De nos jours, l’évaluation de la qualité d’un milieu naturel repose traditionnellement sur des analyses ciblant des molécules déjà connues pour être biologiquement actives. Cependant ces molécules ne reflètent que partiellement les effets biologiques observés et la complexité des matrices environnementales. Par ailleurs, les contaminants dans l’environnement subissent des phénomènes de dégradation (hydrolyse, biodégradation, photodégradation). Ces processus peuvent conduire à la génération de produits de transformation qui sont encore trop peu pris en compte dans l’évaluation du risque, alors qu’ils sont susceptibles d’occasionner des effets toxiques plus importants que les molécules mères. L’impact écotoxicologique de ces mélanges nécessite préalablement l’obtention d’une vision globale quant à la présence et au devenir de ces molécules.Dans ce contexte, ces travaux appliquent une méthodologie pluridisciplinaire afin d’identifier des molécules préoccupantes et pertinentes à surveiller. Pour cela, ce travail s’appuie sur des analyses ciblées ultra-traces, des outils bioanalytiques, et des analyses non ciblées, qui ont été appliqués sur des échantillons environnementaux ou issus d’études en laboratoire mimant l’évolution des matrices environnementales. Au final, cette étude a permis : (1) d’identifier des molécules préoccupantes en estuaire de Seine sur la base de leur occurrence et de leur persistance, (2) d’identifier de nouveaux produits de transformation et (3) d’identifier les molécules responsables d’activités biologiques dans des matrices très complexes. / To date, environmental risk assessment is based on a restricted number of molecules assessed by targeted chemical analyses. However, this approach give a partial picture of co-occurrence of known and unknown compounds. Moreover, in the aquatic environment, chemicals are not completely mineralized and are subject to abiotic and biotic processes. Transformation products (TPs) can be more toxic and more persistent than the parent compound. However, TPs are not typically included in classical monitoring and risk assessment. Because of complexity and variability of these matrices and the restricted number of molecules focused in targeted chemical analyses, selection of relevant molecules for environmental monitoring is often laborious.In this context, an integrative approach was used in order to identify chemicals of concern for a classical monitoring. This work has been realized on environmental complex samples and on laboratory-generated samples. A combination of targeted, non-targeted analyses and in vitro bioassays was performed and allowed to: (1) identify polar chemical of concern in the Seine estuary on the basis of occurrence and persistence, (2) identify new transformation products and (3) identify compounds responsible of biological activity observed in complexes matrices.

Extensive amounts of pharmaceuticals and personal care products (organic emerging pollutants) are introduced into the environment mainly through wastewater treatment plants discharges either effluent wastewater reaching into the aquatic environment or sewage sludge which is spread onto agricultural land. These compounds are not regulated and their negative effects on humans and wildlife are unknown. One of the main challenges of analytical chemistry is to develop selective and sensitive methods for the detection and quantitation of pharmaceuticals and personal care products and their transformation products in complex matrices. The research presented in the thesis is focused on the development of new methods based on the use of hollow fiber liquid- phase microextraction (HF-LPME) technique and liquid chromatography for the determination of some of the most consume pharmaceuticals and personal care products in wastewaters, environmental waters and sewage sludge. / Tones de substàncies biològicament actives són alliberades contínuament al medi ambient, a través de la descàrrega d’aigües residuals als medis aquàtics o de biosòlids en l’agricultura. La presència d’aquestes substàncies (contaminants emergents) en el medi ambient ha generat una gran preocupació perquè es desconeix com actuen i quins són els mecanismes implicats en la seva transformació i/o transport. Un dels reptes de la química analítica és dissenyar mètodes selectius i sensibles per a la determinació de contaminants emergents en matrius complexes. La recerca presentada en aquesta tesi es centra en el desenvolupament de nous mètodes analítics basats en l’ús de la microextracció enfase líquida amb fibra buida (HF-LPME) i la cromatografia líquida per a la determinació d’alguns fàrmacs i productes d’higiene personal en aigües residuals, medis aquàtics i biosòlids.

