Cities are sources of persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), to surrounding regions and beyond. A spatially resolved, (5×5 km2), dynamic contaminant fate model named Spatially Oriented or SO-MUM was developed by coupling the fugacity based Multimedia Urban Model (MUM) (Diamond et al., 2001; Diamond et al., 2010c) and the Boundary Layer Forecast Model and Air Pollution Prediction System (BLFMAPS) which was developed at Environment Canada (Daggupaty et al., 2006). MUM was updated to contain a revised surface film sub-model which takes into account the dynamic nature of surface films. SO-MUM was illustrated by application to the City of Toronto, Canada. Spatially resolved air emissions of Σ88PCB were estimated to be ~230 (40-480) kg y-1, 280 (50-580) g y-1 km-2, and 90 (16-190) mg y-1 capita-1 and Σ26PBDE were estimated to be 28 (6-63) kg y-1, 34 (7-77) g y-1 km-2 and 11 (2-25) mg y-1 capita-1. These emissions were back-calculated from measured air concentrations and spatial chemical mass inventories yielding emission rates per mass inventory of 0.4 (0.05-1.6) and 0.1 (0.01-0.7) g kg-1inventory y-1, for Σ88PCBs and Σ26PBDEs, respectively. Approximately 30% and 16% of PCB and PBDE emissions emanate from the city’s downtown. Air advection accounted for ~95% (PCB) and ~70% (PBDE) of total air emission losses with the remaining balance depositing to the city. The metric “Urban Travel Distance” or UTD was introduced for quantifying the extent of an urban plume resulting from spatially heterogeneous emissions. For PCBs and PBDEs the UTDs were ~25 and ~30 km. The updated surface film sub-model indicated that films “bounce” higher vapor pressure semi-volatile organic compounds (SVOCs) back into the air but they act as a transient sink from air for lower vapor pressure SVOCs, thereby facilitating transport to surface waters. Model calculations suggest that if the PCB inventory is reduced, volatilization from near-shore Lake Ontario will become a net source of PCBs to air, but that neither near-shore Lake Ontario nor soil would become a significant volatilization PBDE source to air.

Cities are sources of persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), to surrounding regions and beyond. A spatially resolved, (5×5 km2), dynamic contaminant fate model named Spatially Oriented or SO-MUM was developed by coupling the fugacity based Multimedia Urban Model (MUM) (Diamond et al., 2001; Diamond et al., 2010c) and the Boundary Layer Forecast Model and Air Pollution Prediction System (BLFMAPS) which was developed at Environment Canada (Daggupaty et al., 2006). MUM was updated to contain a revised surface film sub-model which takes into account the dynamic nature of surface films. SO-MUM was illustrated by application to the City of Toronto, Canada. Spatially resolved air emissions of Σ88PCB were estimated to be ~230 (40-480) kg y-1, 280 (50-580) g y-1 km-2, and 90 (16-190) mg y-1 capita-1 and Σ26PBDE were estimated to be 28 (6-63) kg y-1, 34 (7-77) g y-1 km-2 and 11 (2-25) mg y-1 capita-1. These emissions were back-calculated from measured air concentrations and spatial chemical mass inventories yielding emission rates per mass inventory of 0.4 (0.05-1.6) and 0.1 (0.01-0.7) g kg-1inventory y-1, for Σ88PCBs and Σ26PBDEs, respectively. Approximately 30% and 16% of PCB and PBDE emissions emanate from the city’s downtown. Air advection accounted for ~95% (PCB) and ~70% (PBDE) of total air emission losses with the remaining balance depositing to the city. The metric “Urban Travel Distance” or UTD was introduced for quantifying the extent of an urban plume resulting from spatially heterogeneous emissions. For PCBs and PBDEs the UTDs were ~25 and ~30 km. The updated surface film sub-model indicated that films “bounce” higher vapor pressure semi-volatile organic compounds (SVOCs) back into the air but they act as a transient sink from air for lower vapor pressure SVOCs, thereby facilitating transport to surface waters. Model calculations suggest that if the PCB inventory is reduced, volatilization from near-shore Lake Ontario will become a net source of PCBs to air, but that neither near-shore Lake Ontario nor soil would become a significant volatilization PBDE source to air.

