Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-03-27T15:24:14Z No. of bitstreams: 1 Tese de Maria Andréa da Silva.pdf: 2665297 bytes, checksum: 5d7613a0f2ca73967ba58859bd84a7f5 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-04-15T14:01:43Z (GMT) No. of bitstreams: 1 Tese de Maria Andréa da Silva.pdf: 2665297 bytes, checksum: 5d7613a0f2ca73967ba58859bd84a7f5 (MD5) / Made available in DSpace on 2013-04-15T14:01:43Z (GMT). No. of bitstreams: 1 Tese de Maria Andréa da Silva.pdf: 2665297 bytes, checksum: 5d7613a0f2ca73967ba58859bd84a7f5 (MD5) Previous issue date: 2012 / CAPES / Neste trabalho foram usados amostradores passivos POCIS e Chemcatcher com a técnica de Extração em Fase Sólida SPE e a Cromatografia Gasosa acoplada à Espectrometria de Massas, GC/MS. O objetivo geral do trabalho foi desenvolver uma metodologia para os amostradores passivos POCIS e Chemcatcher para a análise de agrotóxicos em água superficial e os objetivos específicos: estudar o desempenho dos amostradores passivos através de desenvolvimento de metodologia SPE e GC/MS, calibrar em laboratório, determinando as taxas de amostragem e implantar os amostradores na região do Vale do São Francisco, em Petrolina, Pernambuco. O sorvente usado na SPE foi à base de sílica modificada (C18) e os solventes foram metanol e diclorometano. A validação do método foi feita para disco e cartucho, onde, o LD para disco variou de 0,0080 a 0,096 μg L-1 e para cartucho 0,0070 a 0,43 μg L-1, o LQ de 0,026 a 0,32 μg L-1 e 0,024 a 1,4 μg L-1, respectivamente. Os percentuais de recuperação para o disco variaram de 70,0 a 119,9 para disco e 70,2 a 119,7 para cartucho. Os desvios-padrões para o disco variaram de 2,86 a 19,9 e para cartucho 1,89 a 19,8. A repetitividade com 95% de confiança para disco variou de 0,0070 a 0,089 e 0,0070 a 0,41 para cartucho. As taxas de amostragem para os dispositivos POCIS e Chemcatcher variaram, respectivamente: para 1 dia: sem membrana, 0,105 a 0,693 L dia-1 e 0,100 a 0,757 L dia-1; com membrana PES < 0,0080 a 0,069 L dia-1 e <0,0080 a 0,050 L dia-1; com malha de nylon 0,103 a 0,333 L dia-1 e 0,093 a 0,33 L dia-1. Para 3 dias com renovação de água: com membrana PES < 0,011 a 0,083 L dia-1 e < 0,011 a 0,042 Ldia-1; com malha de nylon 0,077 a 0,80 L dia-1 e 0,074 a 0,95 L dia-1. Durante três dias sem renovação de água: com malha de nylon 0,067 a 0,28 L dia-1 e 0,064 a 0,31 L dia-1. Taxas de amostragem teóricas foram calculadas em função dos coeficientes de difusão dos pesticidas em água e do desenho e configuração dos dois modelos de amostradores passivos. As taxas de amostragem para o POCIS e Chemcatcher variaram respectivamente de 0,11 a 0,23 L dia-1 e 0,077 a 0,16 L dia-1. Considerando-se um ambiente aquático com baixa contaminação (ao nível do LQ do método) o tempo de exposição dos amostradores para captar os pesticidas pode variar, a depender do composto, de 3 a 9 dias para o POCIS e de 4 a 10 dias para o Chemcatcher. O desempenho dos dois modelos pode ser considerado semelhante e seu uso com a técnica SPE e GC/MS é uma alternativa para a metodologia de determinação de pesticidas em água, uma vez que o procedimento é simples, rápido e econômico. / Salvador

In this thesis occurrence of emerging pollutants in different compartments of aquatic environment was studied. Different environmental matrices were covered: wastewater, surface water and fish tissues with the focus on pharmaceuticals, illicit drugs and perfluorinated compounds. Although numerous pharmaceuticals have been already detected in aquatic environment all over the world, still there is need for new reliable methods for their detection and quantification. The output of the study is three multi-residue methods for the analysis of pharmaceuticals and illicit drugs in water and fish samples. Their main advantage is that wide range of compounds from different classes is covered, which enables obtaining maximum information with minimum analytical effort. All the methods were validated including such key parameters as limits of quantification, selectivity, recovery and repeatability, and showed excellent performance allowing determination of target compounds