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)

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

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

Development of a multi-residue method for scrutinizing psychotropic compounds in natural waters

International audienceThe present work describes a multi-residue SPE-UPLC–MS/MS method aiming at the characterization of 68 compounds in natural waters, including parent compounds as well as their major metabolites and glucuronide conjugates. Development was conducted toward the quantitative determination of a broad range of analytes belonging to different class of psychotropic drugs such as benzodiazepines, antidepressants, stimulants, opiates and opioids, anticonvulsants, anti-dementia drugs, analgesic and anti-inflammatory drugs (as anthropic indicators) in the low ng L−1 range of concentration. Satisfactory extraction recoveries >70% were obtained for the majority of analytes (49 out of 68) allowing low limits of quantification. LOQ ranged between 0.1 and 17.8 ng L−1 and were lower than 5 ng L−1 for 94% of investigated analytes. Furthermore, addition of 25 isotopic labeled standards allowed to ensure reliability of the optimized method. Quantification errors were typically below 15% with relative standard variations <10% in intermediate precision conditions. Finally, the developed method was implemented in natural waters; sampling campaigns were conducted in the Seine River as a demonstration of the applicability and adequation of the method for its purpose. As a result, 48 out of 68 analytes were identified or quantified; some of them like memantine, rivastigmine, zolpidem 4-phenyl-carboxylic acid, zolpidem 6-carboxylic acid for one of the first time in surface waters. Among investigated psychotropic compounds and metabolites, tramadol, codeine, oxazepam, venlafaxine, O-desmethylvenlafaxine, gabapentin, carbamazepine and 10,11-dihydro-10,11-dihydroxycarbamazepine were found to be the most abundant

Lignes directrices pour la conduite et la validation d'études de stabilité des paramètres physico-chimiques dans le domaine de l'eau

The aim of this document is to make recommendations for performing stability studies of parameters during the chain of measurement of physico-chemical parameters-organic micropollutants, inorganic and organometallic micropollutants, nutrients and macropolluants in aqueous matrices: surface waters, ground waters, wastewaters (ERU, ERI) and solid matrices: suspended solids (SS), sediments, biota, and sludge. It covers sampling operations, transport operations and laboratory storage operations. The purpose of this document is to: • Define the concepts, the necessary key elements for understanding the stability problem of chemical and physico-chemical parameters in the framework of monitoring programs; • Propose strategies and methodological tools for the implementation of stability studies, by comparing and discussing them; • Propose methodologies to define acceptability criteria for key "parameter-support" couples of interest. The stability period covered by this document covers the period from the end of sampling to the start of the first operation of the analysis process in order to limit the evolution of the parameter under consideration.Ce document a pour objectif de faire des recommandations pour la réalisation d'études de stabilité de paramètres au cours de la chaîne de mesure de paramètres physico-chimiques : micropolluants organiques, micropolluants inorganiques et organométalliques, nutriments et macropolluants dans les matrices aqueuses : eaux de surface (ESU), eaux souterraines (ESO), eaux résiduaires (ERU, ERI) et les matrices solides : matières en suspension (MES), sédiments, biote, boues. Il couvre les opérations de prélèvements, les opérations de transports et les opérations de stockage en laboratoire. Ce document a pour objet de : - Définir les concepts, éléments clés nécessaires à la compréhension de la problématique de stabilité des paramètres chimiques et physico-chimiques dans le cadre des programmes de surveillance ; - Proposer des stratégies et des outils méthodologiques de mise en oeuvre des études de stabilité, en les comparant et les discutant ; - Proposer la méthodologie de définition des critères d'acceptabilité pour les couples paramètres-supports d'intérêt. La période de stabilité à laquelle s'intéresse ce document couvre le délai qui s'étend de la fin de l'échantillonnage au démarrage de la première opération du processus d'analyse en vue de limiter l'évolution du paramètre considéré

Recommandations pour garantir la qualité des données de surveillance par échantillonnage passif. Outils émergents

The report prepared up within the AQUAREF program for 2015 provides recommendations to ensure the quality of passive sampling monitoring data. This type of sampling method could in the future be used in regulatory monitoring, and it seems necessary to prepare the tools, procedure that will be able to ensure the reliability of such data. The report first proposes an organization of the chain of responsibilities between: * the customer, * a pilot in charge of contacts with customer, sampling operations and of the the final report * and the laboratory which would be in charge of the analytical part on the passive sampling tool transmitted by the pilot. This organization is considered as an example. Other organizations are possible, provided they specify the different roles and responsibilities identified. Based on this scheme recommendations are proposed on: * technical aspects (method validation, estimation of quantification limits, quality control) in the laboratory or in the field, * the organizational aspects (traceability, documentation, report). Proposals are also made for the acquisition of additional information on the characteristics of the water body to take into account some of these characteristics in the calculation of the result or to improve the interpretation of results. Finally some preliminary proposals are made for scenarios on data exchange.Ce rapport rédigé dans le cadre du programme de travail d’AQUAREF pour l’année 2015 propose des recommandations pour garantir la qualité des données de surveillance par échantillonnage passif. Ce type d’échantillonnage pourrait dans l’avenir être utilisé en contexte réglementaire et il est indispensable de démarrer des réflexions sur les outils, processus permettant d’assurer la fiabilité de ces données. Le rapport propose tout d’abord une organisation de la chaine des responsabilités entre :  - le client ou commanditaire,  - un pilote en charge du contact avec le client, des opérations d’échantillonnage et de la restitution du résultat final, - et le laboratoire qui serait en charge de la partie analytique sur l’outil d’échantillonnage passif transmis par le pilote.  Cette organisation n’est qu’un exemple. D’autres organisations sont possibles pour autant qu’elles précisent bien les différents rôles et responsabilités identifiées.  Sur la base de ce schéma des recommandations sont faites sur : - les aspects techniques (validation de méthodes, estimation des limites de quantification, contrôles qualité) au laboratoire ou sur le terrain,  - sur les aspects organisationnels (traçabilité, documentation, rapport).    Des propositions sont également faites pour l’acquisition d’informations complémentaires sur les caractéristiques de la masse d’eau échantillonnée afin de prendre en compte le cas échéant ces paramètres pour l’estimation du résultat ou bien pour aider à l’interprétation des résultats. Enfin, quelques propositions préliminaires sont faites concernant les scénarios d’échanges informatiques des données.  

Positionnement et actions d'AQUAREF sur l'analyse non ciblée pour la surveillance des milieux aquatiques

National audiencePrésentation des travaux et réflexions du consortium Aquaref sur l'intérêt de l'analyse chimique non ciblée pour anticiper la surveillance de demain. Présentation 1/des premiers résultats d'essais collaboratifs pour l'harmonisation des méthodologies et 2/ de l'étude de démonstration dans le cadre du réseau de surveillance prospective