Endocrine disrupting chemicals in wild animals, including fish, can disrupt reproduction by causing intersexuality. Organic pollutants, specifically polychlorinated biphenyls (PCBs), have been shown to be estrogenic or anti-androgenic likely contributing to intersexuality in males. Organic pollutants persist in the environment despite being restricted for use in the United States. Bluegills, Lepomis macrochirus, play a crucial role in lake food webs as forage and sport fish and may be affected by PCBs. In the current study, male bluegills collected in 2010 from selected Illinois lakes were analyzed to quantify PCB body residues and the incidence of intersexuality (n=200). Experiments were then conducted in 2011 and 2012 to assess the reproductive output of mature males with varying PCB body residues paired with mature females containing no detectable PCB body residues held in uncontaminated 0.05-hectare research ponds (Southern Illinois University Touch of Nature Pond Facility). Lake-specific male bluegill whole-body tissue PCB body residues ranged from below reporting limit to 2 mg/kg dry weight (non-lipid normalized basis) and varied significantly among lakes (F7,32= 9.59, p<0.0001). No male intersex bluegills were found. In both reproductive experiments, abundance of young declined as male PCB body residues increased (F 4,18 = 13.28; P=0.002). Adult survival was unrelated to reproductive output. Taken together, these results suggest PCBs, which are ubiquitous in aquatic and terrestrial habitats, have the ability to alter male reproductive performance, and possibly population dynamics and community structure through reduced recruitment, in the absence of overt intersexuality.

abstract: This dissertation is focused on environmental releases from U.S. wastewater infrastructure of recently introduced, mass-produced insecticides, namely neonicotinoids as well as fipronil and its major degradates (sulfone, sulfide, amide, and desulfinyl derivatives), jointly known as fiproles. Both groups of compounds recently have caught the attention of regulatory agencies worldwide due to their toxic effects on pollinators and on aquatic invertebrates at very low, part-per-trillion levels (Chapter 1). Mass balance studies conducted for 13 U.S. wastewater treatment plants (WWTPs) showed ubiquitous occurrence (3-666 ng/L) and persistence of neonicotinoids (Chapter 2). For the years 2001 through 2016, a longitudinal nationwide study was conducted on the occurrence of fiproles, via analysis of sludge as well as raw and treated wastewater samples. Sludge analysis revealed ubiquitous fiprole occurrence since 2001 (0.2-385 µg/kg dry weight) and a significant increase (2.4±0.3-fold; p<0.005) to elevated levels found both in 2006/7 and 2015/6. This study established a marked persistence of fiproles during both wastewater and sludge treatment, while also identifying non-agricultural uses as a major source of fiprole loading to wastewater (Chapter 3). Eight WWTPs were monitored in Northern California to assess pesticide inputs into San Francisco Bay from wastewater discharge. Per-capita-contaminant-loading calculations identified flea and tick control agents for use on pets as a previously underappreciated source term dominating the mass loading of insecticides to WWTPs in sewage and to the Bay in treated wastewater (Chapter 4). A nationwide assessment of fipronil emissions revealed that pet products, while representing only 22±7% of total fipronil usage (2011-2015), accounted for 86±5% of the mass loading to U.S. surface waters (Chapter 5). In summary, the root cause for considerable annual discharges into U.S. surface waters of the neonicotinoid imidacloprid (3,700-5,500 kg/y) and of fipronil related compounds (1,600-2,400 kg/y) is domestic rather than agricultural insecticide use. Reclaimed effluent from U.S. WWTPs contained insecticide levels that exceed toxicity benchmarks for sensitive aquatic invertebrates in 83% of cases for imidacloprid and in 67% of cases for fipronil. Recommendations are provided on how to limit toxic inputs in the future. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2017

