For this work the Geo-referenced Regional Exposure Assessment Tool for European Rivers (GREAT-ER) was developed further to support river basin management and the implementation process within the EU Water Framework Directive (WFD). This was achieved through predicting spatially resolved pharmaceutical exposure concentrations in whole watersheds. A major focus of this thesis has been placed on modeling challenging watersheds, whereby challenging can refer to hydrological conditions in a watershed as well as to specific emission patterns that occur within the watersheds. The adapted methodology improves the prediction accuracy in such watersheds with GREAT-ER with respect to pharmaceutical exposures, but can also lead to improved results in other application areas. The possibilities of the latest model version are demonstrated by the extensive inclusion of local and regional conditions. In watersheds with highly variable and seasonally changing hydrological situations, GREAT-ER has been applied satisfactorily for the first time, and additionally, the developed approach can be transferred to equivalent watersheds worldwide. Comparison with monitoring data confirms that some of the adjustments have resulted in significantly improved model predictions, especially when hydrological and local conditions are specifically addressed. For example, explicit consideration of local drug emissions from hospitals or private medical practices (e.g., for x-ray contrast agents) can improve predictions at the local scale without compromising regional exposure estimates. Pharmaceuticals that have low concentrations and are barely detectable with established analytical methods can be evaluated with model simulations. In addition, current management strategies implemented under the WFD has been replicated and evaluated. These management scenarios simulated with the model allow an a priori evaluation of risk reduction measures. In combination with targeted monitoring approaches, it was shown that the GREAT-ER model can serve as a valuable tool for exposure and risk assessment of pharmaceuticals even in challenging watersheds. This and the useful combination of targeted monitoring and GREAT-ER simulations and the ability of the modeling approach to predict the expected range of spatial surface water concentrations is demonstrated by three selected journal articles.

Thanks to their adaptability and high efficiency compared to traditional carbon based surfactants, silicone surfactants are a success in many different applications, from pesticides to cosmetics, polyurethane foam, textile and car care products. In spite of those numerous applications, no analytical method existed for their trace determination in environmental samples and no data have been available regarding their environmental occurrence and fate. An analytical method for the trace analysis of trisiloxane surfactants in the aqueous environment was developed and validated. The method, based on liquid-liquid extraction and HPLC-MS/MS, reaches limits of quantification in the ng L-1 range and allows an individual quantification of every homologue of the targeted trisiloxane surfactant. The newly developed analytical method was applied to analyze 40 river water samples. The targeted trisiloxane surfactant was detected in 14 samples, between 1 ng L-1 and 100 ng L-1. The results showed that the studied trisiloxane surfactant does not ubiquitously occur in the aquatic environment in measurable concentrations, but can reach surface waters on a local scale. In order to assess the persistence of the trisiloxane surfactant in surface waters, its hydrolysis was studied in the lab, under various conditions (temperature, pH, and concentration). The half-lifes at pH 7 and 2 mg L-1 were found to be between 29 days and 55 days at 25°C and between 151 days and 289 days at 12°C. Taking only into account the hydrolysis, these results indicate that the trisiloxane surfactant could persist several weeks in surface waters. A degradation product of the trisiloxane surfactant was tentatively identified by high resolution mass spectrometry. When used as agricultural adjuvants, trisiloxane surfactants may reach the soil compartment and might further leach to ground water. The behavior of the trisiloxane surfactant on soil was therefore investigated to assess the possibility to reach ground water. With a sorption batch equilibrium method, distribution coefficients between water and soil (Kd, Koc, and Kclay) were estimated for two standard soils (loam and sandy loam) and for every homologue of the trisiloxane surfactant. The obtained values for Kd were between 15 L kg-1 and 135 L kg-1, indicating that the trisiloxane surfactant is only slightly mobile in soil. To further investigate the possibility of leaching to ground water after application on agricultural fields, the leaching in soil was simulated in the lab in a soil column. The experimental settings were designed to simulate a worst case scenario where the application of the trisiloxane surfactant is done on quartz sand and is immediately followed by a heavy rainfall. Even in these conditions, less than 0.01 % of the initially applied trisiloxane surfactant leached through 20 cm of quartz sand. Based on the Kd values and the results of the leaching in soil column, the studied trisiloxane surfactant is considered to be unlikely to leach to ground water after application as an agricultural adjuvant.

