La question de la contamination du milieu marin par les produits pharmaceutiques et de soin personnel (PPCP) se pose depuis une vingtaine d’années seulement. La principale source de contamination de ces substances se révèle être les stations d’épuration (STP) rejetant directement ou non leurs effluents traités en mer, les traitements employés dans ces stations n’étant pas toujours efficaces pour éliminer ces substances. Le premier objectif de la thèse a été d’évaluer l’état des lieux de la contamination du milieu marin par les PPCP, par une étude approfondie de la littérature, et ce dans les différents compartiments du milieu marin, l’eau de mer, les sédiments et les organismes. La contamination du milieu marin est évaluée principalement par des mesures ponctuelles in situ des concentrations des molécules. Cependant, pour obtenir une vision globale de la répartition de ces contaminants, la multiplication des campagnes d’échantillonnage rend cette méthodologie coûteuse en temps et en matériel. Des approches basées sur la modélisation des concentrations environnementales dans le milieu, par la détermination de concentrations environnementales prévisibles (PEC), peuvent être utilisées en complément ou à la place des mesures in situ. Les PEC constituent la première étape de l’évaluation du risque environnemental (ERE) et permettent d’évaluer l’exposition des organismes non cibles à ces substances. Cependant, pour être précise, cette estimation des concentrations doit être affinée en tenant compte des caractéristiques propres au site étudié. Le deuxième objectif de la thèse a été de proposer une méthodologie de calcul des PEC affinée de molécules pharmaceutiques et de leurs métabolites en zone côtière à l’aide d’un modèle hydrodynamique adapté. Deux molécules modèles ont été choisies, la carbamazépine et la venlafaxine. Afin d’évaluer le risque posé par les molécules pharmaceutiques, il est nécessaire de connaître les effets de ces substances sur les organismes. Actuellement, peu de données sont disponibles sur les organismes marins, contrairement aux organismes d’eau douce. De plus, l’ERE est bien souvent basée sur les résultats de tests standardisés, étudiant les effets à l’échelle de l’individu à des concentrations plus élevées que dans l’environnement. D’autres tests, effectués à des niveaux d’organisation biologique plus bas, sont plus sensibles à des faibles concentrations d’exposition, et sont donc plus pertinents en milieu marin. Le dernier objectif de la thèse a été d’étudier les effets du diclofénac sur la production des prostaglandines, cibles du mécanisme d’action connu de cette molécule, chez des moules méditerranéennes exposées. / The last twenty years, the issue of PPCP contamination of the marine environment caused a growing concern among scientific community. PPCP enter the environment mainly through wastewater treatment plants (WTP), not able to remove completely these substances. The first objective of the thesis was to assess the current state of knowledge on the PPCP occurrence in the different compartments of the marine environment (seawater, sediments and organisms) through a literature review. The contamination of the marine environment is generally assessed by “one-time” measures in situ. However, such monitoring campaigns are time-consuming and costly. Some approaches based on the determination of the predicted environmental concentrations (PEC) could be applied alternatively or complementarily to in situ measures. The PEC calculation is the first step of environmental risk assessment (ERA), to assess the exposure of non target organisms to these substances. However, this estimation needs to be refined to be accurate, by integrating site-specific information. The second aim of the thesis was to propose refined PEC calculation methodologies of pharmaceuticals and their metabolites in a coastal zone using an adapted hydrodynamic model. Two model compounds were chosen, carbamazepine and venlafaxine. In order to assess the environmental risk of pharmaceuticals, it is needful to assess their effects on organisms. Nowadays, few ecotoxicological data are available on marine organisms, contrary to freshwater organisms. Regulatory concept of ERA is often based on a set of short term standard tests carried out at high concentrations. Other tests, implemented at lower organizational levels, are more sensitive to low exposure levels and are more relevant for the marine risk assessment. The last objective was to study the effects of diclofenac on PG production, based on its mode of action, on marine mussels exposed.

