Les substances émergentes dans les écosystèmes aquatiques français : une application aux alkylphénol-polyéthoxylés et aux substances pharmaceutiques

Les alkylphénol-polyéthoxylés et les substances pharmaceutiques appartiennent à la classe des contaminants émergents qui sont depuis peu étudiés dans les milieux naturels. Ces composés d’usage très répandu (aussi bien en termes d’applications qu’en termes de quantité) sont introduits dans le milieu aquatique, via les stations d’épuration, principalement et sont susceptibles d’engendrer des effets toxiques sur les organismes vivants dans ces milieux. La première partie de ce travail de thèse a consisté en le développement et la validation de différentes méthodologies d’échantillonnage (ponctuel et intégratif (POCIS)), de différents protocoles d’extraction (SPE, extraction assistée par micro-ondes) et d’analyse (CL/SM, CL/SM/SM), nécessaires pour un dosage fiable des alkylphénol-polyéthoxylés et des substances pharmaceutiques dans les différents compartiments des systèmes aquatiques (phases dissoute, particulaire et sédimentaire, organismes biologiques). Ensuite, un bilan de la contamination de différents systèmes aquatiques (le bassin de d’estuaire de Seine, la Garonne et la Gironde, la baie de la Vilaine, la baie de l’Authie, l’Adour, la rade de Marseille) a été dressé. Une contamination généralisée par ces composés a été mise en évidence pour l’ensemble des sites étudiés. Les concentrations mesurées apparaissent extrêmement variables selon la classe de molécule considérée, les sites et le temps avec des concentrations comprises entre le ng.l-1 et la dizaine de µg.l-1 pour les phases dissoutes et de la dizaine de ng.g-1 et la dizaine de µg.g-1 pour les phases solides (plusieurs centaines de µg.g-1 dans les boues d’épuration). Ces études ont également permis de documenter la présence et le devenir des molécules ciblées dans les stations d’épuration et ont permis d’en évaluer l’efficacité quant l’abattement des substances incriminées. Enfin, ces travaux ont également permis de mettre en évidence des phénomènes de partition entre les phases dissoutes et les phases solides ainsi que des phénomènes de transferts vers les organismes du milieu.Alkylphenol-polyethoxylates and pharmaceutical substances belong to the class of the emerging contaminants which have been recently studied in natural environments. These compounds of very widespread use (in terms of applications as well as in terms of quantity) are introduced into the aquatic environment, via the wastewater treatment plants, mainly, and are likely to generate toxic effects on the living organisms in these systems. The first part of this work consisted in the development and validation of various methodologies of sampling (grab sampling and integrative sampling (POCIS)), of various protocols of extraction (SPE, microwaves assisted extraction) and of analysis (LC/MS, LC/MS/MS), necessary for a reliable quantification of alkylphenol-polyethoxylates and pharmaceutical substances in the various compartments of aquatic systems (phases dissolved, particulate and sedimentary, biological organisms). Then, an assessment of the contamination of numerous aquatic systems (the catchment area of the Seine estuary, the Garonne and the Gironde, the bay of Vilaine, the bay of Authie, the Adour, the Mediterranean coast of Marseilles) was undertaken. A generalized contamination by these compounds was highlighted for all the studied sites. The measured concentrations appear to be extremely variable according to the class of molecule considered, the sites and time with concentrations ranging from the ng.l-1 to tens of µg.l-1 for the dissolved phases and from tens of ng.g-1 to tens of µg.g-1 for the solid phases (several hundreds of µg.g-1 in the clarification sludge). These studies also made it possible to document the presence and the fate of these molecules in the French wastewater treatment plant and made it possible to evaluate their effectiveness to remove the studied compounds. Lastly, this work also made it possible to highlight phenomena of partition between the dissolved phases and the solid phases as well as phenomena of transfers through the biological organisms

Les substances émergentes dans les écosystèmes aquatiques français : une application aux alkylphénol-polyéthoxylés et aux substances pharmaceutiques

