affect the ecological balance of aquatic systems, as well as human health, and therefore it is necessary to control their presence in water bodies. The objective of this thesis is the development of analytical methodologies for the determination of phosphorus species and organic micropollutants in water samples. Firstly, two speciation methods for the determination of simple and condensate phosphorus oxoanions have been developed, using HPLC separation coupled to ICP-AES in one methodology and to ICP-MS in the other. Two analytical methodologies have been developed for the determination of endocrine disrupting compounds using PDMS rod extraction. The determination was carried out by GC-MS for flame retardants and by HPLC-DAD for phenolic compounds. Finally, a multiresidue method based on SPE followed by LC-MS/MS have been developed for the determination of 35 analytes, including pharmaceuticals, corrosion inhibitors, and pesticides, in water samples
La contaminació de l’aigua per compostos d’origen antropogènic pot afectar tant al medi ambient com a la salut humana i per tant és necessari controlar-ne la presència. L’objectiu de la tesi és desenvolupar metodologies analítiques per a determinació de espècies de fòsfor i microcontaminants orgànics en mostres d’aigua. En primer lloc, s’han desenvolupat dos mètodes d’especiació per a la determinació de oxoanions de fòsfor simples i condensats, mitjançant separació per HPLC acoblada a ICP-AES en un mètode, i a ICP-MS en l’altre. També s’han desenvolupat dos mètodes utilitzant extracció amb cordó de PDMS per a la determinació de compostos que actuen com a disruptors endocrins. La determinació es va portar a terme per GC-MS per als retardants de flama bromats i per HPLC-DAD per als compostos fenòlics. Finalment es va desenvolupar un mètode multiresidu basat en SPE seguit de LC-MS/MS per a la determinació de 35 analits, incloent compostos farmacèutics, inhibidors de la corrosió i plaguicides

As the population in water stressed areas increases, it is critical that wastewater treatment plants (WWTPs) continue to replenish depleted water supplies, and serve as an alternative water source. WWTPs depend on microorganisms in activated sludge to remove pollutants from wastewater and therefore an understanding of how these microorganisms are affected by various conditions and pollutants is needed. Also, as consumer products and industrial processes evolve, so do the pollutants they discharge to wastewater. In order to keep pace with these changes, understanding the effects of emerging contaminants to WWTP processes is essential. The research herein assesses microbial community dynamics of the response of nitrifying microorganisms in activated sludge to variation in ammonia concentration and evaluates the impact of engineered nanoparticles on activated sludge microbial communities and other emerging pollutants, such as antibiotic resistance genes and disinfection by-products. In order to assess microbial community dynamics of the response of nitrifying microorganisms to removal of ammonia in the feed, nitrifying activated sludge reactors were operated at various relevant temperatures and the nitrifying microbial community was characterized using activity assays and bio-molecular techniques. We found that Nitrospira spp. were the dominant nitrifying microorganisms, exhibiting stable relative abundance across multiple trials and over a range of temperatures. These results indicate the possibility of comammox bacteria in the system and highlight the complexity of nitrifying microbial communities in activated sludge relative to past understanding. Both microbial and chemical impacts of engineered nanoparticles on WWTP processes were also investigated. Metagenomic analysis of DNA extracted from activated sludge sequencing batch reactors dosed with gold nanoparticles with varied surface coating and morphology indicated that nanoparticle morphology impacted the microbial community and antibiotic resistance gene content more than surface coating. However, nanoparticle fate was controlled by surface coating more than morphology. Disinfection by-product formation in the presence of nanoparticles during WWTP disinfection was assessed using silver, titanium dioxide, ceria, and zero valent iron nanoparticles. Silver nanoparticles were found to enhance trihalomethane formation, which was attributed to the citrate coating of the nanoparticles. These studies both raise concern over the relationship between engineered nanoparticles and other emerging concerns in WWTPs, and take a step towards informing nanoparticle design in a manner that limits their associated environmental impact.
Ph. D.

Alkylphenol ethoxylates (APEs) are widely used in industrial and household products as surfactants. APEs degrade into more toxic ethoxylates, such as 4-nonylphenol (NP), which has been shown to be an endocrine disruptor and enhance the growth of tumor cells. Nonylphenol is wider spread in Pacific estuaries than originally thought. Organisms in Morro Bay, California contain some of the highest concentrations of NP reported, while containing few other contaminants. As a benthic mud-dwelling fish, the arrow goby (Clevelandia ios) may be exposed to high levels of NP due to high contaminant sequestration rates in anaerobic mud. While ecotoxicology suggests that nonylphenol is in high concentration within C. ios tissues along with tissue level biological abnormalities, the molecular effects of nonylphenol on these fish have yet to be investigated. Utilizing proteomic techniques including two-dimensional gel electrophoresis and subsequent identification via MALDI-TOF/TOF mass spectrometry, there is evidence for change in expression of proteins involved in energy metabolism, biotransformation, regulation and cellular structure.