La contamination des milieux côtiers par des contaminants émergents est une préoccupation sociétale récente ce qui explique le peu de données disponibles, à ce jour dans ce milieu. Pourtant, certains de ces contaminants sont susceptibles de générer des effets écotoxiques sur les organismes aquatiques du milieu marin. Trois voies d’introduction de contaminants dans l’environnement marin sont communément identifiées : l’apport indirect depuis les bassins versants à travers les fleuves côtiers et les apports directs soit lors d’activités récréatives, soit par le rejet d’effluents d’eaux usées. Ce travail de thèse s’est focalisé sur les apports directs. L’objectif principal de cette thèse a été d’établir un état des lieux de la contamination du milieu marin par les pharmaceutiques et les produits de soin (PPCP) et d’évaluer leur apport par les activités récréatives et les eaux usées. Pour évaluer l’impact des activités de baignade sur la contamination marine, des analyses d’occurrence de filtres UV, substances principalement contenues dans les crèmes solaires ont été réalisées en zones côtières dans l’eau de mer et dans des organismes aquatiques, les moules. Les résultats de ces mesures ont montré des variations saisonnières et intra journalières de la concentration de filtres UV dans le milieu côtier, confirmant l’apport de ces substances par les activités récréatives. Le traitement par les stations d’épuration (STEP) ne permet pas une élimination complète de certains PPCP persistants. Pour évaluer l’impact des effluents de STEP sur les milieux récepteurs, des molécules pharmaceutiques et leurs formes conjuguées ont été recherchées dans des effluents domestiques et d’hôpitaux et en entrée et sortie de STEP. Les concentrations faibles de molécules conjuguées retrouvées en sortie de STEP ont démontré que les molécules conjuguées ne représentaient pas des marqueurs pertinents de la contamination marine par les eaux usées. Cependant les eaux usées traitées de manière partielle sont parfois rejetées directement dans le milieu marin via des émissaires en mer d’où l’importance de l’évaluation de cet apport. Les données acquises sur l’occurrence d’une molécule pharmaceutique, la venlafaxine et ses produits de transformation en sortie d’émissaire en mer a permis de confirmer la présence de ses molécules dans le milieu marin et l’importance d’inclure les métabolites dans les programmes de surveillance de la contamination marine. / Contamination of coastal environments by emerging contaminants is a recent societal concern, explaining the lack of data available today in this environment. However, some of these contaminants are likely to cause ecotoxic effects on aquatic organisms in the marine environment. Three ways of contaminants introduction into the marine environment are commonly identified: indirect inputs with catchments through coastal rivers and direct inputs through recreational activities and through the wastewater effluents. This work focused on direct contributions. The main objective of this thesis was to assess the current state of the contamination of the marine environment by pharmaceuticals and care products (PPCP) and to evaluate their contribution by the recreational activities and the wastewater releases. In order to assess the impact of bathing activities on marine contamination, occurrence studies of UV filters, substances mainly contained in sunscreens, have been carried out in coastal areas in seawater and in aquatic organisms and more precisely in mussels. The results showed seasonal and intra-day variations in the concentration of UV filters in the coastal environment, confirming that recreational activities contribute to introduce these substances in marine environment. Wastewater treatment plants (WWTP) does not allow the complete elimination of some persistent PPCPs. To evaluate the impact of WWTP effluents on the receiving environment, pharmaceuticals and their conjugated forms were analyzed in domestic and hospital effluents and in WWTP influents and effluents. The low concentrations of conjugated found in WWTP effluents demonstrated that the conjugated were not represented relevant markers of marine contamination by wastewater. However, partially treated wastewater is sometimes discharged directly into the marine environment via marine outfalls, hence the importance of assessing this input. The data on the occurrence of a pharmaceutical molecule, venlafaxine and its transformation products at marine outfall, confirmed the presence of its molecules in the marine environment and the importance of including metabolites in monitoring programs of marine contamination.

Pharmaceutical and personal care products (PPCPs) triclosan and nonylphenol, were investigated throughout wastewater treatment in a publicly owned treatment works (POTW). Both compounds react quickly upon chlorination under laboratory conditions, transforming into mono and dichlorinated species. A novel quantitative analytical method employing mass spectrometry was demonstrated on Delaware POTW wastewater samples. Specific transformation products were not detected and the concentration of precursor analytes was not found to be statistically different after treatment. Under tertiary chlorination conditions, transformation products are not produced. ESI-MS was used to explore triply charged, highly hydrated lanthanide ions and charge reduction was directly observed in the MS collision cell. This process proceeded via proton transfer, proved by a strong correlation between the minimum number of water molecules required to stabilize the Ln3+ and the first hydrolysis constant (R2=0.92). The effect of different solvents on the surface activity of ions under electrospray ionization (ESI) was investigated using dilute ionic liquids and the relative surface activity of a given pair of ions could be reversed by moving from a relatively polar solvent to a relatively non-polar one. / Graduate

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Large and ever-increasing numbers of chemicals, including large quantities of a broad spectrum of organic compounds are used in modern society. More than 30 000 of the more than 100 000 chemical substances registered in the EU are estimated to be daily used, of which many will be discharged into the waste-streams handled by municipal sewage treatment plants (STPs). The main objective of the work underlying this thesis was to improve understanding of the relationships between the characteristics of sewage contaminants and their sewage treatment efficiency. Further objectives were to examine the relationships between socio-economic uses of chemicals and sludge quality, and the effects of regulatory actions on sludge quality. The quality of the sewage sludge and the levels and distribution patterns of the sludge contaminants, both within and between the STPs, seem to remain quite constant over time. The overall findings indicate that the levels of contaminants in sewage sludge seem to be largely independent of the location, size and treatment techniques applied at the STPs, and generally, of the types of human activity connected to them. The total and relative concentrations of the sludge contaminants were found to be fairly constant on a dry weight basis, with some exceptions, indicating that the pollutants originate from broad usage and diffuse dispersion rather than (industrial) point sources. The proportion of cyclic methylsiloxanes recovered in sludge seems to strongly depend on their vapour pressure, which decreases with the number of siloxane units. The higher water solubility and biodegradability of organophosphorus flame retardants and plasticizers than polybrominated diphenyl ethers (PBDEs) were also reflected in lower percentages (relative to their national use) found in sludge. Significant time-trends in levels of a-third of the sludge contaminants included in the annual national measurement program were detected over a period of seven years. The levels of compounds displaying significant time-trends generally decreased following declines in the quantities used nationally. However, a quarter of these compounds showed increasing trends, of which the linear methylsiloxanes followed the same trend as used quantities. The decaBDE was also found to be increasing in sludge, probably as a result of the phase-out of pentaBDE and octaBDE. The results indicate that the STP removal efficiency of anthropogenic substances, in Sweden, is generally good and that STPs, at least those in cold climates, do not efficiently remove certain polar contaminants. A non-targeted screening (by use of environmetrics and GCxGC-TOFMS) was performed and found to fulfil the objective to assess the STP removal efficiency, with emphasis to systematically analyse which compound classes that are not efficiently removed using the current STP technology. Many polar aromatic compounds were identified to be poorly removed. The acquired data on levels, profiles and variations in sludge contaminants (sludge quality) extend both the available information and understanding of the degree and nature of sludge contamination, which should help attempts to track changes in its contaminants and revisions, if necessary, of guideline values. This thesis also contributes to improve the knowledge base for the development of future STP technologies, and that archived sewage sludge can be used in retrospective analysis of new and emerging pollutants.