Humic substances are macromolecules that naturally occur in all environments in which vegetation matter are present. In general, humic acid is part of humic substances which form the major fraction of the dissolved organic matters in surface water and represents 90% of dissolved organic carbon. Humic acid plays a fundamental role in many ecosystems since it interacts with toxic metal ions present in the system, resulting in a decrease in the bio-availability of such ions. Moreover, the availability of humic acid in water can react with other chemical compounds, such as chlorine to form trihalomethanes (including chloroform) and causes an increasing risk of cancer and may be linked to heart, lung, kidney, liver, and central nervous system damage. Therefore, humic acid removal in water treatment processes is very important in order to achieve the drinking water standards. Heavy metals are significant contaminants in aqueous system. All heavy metals can produce toxicity when ingested in sufficient quantities, but there are several important ones such as lead, mercury, copper, cadmium, arsenic, nickel and silver. These heavy metals are so pervasive and produce toxicity at low concentrations. Moreover, they may build up in biological systems and become a significant health hazard. / Adsorption is approved as an effective and simple method for water and wastewater treatment process. Many adsorbents then are developed for use in adsorption process such as montmorillonite, peat, activated carbon, etc. In this research, humic acid and heavy metals were mainly selected for adsorption study. In the sorption experiment, several adsorbents such as synthesised zeolite (SZ), natural zeolite (NZ), powdered activated carbon (PAC) and fly ash (FA), were selected to examine the application of HA and heavy metals both in individual and simultaneous adsorption, The characteristics and interactions of the adsorbents with HA and heavy metals were systematically studied by batch laboratory experiments. In the beginning, the adsorption of HA onto SZ, NZ, PAC and FA was investigated and their adsorption capacity was compared. The equilibrium adsorption of HA on SZ, NZ, PAC and FA was found to be 84.1, 67.8, 81.2 and 34.1 mg/g, respectively, at 30 oC and pH 5.0. Dynamic adsorption data show that these adsorbents could reach their adsorption equilibrium after 50 hours. From pH analysis, HA adsorption is favoured at low pH and an increase in pH will lead to the reduction of HA adsorption. SZ and NZ adsorption capacity were affected by the changing of solution temperature; however, in PAC and FA sorption study, there was no significant effect observed. Two heavy metal ions (Cu, Pb) removal by the adsorbents was then conducted. The results showed that the equilibrium sorption capacity of Cu and Pb ions on SZ, NZ, PAC and FA were 43.5, 24.2, 19.7, 28.6 and 190.7, 129.0, 76.8 mg/g, respectively at 30 oC and a pH value of 5. The appropriate pH for Cu and Pb removal was found to be 5 and 6. In most dynamic cases, these adsorbents needed at least 50 hours to reach the adsorption equilibrium. Only adsorption on FA required more than 150 hours to reach the equilibrium. / In simultaneous adsorption experiments, the influences of HA and heavy metal concentration (in the range of 10 to 50 mg/L for HA and 10 to 30 mg/l for heavy metals) on the HA-heavy metal complexation were investigated. The results demonstrated that increasing HA concentration mostly affected Cu adsorbed on SZ, FA and PAC and Pb adsorbed on SZ, NZ and PAC. For HA adsorption, the adsorption rate decreased rapidly with increased initial metal ion concentration. Moreover, the adsorption of heavy metals increased with increased heavy metals concentration in the presence of HA. In the presence of heavy metal ions, the order of HA adsorption followed PAC > FA > SZ > NZ. According to the results, the individual and simultaneous adsorption of HA and heavy metals on each adsorbent achieved a different trend. It mainly depended on the adsorption property of both adsorbates (HA and heavy metals) and adsorbents (SZ, NZ, PAC and FA) and also the operation factors such as pH, concentration, temperature and operation time. Even though this experiment could not obtain high adsorption performance, especially in coadsorption, as compared with other adsorbents, the adsorbents in this study represented a higher adsorption capacity and provide the potential for further development.