Master of Science / Department of Chemical Engineering / Larry E. Erickson / Polycarbonate products have been used extensively world wide for decades because they are lightweight, shatter-resistant and considered to be safe. Polycarbonate is a thermoplastic that is used to make compact discs, phones, lenses, and food contact products such as water bottles, baby bottles and food storage containers. For more than half century, there has been interest in polycarbonate (PC) products and the monomer bisphenol-A (BPA) because BPA can leach from food polycarbonate containers. The environmental fate for both chemicals in air, water and soil is of interest, also. To understand the fate of polycarbonate, its main degradation pathways, main degradation mechanisms and main products are reviewed. These pathways are thermal degradation, photo-degradation and hydrolysis under different conditions. Furthermore, key topics like PC degradation kinetics and PC chemical resistance are part of this comprehensive discussion. The biodegradation of BPA has been thoroughly studied. About twelve lab methods for environmental fate are summarized and reviewed to understand the “big picture” for BPA degradation. This includes screening tests, which assess the ready and inherent degradability, to simulation tests for surface waters, soils and wastewater treatment systems. The testing of all methods is examined under conditions close to the real environment fate. Furthermore, the fate distribution for BPA based on the Equilibrium Criterion Model (EQC) model is reviewed. Extensive research on polycarbonate and BPA has been conducted in the last fifty years. During this time, both chemicals have been studied and tested by industry and government agencies. The pharmacological test results from major studies indicate that consumer exposure to BPA at concentrations normally experienced in daily living does not pose a risk to human health. On the other hand, minor toxicological studies indicate potential risks to human health. Research on health and safety are continuing.

No description available.

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are naturally produced in aquatic ecosystems e.g. by algae. Many OH-PBDEs have been observed to be highly bioactive and to cause adverse effects through several pathways, e.g. via disrupting oxidative phosphorylation (OXPHOS). The levels of some OH-PBDEs have increased in Baltic biota over the past decades. This may be associated with the nutrient enrichment of the Baltic Sea, which has favored growth of some of the OH-PBDE producers. Ceramium tenuicorne has been suggested to be a producer of OH-PBDEs in the Baltic Sea, which is supported by the results presented in this thesis. The levels of OH-PBDEs were observed to fluctuate greatly in C. tenuicorne over the summer season, and to correlate with the levels of pigments in the algae. However, the observed congener pattern in C. tenuicorne questioned theories regarding the mechanism of their biosynthesis. The results indicate a much more selective pathway for biosynthesis than previously suggested for the production of OH-PBDEs. One of the most abundant OH-PBDEs in C. tenuicorne, 6-OH-BDE137, has previously been observed to be toxic to bacteria, fungi, and crustaceans. Furthermore, Baltic gammarids seemed to change their feeding preferences towards less grazing on C. tenuicorne during the production peek of OH-PBDEs in the alga. This suggests that OH-PBDEs may serve as allelochemical defense agents for C. tenuicorne. The transport and fate of OH-PBDEs through a Baltic food chain was also studied, including C. tenuicorne, Gammarus spp., three-spined stickleback (Gasterosteus aculeatus), and perch (Perca fluviatilis). A small portion of the OH-PBDEs were observed to be methylated in the alga, or by associated bacteria. The methylated OH-PBDEs biomagnified in the food chain up to perch, in which they were converted back to the OH-PBDEs via demethylation. The OH-PBDEs and their methylated counterparts were also partially debrominated in the food chain, which resulted in high concentration of 6-OH-BDE47 in the perch. This congener is the most toxic OH-PBDE with regards to OXPHOS disruption. Another biotransformation of OH-PBDEs was identified in Baltic Sea blue mussels (Mytilus edulis). High concentrations of OH-PBDEs were conjugated with lipophilic moieties, e.g. fatty acids. This increases the residence time of the OH-PBDEs in the mussels. Mussels have been suggested to conjugate steroids with fatty acids as a means to regulate hormone levels. The conjugation of OH-PBDEs to fatty acids may occur due to intrusion into this pathway. Methods were developed to include quantification of conjugated OH-PBDEs in the analysis of mussels. OH-PBDEs were also quantified in blood from Baltic Sea grey seals (Halichoerus grypus). Seals originating from the Baltic proper were observed to be more highly exposed to 6-OH-BDE47 than seals from the Gulf of Bothnia. However, the levels of OH-PBDEs were generally low. A major effort was invested into securing these results, including development of a new analytical method. Blood obtained from dead seals is a difficult matrix for quantification of OH-PBDEs, and previous attempts using an established method yielded unsatisfactory results. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.</p>

