Rôle de la sorption et de la biodégradation dans l'élimination de micropolluants par des procédés d'épuration biologique : application aux molécules anticancéreuses traitées par bioréacteur à membrane

Les travaux de recherche effectués dans le cadre de ce travail de thèse ont eu pour objectif de caractériser le rôle joué par les mécanismes de sorption et de biodégradation dans l’élimination de micropolluants organiques par les boues biologiques, et notamment celles de bioréacteur à membrane. La première étape a consisté en la mise au point d’une méthode d’analyse de molécules anticancéreuses depuis les phases aqueuse et solide des boues. L’extraction des molécules contenues dans la phase aqueuse a été réalisée par une combinaison de cartouches SPE permettant la récupération sélective d’espèces acides, neutres et basiques. L’extraction depuis la phase solide a été rendue possible grâce à l’utilisation de la technique sous solvant pressurisé et à chaud PLE, suivie par une étape de purification directement inspirée de la méthode développée pour la phase aqueuse. Une procédure originale de préparation d’échantillons de boues a été proposée pour estimer rigoureusement le phénomène de sorption. Le modèle de Freundlich est celui qui a donné les corrélations les plus satisfaisantes et a été sélectionné. La détermination des paramètres du modèle a mis en évidence des comportements de sorption différents pour les molécules ciblées, mais toujours caractérisés par des aptitudes de sorption faibles. La mise en relation des propriétés physico-chimiques des molécules, des boues et des paramètres de sorption n’a pas révélé de corrélations évidentes entre ces différents paramètres et ne permet pas de proposer de modèle capable de prédire la sorption en fonction des caractéristiques des boues et des polluants. La caractérisation du comportement d’un cocktail d’anticancéreux lors du traitement par un pilote de bioréacteur à membrane externe a révélé que le mécanisme majeur à l’origine de leur élimination était la biodégradation. Les interactions entre les microorganismes et les micropolluants ciblés sont liées au cométabolisme. Une étude approfondie du mécanisme a révélé que ces mêmes interactions étaient à l’origine d’une limitation de la biodégradation et doivent être intensifiées pour améliorer les performances de traitement sur ce point. ABSTRACT : The aim of the present work was to characterize the sorption mechanisms and biodegradation role in the removal of some organic micropollutants (i.e. anticancer drugs) by biological sludges, including those of membrane bioreactor (MBR). The first step consisted in the development of an analytical method for the trace determination of anticancer drugs from sludge aqueous and solid phases. The extraction from the aqueous matrix was performed by a combination of SPE cartridges, allowing the selective recovery of acid, neutral and basic species. The extraction from the solid matrix was possible thanks to an extractive step performed by pressurized liquid extraction, followed by a purification step whose procedure was directly inspired from the method developed for aqueous samples. An original procedure for the conditioning of sludge samples before sorption experiments has been proposed. The Freundlich isotherm gave the satisfactoriest correlations and has been selected. The determination of the model parameters highlights different trends of sorption between targeted compounds, but always characterized by low sorption affinities. Physico-chemical properties of both compounds and sludge did not show any link with sorption parameters. Consequently, it is not possible to propose a predictive model for the sorption of polar micropollutants depending on both compounds and sludge properties. The removal of a “cocktail” of anticancer drugs by treatment through a side stream pilot-scale MBR has been investigated. Biodegradation appeared as the prevailing mechanism and was explained by cometabolic interactions. However, these interactions were also responsible for the limitation of biodegradation phenomenon and must be intensify to enhance the removal of these compounds

Optimisation of pressurized liquid extraction using a multivariate chemometric approach for the determination of anticancer drugs in sludge by ultra high performance liquid chromatography–tandem mass spectrometry