at trace levels. Consequently, the methods were applied for the monitoring of POCs in different environmental samples. Wide occurrence of pharmaceuticals in Swedish WWTP effluents was shown. Rather high concentrations for the representatives of anti-hypertension drugs, some antibiotics and anti-depressants were detected. This fact stresses the importance of WWTP´ effluent monitoring as it is the main source of PPCPs in the aquatic environment. Passive sampling approach was tested for the monitoring of POCs in wastewater. Both standard configurations of POCIS were calibrated under the field conditions for a broad range of contaminants. Sampling rate values were calculated for the case of wastewater effluent. This is a significant contribution to the potential widespread application of POCIS for environmental monitoring programs. Analysis of biota samples is an essential part in the assessment of pollutants? fate in aquatic environment. Therefore, the screening of antibiotics in fish available at the Czech market was carried out. Thirty-two antibiotics from different classes were analyzed. The fish and shrimp samples were bought from the three biggest supermarkets in České Budějovice, which belong to a network of shops covering the whole Czech Republic. In total 97 samples were obtained. Found concentrations did not exceed MRL values established in the European Union. No antibiotics were detected in the fish of Czech origin. Still, presence of antibiotic residues in edible fish tissues could be a matter of concern and the sign of improper use of antibiotics in aquaculture industry, what consequently can cause adverse effects for the environment and human health.

This thesis deals with the passive sampling of polar compounds from water using passive samplers POCIS (Polar Organic Chemical Integrative Sampler). These devices were exposed for 4 weeks in the waste water at the inflow of municipal waste water treatment plant in Brno – Modřice, and also at the outflow of the treated water. After exposition sequestered compounds were released by extraction with a mixture of methanol, toluene and dichlormethane. Extracts were analysed by liquid chromatography/mass spectrometry with electrospray ionization. Further, methylated and trimethylsilylated extracts were analysed by orthogonal comprehensive two-dimensional gas chromatography with mass spectrometric detection. Separated compounds were identified on the base of their retention and mass spectra.

Malgré une sensible baisse des ventes depuis quelques années, la France reste le premier utilisateur européen de phytosanitaires. Ceci n’est pas sans conséquences sur l’environnement et les organismes non visés par ces produits. De nombreuses études ont permis d’une part de mieux comprendre les phénomènes de transfert des pesticides dans les compartiments eau-air sols et d’autre part de mettre en évidence leur contamination. Les données concernant l’eau sont plus nombreuses du fait de son statut de réceptacle ultime des pollutions.et des normes établies par les textes réglementaires. La Directive Cadre européenne sur l’Eau (DCE) adoptée en 2000 vise à atteindre le bon état chimique et écologique des eaux d’ici 2015 avec une obligation de résultats. Le bon état chimique dépend du respect des normes de qualité environnementales (NQE) établies notamment pour 24 pesticides. En 2012, 5% des points de mesure en cours d’eau et 19% des points de mesure en eaux souterraines ne respectent pas ces NQE.Le Languedoc Roussillon est depuis de nombreuses années la première région viticole de France et souffre d’une pression phytosanitaire importante. En 2014, un rapport de l’Agence Régionale de Santé (ARS) fait même état de l’utilisation encore récente de pesticides interdits (simazine, terbuthylazine…) depuis le début des années 2000. L’ARS a de plus affirmé que la plupart des cas de non-conformité avérés pouvaient être rattachés à la présence d’activité agricole dans le bassin versant du captage.Remédier à ces contaminations passe par le suivi de la qualité des eaux et la caractérisation de la pollution. Les outils actuels s’avèrent ne pas être toujours représentatifs de cette pollution ;de nouveaux outils sont donc mis au point. L’étude présentée ici porte sur l’utilisation de l’échantillonnage passif de type POCIS (Polar Organic Chemical Integrative Sampler) pour le suivi de la contamination en pesticides de trois bassins versants languedociens : Paulhan,Puissalicon, Roujan.Dans un premier temps, l’étude des limites possibles du dispositif POCIS a été faite pour évaluer son applicabilité dans les conditions d’exposition imposées par le terrain. Le comportement des molécules au sein de l’outil a été étudié pour une meilleure compréhension des phénomènes de diffusion qui s’y produisent. Ces études ont mené à la mise en place de calibrations en laboratoire en conditions contrôlées. [...] La mise en place des dispositifs POCIS sur les trois sites d’études a mis en évidence la prédominance de pesticides utilisés en viticulture et a montré tout l’intérêt de l’outil d’un point de vue qualitatif. La comparaison de l’outil avec l’échantillonnage automatisé montre des disparités entre concentration réelle et concentration estimée via le POCIS. Ce dernier reste à améliorer d’un point de vue quantitatif pour obtenir un échantillonneur fiable et robuste pour ce type de milieu d’exposition. / Despite a noticeable sales decrease since few years, France remains the first european user of phytosanitary products. This is not without consequences on the environment and the untargeted organisms. Several studies allowed on one hand to better understand phenomena of pesticides transfer in water-air and soils compartments and on the other hand to highlight their contamination. Data concerning the water are more numerous cause of its status of ultimate receptacle of pollution and standards established by regulatory texts. The european Water Framework Directive (WFD) adopted in 2000 aims to achieve good chemical and ecological status of water bodies by 2015 with an obligation of results. The good chemical status depends on respect for the Environmental Quality Standards (EQS) established, for instance, for 24 pesticides. In 2012, 5% of river measurement points and 19%of groundwater measurement points do not respect these EQS. For many years, Languedoc Roussillon is the first wine-producing region of France and suffers from a significant pesticide pressure. In 2014, a report from the Regional Health Agency (RHA) has mentioned a relatively recent use of banned pesticides since the early 2000’s like simazin and terbutylazin. Moreover, RHA stated that most of recognized cases of non-compliance could be linked to the presence of agricultural activity in the catchment basin.[...] The establishment of POCIS devices on the three study sites showed the predominance ofpesticides used in viticulture and showed all the interest of the tool on a qualitative point ofview. The comparison of the tool with the automated sampling shows disparities between real concentration and concentration estimated with the POCIS. However, it remains to improvethe tool on a quantitative way to obtain a reliable and robust sampler for this type of exposure medium.

Perfluoroalkyl substances (PFASs) are global environmental contaminants and a need for monitoring levels has arisen due to their persistency and their ability to bioaccumulate. One relatively novel method of monitoring for both long and short time intervals and generating time-weighted average (TWA) concentrations is passive sampling for which no power, maintenance and supervision is required. The polar organic compound integrative sampler (POCIS) with a weak anion exchange (WAX) sorbent and the POCIS with a hydrophilic-lipophilic balance (HLB) adsorbent were calibrated for PFASs in a laboratory uptake experiment, and applied at a drinking water treatment plant (DWTP) in Stockholm, Sweden.   