The widespread environmental occurrence of chemical pollutants presents an ongoing threat to human and ecosystem health. This challenge is compounded by the diversity of chemicals used in industry, commerce, agriculture and medicine, which results in a spectrum of potential fates and exposure profiles upon their inevitable release into the environment. This, in turn, confounds risk assessment, where challenges persist in accurate determination of concentrations levels, as well as spatial and temporal distributions, of pollutants in environmental media (e.g., water, air, soil and sediments). Passive sampling technologies continue to gain acceptance as a means for simplifying environmental occurrence studies and, ultimately, improving the quality of chemical risk assessment. Passive samplers rely on the accumulation of a target analyte into a matrix via molecular diffusion, which is driven by the difference in chemical potential between the analyte in the environment and the sampling media (e.g., sorbent phase). After deployment, the target analyte can be extracted from the sampling media and quantified, providing an integrated, time-weighted average pollutant concentration via a cost-effective platform that requires little energy or manpower when compared to active (e.g., grab) sampling approaches. While a promising, maturing technology, however, limitations exist in current commercially available passive samplers; they are typically limited in the types of chemicals that can be targeted effectively, can require long deployment times to accumulate sufficient chemical for analysis, and struggle with charged analytes. In this dissertation, we have designed a next-generation, nanofiber sorbent as a passive sampling device for routine monitoring of both legacy and emerging organic pollutant classes in water and sediment. The polymer nanofiber networks fabricated herein exhibit a high surface area to volume ratio (SA/V values) which shortens the deployment time. Uptake studies of these polymer nanofiber samplers suggest that field deployment could be shortened to less than one day for surface water analysis, effectively operating as an equilibrium passives sampling device, and twenty days for pore water analysis in soil and sediment studies. By comparison, most commercially available passive sampler models generally require at least a month of deployment before comparable analyses may be made. Another highlight of the nanofiber materials produced herein is their broad target application range. We demonstrate that both hydrophobic (e.g., persistent organic pollutants, or POPs, like PCBs and dioxin) and hydrophilic (e.g., emerging pollutant classes including pesticides, pharmaceuticals and personal care products) targets can be rapidly accumulated with our optimal nanofibers formulations. This suggests that one of our devices could potentially replace multiple commercial passive sampling devices, which often exhibit a more limited range of analyte targets. We also present several approaches for tailoring nanofiber physical and chemical properties to specifically target particular high priority pollutant classes (e.g., PFAS). Three promising modification approaches validated herein include: (i) fabricating carbon nanotube-polymer composites to capture polar compounds; (ii) introducing surface-segregating cationic surfactants to target anionic pollutants (e.g., the pesticide 2,4-D and perfluorooctanoic acid or PFOA); and (iii) use of leachable surfactants as porogens to increase nanofiber pore volume and surface area to increase material capacity. Collectively, outcomes of this work will guide the future development of next generation passive samplers by establishing broadly generalizable structure-activity relationships. All told, we present data related to the influence on the rate and extent of pollutant uptake in polymer nanofiber matrices as a function of both physical (specific surface area, pore volume, and diameter) and chemical (e.g., bulk and surface composition, nanofiber wettability, surface charge) nanofiber properties. We also present modeling results describing sampler operation that can be used to assess and predict passive sampler performance prior to field deployment. The electrospun nanofiber mats (ENMs) developed as passive sampling devices herein provide greater functionality and allow for customizable products for application to a wide range of chemical diverse organic pollutants. Combined with advances in and expansion of the nanotechnology sector, we envision this product could be made commercially available so as to expand the use and improve the performance of passive sampling technologies in environmental monitoring studies.

The advancement in synthetic chemicals commonly referred to as contaminants of emerging concern (CECs) and their application has led to an increase in environmental pollution. The use of septic tanks otherwise referred to as onsite water treatment systems (OWTS), promotes the introduction of CECs into the environment while allowing little in the way of remediation. In order to study the impacts of CECs from OWTS as they infiltrate the environment and the aquifer system, water, sediment, and vegetation samples were collected around a sinkhole lake surrounded by residential housing using OWTSs. The main question of this research project is what is the fate of CECs from OWTSs effluent within the catchment of a sinkhole lake? Liquid chromatograph mass spectrometry was used to analyze the samples for the presence of CECs. It was found that the relative quantity of CECs in the individual constituents is dependent upon 1) the hydrophobicity and polarity of the individual compound, 2) the specific sampling site, 3) the topography gradient, and 4) for vegetation the connectedness of the sample type to the sediment. The implications derived from this study can be applied in environmental engineering, urban and suburban planning, environmental monitoring, and should be considered when residents use well water as their source of potable water.

2012 - 2013
In recent years, fate, occurrence and potential adverse effect of emerging contaminants (ECs) in the environment have received an increased attention by scientific community. The ECs are a broad category of chemicals, mainly organic compounds, that are not currently covered by existing regulations but they may be candidates for future regulation, as they may be potential threats to human health and environmental safety. The ECs are mainly substances of anthropogenic origin, introduced continuously into the environment in large quantities and distributed ubiquitously in the ecosystem, due to their wide consumption. Recent studies have indicated that most of them are environmentally persistent, bioactive, and certain have a high potential for bioaccumulation. In literature data are still too few regarding their toxicity, distribution and fate and consequently, it is not still possible to assess their real impact on the environment and on human health. For these reasons it is important to design analytical procedures for monitoring specific environmental compartments and to provide the basis for drawing conclusions about the occurrence, the persistence and hazard of ECs in the environment. Currently, the main objectives of the research and monitoring of ECs are the development of accurate and sensitive analytical methods able to simultaneously analyze multiple chemical classes of ECs in different environmental compartments with different complexity. In line with these requirements, in this PhD project, three multi-residue methods were developed for the determination of three different classes of ECs in different and complex environmental matrices... [edited by Author]
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Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG
This paper describes the use of analytical methodology for removal of emerging contaminants sulfamethoxazole (SMX), 17α-ethinylestradiol (EE2) and estrone (E1) in water samples. Was used to remove the natural adsorbents Banana and Typha angustifolia L.in raw and treated in acidic medium. The detection and quantification was performed by high performance liquid chromatography (English, HPLC). There was a characterization of bioadsorventes by Infrared Spectroscopy East and X-ray diffraction The point of zero charge of in natura banana peels and treated with HCl was approximately 5.6 and 4.3, respectively, while point of zero charge of Typha angustifolia in natura leaves and treated with HCl was approximately 5.5 and 4.5, respectively. It was determined that the pH only influences the adsorption exerted SMX, and the pH 2 and 8 were most suitable. However, we chose to work with natural pH of the mixtures of the compounds (pH = 5.25). This study used multivariate methods (full 23 factorial design and response surface) to verify the best chemical variables. The optimized and used for construction of isotherms conditions were: cattail in kind (m = 0.38 g; t = 65 min), cattail HCl (m = 0.75 g; t = 64 min), fresh banana (m = 0, 55g, t = 62 min) and banana HCl (m = 0.76g; t = 66 min). There was the determination of LD figures of merit (SMX = 0.02 mg L-1, EE2 = 0.03 mg L-1, E1 = 0.03 mg L-1) QL (SMX = 0.05 mg L-1, EE2 = 0.05 mg L-1, E1 = 0.05 mg L-1), the selectivity was determined by building fortified calibration curves with water samples. The linearity was determined by the correlation coefficient (r = 0.99), recovery values were between 59.9% and 93.6% for the compounds and accuracy of results presented at most 14.7%. The proposed methodology has been applied to real matrix with removal percentages close to 100%.
