An in situ intercomparison exercise on passive samplers for the monitoring of metals, polycyclic aromatic hydrocarbons and pesticides in surface water

An intercomparison exercise on passive samplers (PSs) was organized in summer 2010 for the measurement of selected metals, polycyclic aromatic hydrocarbons (PAHs) and pesticides in surface waters. Various PSs were used and compared at 2 rivers sites and one marine lagoon. A total of 24 laboratories participated. We present selected significant outputs from this exercise, including discussion on quality assurance and quality control for PSs, the interlaboratory variability of field blanks, time weighted average water concentrations and its uncertainties, the representativity of DGT samples, the ability of PSs to lower limits of detection, PAH fingerprints in various PSs compared with spot samples, and the relevance of the permeability reference compounds (PRC) approach for POCIS with pesticides. These in situ intercomparison exercises should enable to progress on the harmonization of practices for the use of passive sampling, especially for priority chemical monitoring and regulatory programs in compliance with the Water Framework Directive (WFD) and Marine Strategy Framework Directive (MSFD)

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

Non-target screening and environmental specimen banking: French perspectives

International audienceIn 2016, French regulatory bodies launched a new and ambitious monitoring program so called “prospective monitoring network”, in view of improving and promoting knowledge acquired about the occurrence of contaminants in water environments. Among various actions supported by this program, a specific one is focused on non-target screening strategies. It aims, in particular to demonstrate and highlight the potential of suspect- and non-target screening approaches for retrospective analysis in connection with environmental specimen banking (either physical samples or digital data). In fact, some mass spectral data banks have been recently built at the level of the research community but outside from conventional ESBs arena and without complete raw data storage, which reduce potential data reprocessing. Among its major advantages: retrospective analysis and elucidation of unknown compounds; alternatives to specimen banking of conventional matrix can be highlighted. As instance, a prototype of a 'Digital Sample Freezing Platform' has been developed by the NORMAN network, to host full scan liquid chromatography-mass spectrometry data, allowing for retrospective analysis of any environmental sample for a wide range of pollutants. In this context the action of AQUAREF aims to address the following points, essential for improved design of ESBs for NTS applications and to ensure the exploitability of such ESB:•Appropriate codification to allow an efficient data exchange •Key metadata that have to be stored and made available •Properties of samples and data, accessibility, promotion•Metrological infrastructure: long term storage, QA/QC, SOP, …The proposal will present French works that are currently performed by AQUAREF consortium (French Reference Laboratory for Water and Aquatic Environment)

A French collaborative study to evaluate the impact of acquisition workflow with LC-HRMS on environmental data

International audienceAQUAREF, the French national reference laboratory of aquatic environment monitoring, is a consortium of five French national research institutes (BRGM, IFREMER, INERIS, Irstea and LNE) joined together to reinforce the French expertise in aquatic environments monitoring. AQUAREF aims at developing and testing the operational applicability of new tools and innovative strategies for the identification of emergent contaminants in a more relevant and cost-effective way. High resolution mass spectrometry coupled with chromatography already presents great interest for non-targeted and suspected screening approaches. However, in order to integrate these new methodologies for the aquatic environment monitoring, the different laboratory practices should be well identified and harmonized. In that way a collaborative trial was made with 11 French laboratories using LC-HRMS with several different equipments.The aim of this intercomparison exercise was to identify the impact of chromatographic methods (shift of retention time,ionization, …), specificity of equipment (detection, fragmentation, …) and source of databases (intern obtained from standard injections or extern by the use of bibliographic, constructor or on-line databases) on identification of compounds.Two test materials were sent to the laboratories: a solution spiked with standards and a river SPE extract (unspiked). In addition, both material tests were analysed with a unique analytical method imposed by AQUAREF and with the laboratories own methods in positive and negative electrospray ionisation modes.Raw analytical data were firstly processed (both standard mix solution and river SPE extract) with a targeted or suspected screening approaches (levels of confidence 1 or 2 from the classification of Schymanski - (Schymanski et al., 2014) based on a list of 30 compounds and target database of each laboratories. Then, the river SPE extract was treated for suspect compound identification based on a common database of 16 compounds.For the targeted and suspected screening approaches, the results highlighted that:•The most relevant compounds were identified in river SPE extract by all expert laboratories. More than 100 compounds were determined between all laboratories.•For compounds identification, the mastering level is better in the positive electrospray ionization mode than the negative one;•A generic chromatographic method can cover a wide range of molecules but from the standard mix analysis, exclusions could be observed•there is a need of homogenization surrounding qualification of data compliance (validation criteria) in addition to the implementation of Schymanski classification •Need to implement QA/QC validation steps (blank, internal standards, …)•This exercise has been helpful because it has served to share common difficulties (not distinguishable isomers, sample contaminations…) between expert laboratories. Concerning communication to the end users, there is a need to clarify the expression of results, by being clear about limitations (data compliance, false negative/positive, etc…)

Les pièges à particules : principes, état de l'art et perspectives pour la surveillance des milieux aquatiques - focus sur les cours d'eaux

