Bioanalytical characterization and source identification of a high glucocorticoid contamination in a river under urban and industrial pressures
Synthetic glucocorticoids (GCs) are a group of steroids that are massively used as anti-inflammatory drugs to treat a broad spectrum of deseases such as asthma or arthritis. They may enter surface waters via urban, hospital and/or pharmaceutical industry effluents and were already detected in surface waters at concentrations ranging from < 1 to tens of ng/L. In organisms, GCs are designed to act through the glucocorticoid receptor (GR) and some studies have reported adverse effects on aquatic vertebrates, such as fish. Overall, there is still a need for knowledge on the sources and driver compounds for GR activity in different contexts. In the frame of a French national survey of EDCs in surface waters using in vitro bioassays, we previously identified a hotspot river site with high GR activity. To further identify the source(s) and the nature of this contamination, an investigative monitoring based on bioassay (MDA-Kb2) and chemical analyses was implemented in the current study. A contamination mapping was established on the basis of bioassay data, along a 40 km streatch upstream and downstream of the contaminated site allowing identification of the discharge of the contamination in the river and of its highly probable industrial origin in the sewerage network, although the contribution of waste waters from a hospital could not be excluded. By using a suspect screening approach based on HR-MS, fluticasone propionate as well as few other GCs were identified in the samples. Mass balance analysis based on quantitave chemical analysis confirmed fluticasone propionate main role in the measured GR activity. The high mobility and persistence of this contamination points out possible high environmental concern in terms of its fate and hazard for aquatic organisms.
(03/06/2021)
INERIS, SEBIO, INERIS, URCA, ULH, NU, URCA, CNRS, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, M2C, UNICAEN, NU, INSU - CNRS, UNIROUEN, NU, CNRS
Nation-Wide Monitoring Campaign of 53 Contaminants of Emergent Concern in Surface Waters and Sediment (EMNAT 2018): Occurrence and PNEC Exceedance Evaluation
The overall objective of the 2018 campaign to monitor substances of emerging concern in surface water (continental and coastal) and sediment, known as EMNAT 2018, is to provide the exercise of prioritization of emerging substances, which is being carried out in 2020, with monitoring data. This exercise should make it possible to update the list of relevant substances to be monitored (SPAS) as part of future WFD monitoring programmes, which will be implemented in the next water body management cycle (2022).This campaign, led by Ineris, collected nearly 14,000 data regarding 53 substances of emerging concern (36 biocides and 17 surfactants, selected by the Prioritization Experts Committee) in surface water and sediments on a total of 98 sites in metropolitan France and in the overseas departments and regions (DROM). Frequencies of quantification and concentration levels were determined and discussed. Warning indicators, calculated from PNEC (predicted no-effect concentrations), allowed to estimate the criticality of the risk of exceeding them (frequency and degree of PNEC exceedance).Regarding impregnation levels in the environment, with respect to surfactants, Linear Alkybenzene Sulfonic acids (LAS) were the most frequently quantified substances and at the highest median concentrations in water and sediment samples, in metropolitan France and in the DROM. Regarding biocides, fipronil was the most frequently quantified substance in water samples in metropolitan France and in the DROM, but at lower median concentrations than other biocides. Methyl nonyl ketone was the most frequently quantified substance and at higher median concentrations in sediment samples from metropolitan France and in the DROM.Based on the available PNECs, the highly critical substances with respect to exceeding the PNEC are:- LAS C11, C12 and C13 in mainland and the DROM water and sediment samples, - methyl nonyl ketone in mainland and the DROM sediment samples, - fipronil and methylisothiazolinone in mainland water samples, and - fipronil, octylisothiazolinone, methyl nonyl ketone and a triethanolamine based esterquat in mainland sediment samples.