O presente trabalho descreve a utilização de metodologia analítica para remoção dos contaminantes emergentes sulfametoxazol (SMX), 17α-etinilestradiol (EE2) e estrona (E1) presentes em amostras de água. Para remoção utilizou-se os adsorventes naturais Banana e Typha Angustifolia L.in natura e tratados em meio ácido. A detecção e quantificação foi realizada por Cromatografia Liquida de Alta Eficiência (do inglês, HPLC). Fez-se a caracterização dos bioadsorventes através de Espectroscopia de Infravermelho Médio e Difração de Raios X. O ponto de carga zero da casca de banana in natura e tratada com HCl foi de aproximadamente 5,6 e 4,3, respectivamente, enquanto que o ponto de carga zero das Folhas da Typha angustifolia in natura e tratada com HCl foi de aproximadamente 5,5 e 4,5, respectivamente. Determinou-se que o pH exercia influência apenas na adsorção do SMX, sendo os valores de pH 2 e 8 os mais indicados. Contudo, optou-se por trabalhar com pH natural da misturas dos compostos (pH = 5,25). Este trabalho utilizou métodos multivariados (planejamento fatorial completo 23 e superfície de reposta) para verificar as melhores variáveis químicas. As condições otimizadas e utilizadas para construção das isotermas foram: taboa in natura (m = 0,38g; t = 65 min), taboa HCl (m = 0,75g; t = 64 min), banana in natura (m = 0,55g; t = 62 min) e banana HCl (m = 0,76g; t = 66 min). Fez-se a determinação das figuras de mérito LD (SMX = 0,02mg L-1, EE2 = 0,03 mg L-1, E1= 0,03 mg L-1), LQ (SMX = 0,05mg L-1, EE2 = 0,05mg L-1, E1= 0,05mg L-1), a seletividade foi determinada através da construção de curvas de calibração fortificadas com amostras de água. A linearidade foi determinada pelos valores de coeficiente de correlação (r = 0,99), os valores de recuperação ficaram entre 59,9% e 93,6% para os compostos e a precisão apresentou resultado de no máximo 14,7%. A metodologia proposta foi aplicada em matriz real com porcentagens de remoção próximas a 100%.

In the last decades, the scientific community has been involved in the research of new kinds of contaminants generally known as of “emerging concern” (CECs). The harmfulness of CECs, even at small concentrations as well as, property of bioaccumulation and persistence, makes them extremely dangerous for the human health. The scientific community is constantly researching about novel treatments able to achieve the removal of these contaminants. Advanced Oxidation Processes (AOPs) are considered one of the most useful treatments to achieve CECs degradation. Among the AOPs, Fenton and photo‐Fenton processes are particularly powerful, cheap and easily managed. Nevertheless, some setting requirements of Fenton processes have limited their application at industrial scale. One of the most important limits is the necessity to operate a tight control of the pH in order to avoid iron precipitation (optimum pH~2.8). Unfortunately, the optimum pH for Fenton reaction is essentially far from the normal values of the wastewater treatment plant (WWTP) effluents. Scientific community is then working on the improvement of the operating conditions of Fenton processes in order to improve the applicability in wastewater treatment. These modifications are essentially focused on the possibility to perform the treatment at circumneutral pH (Fenton and photo‐ Fenton like processes). Fenton like processes can be carried out in heterogeneous or homogeneous way according to the phase of the catalyst into the solution. In this study was firstly confirmed the suitability of Fenton based processes in recalcitrant compounds removal. Fenton, UV‐A photo‐Fenton and UV‐C photo‐Fenton were, in fact, applied for atrazine removal from secondary effluent (SE) of municipal wastewater treatment plant (MWWTP). UV‐A and UV‐C photo‐Fenton allowed remove 50% and 100% of the initial atrazine content respectively. The main objective of this thesis was then the assessment of photo‐Fenton’s suitability for recalcitrant contaminant at circumneutral pH. Thus, homogeneous photo‐Fenton like at neutral pH was applied for sulfamethoxazole (SMX) removal. In order to avoid iron precipitation, chelating agents were used to keep soluble the iron at circumneutral pH. The chelating ability of four chelating agents (ethylenediaminetetraacetic acid‐EDTA, nitrilotriacetic acid‐NTA, oxalic acid and tartaric acid) was tested. Then, once determined the optimum molar ratio L:Fe for iron chelation (1.5:1 for EDTA and NTA, 10:1 for tartaric acid and 20:1 for oxalic acid), their catalytic activity was evaluated when employed in photo‐Fenton like for SMX removal. The highest SMX percentage removal, together with the minimum chelating agents required and the better property of biodegradability and low toxicity, demonstrated the suitability of NTA for the purpose. A further study on the stability of the chelates under reaction was carried out. The operating conditions adopted for the treatment significantly influence the stability of the chelate solution. Thus, in order to proper control the parameter set up the behavior of chelates has been study under thermal, oxidative and photochemical stress. It was demonstrated as the temperature control can represent an interesting tool to extend the chelates lifetime under oxidative and photochemical stress. By adopting different H2O2 doses, a linear correlation between doses and chelate decomposition could be identified. The better suitability of UV‐A irradiation, against UV‐C and Xe lamp, to preserve the iron chelate solution was demonstrated. Moreover, the influence of the influent characteristics on the process efficiency needed to be also considered. Thus, different water matrices were used for the experiments. The efficiency of photo‐Fenton like catalyzed by Fe(III)‐NTA has been compared when applied to different aqueous matrixes (Milli‐Q water, tap water, secondary effluent wastewater and well water). It was demonstrated as the ions content, especially Ca2+ and Mg2+, significantly compromise the process of chelation. High alkalinities and organic matter, instead, mainly influenced the phase of process, when acting as radicals scavengers, reduced the amount available for SMX oxidation. Some strategies were then adopted to promote SMX removal. Between them, Mn2+ mediated photo‐Fenton like showed somehow possibility for improvement. Highest removal rate was in fact exhibited in the first minutes of reaction when adding Mn2+ to the solution in ratio molar Mn:Fe 0.5:1. The conclusive study of the thesis regarded the assessment of the Br‐ presence on the efficiency achievable in recalcitrant compounds removal when applying UV/PS/Fe2+ for removal of benzophenone‐4 (BZ4), nitrobenzene (NB), nitrobenzoic acid (NBA), atrazine (ATZ) and ampicilline (AMP). Br‐ demostrated to be a strong inhibitor in the removal of all the considered contaminants except for NB when, the removal was instead enhanced in bromide containing water.