In the calibration study, all of the 14 studied PFASs were taken up by both passive samplers. Two and three out of the 14 studied PFASs had reached equilibrium after 28 days using POCIS WAX (PFBA and PFTeDA) and POCIS HLB (PFBA, PFPeA and PFTeDA), respectively. The sampling rate (Rs), which is the extracted water in liters per day, ranged between 0.003 and 0.10 L day-1 for the POCIS WAX and between 0.00052 and 0.13 L day-1 for the POCIS HLB. In general, Rs increased with increasing perfluorocarbon chain-length (C4 to C8) and for a perfluorocarbon chain-length longer than C8, Rs decreased with increasing perfluorocarbon chain-length (C8 to C13) for both passive samplers. FOSA had the highest Rs-value (0.10 and 0.13 L day-1) for both POCIS WAX and POCIS HLB, respectively. The POCIS WAX had a higher uptake for the short-chained PFASs PFBA (134 ng after 28 days), PFPeA (410 ng) and PFHxA (834 ng), compared to the POCIS HLB (0.5 ng, 58 ng, and 373 ng, respectively). For all other compounds, the accumulated amounts in the POCIS HLB were in the same range as in the POCIS WAX.   The application of the passive samplers at the DWTP showed that both passive samplers could detect ultra-trace (pg to ng L-1) levels of PFASs. A comparison of the TWA concentration showed that the two passive samplers had a good linear correlation (R2 = 0.63), but the TWA concentrations derived by POCIS WAX was approximately 40% higher compared to POCIS HLB. A comparison between the passive samplers and the grab samples did not show a correlation (R2 = 0.24 for POCIS WAX and R2 = 0.10 for POCIS HLB). The application also included a comparison of the removal efficiency in the conventional DWTP and a pilot plant with additional treatments steps of granulated activated carbon (GAC) and nanofiltration (NF). For the full-scale DWTP the average removal efficiency was 32% and high removal efficiency was observed for PFBA (81%). For the pilot plant, the removal efficiency was 100% for all the detected PFASs in the raw water. / Perfluoroalkylsubstanser (PFAS) har blivit uppmärksammade som globala miljöföroreningar, och ett behov av att övervaka dessa ämnens förekomst i miljön har uppkommit på grund av hög persistens i kombination med hög förmåga att bioackumulera. En relativt ny metod för tidsintegrerad provtagning är så kallad passiv provtagning. En adsorbent placeras i fält och ackumulerar PFAS från vattnet. Tillgång till elektricitet behövs inte, och behov av övervakning och underhåll är minimalt. I denna studie kalibrerades en så kallad ’polar organic compound integrative sampler’ (POCIS) för mätning av PFAS genom upptagsexperiment med två olika adsorbenter: en svag anjons adsorbent (WAX) och en hydrofil-lipofil balanserad adsorbent (HLB). Metodiken tillämpades sedan på vatten från ett dricksvattenverk i Stockholm, Sverige.   Upptagsexperimenten utfördes med 14 PFAS och samtliga togs upp av båda adsorbenterna. Två respektive tre av de studerade PFAS uppnådde jämvikt efter 28 dagar för WAX (PFBS och PFTeDA) samt HLB (PFBA, PFPeA och PFTeDA). Upptagshastigheten (Rs), det vill säga den volym som extraheras per dag, varierade mellan 0,003 och 0,1 L dag-1 för WAX och mellan 0,00052 och 0,13 L dag-1 för HLB. Generellt ökade Rs med en ökande längd på kedjan av perfluorerade kol upp till C8, för att sedan avta med ökande kedjelängd. FOSA hade det högsta Rs-värdet (0,10 och 0,13 L dag-1) för både WAX och HLB. WAX hade ett högre upptag (upp till 134, 410 och 834 ng) för PFAS med kort perfluorerad kolkedja (PFBA, PFPeA respektive PFHxA) jämfört med HLB (upp till 0,5, 58, och 373 ng). Den ackumulerade mängden för alla andra PFAS överensstämde väl mellan de båda provtagarna.   Mätning av PFAS halter i dricksvattenverket med hjälp av POCIS WAX och POCIS HLB visade att även PFAS kunde detekteras även vid miljörelevanta halter. En jämförelse mellan de båda passiva provtagarna visade på ett linjärt samband (R2 = 0,63), men där POCIS WAX hade en tendens att överskatta koncentrationen med ca 40%. En jämförelse mellan de passiva provtagarna och traditionell uppsamlingsprovtagning visade på låg överrensstämmelse (R2 = 0.24 för POCIS WAX och 0.10 för POCIS HLB). Vid tillämpningen gjordes även en beräkning för reningseffektiviteten av PFAS i dricksvattenverket och i en pilotanläggning där ytterligare rening med granulerat aktivt kol (GAC) och nanofiltration (NF) används. I dricksvattenverket var den genomsnittliga reningen 32%, med den högsta reningseffektiviteten för PFBA (81%). I pilotanläggningen var reningen 100% för alla upptäckta PFAS i råvattnet.