Orientador: Pedro de Magalhães Padilha / Banca: Arnaldo Alves Cardoso / Banca: André Henrique Rosa / Banca: Eny Maria Vieira / Banca: Ana Rita de Araújo Nogueira / Resumo: O presente trabalho descreve a utilização de filmes de TiO2 e TiO2 modificados com prata, preparados pelo método sol-gel, na fotodegradação de fenol e fluidos de corte. Os filmes foram imobilizados em substratos de vidro pela técnica de "dip-coating" e caracterizados por espectrofotometria no UV-Vis, difração de raios-X, microscopia eletrônica de varredura (MEV) e microscopia eletrônica de varredura de alta resolução (FEG-MEV). Dentre os filmes de TiO2, o que apresentou maior atividade foi o filme denominado TiO2 misto 24 h, que degradou em torno de 65% (pH= 5,0) dos poluentes orgânicos estudados. O filme modificado apresentou um aumento de cerca de 20% na degradação dos mesmos poluentes quando comparado ao filme de TiO2 misto 24 h. Também foi estudada a fotodegradação de fluidos de corte empregando o TiO2 P 25 em função do pH das amostras. A maior porcentagem de degradação, foi obtida em pH= 8,0 para todos os fluidos estudados. / Abstract: The present work describes the use of immobilized films of TiO2 and TiO2 modified with silver, prepared by the sol-gel method, in the photodegradation of phenol and cutting fluids. TiO2 films had been immobilized in glass substrate by the dip-coating technique and characterized by UV-visible spectroscopy, X-ray diffraction, scanning electron microscopy (SEM) and field emission gun - scanning electron microscopy (FEG-SEM). Among the TiO2 films, what presented greater activity was the one called film mixing TiO2 24 h, which degraded around 65% (pH= 5,0) of the studied organic pollutants. The modified film presented an increase of about 20% in the photodegradation of the same pollutants when compared to the film mixing TiO2 24 h. The fotodegradation of cut fluid using TiO2 P 25 as a function of pH of the samples was also studied. The greater percentage of photodegradation, was gotten in pH= 8,0 for all studied fluids. / Doutor

M.Sc. / This study was carried out to investigate the removal of organic and inorganic pollutants from water using phosphorylated and nonphosphorylated cyclodextrin polymers. The β-cyclodextrin was functionalized using various phosphorylating agents and the derivatives obtained were characterised with Fourier Transform-Infrared (FT-IR), Nuclear Magnetic Resonance (NMR) spectroscopy and mass spectrometry. These derivatives were polymerized using hexamethylene diisocyanate (HMDI) as a cross-linking agent. The polymers were obtained in good yields ranging from 72 % to 93 %. They were characterised using Fourier Transform-Infrared (FT-IR), Scanning Electron Microscopy/Energy Dispersive X-ray spectroscopy (SEM)/EDXS), Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA) to confirm the presence of phosphorus groups after polymerization. The removal of cadmium (II), chromium (III), trichlorophenol (TCP) and pentachlorophenol (PCP) was investigated in batch-mode experiments under varying conditions of pH, initial concentration and contact time. The concentration of heavy metal ions in water was determined using inductively-coupled plasma-optical emission spectroscopy (ICP-OES) and that of organic pollutants was determined using ultraviolet-visible (UV-Vis) spectroscopy. The polymers were found to adsorb up to chromium (III) better than cadmium (II) at pH 6.5. The maximum percentage removal of chromium (III) ranged between 83.9 % and 95 % whilst that of cadmium (II) ranged from 24.5 % to 39 %. There was no significant difference in the adsorption capacity of phosphorylated and phosphorus-free polymers in the removal of metals. However, phosphorylation improved the efficiency of the polymers in the removal of chlorophenols. The maximum percentage removal of TCP ranged from 17 % to 80.1 % whilst that of PCP ranged from 23 % to 77.2 %. The results obtained in this study demonstrate that the polymers are promising materials for the removal of Cr (III), TCP and PCP from water.