The present paper describes an analytical method for the determination of 2 widely administered anticancer drugs, ifosfamide and cyclophosphamide, contained in sewage sludge. The method relies on the extraction from the solid matrix by pressurized liquid extraction, sample purification by solid-phase extraction and analysis by ultra high performance liquid chromatography coupled with tandem mass spectrometry. The different parameters affecting the extraction efficiency were optimized using an experimental design. Solvent nature was the most decisive factor for the extraction but interactions between some parameters also appeared very influent. The method was applied to seven different types of sludge for validation. The performances of the analytical method displayed high variability between sludges with limits of detection spanning more than one order of magnitude and confirming the relevance of multi-sample validation. Matrix effect has been determined as the most limiting analytical step for quantification with different extent depending on analyte and sludge nature. For each analyte, the use of deuterated standard spiked at the very beginning ensured the complete compensation of losses regardless of the sample nature. The suitability of the method between freshly spiked and aged samples has also been verified. The optimized method was applied to different sludge samples to determine the environmental levels of anticancer drugs. The compounds were detected in some samples reaching 42.5 μg/kgDM in ifosfamide for the most contaminated sample

Rôle de la sorption et de la biodégradation dans l'élimination de micropolluants par des procédés d'épuration biologique (application aux molécules anticancéreuses traitées par bioréacteur à membrane)

Les travaux de recherche effectués dans le cadre de ce travail de thèse ont eu pour objectif de caractériser le rôle joué par les mécanismes de sorption et de biodégradation dans l élimination de micropolluants organiques par les boues biologiques, et notamment celles de bioréacteur à membrane. La première étape a consisté en la mise au point d une méthode d analyse de molécules anticancéreuses depuis les phases aqueuse et solide des boues. L extraction des molécules contenues dans la phase aqueuse a été réalisée par une combinaison de cartouches SPE permettant la récupération sélective d espèces acides, neutres et basiques. L extraction depuis la phase solide a été rendue possible grâce à l utilisation de la technique sous solvant pressurisé et à chaud PLE, suivie par une étape de purification directement inspirée de la méthode développée pour la phase aqueuse. Une procédure originale de préparation d échantillons de boues a été proposée pour estimer rigoureusement le phénomène de sorption. Le modèle de Freundlich est celui qui a donné les corrélations les plus satisfaisantes et a été sélectionné. La détermination des paramètres du modèle a mis en évidence des comportements de sorption différents pour les molécules ciblées, mais toujours caractérisés par des aptitudes de sorption faibles. La mise en relation des propriétés physico-chimiques des molécules, des boues et des paramètres de sorption n a pas révélé de corrélations évidentes entre ces différents paramètres et ne permet pas de proposer de modèle capable de prédire la sorption en fonction des caractéristiques des boues et des polluants. La caractérisation du comportement d un cocktail d anticancéreux lors du traitement par un pilote de bioréacteur à membrane externe a révélé que le mécanisme majeur à l origine de leur élimination était la biodégradation. Les interactions entre les microorganismes et les micropolluants ciblés sont liées au cométabolisme. Une étude approfondie du mécanisme a révélé que ces mêmes interactions étaient à l origine d une limitation de la biodégradation et doivent être intensifiées pour améliorer les performances de traitement sur ce point.The aim of the present work was to characterize the sorption mechanisms and biodegradation role in the removal of some organic micropollutants (i.e. anticancer drugs) by biological sludges, including those of membrane bioreactor (MBR). The first step consisted in the development of an analytical method for the trace determination of anticancer drugs from sludge aqueous and solid phases. The extraction from the aqueous matrix was performed by a combination of SPE cartridges, allowing the selective recovery of acid, neutral and basic species. The extraction from the solid matrix was possible thanks to an extractive step performed by pressurized liquid extraction, followed by a purification step whose procedure was directly inspired from the method developed for aqueous samples. An original procedure for the conditioning of sludge samples before sorption experiments has been proposed. The Freundlich isotherm gave the satisfactoriest correlations and has been selected. The determination of the model parameters highlights different trends of sorption between targeted compounds, but always characterized by low sorption affinities. Physico-chemical properties of both compounds and sludge did not show any link with sorption parameters. Consequently, it is not possible to propose a predictive model for the sorption of polar micropollutants depending on both compounds and sludge properties. The removal of a cocktail of anticancer drugs by treatment through a side stream pilot-scale MBR has been investigated. Biodegradation appeared as the prevailing mechanism and was explained by cometabolic interactions. However, these interactions were also responsible for the limitation of biodegradation phenomenon and must be intensify to enhance the removal of these compounds.TOULOUSE-INP (315552154) / SudocSudocFranceF