Introdução: É cada vez mais preocupante a escassez de água e a qualidade dos recursos hídricos. Nas últimas décadas diversos estudos têm apontado a presença de fármacos em água destinada ao consumo humano, caracterizando a existência de rotas de exposição que podem representar riscos para a saúde humana e meio ambiente. Devido a escassez de dados sobre o comportamento ambiental e toxicidade na exposição crônica a baixas doses a fármacos, sua ocorrência em água é uma preocupação para comunidade científica, reguladores e população. Diversos estudos recentes têm sugerido critérios para a definição de fármacos prioritários, ou seja, abordagens com componentes ou fatores que atribuem grau de relevância aos contaminantes. Devido aos altos custos e necessidade de testes adicionais, uma das alternativas propostas para avaliação do comportamento ambiental e toxicidade têm sido os modelos in silico. Objetivos: Estudar o comportamento ambiental e o potencial de toxicidade de ingredientes farmacêuticos ativos(IFAs) para fins de identificação de contaminantes prioritários por meio da aplicação de ferramentas computacionais e modelos in silico. Métodos: Foram selecionados fármacos considerados relevantes para o Brasil conforme critérios de inclusão específicos. Para os fármacos selecionados, foram realizadas buscas de dados experimentais em bases de dados de agências internacionais e predições de propriedades físico-químicas, transporte e mobilidade no ambiente, persistência, bioacumulação e toxicidade, através de modelos in silico e ferramentas desenvolvidas pela USEPA e OECD: EPISuite (v 4.1, EPA, 2011), PBT Profiler (EPA, v.2.0, 2012) TEST© - Toxicity Estimation Software Tool (v.4.1, EPA, 2012) e QSAR Toolbox (v.3.2, OECD de 2013). Foi utilizado o método de priorização do software ToxPi GUI (Carolina Center for Computational Toxicology/Universidade da Carolina do Norte), para obtenção de um Índice de Prioridade Toxicológica (Toxicological Priority Index-ToxPi) e definição dos agentes prioritários com base nos resultados das predições e dados da literatura Resultados: Foram obtidos dados e predições de propriedades físico-químicas, transporte e mobilidade no ambiente, persistência, bioacumulação e toxicidade para os 39 IFAs selecionados. Com base nestes dados, foi obtido um perfil de priorização baseado no ToxPi. Conclusão: Fármacos de diferentes classes podem apresentar características físico-químicas e de comportamento ambiental que lhes conferem alto potencial de exposição ambiental, e apesar do uso seguro nas condições posológicas, há diversos ingredientes ativos com potencial de toxicidade e que podem representar alta preocupação em exposições crônicas As ferramentas computacionais podem ser uma importante ferramenta para avaliação do comportamento ambiental e da toxicidade e identificação preliminar de agentes prioritários. / Introduction: It is a subject of more concern the shortage of water and quality of water sources. For the past decades a variety of studies have pointed the presence of pharmaceuticals in water intended for human consumption, characterizing routes of human and environmental exposure over potential health risks. Due to lack of environmental fate and toxicity data on chronic exposure to low doses of pharmaceuticals, their occurrence in water worries the scientific community, regulators and population. Many recent studies have suggested criteria for the definition of prioritary pharmaceuticals, i.e. approaches of components and factors that attach the relevance of contaminants. Also due to high costs and the necessity for additional tests, one of the alternatives suggested for the assessment of environmental fate and toxicity are in silico models. Objective: To study the environmental fate and the potential of toxicity in active pharmaceutical ingredients (API) in order to identify the prioritary contaminants through the application of computational tools and in silico models. Methods: Pharmaceuticals considered relevant to Brazil were selected according to specific inclusion criteria. For selected pharmaceuticals, experimental data searches were made in databases of international agencies and predictions of physicochemical, transport and mobility properties in the environment, persistence, bioaccumulation and toxicity, through in silico models and tools developed by the USEPA and OECD: EPISuiteTM (v 4.1, EPA, 2011), PBT Profiler (EPA, v.2.0, 2012) TEST© Toxicity Estimation Software Tool (v.4.1, EPA, 2012) and QSAR Toolbox (v.3.2, OECD, 2013). The priorization method of software ToxPi GUI (Carolina Center for Computational Toxicology/University of North Carolina) was used in order to obtain a Toxicological Priority index - ToxPi and a definition of prioritary agents based on results of the predictions and data from literature. Results: Data and predictions of physicochemical, transport and mobility properties in the environment, persistence, bioaccumulation and toxicity were obtained to the 39 selected APIs. It was obtained a profile of priorization based on ToxPi with these data. Conclusion: Different classes of pharmaceuticals may have physicochemical and environmental fate properties that give them high potential of environmental exposure, and in spite of the safe use in posological conditions, there are several active ingredients with toxicity potential that may represent high concern in chronic exposures. The computational tools may be an important tool for environmental fate and toxicity assessments in order to identify preliminary prioritary agents.