[Departement_IRSTEA]Eaux [TR1_IRSTEA]BELCA [ADD1_IRSTEA]Systèmes aquatiques soumis à des pressions multiples [Relecteur_IRSTEA]Yari, A. ; Ghestem, J.P.Particulate matters are a central point in the assessment of water bodies. A wide range of techniques is available for sampling of particulate matters (TSS / Sediment) in aquatic systems. The relevance of each technique is determined by the flows and dynamics of the particulate matters, the data requirements (limit of quantification, accuracy, uncertainty, representativity ...) and available resources. These factors determine the sampling strategy and method to be adopted and how the sample should be handled (transported and stored) after collection. It is therefore essential to pay particular attention to the following question: Which sampling approach (s) will provide the most representative sample? Sediment traps are collectors, boxes, or baskets, placed in the water column and which capture the particulate matters continuously by decantation. Once deployed, the water passes through the system in which a decrease in the velocity of the flow occurs, causing the particulate matters to decant in the tool. The objective of this action is to evaluate the potential of sediment traps in the monitoring of chemical contamination of aquatic environments. The main observations show that sediment traps can be integrated into strategies for the chemical monitoring of aquatic environments' contamination, in particular to: - Integrate the variability of contaminant concentrations in particulate matter; - Track chemical contamination of water bodies; - Improve the representativeness of the assessment of chemical contamination of aquatic environments by an integrated measure, in addition to integrative samplers; - Meet chemical monitoring requirements for EQS and whole water; in addition to passive integrative samplers; - Estimate flows of particulate contaminants.La prise en compte des particules est un point central de l'évaluation des masses d'eaux. Un large éventail de techniques est disponible pour l'échantillonnage des particules (MES/Sédiments) dans les systèmes aquatiques. La pertinence de chaque technique est déterminée par les flux et dynamiques des particules, les exigences sur les données (limite de quantification, exactitude, incertitude, représentativité, ...) et les ressources disponibles. Ces facteurs déterminent la méthode d'échantillonnage à adopter et la manière dont l'échantillon devra être manipulé (transporté et stocké) après la collecte. Il est donc indispensable de porter une attention particulière à la question suivante : quelle(s) approche(s) d'échantillonnage fournira (ont) 'échantillon le plus représentatif ? Les pièges à particules sont des collecteurs, boîtes, ou paniers, placés dans la colonne d'eau et qui capturent les particules en continu par décantation. Une fois déployé, l'eau passe au travers du système au sein duquel une diminution de la vitesse du débit s'opère, provoquant la décantation des particules dans l'outil. L'objectif de cette action est d'évaluer le potentiel des pièges à particules dans le cadre de la surveillance de la contamination chimique des milieux aquatiques. Les principales observations démontrent que les pièges à particules peuvent être intégrés dans des stratégies de surveillance de la contamination chimique des milieux aquatiques, notamment pour : - Intégrer la variabilité des concentrations en contaminants dans les particules; - Suivre en tendance la contamination chimique des masses d'eau ; - Améliorer la représentativité de l'évaluation de la contamination chimique des milieux aquatiques par une mesure intégrée, en complément d'échantillonneurs intégratifs ; - Répondre aux exigences de surveillance de l'état chimique NQE et fraction eau totale ; en complément d'échantillonneurs intégratifs passifs ; - Estimer des flux de contaminants particulaire

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

Validation and uncertainties evaluation of an isotope dilution-SPE-LC–MS/MS for the quantification of drug residues in surface waters

International audienceThe present work describes the development and validation of a reference method conducted at the French National Institute of Metrology (LNE) for the quantitative determination of psychoactive compounds in the dissolved fraction of surface waters. More specifically an isotope dilution-SPE-LC-MS/MS based method has been implemented for the characterization of a broad range of analytes belonging to different classes of psychotropic drugs such as benzodiazepines, antidepressants, stimulants, opiates and opioids, anticonvulsants, anti-dementia drugs, analgesics as well as the anti-inflammatory drug diclofenac in the low ng L(-1) range of concentration. Full validation of the method was performed following procedures described by the French standard NF T90-210. Limits of quantification between 0.14 and 3.54 ng L(-1) were obtained. Method recoveries from 71 to 123% were observed with standard deviation below 10% in intermediate precision conditions. Accuracy was determined for every compound: measurement errors were between -4 and +1% and standard deviations in intermediate precision conditions were included within a 1-9% interval. Finally, measurement uncertainties were evaluated following the Guide to the expression of uncertainty in measurement (GUM). Expanded uncertainties (k=2) ranged from 2% for carbamazepine, EDDP (2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine) and venlafaxine to 17% for diazepam. The validated method was implemented to Seine river surface waters demonstrating its fitness for purpose. All compounds were detected and 22 out of 25 analytes were quantified. More specifically, measured concentration ranged from 0.39 ng L(-1) for MDMA (3,4-methylene-dioxy-N-methylamphetamine) to 182 ng L(-1) for gabapentine