Elimination of an anticancer drug (cyclophosphamide) by a membrane bioreactor: comprehensive study of mechanisms

The mechanisms of elimination of an anticancer drug (cyclophosphamide) by a membrane bioreactor were investigated. The membrane bioreactor was run for 153 days with a sludge retention time (SRT) of 20 days. A removal efficiency of 60% was observed despite some variations in the influent. This removal was higher than reported in most of the studies in the literature. Biodegradation was the predominant removal mechanism and sorption onto sludge could be neglected

MAB2.0 project: Integrating algae production into wastewater treatment

Different species of microalgae are highly efficient in removing nutrients from wastewater streams and are able to grow using flue gas as a CO2 source. These features indicate that application of microalgae has a promising outlook in wastewater treatment. However, practical aspects and process of integration of algae cultivation into an existing wastewater treatment line have not been investigated. The Climate-KIC co-funded Microalgae Biorefinery 2.0 project developed and demonstrated this integration process through a case study. The purpose of this paper is to introduce this process by phases and protocols, as well as report on the challenges and bottlenecks identified in the case study. These standardized technical protocols detailed in the paper help to assess different aspects of integration including biological aspects such as strain selection, as well as economic and environmental impacts. This process is necessary to guide wastewater treatment plants through the integration of algae cultivation, as unfavourable parameters of the different wastewater related feedstock streams need specific attention and management. In order to obtain compelling designs, more emphasis needs to be put on the engineering aspects of integration. Well-designed integration can lead to operational cost saving and proper feedstock treatment enabling algae growth

Role of sorption and biodegradation in the removal of micropollutants by biological processes : application to anticancer drugs treated by membrane bioreactor

Les travaux de recherche effectués dans le cadre de ce travail de thèse ont eu pour objectif de caractériser le rôle joué par les mécanismes de sorption et de biodégradation dans l’élimination de micropolluants organiques par les boues biologiques, et notamment celles de bioréacteur à membrane. La première étape a consisté en la mise au point d’une méthode d’analyse de molécules anticancéreuses depuis les phases aqueuse et solide des boues. L’extraction des molécules contenues dans la phase aqueuse a été réalisée par une combinaison de cartouches SPE permettant la récupération sélective d’espèces acides, neutres et basiques. L’extraction depuis la phase solide a été rendue possible grâce à l’utilisation de la technique sous solvant pressurisé et à chaud PLE, suivie par une étape de purification directement inspirée de la méthode développée pour la phase aqueuse. Une procédure originale de préparation d’échantillons de boues a été proposée pour estimer rigoureusement le phénomène de sorption. Le modèle de Freundlich est celui qui a donné les corrélations les plus satisfaisantes et a été sélectionné. La détermination des paramètres du modèle a mis en évidence des comportements de sorption différents pour les molécules ciblées, mais toujours caractérisés par des aptitudes de sorption faibles. La mise en relation des propriétés physico-chimiques des molécules, des boues et des paramètres de sorption n’a pas révélé de corrélations évidentes entre ces différents paramètres et ne permet pas de proposer de modèle capable de prédire la sorption en fonction des caractéristiques des boues et des polluants. La caractérisation du comportement d’un cocktail d’anticancéreux lors du traitement par un pilote de bioréacteur à membrane externe a révélé que le mécanisme majeur à l’origine de leur élimination était la biodégradation. Les interactions entre les microorganismes et les micropolluants ciblés sont liées au cométabolisme. Une étude approfondie du mécanisme a révélé que ces mêmes interactions étaient à l’origine d’une limitation de la biodégradation et doivent être intensifiées pour améliorer les performances de traitement sur ce point.The aim of the present work was to characterize the sorption mechanisms and biodegradation role in the removal of some organic micropollutants (i.e. anticancer drugs) by biological sludges, including those of membrane bioreactor (MBR). The first step consisted in the development of an analytical method for the trace determination of anticancer drugs from sludge aqueous and solid phases. The extraction from the aqueous matrix was performed by a combination of SPE cartridges, allowing the selective recovery of acid, neutral and basic species. The extraction from the solid matrix was possible thanks to an extractive step performed by pressurized liquid extraction, followed by a purification step whose procedure was directly inspired from the method developed for aqueous samples. An original procedure for the conditioning of sludge samples before sorption experiments has been proposed. The Freundlich isotherm gave the satisfactoriest correlations and has been selected. The determination of the model parameters highlights different trends of sorption between targeted compounds, but always characterized by low sorption affinities. Physico-chemical properties of both compounds and sludge did not show any link with sorption parameters. Consequently, it is not possible to propose a predictive model for the sorption of polar micropollutants depending on both compounds and sludge properties. The removal of a “cocktail” of anticancer drugs by treatment through a side stream pilot-scale MBR has been investigated. Biodegradation appeared as the prevailing mechanism and was explained by cometabolic interactions. However, these interactions were also responsible for the limitation of biodegradation phenomenon and must be intensify to enhance the removal of these compounds