Introdução: É cada vez mais preocupante a escassez de água e a qualidade dos recursos hídricos. Nas últimas décadas diversos estudos têm apontado a presença de fármacos em água destinada ao consumo humano, caracterizando a existência de rotas de exposição que podem representar riscos para a saúde humana e meio ambiente. Devido a escassez de dados sobre o comportamento ambiental e toxicidade na exposição crônica a baixas doses a fármacos, sua ocorrência em água é uma preocupação para comunidade científica, reguladores e população. Diversos estudos recentes têm sugerido critérios para a definição de fármacos prioritários, ou seja, abordagens com componentes ou fatores que atribuem grau de relevância aos contaminantes. Devido aos altos custos e necessidade de testes adicionais, uma das alternativas propostas para avaliação do comportamento ambiental e toxicidade têm sido os modelos in silico. Objetivos: Estudar o comportamento ambiental e o potencial de toxicidade de ingredientes farmacêuticos ativos(IFAs) para fins de identificação de contaminantes prioritários por meio da aplicação de ferramentas computacionais e modelos in silico. Métodos: Foram selecionados fármacos considerados relevantes para o Brasil conforme critérios de inclusão específicos. Para os fármacos selecionados, foram realizadas buscas de dados experimentais em bases de dados de agências internacionais e predições de propriedades físico-químicas, transporte e mobilidade no ambiente, persistência, bioacumulação e toxicidade, através de modelos in silico e ferramentas desenvolvidas pela USEPA e OECD: EPISuite (v 4.1, EPA, 2011), PBT Profiler (EPA, v.2.0, 2012) TEST© - Toxicity Estimation Software Tool (v.4.1, EPA, 2012) e QSAR Toolbox (v.3.2, OECD de 2013). Foi utilizado o método de priorização do software ToxPi GUI (Carolina Center for Computational Toxicology/Universidade da Carolina do Norte), para obtenção de um Índice de Prioridade Toxicológica (Toxicological Priority Index-ToxPi) e definição dos agentes prioritários com base nos resultados das predições e dados da literatura Resultados: Foram obtidos dados e predições de propriedades físico-químicas, transporte e mobilidade no ambiente, persistência, bioacumulação e toxicidade para os 39 IFAs selecionados. Com base nestes dados, foi obtido um perfil de priorização baseado no ToxPi. Conclusão: Fármacos de diferentes classes podem apresentar características físico-químicas e de comportamento ambiental que lhes conferem alto potencial de exposição ambiental, e apesar do uso seguro nas condições posológicas, há diversos ingredientes ativos com potencial de toxicidade e que podem representar alta preocupação em exposições crônicas As ferramentas computacionais podem ser uma importante ferramenta para avaliação do comportamento ambiental e da toxicidade e identificação preliminar de agentes prioritários. / Introduction: It is a subject of more concern the shortage of water and quality of water sources. For the past decades a variety of studies have pointed the presence of pharmaceuticals in water intended for human consumption, characterizing routes of human and environmental exposure over potential health risks. Due to lack of environmental fate and toxicity data on chronic exposure to low doses of pharmaceuticals, their occurrence in water worries the scientific community, regulators and population. Many recent studies have suggested criteria for the definition of prioritary pharmaceuticals, i.e. approaches of components and factors that attach the relevance of contaminants. Also due to high costs and the necessity for additional tests, one of the alternatives suggested for the assessment of environmental fate and toxicity are in silico models. Objective: To study the environmental fate and the potential of toxicity in active pharmaceutical ingredients (API) in order to identify the prioritary contaminants through the application of computational tools and in silico models. Methods: Pharmaceuticals considered relevant to Brazil were selected according to specific inclusion criteria. For selected pharmaceuticals, experimental data searches were made in databases of international agencies and predictions of physicochemical, transport and mobility properties in the environment, persistence, bioaccumulation and toxicity, through in silico models and tools developed by the USEPA and OECD: EPISuiteTM (v 4.1, EPA, 2011), PBT Profiler (EPA, v.2.0, 2012) TEST© Toxicity Estimation Software Tool (v.4.1, EPA, 2012) and QSAR Toolbox (v.3.2, OECD, 2013). The priorization method of software ToxPi GUI (Carolina Center for Computational Toxicology/University of North Carolina) was used in order to obtain a Toxicological Priority index - ToxPi and a definition of prioritary agents based on results of the predictions and data from literature. Results: Data and predictions of physicochemical, transport and mobility properties in the environment, persistence, bioaccumulation and toxicity were obtained to the 39 selected APIs. It was obtained a profile of priorization based on ToxPi with these data. Conclusion: Different classes of pharmaceuticals may have physicochemical and environmental fate properties that give them high potential of environmental exposure, and in spite of the safe use in posological conditions, there are several active ingredients with toxicity potential that may represent high concern in chronic exposures. The computational tools may be an important tool for environmental fate and toxicity assessments in order to identify preliminary prioritary agents.

Les eaux usées traitées d'origine domestique présentent généralement une charge non négligeable en virus entériques pathogènes de l'Homme, malgré leur traitement. Afin de pouvoir à terme comparer les risques sanitaires associés à différents modes de gestion de ces eaux usées, nous avons entrepris un travail sur (i) la prévision des quantités de virus entériques excrétés à partir des données épidémiologiques relatives aux gastroentérites aiguës, (ii) le devenir environnemental de ces virus lorsque les eaux usées sont rejetées en rivière, et (iii) le devenir de ces virus lorsqu'ils sont apportées au sol par irrigation. L'étude a porté sur un bassin de collecte des eaux usées de 240 000 habitants à proximité de Clermont-Ferrand, sur les rivières Artière et Allier et la nappe alluviale de l'Allier potentiellement contaminées par les rejets d'eau usée, et sur un sol du périmètre d'irrigation réutilisant ces eaux. Les concentrations en divers virus ont été suivies sur la même période dans les eaux usées brutes et traitées, dans les eaux douces de surface et souterraine. Nous avons proposé une méthode d'estimation du nombre journalier de nouveaux cas de gastroentérites aiguës d'étiologie virale en 2015-2016 à partir de données épidémiologiques et avons combiné ces estimations à un modèle d'excrétion virale pour évaluer les quantités de virus entériques arrivant à la station d'épuration. Le devenir des virus a été modélisé en tenant compte d'un abattement en station d'épuration et de dilutions-mélanges en rivières. Le devenir des virus apportés au sol par les eaux usées traitées réutilisées en irrigation agricole a été étudié sur un sol bien représenté dans le périmètre en utilisant un virus modèle. Ce devenir a été décrit par un modèle combinant transfert, immobilisation réversible et élimination, et en distinguant eau mobile et eau immobile comme virus libres et virus adsorbés sur des colloïdes en suspension. La méthode permettant de passer de l'épidémiologie à une excrétion de virus nous a permis de bien simuler les arrivées de virus à la station d'épuration avec un pic hivernal et l'impact prépondérant des norovirus GII sur les cas de gastroentérites virales. La simulation de l'abattement en station d'épuration et des phénomènes de dilutions-mélanges en rivière permet de simuler correctement la charge virale en aval du rejet d'eaux usées, mais leur devenir ultérieur reste mal caractérisé. Apporté au sol, le virus modèle était progressivement éliminé ou immobilisé de façon irréversible avec un abattement journalier de 0.38 log10. La fraction réversiblement immobilisée pouvait être estimée par une isotherme de Freundlich. L'ajout de Mg2+ a favorisé l'immobilisation du virus comme son adsorption sur des colloïdes dispersés dans l'eau mobile. Alors que les eaux usées stérilisées n'avaient pas d'effet majeur sur l'immobilisation du virus par rapport à une solution artificielle de sol en raison d'effets antagonistes des composés organiques et des cations minéraux, l'eau souterraine riche en Mg2+ favorisait l'immobilisation des virus. Un volet plante réalisé en marge de ce travail a montré l'impact d'irrigations sur les contaminations de surface et après internalisation via les racines. Complétée et améliorée, notre étude pourrait être couplée à une évaluation quantitative des risques viraux. / Urban treated wastewaters may be heavily contaminated by human pathogenic enteric viruses that cause acute gastroenteritis, despite their treatment. In order to compare health risks of different wastewater management scenarios, we investigated (i) how to predict virus shedding from epidemiological data on acute gastroenteritis, (ii) the environmental fate of these viruses when wastewaters are discharged into rivers, and (iii) the fate of these viruses when they are brought to the soil by irrigation. Our study focused on a wastewater collection basin of 240,000 inhabitants near Clermont-Ferrand, on the Artière and Allier Rivers and the Allier alluvial groundwater potentially contaminated by wastewater discharges, and on a soil in