Les alkylphénol-polyéthoxylés et les substances pharmaceutiques appartiennent à la classe des contaminants émergents qui sont depuis peu étudiés dans les milieux naturels. Ces composés d’usage très répandu (aussi bien en termes d’applications qu’en termes de quantité) sont introduits dans le milieu aquatique, via les stations d’épuration, principalement et sont susceptibles d’engendrer des effets toxiques sur les organismes vivants dans ces milieux. La première partie de ce travail de thèse a consisté en le développement et la validation de différentes méthodologies d’échantillonnage (ponctuel et intégratif (POCIS)), de différents protocoles d’extraction (SPE, extraction assistée par micro-ondes) et d’analyse (CL/SM, CL/SM/SM), nécessaires pour un dosage fiable des alkylphénol-polyéthoxylés et des substances pharmaceutiques dans les différents compartiments des systèmes aquatiques (phases dissoute, particulaire et sédimentaire, organismes biologiques). Ensuite, un bilan de la contamination de différents systèmes aquatiques (le bassin de d’estuaire de Seine, la Garonne et la Gironde, la baie de la Vilaine, la baie de l’Authie, l’Adour, la rade de Marseille) a été dressé. Une contamination généralisée par ces composés a été mise en évidence pour l’ensemble des sites étudiés. Les concentrations mesurées apparaissent extrêmement variables selon la classe de molécule considérée, les sites et le temps avec des concentrations comprises entre le ng.l-1 et la dizaine de µg.l-1 pour les phases dissoutes et de la dizaine de ng.g-1 et la dizaine de µg.g-1 pour les phases solides (plusieurs centaines de µg.g-1 dans les boues d’épuration). Ces études ont également permis de documenter la présence et le devenir des molécules ciblées dans les stations d’épuration et ont permis d’en évaluer l’efficacité quant l’abattement des substances incriminées. Enfin, ces travaux ont également permis de mettre en évidence des phénomènes de partition entre les phases dissoutes et les phases solides ainsi que des phénomènes de transferts vers les organismes du milieu.Alkylphenol-polyethoxylates and pharmaceutical substances belong to the class of the emerging contaminants which have been recently studied in natural environments. These compounds of very widespread use (in terms of applications as well as in terms of quantity) are introduced into the aquatic environment, via the wastewater treatment plants, mainly, and are likely to generate toxic effects on the living organisms in these systems. The first part of this work consisted in the development and validation of various methodologies of sampling (grab sampling and integrative sampling (POCIS)), of various protocols of extraction (SPE, microwaves assisted extraction) and of analysis (LC/MS, LC/MS/MS), necessary for a reliable quantification of alkylphenol-polyethoxylates and pharmaceutical substances in the various compartments of aquatic systems (phases dissolved, particulate and sedimentary, biological organisms). Then, an assessment of the contamination of numerous aquatic systems (the catchment area of the Seine estuary, the Garonne and the Gironde, the bay of Vilaine, the bay of Authie, the Adour, the Mediterranean coast of Marseilles) was undertaken. A generalized contamination by these compounds was highlighted for all the studied sites. The measured concentrations appear to be extremely variable according to the class of molecule considered, the sites and time with concentrations ranging from the ng.l-1 to tens of µg.l-1 for the dissolved phases and from tens of ng.g-1 to tens of µg.g-1 for the solid phases (several hundreds of µg.g-1 in the clarification sludge). These studies also made it possible to document the presence and the fate of these molecules in the French wastewater treatment plant and made it possible to evaluate their effectiveness to remove the studied compounds. Lastly, this work also made it possible to highlight phenomena of partition between the dissolved phases and the solid phases as well as phenomena of transfers through the biological organisms

Creation of a New European Metrology Network on Pollution Monitoring (POLMO)

Driven by a wide set of European regulations, strategies and action plans, to cope with and to minimize environmental pollution in Europe, the need for pollution monitoring especially on chemicals and radionuclides is constantly growing in importance as it supports the ambition of the European Union: “In 2050, we live well within the planet’s ecological limits”. This can be reached only on the basis of high-quality data on pollution monitoring as well as strong metrological cooperation between all relevant European partners and stakeholders. To foster this goal a strong, collaborative, multi-disciplinary, long-term and self-sustaining “European Metrology Network on pollution monitoring”, as a metrological reference infrastructure, needs to be generated and managed. Such a metrological network will be developed over the next years within the framework of an EMPIR network project called POLMO.POLMO will focus first on chemicals and radionuclides pollution in the different compartments of the environment (water, air, soil) but also will strive to expand its expertise to other areas such as light or noise pollution on longer terms. The detailed objectives of the POLMO network are:To become an international point of focus and create stronger connections for all the different stakeholder communities (active networks and associations, research centres, testing laboratories, manufacturers, industry, standardization bodies, regulators) with NMIs/DIs. This should allow new approaches to meet stakeholder requirements by developing multidisciplinary metrological research overpassing current regulatory principles.To maximize efficiency of NMIs/DIs activity and minimise resources (human, infrastructures, financial) as well as knowledge, data and best-practice transfers between NMIs/DIs and with the main EU organisations as well as stakeholders in the POLMO context.Demonstrate the role of metrology in the European research area. Moreover, to define the place and role of the metrology in the pollution monitoring chain of measurements and to demonstrate its added value and benefit.To maximize and accelerate dissemination of reliable metrology practices for pollution monitoring through mutually recognized and agreed approachesThe goal of this poster is to describe how the POLMO Metrology Network will be implemented from mid 2022 in particular by the means of an EMPIR JNP (Joint Network Programme) in the framework of EURAMET (European Association of National Metrology Institutes). The project could support the need for harmonization and reliability of e-DNA measurements, as necessary to support their recognition, by organizing the development of missing metrological tools at European leve