Le POCIS (Polar Organic Chemical Integrative Sampler) est un outil d'échantillonnage intégratif alternatif aux techniques d'échantillonnages classiques (ponctuelle ou automatisée) dédié à la mesure de micropolluants organiques relativement hydrophiles dans les eaux. Cet outil permet d'intégrer les concentrations dans le temps (CTWA, Time-Weighted Average Concentration) et, dans certains cas, d'abaisser les limites de quantification. Une revue bibliographique détaillée a montré la forte variabilité des données de performances du POCIS mesurées en laboratoire (notamment les taux d'échantillonnage ou Rs). Cette variabilité résulte en majeure partie de systèmes expérimentaux d'étalonnage différents selon les études et pas toujours renseignés. Dans la littérature, les CTWA obtenues in situ sont comparées aux concentrations obtenues après échantillonnage classique, tel que mis en œuvre actuellement dans les programmes de surveillance européens ; ces concentrations sont dans la plupart des cas du même ordre de grandeur, même si elles ne représentent pas tout à fait la même information. Avec comme objectif d'obtenir des CTWA les plus justes et robustes possibles, nous avons étudié le comportement du POCIS « pharmaceutique » en laboratoire vis-à-vis de 56 micropolluants (hormones, pharmaceutiques, alkylphénols, pesticides, filtre UV), dans un système expérimental d'étalonnage conçu spécifiquement pour contrôler l'ensemble des conditions expérimentales ayant une influence sur les Rs. Nous avons ainsi déterminé 43 Rs robustes et démontré que le POCIS est bien adapté à l'échantillonnage de la plupart des molécules étudiées. De plus, l'allure des cinétiques d'accumulation est expliquée à l'aide des propriétés physico-chimiques des molécules (log D , surface polaire). Cinq homologues deutérés ont été identifiés en tant que PRC (Performance Reference Compounds), c'est-à-dire qu'ils peuvent être utilisés pour corriger les différences de conditions entre le laboratoire et le terrain. Nous avons également comparé le POCIS au Chemcatcher « polaire » en laboratoire et montré qu'en terme de domaine d'application et de performances, le POCIS est mieux adapté pour les micropolluants étudiés. Enfin, nous avons testé la justesse et la robustesse du POCIS lors de deux essais inter-laboratoires (EIL). Le premier EIL, portant sur l'étalonnage de l'outil en laboratoire, a démontré la robustesse de ses performances pour 3 pesticides. Le deuxième EIL in situ a démontré la pertinence du POCIS pour échantillonner des hormones, des pharmaceutiques et des pesticides dans un effluent de station d'épuration. Cette thèse permet d'avancer dans le domaine des connaissances sur l'outil POCIS et de favoriser son application dans le cadre de la directive sur l'eau / The POCIS (Polar Organic Chemical Integrative Sampler) is an alternative integrative sampling tool to conventional sampling methods (grab or automated) for measuring hydrophilic organic micropollutants in water. This tool permits to supply time-weighted average concentrations (TWAC) and, sometimes, to decrease limits of quantification. A detailed bibliographic review showed the important variability of POCIS performance data measured in laboratory (notably the sampling rates or Rs). This variability is in majority due to different experimental calibration systems, not always well detailed, among studies. In the literature, in situ TWAC are compared to concentrations from conventional sampling, actually used in European monitoring programs ; these concentrations are generally of the same order of magnitude, even if they do not represent the same information. In order to obtain accurate and robust TWAC, we studied in laboratory the “pharmaceutical” POCIS behavior for 56 micropollutants (hormones, pharmaceuticals, alkylphenols, pesticides, UV filter), in a calibration system specifically made for controlling the whole experimental conditions having an influence on Rs. We determined 43 robust RS and demonstrated that POCIS is well adapted for sampling most of studied molecules. Moreover, the pattern of kinetic accumulations is explained using molecule physical-chemical properties (log D, polar surface). Five deuterated homologues were identified as PRCs, meaning that they can be used for correcting differences in conditions between the laboratory and the field. We also compared the POCIS with the “polar” Chemcatcher and we showed that in term of application field and performances, the POCIS is better adapted for studied micropollutants. At last, we tested the accuracy and the robustness of the POCIS during two inter-laboratory studies (ILSs). The first ILS, dealing with the laboratory calibration of the tool, demonstrated performance robustness for 3 pesticides. The second in situ ILS demonstrated the relevance of the POCIS for sampling hormones, pharmaceuticals and pesticides from a waste water treatment plant effluent. This thesis permits to improve knowledge on the POCIS and to promote its application for the water framework directive

