In any oil production company, one of the problems that is faced on a daily basis and which sometimes hinders the operation is corrosion. In the presence of dissolved oxygen in the water inside any vessel, tank, or pipeline, the oxygen attacks the steel to form iron oxides, and this result in corrosion of the steel. To prevent this, corrosion inhibitors are added to the oil and gas streams. These chemicals are based on aliphatic amines, which are soluble in water, to form a film to coat the steel and prevent it from the oxygen attacks. As a chemist in the laboratory, filming amines residuals should be monitored and optimized in order to make sure the system is protected against corrosion and that no excess chemical remains. This is classically done by lengthy liquid-liquid extraction of filming amines followed by colorimetric determination using spectrophotometry of the extract. SPME is an easy, rapid, and solvent free extraction technique which can be easily coupled with GC for separation and quantification, and is a good candidate to be used for this job. In this thesis, an introduction about corrosion problems and how to control and monitor them in the oil and gas industry will be shared, as well as a literature review about various methods used to determine amines in different matrices, followed by a description of the SPME procedure, including its theory, modes, fibers, and method development procedures. A flow-through system was used to simulate the process of flowing streams in pipelines during oil production and to provide unlimited sample volumes, which contributes iv to simplifying the calculation of the distribution constant between fiber and solution. Two different agitation methods were compared, which are stirring and sonication, in order to optimize the extraction time profiles of analytes. A method was developed to determine amines, using a flow-through system at the lowest detection limit possible. Different parameters were examined such as variation of pH, salt addition, and sand addition. It was found that the pH of the solution has to be adjusted in order to get better sensitivity for the desired analytes. Finally, in-fiber kinetic calibration was used to calculate the concentration of solutions at a short extraction time. This was possible by applying the dominant desorption approach using the same analytes as standards in the fiber. The experiment was successful in shortening the extraction time from 3 hours to 20 minutes, with less than 20% variation in concentrations between the actual and the calculated.

In any oil production company, one of the problems that is faced on a daily basis and which sometimes hinders the operation is corrosion. In the presence of dissolved oxygen in the water inside any vessel, tank, or pipeline, the oxygen attacks the steel to form iron oxides, and this result in corrosion of the steel. To prevent this, corrosion inhibitors are added to the oil and gas streams. These chemicals are based on aliphatic amines, which are soluble in water, to form a film to coat the steel and prevent it from the oxygen attacks. As a chemist in the laboratory, filming amines residuals should be monitored and optimized in order to make sure the system is protected against corrosion and that no excess chemical remains. This is classically done by lengthy liquid-liquid extraction of filming amines followed by colorimetric determination using spectrophotometry of the extract. SPME is an easy, rapid, and solvent free extraction technique which can be easily coupled with GC for separation and quantification, and is a good candidate to be used for this job. In this thesis, an introduction about corrosion problems and how to control and monitor them in the oil and gas industry will be shared, as well as a literature review about various methods used to determine amines in different matrices, followed by a description of the SPME procedure, including its theory, modes, fibers, and method development procedures. A flow-through system was used to simulate the process of flowing streams in pipelines during oil production and to provide unlimited sample volumes, which contributes iv to simplifying the calculation of the distribution constant between fiber and solution. Two different agitation methods were compared, which are stirring and sonication, in order to optimize the extraction time profiles of analytes. A method was developed to determine amines, using a flow-through system at the lowest detection limit possible. Different parameters were examined such as variation of pH, salt addition, and sand addition. It was found that the pH of the solution has to be adjusted in order to get better sensitivity for the desired analytes. Finally, in-fiber kinetic calibration was used to calculate the concentration of solutions at a short extraction time. This was possible by applying the dominant desorption approach using the same analytes as standards in the fiber. The experiment was successful in shortening the extraction time from 3 hours to 20 minutes, with less than 20% variation in concentrations between the actual and the calculated.

Les approches physico-chimiques étant insuffisantes pour évaluer l'impact de la pollution sur les écosystèmes , de nombreux bioessais, variant de par le niveau d'organisation représenté, ont été développés. Parmi ces essais on trouve les essais en microcosme aquatique de laboratoire qui sont un compromis entre les essais monospécifiques standards de laboratoire, méthodes couramment employées mais très simplifiées et peu représentatives sur le plan écologique et les essais en mésocosme extérieurs, plus représentatifs mais coûteux, lourds à mettre en œuvre, moins réplicables et plus difficiles à interpréter. Dans ce travail, nous nous sommes plus particulièrement intéressés à l'essai initialement développé par Clément et Cadier (1998). Cet outil permet d'évaluer l'effet de substances ou de matrices potentiellement contaminées sur un écosystème artificiel composé d'eau et de sédiment, dans lesquels sont introduites simultanément 5 espèces aquatiques d'eau douce usuellement employées dans des essais de toxicité mono-spécifiques : l'algue Pseudokirchneriella subcapitata, la lentille d'eau Lemna minor, la daphnie Daphnia magna, l'amphipode Hyalella azteca et l'insecte Chironomus riparius. Cet essai en microcosme a été utilisé dans de nombreux projets depuis sa conception mais sa variabilité demeurait la principale limite malgré les améliorations successives. Le principal objectif de ce travail était donc d'optimiser l'essai. La principale amélioration testée a été le renouvellement continu de l'eau du système, qui a permis de stabiliser les paramètres physico-chimiques de la colonne d'eau des microcosmes et la densité algale, et ainsi d'améliorer le développement des organismes et la réplicabilité de l'essai. Le cadmium a été utilisé comme contaminant modèle afin d'évaluer les développements méthodologiques proposés. La diminution de la variabilité en présence de renouvellement d'eau augmente la capacité à détecter des effets sublétaux sur les organismes pélagiques avec les tests statistiques classiques. Le développement d'un cadre de modélisation dynamique a permis de comparer la sensibilité des daphnies au cadmium dans des expériences aux profils d'exposition différents. / The physico-chemical approaches are insufficient to assess the impact of pollution on ecosystems. Thus many bioassays, varying in the level of organization represented, have been developed, as laboratory aquatic microcosm tests. These tests are a compromise between single-species tests, which are standard laboratory methods commonly used but highly simplified and not very ecologically representative, and outdoor mesocosm tests, which are more representative but more expensive, heavy to implement, less replicable and more difficult to interpret. In this work, we focused on the bioassay originally developed by Clément and Cadier (1998). This tool allows to evaluate the effect of substances or potentially contaminated matrices on an artificial ecosystem consisting of water and sediment in which are introduced simultaneously five freshwater aquatic species commonly used in monospecific toxicity testing : the algea Pseudokirchneriella subcapitata, the duckweed Lemna minor, the daphnia Daphnia magna, the amphipod Hyalella azteca and the insect Chironomus riparius. This test was used in many projects since its conception but its variability remains the main limitation despite successive improvements. The main objective of this study was to optimize the test. The main improvement was continuous renewal of the water system, which helped to stabilize the physico-chemical parameters of the water column and algal density, and thus improve the development of organisms and replicability of the test. Cadmium was used as a model contaminant to evaluate the proposed methodological developments. The decrease in variability in flowthrough microcosms increases the ability to detect sublethal effects on pelagic organisms with conventional statistical tests. The development of a dynamic modeling framework was used to compare the sensitivity of Daphnia to cadmium in experiments with different exposure pattern.