Anthropogenic contaminants have been well documented in Southern California coastal marine waters and are largely associated with point source pollution entities like waste water treatment plants (WWTPs). This study measured known and suspected contaminants capable of disrupting physiological and endocrine functions in marine organisms. Thyroid endocrine and hepatic contaminant concentrations were measured in English Sole (Parophrys vetulus) and Hornyhead Turbot (Pleuronichthys verticalis) residing at a WWTP outfall location and two other locations, up- and down-current from the outfall. Fish from the outfall and down current locations had higher levels of contaminant compounds and altered thyroid endocrine physiology compared to the up-current reference location. Selected contaminants were significantly correlated with thyroid endocrine parameters, consistent with observed differences in contaminant levels among sites.

Objectives To evaluate the association between exposures to the main chemical contaminants released by the industry in freshwater and the rise in cancer cases among the population in China. Methods A systematic review was undertaken of the scientific literature compiled in the MEDLINE (via PubMed©), Google scholar, Web of Knowledge. The descriptors used were "cancer", "water pollution”, “industry” and “chemical", limited to studies that relevant to the research questions. Articles selected were of any type in English, from the inception of the indexing of the primary source until July 28th of 2013. With the quantitative data, Health impact assessment formulas are developed and then applied to subsequent data to make estimate. Results The search generated 306 articles, from which 10 were selected after applying the inclusion and exclusion criteria. The analysis of freshwater contaminants that attributed to industry in this review included aromatic amine, vinyl chloride, benzene, hexavalent Chromium, dioxin, and others of industrial origin. The majority of the studies find a significant link between exposure to drinking water contaminants and the increase in cancer cases, especially in the rural areas. In some of the studied populations a significant dose-response relationship was observed. Discussion After reviewing the included studies and the estimation of health impact assessment, I concluded that the association between cancer risks and industrial contamination in freshwater resources in China does indeed exist. While there are several other factors that interact the cancer risks, such as agriculture related water pollution and rapid growth of population. Taking into account that most of the articles were located in western countries, more Chinese studies are required in order to know the effect of freshwater contamination on cancer risks, in particular among those who lived in rural industry area. Conclusion This study provides the first estimated health impacts based on the relationship between industrial freshwater pollution and cancer risks, supporting decision makers to formulate public health recommendations to ensure a safer and healthier environment in the future. However, further study is critically needed for the prevention of this form of contamination.
published_or_final_version
Public Health
Master
Master of Public Health

Every year, new trace chemicals are detected in natural waters as well as treated wastewater effluents all over the world. Public health and environmental concerns have driven the development of new technologies to treat water and eliminate chemicals that may pose risk to humans and wildlife. This work presents a detailed statistical analysis on the removal of some of the most widely occurring chemicals of emerging concern in wastewater based on information available in the literature. Results show that existing water treatment processes only partially eliminate most of these contaminants. Advanced oxidation processes (AOPs) are some of the technologies that have shown the most promising results for the removal of recalcitrant organics in water. Hydrogen peroxide photolysis (UV/H₂O₂) and Fenton’s reaction are some examples of AOPs that use hydroxyl radicals to oxidize organics. The kinetics of UV/H₂O₂ and Fenton’s reaction were studied from the experimental and mathematical points of view. Comprehensive models with no adjustable parameters successfully accounted for radical initiation via photolysis of H₂O₂ or radical initiation via Fenton’s mechanism; reaction of organic targets such as p-cresol and nonylphenol with hydroxyl radicals; and recombination mechanisms, as well as changes in solution pH due to evolution of carbon dioxide because of target mineralization. The presence of radical scavengers was successfully handled by the models, suggesting that they can be generalized to the treatment of complex matrices. The UV/H₂O₂ model was also extended to solar catalyzed applications. Using an atmospheric solar irradiation model (SMART) and data from the Giovanni-NASA online database, ground-level solar spectral irradiance were obtained and used as model inputs. The kinetic model provided an excellent fit to experimental results obtained with p-cresol and fluorescein targets using no fitted parameters. The UV/H₂O₂ process was also studied in commercial flow-through UV reactors with monochromatic and polychromatic light sources. Organic targets of interest such as pcresol can be degraded effectively in these reactors at relatively low peroxide concentrations. Results with wastewater effluents suggest that these commercial reactors can be used for AOP tertiary treatment as a way to reduce dissolved organic matter and eliminate potential harmful chemicals present in the water.

