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)

Volatile metal and metalloid species (Pb, Hg, Se) in a European urban atmosphere (Bordeaux, France)

cited By 43International audienceAmbient air measurements of volatile metal and metalloid compounds were conducted in a European urban environment (Bordeaux, France). Air samples were collected with a cryogenic trap and analyzed by low-temperature gas chromatography with ICP/MS detection. Indoor and outdoor sites were studied. Tetraalkyllead compounds (Me(4-n)Et(n)Pb, n = 0-4) and elemental mercury were found to be the major volatile metal species. Average concentrations of 15.5 and 2.7 ng/m3 as metal have been reported respectively for total alkyllead species and elemental mercury in open area. These results illustrate the general phasing out of atmospheric lead initiated in the past decade. Accumulation of dimethyl selenide has been recorded in a building probably originating from human breath. Volatile metal species distribution in the different sites is discussed with regards to meteorological conditions and automotive traffic parameters. Occurrence of unknown volatile metal and metalloid species likely to occur in urban environment is also reported and discussed

Speciation analysis for organotin compounds in sediments by capillary gas chromatography with flame photometric detection after microwave-assisted acid leaching

cited By 61International audienceA rapid method is described for the speciation of butyl-and phenyltin compounds in sediments. The procedure was based on the quantitative microwave-assisted leaching of the target compounds from a sediment sample with ethanoic acid followed by their derivatization with sodium tetraethylborate in the aqueous phase. The ethyl derivatives of the analyte compounds were subsequently extracted into iso-octane and separated by capillary GC. A modified flame photometer with a graphite burner fitted with a 610 nm bandpass filter was used for detection. A desulfurization procedure used prior to GC was optimized and then incorporated into the analytical scheme in order to remove the sulfur present in sediments which would otherwise interfere with the detection of the organotin compounds. The leaching of the analyte species in a focused microwave field took only 3-4 min and the analysis time was limited by the duration of the gas chromatographic run (15 min). The effects of pH, temperature and time for ethylation of methyl-, butyl-, phenyl-, octyl- and dodecyltin compounds were evaluated. The possibility of accelerating the ethylation, by using a focused microwave field, was examined. The detection limit of the procedure was 10 ng g-1 for 0.5 g of sediment. A typical precision for this determination was 5-10%. The method developed was validated by analysing two CRMs (NRCC PACS-1 and BCR CRM 462). A series of applications in the Arcachon Bay and Greek coastal monitoring programme demonstrated the presence of butyl and phenyltin species

Towards non‐polluting organotin reagents for synthesis

cited By 19International audienceNew polymer‐supported organotin reagents have been prepared. The reducing ability of a polystyrene‐supported organotin hydride was evaluated by reaction with haloalkanes. The level of organotin pollution was monitored in comparison with that generated by Bu3SnH, using ICP–MS analysis. Copyright © 1995 John Wiley & Sons, Ltd

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

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

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

Polluants émergents : des campagnes prospectives à la surveillance réglementaire, les actions du laboratoire national de référence AQUAREF

National audienceLes polluants dits « émergents » sont pour la plupart mal connus et les méthodes permettant leur surveillance sont souvent peu robustes. Le processus d’identification de ces polluants par de vastes campagnes prospectives puis leur mise en surveillance réglementaire se heurtent donc parfois à des problématiques techniques liées à l’échantillonnage ou à l’analyse. AQUAREF, le laboratoire national de référence pour la surveillance des milieux aquatiques, a contribué à l’ensemble de ce processus, depuis les campagnes prospectives jusqu’à la déclinaison opérationnelle dans la réglementation nationale. Les campagnes nationales récentes ont montré le besoin de prendre en compte de façon précoce les questions de fiabilité des données. Concernant l’échantillonnage par exemple, la maitrise des contaminations ainsi que la connaissance de la stabilité des substances sont apparues comme des points clés pour la fiabilité des données. Suite aux campagnes prospectives, il est nécessaire de permettre une mise en surveillance régulière fiable de ces substances par des recommandations techniques réalistes et adaptées aux besoins des gestionnaires. Enfin AQUAREF joue également un rôle dans le processus de transfert de méthodes vers les laboratoires prestataires. Tous ces éléments ne sont pas spécifiques des polluants émergents mais il semble indispensable qu’ils soient pris en compte très tôt dans le processus d’identification et de surveillance de ce type de polluants

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