>Magister Scientiae - MSc / The global lack of clean water for human sanitation and other purposes has become an emerging dilemma for human beings. The presence of organic pollutants in wastewater produced by textile industries, leather manufacturing and chemical industries is an alarming matter for a safe environment and human health. For the last decades, conventional methods have been applied for the purification of water but due to industrialization these methods fall short. Advanced oxidation processes and their reliable application in degradation of many contaminants have been reported as a potential method to reduce and/or alleviate this problem. Lately, it has been assumed that incorporation of some metal nanoparticles such as magnetite nanoparticles as photocatalyst for Fenton reaction could improve the degradation efficiency of contaminants. Core/shell nanoparticles, are extensively studied because of their wide applications in the biomedical, drug delivery, electronics fields and water treatment. The current study is centred on the synthesis of silver-doped Fe₃O₄/SiO₂/TiO₂ photocatalyst. Magnetically separable Fe₃O₄/SiO₂/TiO₂ composite with core–shell structure were synthesized by the deposition of uniform anatase TiO₂ NPs on Fe₃O₄/SiO₂ by using titanium butoxide (TBOT) as titanium source. Then, the silver is doped on TiO₂ layer by hydrothermal method. Integration of magnetic nanoparticles was suggested to avoid the post separation difficulties associated with the powder form of the TiO₂ catalyst, increase of the surface area and adsorption properties. Lastly and most importantly magnetic nanoparticles upsurge the production of hydroxyl groups or reduced charge recombination. The a synthesized catalysts were characterized using Transmission Electron Microscopy, X-ray Diffraction; Infra-red Spectroscopy, Scanning Electron Microscope and Energy Dispersive Spectroscopy. Other characterization techniques includeVibrating Sample Magnetometry, Brunauer Emmett Teller analysis and Thermogravimetric analysis. The average size of the particles size is 72 nm. Furthermore the photocatalytic performances of the magnetic catalysts were assessed in comparison with that commercial titanium dioxide for the degradation of methylene blue using photochemical reactor under ultra violet light. The results showed that the photocatalytic activity was enhanced using Fe₃O₄/SiO₂/TiO₂ and Ag-Fe₃O₄/SiO₂/TiO₂ compared with that for Fe₃O₄, commercial titanium dioxide powder.

[EN] Emerging organic pollutants include a wide array of different compounds. The main characteristic of these numerous substances is that they do not need to be persistent in the environment to cause negative effects, since their high transformation and removal rates can be offset by their continuous introduction into the environment. One of the main sources of these contaminants is untreated urban wastewaters and wastewater treatment effluents. Most current wastewater treatment plants are not designed to treat these types of substances, for that reason a high portion of these pollutants can escape and enter to the urban water cycle reaching, therefore, the drinking water supply. The problem is exacerbated by the fact that many of these compounds are non-regulated. For the same reason, although concentrations are generally low (ng/l- µg/l), there are worries about their potential and unknown risks of exposures. In this sense, it is known that emerging organic pollutants can have long-lasting effects on development and reproduction, sometimes even in subsequent generations, via epigenetic mechanisms or by mutagenic effects. For all the above reasons, bioindicators such as fishes can be used as an alternative, at least complementary, to monitor their presence. In this sense, in the present thesis was studied whether zebrafish could be established as a bioindicator to detect the presence of these substances in drinking waters through the study of the effects on development and, especially, on reproduction. To accomplish this objective, four studies were carried out. Firstly, it was compared whether keeping the chorion intact or, on the contrary, permeabilized with pronase with the aim to figure out if the chorion acts as a barrier to emerging pollutants. Results from this study suggest using embryos with the chorion intact from the outset when drinking water from different sources was to be tested. In the second study were defined and narrowed down the most sensitive biological parameters to detect the effects of emerging organic pollutants on the development and, especially, on the zebrafish reproduction. Results showed that the hatching, fertility and underdeveloped rates were the most sensitive parameters. In the third study