In agricultural watersheds, streams are intimately connected with croplands and may be inadvertently exposed to agrochemicals such as fertilizers and herbicides. Riparian plants and aquatic primary producers (aquatic plants, phytoplankton and periphyton) may be particularly affected by agrochemicals due to their taxonomic similarity to the intended targets (crop and weed species). The overall objective of this thesis was to assess the effects of fertilizers and the herbicide atrazine on riparian plants and aquatic primary producers. Effects were assessed across varying scales of observation ranging from empirical field studies at the watershed scale to in-situ experimental manipulations in two temperate streams to a laboratory concentration-response experiment. Twenty-four stream/river sites located across the South Nation River watershed, Canada ranged in surrounding agricultural land use (6.7-97.4 % annual crops) and in-stream concentrations of reactive phosphate (4-102 μg/L) and nitrate (3-5404 μg/L). A gradient of atrazine contamination spanning two orders of magnitude (56 d time-weighted-average concentrations of 4-412 ng/L) was observed using polar organic chemical integrative samplers (POCIS). A total of 285 riparian and aquatic plant species were identified with species richness ranging from 43-107 species per site. Atrazine and the percentage of surrounding annual crops had no statistically significant effects on community structure. In contrast, an increase in the percentage of non-native species, a decrease in submerged macrophytes and a decrease in overall floristic quality was observed along a gradient of increasing nitrate. Similarly, periphyton biomass increased with increasing nitrate across the watershed and was associated with the Chlorophyta. In contrast, no clear response was observed in periphyton exposed to nutrient enrichment and atrazine contamination in in-situ periphytometer experiments in two streams. Greenhouse concentration-response experiments provided evidence that the sensitivity of duckweed (Lemna minor) to atrazine was lower in populations previously exposed to the herbicide. However, the overall range in biomass 25% inhibition concentrations was small (19-40 μg/L atrazine). A clear gradient in agrochemical contamination was observed at the watershed scale and this research provided evidence of negative effects on riparian and aquatic primary producers. Effects of nutrients, specifically nitrate, superseded observable effects of the herbicide atrazine.

This diploma thesis has been carried out as a part of the project Utilization of long term (passive) sampling methods combined with in situ microcosms for assessment of (bio)degradation potential (PASSES). In the frame of the project groundwater remediation took place in the premises of Farmak a.s. in Olomouc using a pilot photooxidation unit and efficiency of the remediation was monitored through passive and active sampling methods. Pilot photooxidation unit is a technology based on the H2O2/UV-C photochemical oxidation of organic pollutants. In this work optimization tests of the pilot photooxidation unit were performed. The residence time of the groundwater in the photoreactors, required for its sufficient decontamination from pharmaceuticals and aromatic hydrocarbons, was 2.5 hours. 91% degradation of the pharmaceuticals and 80% degradation of aromatic hydrocarbons were reached during this interval. Although the removal efficiency of the pharmaceuticals by the photooxidation unit was high, the pilot photooxidation unit was not able to effectively remove the pharmaceuticals at the studied locality. By comparing the results of the pharmaceuticals from active and passive groundwater sampling during the remediation attempt, passive Polar Organic Chemical Integrative Sampler (POCIS) was found to be...

Les objectifs de cette étude comparative de deux bassins versants en France et en Ukraine sont de trois ordres. i) déterminer l'occurrence des micropolluants émergents (métaux traces et molécules pharmaceutiques) dans les eaux de surface, ii) permettre leur évaluation qualitative et quantitative et enfin iii) estimer leur distribution en fonction du contexte socio-économique. Cette recherche porte sur l'analyse de l'origine, sur les propriétés physico-chimiques et sur le comportement des micropolluants (métaux traces et molécules pharmaceutiques) dans les eaux des rivières Jalle (Bordeaux, France) et Udy & Lopan (Kharkiv, Ukraine). Un suivi des métaux traces et des produits pharmaceutiques dans les eaux naturelles de surface dans différents contextes et conditions climatiques a été réalisé. La description et l'analyse des facteurs environnementaux et socio-économiques influençant l'hydrochimie locale en vue de conclure sur l'opportunité et l'intérêt des micropolluants émergents comme indicateurs anthropogéniques du contexte socio-économique et environnemental d'un bassin versant ont été mis en oeuvre. L'étude a combiné des techniques de prélèvements d'échantillons d'eau classiques et par capteurs passifs in situ. L'analyse semi quantitative des micropolluants émergents a porté sur les métaux traces (sondes DGT) et les produits pharmaceutiques (POCIS). L'usage de ces capteurs a permis d'évaluer les différentes formes d'éléments, les sources, les variations saisonnières et spatiales, l'accumulation et les risques environnementaux. A partir des données environnementales collectées, acquises, actualisées et validées il a été possible de