The development of analytical methods for emerging contaminants creates many unique challenges for analytical chemists. By their nature, emerging contaminants have inherent data gaps related to their environmental occurrence, fate, and impact. This dissertation is a compilation of three studies related to method development for the structural identification of emerging contaminants, the detection and quantification of chemicals used in unprecedented quantities and applications, and the extraction of compounds from complex matrices where the solvent-solute-matrix interactions are not completely understood. The three studies present analytical methods developed for emerging contaminants in complex matrices, including: fluorochemical surfactants in aqueous film-forming foams, oil dispersant surfactants in seawater, and fullerene nanomaterials in carbonaceous solids. Aqueous film-forming foams, used in military and commercial firefighting, represent environmentally-relevant commercial mixtures that contain a variety of fluorochemical surfactants. Combining the surfactant-selective ionization of fast atom bombardment mass spectrometry with high resolution mass spectrometry, chemical formulas for 11 different fluorochemical classes were identified. Then AFFF-related patents were used to determine the structures. Of the eleven classes of fluorochemicals, ten have little, if any, data on their environmental occurrence, fate, and potential impacts in the peer-reviewed literature. In addition, nine of the identified classes had either cationic or zwitterionic functionalities and are likely to have different transport properties compared to the well-studied anionic fluorochemicals, such as perfluorooctanoate. After the Deepwater Horizon oil spill in the summer of 2010, one of the emergency response methods for the mitigation of the oil's environmental impact was the use of unprecedented amounts of oil dispersant to break down the oil slick and encourage biodegradation. This event illustrated the need for rapid analytical method development in order to respond to the potential environmental disaster in a timely manner. Using large volume injection liquid chromatography with tandem mass spectrometry, an analytical method was developed for the trace analysis of the multiple dispersant surfactant classes and the potential degradation products of the primary surfactant. Limits of detection ranged from 49 ��� 3,000 ng/L. The method provided excellent recovery (86 ��� 119%) and precision (10 ��� 23% RSD), while also accommodating for the high salinity of seawater samples and analyte contamination. Despite the fact that fullerene nanomaterials have been studied for almost three decades, research is still being conducted to fully understand the environmental properties of these materials. Previous studies to extract fullerenes from environmental matrices have resulted in low efficiency, high variability, or the extraction efficiencies have gone unreported. Extraction by ultrasonication with toluene and 1-methylnaphthalene increased the recovery 5-fold of a spiked, isotopically-labeled C������ surrogate from carbon lampblack as compared to that of the conventional approach of extracting with 100% toluene. The study revealed the importance of evaluating experimental variables such as extraction solvent composition and volume, and sample mass, as they have a significant impact on the quantitative extraction of fullerenes from environmental matrices. / Graduation date: 2013 / Access restricted to the OSU Community at author's request from Aug. 15, 2012 - Aug. 15, 2013

Indiana University-Purdue University Indianapolis (IUPUI) / Numerous studies have investigated the fate of pollutants in riparian buffers, but few studies have focused on the control of multiple contaminants simultaneously in riparian zones. To better understand what drives the biogeochemical cycles of multiple contaminants in riparian zones, a 19-month study was conducted in riparian buffers across a range of hydrogeomorphic (HGM) settings in the White River watershed in Indiana. Three research sites [Leary Webber Ditch (LWD), Scott Starling (SS) and White River (WR)] with contrasting hydro-geomorphology were selected. We monitored groundwater table depth, oxidation reduction potential (ORP), dissolved oxygen (DO), dissolved organic carbon (DOC), NO3-, NH4+, soluble reactive phosphorus (SRP), SO42- , total Hg and methylmercury (MeHg). Our results revealed that differences in HGM conditions translated into distinctive site hydrology, but significant differences in site hydrology did not lead to different biogeochemical conditions. Nitrate reduction and sulfate re-oxidation were likely associated with major hydrological events, while sulfate reduction, ammonia and methylmercury production were likely associated with seasonal changes in biogeochemical conditions. Results also suggest that the LWD site was a small sink for nitrate but a source for sulfate and MeHg, the SS site was a small sink for MeHg but had little effect on NO3-, SO42- and SRP, and the WR was an intermediate to a large sink for nitrate, an intermediate sink for SRP, and a small source for MeHg. Land use and point source appears to have played an important role in regulating solute concentrations (NO3-, SRP and THg). Thermodynamic theories probably oversimplify the complex patterns of solute dynamics which, at the sites monitored in the present study, were more strongly impacted by HGM settings, land use, and proximity to a point source.