was analyzed the possible cumulative effect along two generations and/or the possible reversibility of the effects from emerging organic pollutants in zebrafish specimens reared in drinking water. Results showed a non-reversible effect on fertility rate and an alteration of sex ratio towards females in one of the studied water, although in this last case the alteration was reversible. A transgenerational alteration in the germline via epigenetic mechanism from the previous generation is proposed as the most plausible explanation to this effect. Finally, it was developed the fourth study with the aim to discriminate the effects from organic pollutants through three different pathways: male, female or water where the fertilization took place. Results showed a decrease in the fertility rate and in the hatching rate, due to an effect of the water where fertilization took place.The most plausible explanation could be the presence of substances which affect the micropyle and chorion. In addition, it was observed a decrease in the fertility rate due to a female effect, but in this case by an alteration of the oocyte quality. Taking into account the results obtained, it could be stated that the zebrafish is a suitable bioindicator to detect the effects from organic pollutants at very low concentration, when are reared in drinking water throughout their life-cycle. / [ES] Los contaminantes orgánicos emergentes incluyen una amplia gama de compuestos diferentes. La principal característica de estas numerosas sustancias es que no necesitan ser persistentes en el medio para causar efectos negativos, ya que sus altas tasas de transformación y eliminación pueden ser compensadas por su continua introducción en el medio ambiente. Una de las principales fuentes de estos contaminantes son las aguas residuales urbanas no tratadas y los efluentes de tratamiento de aguas residuales. La mayoría de las plantas de aguas residuales actuales no están diseñadas para el tratamiento de este tipo de sustancias, por ello una alta porción de estos contaminantes pueden escapar y entrar al ciclo urbano del agua alcanzando, por lo tanto, el suministro de agua potable. El problema se agrava porque muchos de estos compuestos no están regulados. Por la misma razón, aunque las concentraciones son generalmente bajas (ng/l- µg/l), se desconocen los posibles riesgos a la exposición de estos compuestos. Por otro lado, se sabe que los contaminantes orgánicos emergentes pueden tener efectos a largo plazo sobre el desarrollo y la reproducción, a veces incluso en las generaciones posteriores, a través de mecanismos epigenéticos y/o por efectos mutagénicos. Por todas las razones citadas anteriormente, los bioindicadores como los peces pueden ser usados como una alternativa, al menos complementaria, para controlar su presencia. En este sentido, en la presente tesis se estudió si el pez cebra se podría establecer como bioindicador para detectar la presencia de estas sustancias en aguas potables a través del estudio de los efectos sobre el desarrollo y, en especial, sobre la reproducción. Para lograr este objetivo, se llevaron a cabo cuatro estudios. En primer lugar, se comparó mantener el corion intacto o, por el contrario, permeabilizarlo con pronasa para averiguar si el corion actúa como una barrera a los contaminantes emergentes. Los resultados de este estudio sugieren el uso de embriones con el corion intacto desde el principio, cuando va a ser usada agua potable procedente de diferentes orígenes. En el segundo estudio se definieron y acotaron los parámetros biológicos más sensibles para detectar los efectos de los contaminantes orgánicos emergentes sobre el desarrollo y sobre la reproducción del pez cebra. Los resultados mostraron que los parámetros más sensibles fueron la tasa de eclosión, la tasa de fecundidad y la tasa de especímenes subdesarrollados. En el tercer estudio fue analizado el posible efecto acumulativo a lo largo de dos generaciones y/o la posible reversibilidad de los efectos de los contaminantes orgánicos en especímenes de pez cebra criados en aguas potables. Los resultados mostraron un efecto irreversible en la tasa de fecundidad y una alteración de la proporción sexual hacia hembras en una de las aguas estudiadas, aunque en este último caso la alteración fue reversible. Una alteración transgeneracional en la línea germinal a través de mecanismos epigenéticos de la generación anterior se propone como la explicación más plausible para este efecto. Finalmente, se desarrolló el cuarto estudio con el objetivo de discriminar los efectos de los contaminantes orgánicos a través de tres vías diferentes: macho, hembra o agua donde la fertilización se llevó a cabo. Los resultados mostraron una disminución de la