modéliser la consommation régionale de médicaments dans le cas de (1) la région de Kharkiv, en Ukraine, sur les rivières Lopan et Udy du bassin Seversky Donets et (2) la région de Bordeaux, en France, sur la rivière Jalle, du bassin de la Garonne. Les sites ont été sélectionnés pour représenter une diversité tant du point de vue de l'état de pollution des eaux (nature et flux) que de celui du paysage socio-économique (contexte urbain, social et indicateurs économiques). Les résultats majeurs de cette étude sont : (i) méthodologique pour le développement et la validation de protocoles d'échantillonnage classique et passif (intérêt, limites, recommandations), ii) analytique quant à la mesure des éléments traces des eaux de surface naturelles dans des conditions extrêmes, iii) scientifique par l'obtention d'un jeu de données sur l'hydrochimie des éléments traces ( présence, accumulation, origine et variabilité spatiale et temporelle et iv) prospectif quant à l'usage des métaux traces et de produits pharmaceutiques comme traceurs anthropiques de l'état des eaux naturelles de surfaces et reflet du contexte socio économique. La modélisation socio-économique (statistique) et environnementale (balance de masse) aide à comprendre l'évolution de la qualité des eaux de surface dans leur contexte régional et permet d'identifier certains contaminants comme des indicateurs des activités anthropiques d'un bassin versant et permet de définir une typologie. L'ensemble des résultats de la thèse ont présentés sous la forme d'articles publiés ou soumis dans des revues scientifiques internationales.

The efficiency of wastewater treatment systems is commonly measured by the reductions of parameters such as biological oxygen demand (BOD), chemical oxygen demand (COD) and total suspended solids (TSS) and/or reductions in levels of selected macro compounds (e.g. long-chained hydrocarbons and inorganic compounds). Less attention has generally been paid to micropollutants with high potential toxic effects, such as polycyclic aromatic compounds (PACs), including unsubstituted and alkylated polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes, polychlorinated biphenyls (PCBs), human pharmaceuticals and by-products formed during the treatment process. These organic micropollutants occur in wastewaters at trace and ultra-trace levels, therefore their detection requires advanced, costly analyses and large sample volumes. Furthermore, concentrations of micropollutants can fluctuate widely both diurnally and between days. Thus, in order to understand the fate of micropollutants in wastewaters there is a need to develop sampling techniques that allow representative samples to be readily collected. In the work underlying this thesis two types of diffusive passive samplers, semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs), were used to monitor non-polar and polar organic micropollutants in wastewaters subjected to various treatment processes. The pollutants sequestered in these samplers represent micropollutants in the dissolved phase that are available for aquatic organisms. Further, since they collect pollutants in an integrative manner, i.e. they sample continuously during the selected exposure time (usually approx. one to ca. three weeks), the results provide time-weighted average (TWA) concentrations. In addition, the effects of various environmental factors on the uptake of analyzed micropollutants in POCISs and SPMDs were investigated using laboratory calibration and in situ calibration with performance reference compounds (PRCs). The results confirm that SPMDs are good sampling tools for investigating the efficacy of wastewater treatment processes for removing non-polar PACs and PCBs, and the effects of varying the process settings. In addition, analyses of process streams in municipal sewage treatment plants demonstrated that conventional sewage treatment processes are not optimized for removing dissolved four-ringed PAHs, some of the five-ringed PAHs, and tri- to hexa-chlorinated biphenyls. The removal of bioavailable PACs was enhanced by adding sorbents with high sorption capacities to the sludge used in the activated sludge treatment step, and a biologically activated carbon system was designed that robustly removed bioavailable PACs, with removal efficiencies of 96.9-99.7 percent across the tested ranges of five varied process parameters. In situ SPMD calibration data acquired show that uptake of PACs, described by SPMD sampling rates (Rs), were four to eight times higher than published laboratory calibrated Rs values, mainly due to strong (bio)fouling and turbulence effects. In addition, the laboratory calibration study demonstrated that temperature affects the POCIS uptake of pharmaceuticals. The uptake of four pharmaceuticals was higher, by 10-56 percent, at 18 °C compared to 5 °C. For two of the pharmaceuticals our data indicate that the uptake was lower by 18-25 percent at 18 °C. Our results also indicate that uptake of the studied pharmaceuticals was in the linear phase throughout the 35 day exposure period at both temperatures. Finally, calibration studies enabled aqueous concentrations of micropollutants to be more accurately estimated from amounts collected in the passive samplers.