the irrigation perimeter reusing these wastewaters. Concentrations of various viruses were monitored over the same period in raw and treated wastewaters, as well as in surface and underground freshwaters. We proposed a method based on epidemiological data to estimate the daily number of new cases of acute gastroenteritis of viral etiology in 2015-2016; and we combined these estimates with a viral shedding model to estimate the quantities of enteric viruses arriving at the treatment plant. The fate of viruses has been simulated by taking into account the removal of viruses in the treatment plant and dilution-mixing in rivers. The fate of viruses brought to the soil by treated wastewater reused in agricultural irrigation was studied on a well-represented soil in the perimeter using a surrogate virus. Its fate has been described by a model combining transfer, reversible immobilization and removal; the model distinguished between mobile and immobile waters, as well as between free viruses and viruses adsorbed on colloids in suspension. The method for switching from epidemiology to virus shedding allowed us to accurately simulate virus inflows to the treatment plant, including a winter peak and the prominent role of norovirus GII in viral gastroenteritis cases. The simulation of virus removal in the treatment plant and subsequent dilution-mixing phenomena in rivers allow correctly simulating the viral load in the river downstream of the wastewater discharge, but their subsequent fate remains poorly characterized. When brought to the soil, the surrogate virus was progressively removed or irreversibly immobilized, according to a 0.38 log10 daily removal. The reversibly immobilized fraction could be estimated by a Freundlich isotherm. The addition of Mg2+ favored the immobilization of viruses, as well as their adsorption on colloids dispersed in mobile water. While sterilized wastewater had no major effect on virus immobilization compared to artificial soil solution due to the antagonistic effects of their organic compounds and mineral cations, groundwater rich in Mg2+ favored immobilization of viruses. An additional work, complementary to this PhD, showed the impact of irrigations on vegetable surface and internalized contaminations. After improvement, our study could be coupled with a quantitative viral risks assessment.Key words: enteric virus, sewage, discharge, reuse, irrigation, environmental fate, scenarios, assessment,

Veterinary pharmaceuticals are routinely used in livestock production to treat diseases, prevent infections, and promote growth. However, the potential release of pharmaceuticals from agricultural activities has raised concerns because they may pose detrimental effects to the ecosystems and human health, for example fostering the evolution of antibiotic-resistant bacteria in the natural environment. A better understanding of the environmental fate of veterinary pharmaceuticals is critical to properly assess and mitigate their risks. This dissertation focuses on a major group of veterinary pharmaceuticals, ionophore antibiotics (IPAs), which is sold at over 4 million kilograms per year and constitutes more than one third of the total antibiotic consumption by the livestock industry in the U.S. Despite the extensive usage of IPAs, their environmental fate was not well-understood. Therefore, this study aimed at achieving a comprehensive understanding of the occurrence, persistence, and transformation of IPAs from poultry litter before and after applications to the agricultural lands. Three of the most commonly used members of IPAs were investigated in this study: monensin (MON), salinomycin (SAL), and narasin (NAR). Based on the common management practices of poultry litter, the potential abiotic and biotic transformation reactions of IPAs were examined under varying conditions relevant to the water-soil-litter systems. This dissertation consists of three sections. First, a robust analytical method was developed to quantify IPAs in various environmental compartments, especially in high organic-containing matrices such as poultry litter, and soil and runoff from litter-fertilized lands. Efforts were made to optimize the analytical method with respect to improving extraction recovery, reducing matrix effects, and validating a surrogate standard. Second, lab-scale experiments were set up to determine the chemical properties of IPAs in aqueous environments and to study the abiotic transformation of IPAs, including hydrolysis and photolysis. The results showed that IPAs are prone to hydrolytic transformation in acidic environments, which are likely to be encountered in acidic soils, alum-amended litter (alum: Al₂(SO₄)₃•12H₂O), and acidic runoff. Multiple transformation pathways were proposed based on the identified hydrolysis products. It