Lime Pretreatment of Miscanthus: Impact on BMP and Batch Dry Co-Digestion with Cattle Manure

In Europe, the agricultural biogas sector is currently undergoing fast developments, and cattle manure constitutes an important feedstock. Batch dry digester processes with leachate recirculation prove to be particularly interesting for small-scale plants. However, their startup being relatively slow, the process could be facilitated by co-digestion with energy crops. In this study, Miscanthus xgiganteus was chosen for its high biomass yields and low input requirements. The carbohydrate accessibility of this lignocellulosic biomass is limited but may be improved with alkali pretreatment. The efficiency of lime (CaO) pretreatment with low water addition on the biochemical methane potential (BMP) of miscanthus was investigated through two experimental designs (CaO concentrations ranged between 2.5 and 17.5% and pretreatment lasted 1, 3, or 5 days). The pretreated miscanthus was then co-digested with cattle manure in dry leach bed reactors. CaO pretreatments led to a 14–37% improvement of miscanthus BMP, and a 67–227% increase in the first-order kinetics constant; a high contact time was shown to favor methane production. According to these results and to industrial requirements, miscanthus was pretreated with 5 and 10% CaO for 5 days, then co-digested with manure in dry leach bed reactors. Nevertheless, the promising results of the BMP tests were not validated. This could be related to the high water absorption capacity of miscanthus

Lime Pretreatment of Miscanthus: Impact on BMP and Batch Dry Co-Digestion with Cattle Manure

In Europe, the agricultural biogas sector is currently undergoing fast developments, and cattle manure constitutes an important feedstock. Batch dry digester processes with leachate recirculation prove to be particularly interesting for small-scale plants. However, their startup being relatively slow, the process could be facilitated by co-digestion with energy crops. In this study, Miscanthus xgiganteus was chosen for its high biomass yields and low input requirements. The carbohydrate accessibility of this lignocellulosic biomass is limited but may be improved with alkali pretreatment. The efficiency of lime (CaO) pretreatment with low water addition on the biochemical methane potential (BMP) of miscanthus was investigated through two experimental designs (CaO concentrations ranged between 2.5 and 17.5% and pretreatment lasted 1, 3, or 5 days). The pretreated miscanthus was then co-digested with cattle manure in dry leach bed reactors. CaO pretreatments led to a 14–37% improvement of miscanthus BMP, and a 67–227% increase in the first-order kinetics constant; a high contact time was shown to favor methane production. According to these results and to industrial requirements, miscanthus was pretreated with 5 and 10% CaO for 5 days, then co-digested with manure in dry leach bed reactors. Nevertheless, the promising results of the BMP tests were not validated. This could be related to the high water absorption capacity of miscanthus

Quantification de l’adsorption de molécules médicamenteuses (anticancéreux) sur les boues biologiques : impact de la nature de la boue

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