In recent years, new classes of aquatic pollutants have received growing concerns from the environmentalists due to their unclear effects and increasing release into the water environment. Generally, before entering the aquatic ecosystem, many of these emerging contaminants are deemed safe active ingredients in the commercial products. This may lead to the underestimation of their potential impacts to the environment, once these substances were drained into the natural waters. So far, a wide range of emerging contaminants are still not well studied. In this thesis work, the environmental behaviors for two typical groups of emerging contaminants, which are frequently used in personal care products, are systematically probed in the aquatic ecosystem. One is the hydrophilic compounds - artificial sweeteners and the other one is the moderate hydrophobic compounds - ultraviolet (UV) filters. Acesulfame and sucralose are two of the most commonly used artificial sweeteners, which are a newly recognized class of emerging contaminants due to their widespread occurrence and extreme persistence in water environment. To date, however, their environmental behaviors, fates as well as long term ecotoxicological contributions in our water resources still remain largely unknown. In this work, a photodegradation investigation with UV/TiO2 was performed on these two artificial sweeteners, which projected their potential impacts under prolonged exposure to intensive solar irradiation. Real-time observation of the degradation profiles in both sweeteners illustrated that formation of new photo by-products under prolonged UV irradiation is highly viable. For the first time, acute toxicity for the degradates of these two sweeteners were measured and the enhancement in their ecotoxicity has been observed during the irradiation. In an attempt to neutralize this prolonged environmental threat, the feasibility of UV/TiO2 as an effective mineralization process in wastewater treatment was evaluated for both sweeteners. As a result, relatively higher removal efficiencies for acesulfame and sucralose were achieved in this study. For UV filters, a comprehensive investigation on their environmental behaviors and impacts was described in this thesis, covering the occurrence study in surface water and biota, environmental fate and their ecological risks. In the first step, an analytical method based on ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed for the simultaneous determination of twelve UV filters in the environmental waters, which achieved good sensitivity to sub-ng/L levels. To monitoring their occurrence in local marine environment, the regional distribution of these sunscreen compounds was monitored along the coastline of Hong Kong. At the same time, considering the intensive consumption of sunscreen products in hot weathers, seasonal variation of UV filters between summer and winter was taken into consideration in our occurrence study. Additionally, we also monitored their occurrence in the drinking water supply system of Hong Kong, including the source water in Dongjiang, raw water in local reservoirs and tap water collected from urban communities, to support a good management on the reliable water supply. Furthermore, the distribution results indicated that the incomplete removal of UV filters in the effluents could be a major source for their release into the environmental waters. Aiming to achieve the complete removal of such compounds, a powerful technique of ozonation was employed in this study and the preliminary operational conditions were further provided. Secondly, in order to gain a better understanding of their environmental fate in surface water, a simulative catalytic photodegradation study with UV/TiO2 were performed to investigate the photostability, phototoxicity and the transformation pathways of seven selected UV filters. During the photodegradation, several transformation products were primarily identified. Thirdly, since lipophilic sunscreens were easily accumulated in the biota, we also made efforts to monitor their occurrence in marine organisms of different species, including farmed fish, wild mussels, prawns and sea urchin, which were collected from local offshore areas. Last but not the least, according to the measured concentrations of UV filters in Hong Kong marine environment, we further performed the ecological risk assessment with the approach specific to the marine aquatic compartment, so as to provide the overall understanding on the environmental impacts of these UV filters.

Civil Engineering
Ph.D.