fertilidad y la tasa de eclosión, debido a un efecto del agua donde la fertilización tuvo lugar. La explicación más plausible podría ser la presencia de sustancias que afectan al micropilo y al corion. Además, se observó una disminución en la tasa de fertilidad debido a un efecto hembra, pero en este caso por una alteración de la calidad de los ovocitos. Teniendo en cuenta los resultados obtenidos, se puede afirmar que el pez cebra es un bioindicador adecuado para detectar los efectos de los contaminantes orgánicos en concentraciones muy bajas, cuando / [CAT] Els contaminants orgànics emergents inclouen una àmplia gamma de compostos diferents. La principal característica d'aquestes nombroses substàncies és que no necessiten ser persistents en el medi per causar efectes negatius, ja que les seves altes taxes de transformació i eliminació poden ser compensades per la seva contínua introducció en el medi ambient. Una de les principals fonts d'aquests contaminants són les aigües residuals urbanes no tractades i els efluents de tractament d'aigües residuals. La majoria de les plantes d'aigües residuals actuals no estan dissenyades per al tractament d'aquest tipus de substàncies, per això una alta porció d'aquests contaminants poden escapar i entrar al cicle urbà de l'aigua aconseguint, per tant, el subministrament d'aigua potable. El problema s'agreuja perquè molts d'aquests compostos no estan regulats. Per la mateixa raó, encara que les concentracions són generalment baixes (ng/l- µg/l), es desconeixen els possibles riscos a l'exposició d'aquests compostos. D'altra banda, se sap que els contaminants orgànics emergents poden tenir efectes a llarg termini sobre el desenvolupament i la reproducció, de vegades fins i tot en les generacions posteriors, a través de mecanismes epigenetics i/o per efectes mutagenètics. Per totes estes raons, els bioindicadors com els peixos poden ser usats com una alternativa, almenys complementària, per controlar la seva presència. En aquest sentit, en la present tesi es va estudiar si el peix zebra es podria establir com a bioindicador per detectar la presència d'aquestes substàncies en aigües potables a través de l'estudi dels efectes sobre el desenvolupament i, especialment, sobre la reproducció. Per aconseguir aquest objectiu, es van dur a terme quatre estudis. En primer lloc, es va comparar mantenir el cori intacte o, per contra, permeabilitzar-lo amb pronasa per esbrinar si el cori actua com una barrera als contaminants emergents. Els resultats d'aquest estudi suggereixen l'ús d'embrions amb el cori intacte des del principi, quan va a ser usada aigua potable procedent de diferents orígens. En el segon estudi es van definir i van fitar els paràmetres biològics més sensibles per detectar els efectes dels contaminants orgànics emergents sobre el desenvolupament i sobre la reproducció del peix zebra. Els resultats van mostrar que els paràmetres més sensibles van ser la taxa d'eclosió, la taxa de fecunditat i la taxa d'espècimens subdesenvolupats. En el tercer estudi es va analitzar el possible efecte acumulatiu al llarg de dues generacions i/o la possible reversibilitat dels efectes dels contaminants orgànics emergents en espècimens de peix zebra criats en aigües potables. Els resultats van mostrar un efecte irreversible en la taxa de fecunditat i una alteració de la proporció sexual cap a femelles en una de les aigües estudiades, encara que en aquest últim cas l'alteració va ser reversible. Una alteració transgeneracional en la línia germinal a través de mecanismes epigenètics de la generació anterior es proposa com l'explicació més plausible per a aquest efecte. Finalment, es va desenvolupar el quart estudi amb l'objectiu de discriminar els efectes dels contaminants orgànics a través de tres vies diferents: mascle, femella o aigua on la fertilització es va dur a terme. Els resultats van mostrar una disminució de la fertilitat i la taxa d'eclosió, a causa d'un efecte de l'aigua on la fertilització va tenir lloc. L'explicació més plausible podria ser la presència de substàncies que afecten al "micropilo" i al cori. A més, es va observar una disminució en la taxa de fertilitat a causa d'un efecte femella, però en aquest cas per una alteració de la qualitat dels ovòcits. Tenint en compte els resultats obtinguts, es pot afirmar que el peix zebra és un bioindicador adequat per detectar els efectes dels contaminants orgànics en concentracions molt baixes, quan es crien en l'aigua potable / Martínez Sales, MI. (2016). ZEBRAFISH AS BIOINDICATOR OF EPIGENETIC FACTORS PRESENT IN DRINKING WATER THAT MAY AFFECT DEVELOPMENT AND REPRODUCTIVE FUNCTION [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/64081 / TESIS

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