is also noteworthy that the hydrolysis products of MON still exhibited a toxic effect on the selected microorganism (Bacillus subtilis). SAL and NAR were found to undergo direct photolysis under both UV light and sunlight irradiation. In natural water matrix, IPAs were also degraded by indirect photolysis with hydroxyl radicals generated by light-excited nitrate. Dissolved organic matter can shield IPAs from light and slow down their photolysis. Third, the biodegradation potential of IPAs was first tested in litter and soil microcosms. Factor analysis was conducted to delineate the interaction of water and temperature on IPA degradation in the litter. Litter-fertilized and non-fertilized soil microcosms were compared on the degradation of MON and SAL. Furthermore, the inhibition and biotransformation potential of IPAs were assessed under different redox conditions with litter-enriched cultures. Inhibition tests focused on examining IPAs’ impact on microbial community functions, including denitrification, sulfate-reduction, and methane production. Biodegradation tests were conducted with different electron acceptors, including oxygen, nitrate, sulfate, and organic carbons, with efforts to elucidate primary biotransformation products. On the basis of the results obtained in this study, several recommendations on litter management and IPA selection were made to help mitigate the release and transport of IPAs, as well as enhance their degradation. Overall, this study significantly improved the understanding of the environmental fate of IPAs and the obtained knowledge can aid proper selection of IPAs and management strategies in future applications to minimize the risks of antibiotic micropollutants in the environment.

Thanks to their adaptability and high efficiency compared to traditional carbon based surfactants, silicone surfactants are a success in many different applications, from pesticides to cosmetics, polyurethane foam, textile and car care products. In spite of those numerous applications, no analytical method existed for their trace determination in environmental samples and no data have been available regarding their environmental occurrence and fate. An analytical method for the trace analysis of trisiloxane surfactants in the aqueous environment was developed and validated. The method, based on liquid-liquid extraction and HPLC-MS/MS, reaches limits of quantification in the ng L-1 range and allows an individual quantification of every homologue of the targeted trisiloxane surfactant. The newly developed analytical method was applied to analyze 40 river water samples. The targeted trisiloxane surfactant was detected in 14 samples, between 1 ng L-1 and 100 ng L-1. The results showed that the studied trisiloxane surfactant does not ubiquitously occur in the aquatic environment in measurable concentrations, but can reach surface waters on a local scale. In order to assess the persistence of the trisiloxane surfactant in surface waters, its hydrolysis was studied in the lab, under various conditions (temperature, pH, and concentration). The half-lifes at pH 7 and 2 mg L-1 were found to be between 29 days and 55 days at 25°C and between 151 days and 289 days at 12°C. Taking only into account the hydrolysis, these results indicate that the trisiloxane surfactant could persist several weeks in surface waters. A degradation product of the trisiloxane surfactant was tentatively identified by high resolution mass spectrometry. When used as agricultural adjuvants, trisiloxane surfactants may reach the soil compartment and might further leach to ground water. The behavior of the trisiloxane surfactant on soil was therefore investigated to assess the possibility to reach ground water. With a sorption batch equilibrium method, distribution coefficients between water and soil (Kd, Koc, and Kclay) were estimated for two standard soils (loam and sandy loam) and for every homologue of the trisiloxane surfactant. The obtained values for Kd were between 15 L kg-1 and 135 L kg-1, indicating that the trisiloxane surfactant is only slightly mobile in soil. To further investigate the possibility of leaching to ground water after application on agricultural fields, the leaching in soil was simulated in the lab in a soil column. The experimental settings were designed to simulate a worst case scenario where the application of the trisiloxane surfactant is done on quartz sand and is immediately followed by a heavy rainfall. Even in these conditions, less than 0.01 % of the initially applied trisiloxane surfactant leached through 20 cm of quartz sand. Based on the Kd values and the results of the leaching in soil column, the studied trisiloxane surfactant is considered to be unlikely to leach to ground water after application as an agricultural adjuvant.