Les eaux côtières du Sud du Golfe de Gascogne sont soumises à l’expulsion d’un panache fluvial au niveau de l’estuaire de l’Adour. Ces eaux douces peuvent entrainer de fortes variations des concentrations en matières minérales en suspension (MSM, en mg,l-1), en chlorophylle- a (Chla, en mg,m-3) et en matière organiques dissoutes colorées (MODC, en mg,l-1) contenues dans les eaux côtières. En modifiant la transparence de l’eau et en charriant des nutriments et des bactéries, elles peuvent affecter la productivité biologique et avoir un impact significatif sur la santé humaine. Notre étude a pour but de développer des algorithmes empiriques et de tester l’efficacité des images MODIS-Aqua pour la cartographie des substances particulaires et dissoutes contenues dans les eaux côtières soumises à l'influence du panache de l'Adour. Dans cet objectif, deux missions océanographiques ont été réalisées afin de mesurer simultanément les MSM, la turbidité (en NTU), la Chla et les MODC et la réflectance de télédétection de l’eau in-situ. Deux algorithmes empiriques opérationnels pour la quantification des matières minérales en suspension et de la turbidité ont été développés. Une automatisation du traitement des images MODIS-Aqua déjà corrigées des effets atmosphériques et à la résolution de 250 mètres (produit MYD09GQ) a été réalisée. Ce système opérationnel a permis de cartographier les concentrations en sédiments en suspension contenus dans le panache sur 246 jours, entre 2006 et 2009. La première étude à grande échelle spatiale et temporelle de la dynamique hydro-sédimentaire du panache de l'Adour a ainsi pu être réalisée. Finalement, plusieurs algorithmes ont été proposés pour la quantification des concentrations en chlorophylle-a dans le sud du Golfe de Gascogne. Ces relations empiriques devront être testées sur de nouvelles mesures in-situ afin de préciser leurs limites de validité. Notre étude montre l’apport de l’imagerie satellitaire MODIS pour la surveillance du panache de l'Adour. A plus long terme, un système efficace de surveillance de la qualité des eaux côtières de la côte Aquitaine pourrait être envisagé. / The southern Bay of Biscay coastal waters are under the direct influence of the freshwater plume from the Adour estuary. The river outflow leads to a strong variability in the concentration of mineral suspended matters (MSM in mg l-1), chlorophyll-a (Chla, mg, m-3) and colored dissolved organic matters (CDOM in mg l-1) contained in coastal waters. By changing the transparency of the water and carrying nutrients and bacteria, they may affect biological productivity and have a significant impact on human health. Our study aims to develop empirical algorithms and test the efficiency of MODIS-Aqua imagery to map particulate and dissolved substances contained in coastal waters under the influence of the Adour plume. In this aim, two oceanographic missions were carried out to measure simultaneously the MSM, turbidity, Chla and CDOM and the remote sensing reflectance of water. Two empirical operational algorithms for quantification of suspended mineral matters and turbidity have been developed. An automated processing of atmospherically-corrected MODIS-Aqua-250m product (MYD09GQ product) was performed. This operating system has been used to map the concentrations of suspended sediment content in the plume at 246 days between 2006 and 2009. Thus, the first study at large spatial and temporal scale of the Adour plume dynamics has been achieved. Finally, several algorithms have been proposed in order to quantify the concentrations of chlorophyll-a in the southern Bay of Biscay. These empirical relations must be tested on new in-situ measurements to clarify their validity limits. Our study shows the contribution of the MODIS satellite imagery to monitor the Adour plume. In future, an effective monitoring system of Aquitaine coastal water quality could be considered.

Polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing polycyclic aromatic compound (N-PAC) are widespread toxic pollutants in environments. The fate of PAHs and N-PACs are of great concern because some of these compounds were identified as caricinogenic, mutagenic and teratogenic compounds. As described in literature, dissolved organic matter (DOM) is an important factor in control of their fate; however, the binding behaviors between these compounds and DOM are still not fully understood. The binding constants (KDOC) between humic substances and one selected N-PAC, benzo[h]quinoline, were measured at varying pH levels using fluorescence quenching (FQ) method. As fluorescence characteristics of benzo[h]quinoline change with pH, determination required two optimum sets of excitation and emission wavelength pairs. A simple mixing model was proposed and used to eliminate the inherent fluorescence interference between benzo[h]quinoline (BQ) and its protonated form, benzo[h]quinolinium (BQH+), and to deduce Kmix which represents the overall binding as the sum of that for the individual analogs. The characteristics of humic substances, especially their hydrophobicity and aromaticity, established by principal components analysis of structural and elemental compositions, were the main determinants of their binding affinity with both benzo[h]quinoline and benzo[h]quinolinium (KBQ and KBQH+) across a range of pH values. Hydrophobic interaction is likely to control the binding between humic substance and benzo[h]quinoline and benzo[h]quinolinium, in lower and higher pH ranges (pH<3, pH>6). In contrast, cation exchange seems to control on the binding affinity of benzo[h]quinolinium in the middle range of pH. Determination of PAH concentration is quite essential for investigating the fate of PAHs in environments. Microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was applied as a single step prior to determination of PAH concentrations in water using GC-MS. To optimize the extraction efficiency of PAHs by MA-HS-SPME, the influence of various parameters, including temperature, duration of thermal desorption, microwave irradiation power and duration, and the temperature of the circulating cooling water system, was studied. The proposed method was demonstrated applicable to environmental water samples. In addition, DOM matrix effect did not influence the determination and extraction efficiency of PAHs. Although the proposed simple mixing model can eliminate the fluorescent interference of hydrophobic organic compounds with acid-base pair forms, it is still limited in using for correcting the KDOC measurement of more than two fluorescent compounds simultaneously. A new alternative protocol, complexation-flocculation combined with MA-HS-SPME/GC-MS method, was proposed to determine the binding constants of seleted PAHs to humic substances. The results obtained are comparable with KDOC data reported in literatures. CF-MA-HS-SPME/GC-MS provides some advantages over other methods, such as applicable not limited to fluorescent compounds, faster in determination and capable in measuring varieties of compounds simultaneously.