Metrological Needs for Monitoring Aquatic Environments: From the Demonstration of Metrological Traceability to the Decision Making Process

In Europe, the implementation of the Water Framework Directive WFD, in 2001, marks a strong standpoint. In addition to its objectives of a return to good chemical and good ecological status by the year 2015, it fixes the achievement of trends over space and time. The new requirements that arise from the WFD put considerable financial pressure on water management authorities. Because the overall decision-making process relies most of the time on acquired data, it puts considerable pressures on the display of high quality biological as well as chemical environmental measurements. However, performing measurements implies that i) the demonstration of their metrological traceability ii) the evidence of their achievement thanks to accurate and sensitive analytical methods and iii) their statement with a reliable estimate of expanded uncertainty is thoroughly addressed. Moreover, the measurement representativeness, especially in highly dynamic environment, is of prime interest in a context where comparability over space and time is needed. As a consequence, considerable challenges are dwelt on metrologists with great emphasis on parameters that are under regulation. This paper will discuss a panorama of the unavoidable metrological questions that have to be addressed: from the definition of the measurand to the final estimation of uncertainty; from the initial performances demonstration of methods to the final demonstration of mastery and capabilities through inter comparison laboratories and reference materials. A focus will be made on upcoming alternative monitoring approaches that are seldom addressed from a metrological point of view

Reliability of organic compounds measurement in enviromental monitoring. The key role of analytical standard substance. A study case on alkylphenols

The overall management and decision making system driven by the Water Framework Directive (WFD) and other European water policies is strongly dependent on the quality of monitoring data. Performing fit for purpose measurements implies the demonstration of their metrological traceability, their procuration according to accurate and sensitive analytical methods and a realistic estimate of expanded uncertainty. This can only be achieved by the provision of reference measurement standard substances, whenever possible traceable to the SI, which serve as reference points for the implementation of a traceability infrastructure supporting a monitoring network in Europe. Routine laboratories operating in French water bodies monitoring program have repeatedly expressed to AQUAREF their difficulties regarding alkyphenols, one of the priority substances of the WFD. Accordingly, LNE and INERIS handled a study that aims at assessing the purity of nonylphenols commercially available analytical standard and discusses its impacts. The work highlights that: identity of the organic analytical standard substance reference materials should be clearly documented and demonstrated, purity assessment should be reported with a reliable uncertainty evaluation

Methodological Framework Design to sustain integration of non-target screening into French national water monitoring programs

Non-target analysis for the identification of contaminants of emerging concern or transformation products in the environment are increasingly popular and of great interest in terms of research areas as well as for improvement of regulatory monitoring, such as WFD. AQUAREF, the French Reference Laboratory for Water and Aquatic Environment has defined and implemented a technical program of actions in order to identify and propose some solutions to the main technical and operational locks..

Comparaison de différentes stratégies d’évaluation de la performance dans les essais d’aptitude par comparaisons interlaboratoires

Proficiency Testing (PT) uses interlaboratory comparisons to evaluate the performance of participants for tests or measurements. The statistical design and analytical techniques applied must be appropriate for the stated purpose of each PT. Most PT schemes compare the participant’s deviation from an assigned value with a numerical criterion. Different scoring strategies are available and commonly used, as described in the International Standard ISO 13528, with a new version scheduled for publication at the end of 2015. The different strategies used to determine the assigned value and the criterion to calculate performance statistics are critical because they will lead to different interpretations. It is very important to consider whether the assigned value and its standard uncertainty as well as the criterion are independent of participant results, or are derived from the submitted results. The two strategies will be presented, compared and discussed in perspectives of the concept of comparability and the concept of compatibility that are defined in the International Vocabulary of Metrology (VIM). To do so, a certified reference material was deployed in two proficiency testing schemes. They aimed at determining a set of relevant pesticidesbelonging to two chemical families: triazines and phenylurea - that are part of the list of priority substances of the European Water Framework Directive. Various methods to determine the assigned value from the results of participants were used : the algorithm A on one hand and the Q method and Hampel estimates on the other hand, as introduced in the new version of ISO 13528. Moreover, on the basis of the available estimators, the complementarity use of En and Z score in the perspectives of evaluating the performance of laboratories was addressed