There are many reports indicating the presence of various emerging contaminants (ECs) in treated wastewater and other water sources. The detection of such contaminants in the environment and the ability of these contaminants to pose potential threats to the environment at very low concentrations have led to a need for more efficient treatment technologies. Cyclodextrins (CDs) have gained significant interest as an alternative adsorbent for water and wastewater treatment because of their unique physico-chemical characteristics and excellent selectivity towards organic compounds. The property of CD to form inclusion complexes with various molecules through host-guest interactions has made it a useful compound for the removal of a number of contaminants from water and wastewater. The overall goal of the study is to identify and develop a novel adsorbent for the removal of ECs of interest. The specific objectives are a) to synthesize various beta-cyclodextrin (BCD) based adsorbents by coating BCD onto different supports such as silica, filter paper, iron oxide, and zeolite, b) to perform batch and column experiments using the developed adsorbents, c) to evaluate the performance of the adsorbents in different water matrices such as MQ water, simulated wastewater in presence of humic acid, and real municipal wastewater, d) to study the regeneration potential of the adsorbents. In this research, various (BCD) based hybrid adsorbents were synthesized and their performances were evaluated based on the removal of selected ECs. At first, chemically bonded BCD onto silica particles as hybrid adsorbents were synthesized by using crosslinking agents and copolymers. Three different methods were used to synthesize 14 different BCD coated silica adsorbents. The adsorbent prepared by reacting BCD with hexamethylene diisocyanate (HMDI) as crosslinking agent and dimethyl sulfoxide (DMSO) as solvent showed best results in removing the ECs studied. The adsorbent showed more than 95% removal of 17β-estradiol (in single component) and more than 90% of most of the estrogens (mixture of 12), more than 99% of perfluorooctanoic acid (PFOA) (in single component) and more than 90% of most of the PFCs (mixture of 10), and a maximum of 90% removal in case of BPA. The adsorption capacity of the developed adsorbent was observed to be higher for the removal of 17β-estradiol and PFOA than that of commercially available activated carbon (F400) in MQ water. In order to represent the real environmental scenario, further batch experiments were conducted for the removal of two PFCs (PFOA and PFOS (perfluorooctane sulfonic acid)), 17β-estradiol, and BPA at environmentally relevant concentrations from wastewater. The adsorbent was effective in removing the ECs that were spiked in the secondary effluent of a municipal wastewater treatment plant. Furthermore, the adsorbent was successfully regenerated with methanol over four cycles without significant loss in its adsorption capacity for the removal of PFOA and estrogens. Ozonation as an alternative method of regeneration was also used and the process was also very effective in regenerating the adsorbent over seven successive cycles for the removal of BPA and 17β-estradiol. The characterization of the adsorbents using FTIR, TGA, and TEM confirmed the coating of BCD onto silica particles. The TGA results showed high thermal stability of the adsorbent (upto 300oC). As an alternative to chemical impregnation, another method of synthesis was developed where various BCD based hybrid adsorbents were synthesized by physically impregnating hydroxypropyl BCD (hpBCD) polymer onto three different supports: iron oxides, zeolite, and filter paper. The hpBCD impregnated filter papers were synthesized by solvent evaporation method and different adsorbents were synthesized by varying the polymer loadings. The polymer loading was optimized based on the performance of the modified (polymer impregnated) filter paper in terms of its filtration capacity as well as adsorption capacity to remove PFOA and BPA. The magnetic adsorbent was prepared by mixing hpBCD polymer with iron oxide (Fe3O4) particles. It was observed that by increasing the mixing time of the support (Fe3O4) with the polymer from 48 to 96 hr, the adsorption capacity of the adsorbent (hpBCD polymer coated Fe3O4) could be significantly enhanced. The same approach was also used to synthesize hpBCD polymer coated zeolite adsorbent and both adsorbents (hpBCD/zeolite and hpBCD/Fe3O4) were effective in removing the selected ECs from MQ water, simulated water, and wastewater.
Temple University--Theses

Wastewater is the main source of micropollutants and although treated in urban wastewater treatment plants (WWTPs), it can continue to contain recalcitrant substances, potentially dangerous for the health of living organisms and for the environment.It is therefore necessary to implement appropriate actions to limit its diffusion. Advanced oxidation processes (AOPs), which use hydroxyl radicals for the remediation of organic contaminants in wastewater, are highly effective innovative methods to accelerate the remediation process. AOPs can amplify their action if combined with ozone (O3) and if subjected to mono and polychromatic irradiation. The main objective of the PhD thesis was precisely to apply heterogeneous and homogeneous photolysis and photocatalysis systems in the liquid phase, for the removal of levofloxacin (LFX), a widely used antibiotic belonging to the quinolone family. Comparison of degradation kinetics, chromatographic detection of degradation products and evaluation of toxicity were some of the steps of the work. In detail, this thesis consists of six chapters. Chapter 1 provides an accurate bibliographic analysis, with the aim of giving an overview of the numerous fields of investigation connected with the topic of this thesis: a description of wastewater characteristics and of the Italian legislative decree 152/06 which regulates discharges into the environment, the organization of wastewater treatment plants, the problem of emerging contaminants, including antibiotics and in particular the class of fluoroquinolones, taken into consideration as case study of this thesis, the advanced oxidation processes (AOPs), and, finally, a brief review on the toxicity tests used in this work. Chapter 2 contains the first experiment of this thesis, which consists in the degradation of levofloxacin in distilled water, through the processes of photolysis and heterogeneous photocatalysis with titanium dioxide (TiO2). The first purpose of this chapter was to evaluate the efficiency of heterogeneous photocatalysis with TiO2, a process that in the literature is taken as a "reference" model, a very effective technique. Experimental results obtained demonstrate that this process is effective to remove levofloxacin and its by-products in almost 4 hours, and seems to follow a second-order kinetic. However, this process cannot be applied on a large scale due to of the high costs of treatment for the recovery and separation of the photocatalyst from the solution. Chapter 3 provides an evaluation of the efficiency of TiO2 as photocatalyst immobilized on the surface of a borosilicate tube for the degradation of levofloxacin through a "continuous" irradiation system, different from the "static" system used in chapter 2. In particular, not only a kinetic study was carried out, but also some toxicity tests, including the Vibrio fischeri bioluminescence inhibition test and the phytotoxicity tests on Lepidium sativum and Solanum lycopersicum, in order to better understand the potential applicability of this system. More specifically, in the case of phytotoxicity tests, the last sample of each photodegradation test carried out with the "continuous" system (with and without the TiO2-coated tube) was tested; in the case of the Vibrio fischeri assays, the most representative samples were tested, i.e. those that seemed to present the greatest number of transformation products, on the basis of the chromatograms obtained by liquid chromatography analysis. From experimental results, both photolysis and photocatalysis follow a very similar trend and degradations seem to be modelled with a first-order kinetic. The toxicity tests on Vibrio fischeri showed a low toxicity of the starting solution containing only levofloxacin. All the solutions subjected to photolysis were found to be toxic, while the solutions subjected to photocatalysis highly toxic. This unexpected result has been attributed to the probable detachment of titanium dioxide nanoparticles from the surface of the tube, whose toxicity is also being confirmed by the European Food Safety Authority (EFSA). Phytotoxicity tests confirmed these results showing an inhibition of seed germination, root elongation and growth index in both the plants tested. Chapter 4 is reported in this thesis as an under review article submitted to “Environmental Science and Pollution Research (ESPR)”. In this scientific work, levofloxacin solution was treated using hydrogen peroxide (H2O2), peroxymonosulfate (PMS) and peroxidisulfate (PDS), as oxidizing agents, which respectively provide only OH• radicals, both OH•/SO4•– radical, and SO4•– radicals. The efficiency of the three oxidizing agents was tested in different pH conditions, and the most efficient treatment (simulated radiation/PDS) was applied (and optimized) to remove levofloxacin from a simulated wastewater (SWW). In this case the main transformation products (TPs) were identified by liquid chromatography coupled with mass spectrometry, the degradation pathway was suggested and toxicity tests on Escherichia coli (LMG2092), a Gram-negative bacterium, and Micrococcus flavus (DSM1790), a Gram-positive bacterium, were performed. Experimental results demonstrated that simulated irradiation/H2O2 treatment showed less impact on LFX reduction than the combined AOPs of simulated irradiation/PMS and simulated irradiation/PDS. In contrast, PMS and PDS were able to degrade levofloxacin completely. In particular, the PMS resulted the best in phosphate buffer because it has been able to completely transform LFX into LFX N-oxide in 30 seconds, through a non-radicals mechanism. However, except for phosphate buffer, simulated irradiation/PDS system showed the best performance achieving a complete degradation of LFX after 10 minutes of irradiation in all mediums investigated. This system was successfully applied in simulated wastewater (SWW) by using three different concentrations of PDS to optimize the process, and in all cases the degradation followed a first-order kinetic. Selected samples obtained from the photocatalytic treatment of LFX in SWW with the highest concentration tested of PDS were tested on Escherichia coli and Micrococcus flavus. Both the cultures of Gram-positive and Gram-negative bacteria were not affected after the effective degradation of levofloxacin by the sulphate radical based AOP. Chapter 5 provides a further insight into the potential eco-friendliness of sulphate radicals treatment for the degradation of levofloxacin. In particular, some of the samples obtained from the treatment of levofloxacin with peroxidisulfate in distilled water were subjected to the MTT (3- (4,5-dimethylthiazol-2-yl) -2,5-diphenyltetrazolium) bioassay on human epithelial-like lung cancer cell line A549. These experimental tests were carried out in Greece, at the University of Ioannina. Experimental results demonstrated that there was no toxicity effect on the cells viability. Finally, chapter 6 provides a brief description of the internship period carried out at Hydros S.r.l. (Tito, Potenza). During this experience, I participated in the design of fumes and wastewater treatment systems, and in the optimization of the parameters of the biological process of nitrification/denitrification/oxidation present within a real wastewater treatment plant. In conclusion, I can say that this PhD thesis demonstrates that AOPs may be an alternatve eco-friendly treatment for the removal of contaminants from wastewater effluents. The experimental results tends to demonstrate that solar advanced oxidation processes has the potential to open new feasible remediation strategies for WWTPs effluent tertiary treatment before wastewater reuse in irrigation for instance. However, most investigations are done at lab-scale. For a practical view and commercial uses, much more work is necessary to switch from batch work to a large scale to find out the efficiency and ecotoxicity of the processes.

In recent years, emerging contaminants have attracted the attention of scientific community because of their occurrence and potential hazard towards natural ecosystems. Among emerging contaminants, three major classes of molecules can be identified: pharmaceuticals and personal care products (PPCPs), illicit drugs and microplastics (MPs). After anthropic use, these contaminants enter the environment through several routes, such as the sewage systems or direct input, resulting in a widespread contamination of atmosphere, water, soil and biota. Although the presence of these molecules is well-known, there is still a dearth of information regarding their potential negative effects induced towards aquatic and terrestrial non-target organisms. The majority of the studies on this topic have focused on the investigation of effects at low levels of the biological hierarchy, while limited attention has been addressed to the higher ones, such as individual, population or community level. Whilst PPCPs toxicity has been investigated for more than two decades, only in recent years ecotoxicologist focused their attention on the presence and the potential effects of illicit drugs and microplastics. Thus, the aim of this project was to investigate the effects induced by the exposure to different illicit drugs and microplastics. As in environment these contaminants could interact with a wide range of organisms, resulting in species-specific differential effects at different levels of biological organization, their effects have been investigated on six different model organisms, representative for freshwaters (Daphnia magna and Xenopus laevis), marine (Mytilus gallopovincialis, Ruditapes philippinarum and Paracentrotus lividus) and soil (Achatina reticulata) ecosystems. To reach the goal of the project, a multi-level approach based