Metrological Needs for Monitoring Aquatic Environments: From the Demonstration of Metrological Traceability to the Decision Making Process

In Europe, the implementation of the Water Framework Directive WFD, in 2001, marks a strong standpoint. In addition to its objectives of a return to good chemical and good ecological status by the year 2015, it fixes the achievement of trends over space and time. The new requirements that arise from the WFD put considerable financial pressure on water management authorities. Because the overall decision-making process relies most of the time on acquired data, it puts considerable pressures on the display of high quality biological as well as chemical environmental measurements. However, performing measurements implies that i) the demonstration of their metrological traceability ii) the evidence of their achievement thanks to accurate and sensitive analytical methods and iii) their statement with a reliable estimate of expanded uncertainty is thoroughly addressed. Moreover, the measurement representativeness, especially in highly dynamic environment, is of prime interest in a context where comparability over space and time is needed. As a consequence, considerable challenges are dwelt on metrologists with great emphasis on parameters that are under regulation. This paper will discuss a panorama of the unavoidable metrological questions that have to be addressed: from the definition of the measurand to the final estimation of uncertainty; from the initial performances demonstration of methods to the final demonstration of mastery and capabilities through inter comparison laboratories and reference materials. A focus will be made on upcoming alternative monitoring approaches that are seldom addressed from a metrological point of view

Aquaref - Opérations d’échantillonnage par échantillonnage intégratif passif en cours d’eau et eau littorale dans le cadre des programmes de surveillance DCE – Edition 2021

Les guides échantillonnage Intégratif Passif (EIP) regroupent les recommandations techniques AQUAREF pour la mise en œuvre harmonisée des opérations d’échantillonnage, d’analyse par les échantillonneurs intégratifs passifs dans le cadre des programmes de surveillance des masses d’eaux DCE ou plus largement de surveillance ou de diagnostic des milieux. Ces guides visent à garantir la qualité des données nécessaire à leur exploitabilité. L’arrête surveillance du 26 avril 2022 introduit les EIP comme support de surveillance pour la matrice eau pour l’évaluation des concentrations en moyenne annuelle. Il précise que pour les métaux, cette surveillance par EIP ne concerne que les eaux littorales et que la liste des substances pour lesquelles cette possibilité est ouverte sera définie par une note ministérielle. La bonne pratique des opérations d’échantillonnage et notamment d’échantillonnage intégratif passif conditionne en très grande partie la fiabilité, la comparabilité des données de mesure et donc l’interprétation que l’on pourra en faire. L’opérateur d’échantillonnage intégratif passif prendra toutes les dispositions pour : - assurer la représentativité des échantillonnages et l’intégrité des EIP, avant leur mise en place dans le milieu puis après leur retrait du milieu jusqu’au(x) laboratoire(s) d’analyses ; - éviter la contamination du milieu lors de l’échantillonnage (bottes souillées, espèces invasives, etc.) en s’équipant de protections individuelles propres et en utilisant du matériel nettoyé. Le présent guide formule différentes recommandations en matière d’opérations d’échantillonnage intégratif passif. Ce guide ne peut prétendre au caractère exhaustif de ces recommandations. AQUAREF recommande que pour les dispositions non indiquées dans ce guide, les opérateurs d’échantillonnage prennent comme référence les normes et guides en vigueur, notamment : NF EN ISO 5667-23 (2011) - Qualité de l'eau - Échantillonnage - Partie 23 : lignes directrices pour l'échantillonnage intégratif passif dans les eaux de surface En fonction des contextes, des outils et des demandes, les opérations d’échantillonnage intégratif passif peuvent s’accompagner au moment de la mise en place dans le milieu et du retrait, d’opérations de mesure de paramètres physico-chimiques dans l’eau. Ce guide ne traite pas de ces mesures. On se reportera au « Guide des opérations d'échantillonnage d'eau en cours d'eau » ou au guide « Opérations d’échantillonnage en milieu marin dans le cadre des programmes de surveillance DCE (matrices : eau, sédiment et biote) - Recommandations techniques », disponibles sur le site AQUAREF