on the application of assays at sub-individual (i.e., biochemical biomarkers), tissue (i.e., histological analysis), individual (i.e., mortality, growth rate and/or swimming behavior) and, when possible, population level (i.e., reproduction) was used. Regarding illicit drugs, different experiments were planned to evaluate the effects induced by the exposure to the two most used and environmentally detected illicit stimulants, cocaine (COC) and methamphetamine (METH), to the freshwater cladoceran Daphnia magna. Moreover, considering that illicit drugs occur in aquatic ecosystems as complex mixtures, an additional experiment was planned to evaluate independent and combined effects induced by the exposure to cocaine and its main metabolite benzoylecgonine (BE), towards the Mediterranean mussel Mytilus galloprovincialis. The exposure to environmentally relevant concentrations of COC and METH induced a modulation of the oxidative status, as well as a molecule-specific effect on swimming behavior and reproduction, in D. magna. Similarly, the exposure to COC and BE, both independently and in mixture, induced an alteration of the oxidative status of Mediterranean mussels. These data suggested that illicit drugs might represent a threat for both freshwaters and marine non-target organisms. Regarding microplastics, the attention was focused on two polymers, polystyrene (PS) and polyethylene terephthalate (PET), having different chemico-physical features and environmental fate. In fact, because of its low density, PS tends to float in the water column, while in contrast high-density PET sinks and accumulates to sediments. For this reason, the administration of PS or PET MPs allowed to investigate the toxicity towards organisms with different feeding strategies and ecological role in ecosystems. The effects of regular PS-MPs were evaluated towards two freshwater organisms, namely the cladoceran Daphnia magna and the amphibian Xenopus laevis, Moreover, considering that in environment irregular shaped MPs are most common than regular ones, three experiment were planned to investigate the effects of irregular shaped PET-MPs towards two marineorganisms, the Manila clam Ruditapes philippinatum and the sea urchin Paracentrotus lividus, and a soil organism, the giant snail Achatina reticulata. The results obtained in these experiments showed that MPs were efficiently ingested by all the tested organisms, but no or limited adverse effects occurred, depending on the considered model organism. In conclusion, illicit drugs and microplastics can induce different species-specific adverse effects towards aquatic and terrestrial organisms. Moreover, the project pointed out the usefulness of using a multi-level approach to deeply study the toxicity of emerging pollutants. The integration of information coming from sub-individual and higher levels of the biological hierarchy can allow to shed a light on the propagation of the effects and to explore the complexity of contaminant-induced toxicity. Lastly, the use of different model organisms with different life-history traits and ecological role can allow to explore species-specific differences generated by the exposure to contaminants and to assess the risk of a specific class of contaminations towards the whole ecosystem.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
The oncology institutions work with medicines of high capacity teratogenic, mutagenic and carcinogenic drugs. Antineoplastic agents are referred to as emerging contaminants, and the disturbing factor is that 10 to 50% of the quantity of chemotherapeutic inserted into the human body passes by the metabolism without changes. The human excretions and disposal incorrect of anticancer drugs are a concern due because the potential risk that characterizes this category of effluent in the environment. In Goiânia, wastewater from oncological institutions do not receive specific treatment, being carried by collector networks to Municipal Sewage Treatment Stations, which has no ability to withdraw these contaminants. Given the above, this study aims to characterize the effluent from two oncology clinics and compare them with a source of domestic wastewater through physical, chemical, microbiological and ecotoxicological properties. The physical, chemical and microbiological characteristics were chosen in order to consider the resolution CONAMA 430/2011, using the methodology proposed by Standard Methods for the Examination of Water and Wastewater, and the Environmental Protection Agency, and ecotoxicological analyzes were made on two test organisms, Ceriodaphnia dubia, second the Norm 13373/2010, for chronic and acute toxicity, and Allium cepa, second Fiskejö (1985) for cytotoxicity and genotoxity. As a result, it was found that the effluent from oncology clinics, although do not present differences in physical, chemical and microbiological tests in front of domestic effluent, showed high toxicity, with 100% mortality in Ceriodaphnia dubia, and aberrations of cytotoxic and genotoxic character in Allium cepa, at concentrations in the range of 6.25% in ecotoxicological tests. This shows the importance of this treatment before reaching the collecting public.
As instituições de oncologia trabalham com fármacos de alta capacidade teratogênica, mutagênica e carcinogênica. Os antineoplásicos são denominados como contaminantes emergentes, e o fator preocupante é que de 10 a 50% da quantidade de quimioterápicos inseridos no organismo passam pelo metabolismo humano sem sofrerem alteração. As excretas humanas e despejos incorretos de drogas quimioterápicas são motivos de preocupação devido ao risco potencial que essa categoria de efluente caracteriza para o meio ambiente. No município de Goiânia, as águas residuárias provenientes de instituições oncológicas não recebem tratamento específico, sendo transportadas por redes coletoras até Estações de Tratamento de Esgoto municipais, que não tem capacidade de retirada completa desses contaminantes. Diante do exposto, este trabalho objetiva caracterizar o efluente de duas clínicas de oncologia e compará-los com um efluente de origem doméstica por meio de análises físicas, químicas, microbiológicas e ecotoxicológicas. As análises físicas, químicas e microbiológicas foram escolhidas de forma a contemplar a resolução Conama 430/2011, utilizando a metodologia proposta pelo Standard Methods for the Examination of Water and Wastewater e pela Environmental Protection Agency e as análises ecotoxicológicas foram feitas em dois organismos testes, Ceriodaphnia dubia, para análise da toxicidade crônica e aguda, segundo a Norma NBR 13373/2010 e Allium cepa para ensaio de citotoxicidade e genotoxidade, segundo Fiskejö (1985). Como resultado, constatou-se que os efluentes das clínicas de oncologia, apesar de não apresentarem diferenças físicas, químicas e microbiológicas frente ao efluente doméstico, apresentaram alta toxicidade, com mortalidade de 100% em Ceriodaphnia dubia, e aberrações de caráter citotóxico e genotóxico em Allium cepa, em concentrações na faixa de 6,25% nas análises ecotoxicológicas. O que denota a importância do tratamento deste antes de atingir a rede pública coletora.