(03/06/2021)
INERIS, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, ISA, UCBL, INC-CNRS, CNRS, AFB
Per- and Polyfluoroalkyl Substances (PFAS) in Surface Sediments: Occurrence, Patterns, Non-Physical Drivers and Contribution of Unidentified Precursors in French Aquatic Environments
Sediment acts as a sink for per- and polyfluoroalkyl substances (PFAS), especially for perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs). Recently, non-targeted methods have shown the presence of numerous unknown PFAS in environmental samples. The contribution of these PFAS can be estimated by the Total Oxidisable Precursor assay (TOP), an oxidative method used to convert polyfluoroalkyl precursors (pre-PFAAs) into perfluoroalkyl acids (PFAAs). While sediment properties (grain size and organic carbon fraction, foc) were reported as controlling factors for some PFAS, the influence of non-physico-chemical drivers (e.g. population density) still needs to be investigated. Thus, this work focused on sediments from France and used optimized analytical methods and geographical information system (GIS) to fill these knowledge gaps. Extraction solvent was modified from methanol (MeOH) + ammonium hydroxide to MeOH + ammonium acetate for the analysis of 16 PFAAs, 6 alternative PFAAs and 14 pre-PFAAs covering anionic, neutral and zwitterionic species (n:2 fluorotelomer sulfonamidoalkyl betaines, n:2 FTABs). The optimized method exhibited suitable performances for its application on sediments (n=50) collected in 2018. The TOP assay was adapted to this specific method extraction. Perfluorododecanic acid,perfluorooctane sulfonic acid (PFOS) as well as perfluorooctanoic acid (PFOA) were often detected (76, 74 and 68 % respectively). 6:2 FTAB, 8:2 FTAB and perfluoropentyl propanoic acid (FPePA) were also detected (38, 26 and 36 %, respectively). Median ∑PFAS was 1.3 ng.g-1 dry weight (dw) (range < LOD–23 ng.g-1 dw). 6:2 FTAB and 8:2 FTAB levels ranged from < 0.36 to 6.4 ng.g-1 dw and < 0.50 to 7.4 ng.g-1 dw, which is in the same order of magnitude than L-PFOS (< 0.08–5.1 ng.g-1 dw) advocating for the necessity to include these PFAS in targeted analysis. At nationwide scale, PFOS and ∑PFCAs accounted for 37 ± 25% and 31 ± 21% of ∑PFAS, respectively, while targeted pre-PFAAs accounted for 29 ± 27%, thereby supporting the importance of the latter in sediment and the potential contribution of untargeted pre-PFAAs monitored by the TOP assay (data under acquisition). Correlations between PFAS levels normalized by foc, unidentified pre-PFAAs and non-physico-chemical drivers with GIS are being investigated. Preliminary results showed that PFAS levels were not correlated with sample site position in the hydrographic system (proxy: Strahler number).
(03/06/2021)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, INERIS
La spectrométrie de masse haute résolution pour la recherche de micropolluants organiques dans l’environnement
L’analyse non ciblée connaît une forte période de croissance dans le domaine de l’analyse environnementale, car elle ouvre le champ des investigations de la qualité des milieux à un très grand nombre de composés. Cet article consiste en un retour d’expérience de 12 laboratoires français sur les pratiques et les précautions à considérer lors de la réalisation d’analyses non ciblées, en particulier pour la recherche de composés suspects dans les échantillons issus des milieux aquatiques. En effet, si cette technique apporte des informations nouvelles et très prometteuses, elle n’en reste pas moins une technique complexe qu’il convient d’utiliser avec de nombreuses précautions pour assurer des résultats de qualité. La réflexion commune entreprise dans le groupe de laboratoires, a permis de synthétiser des informations techniques afin de présenter les enjeux de cette méthodologie d’intérêt majeur en analyse environnementale de façon simple et accessible aux laboratoires, demandeurs d’analyse ou toute personne intéressée par ce type d’approche. Les verrous liés à la spécificité des analyses non ciblées, au développement de méthodes et au rendu de résultats ont été développés pour fournir des clés de compréhension pour les laboratoires et les utilisateurs de résultats. Ce travail s’attache ainsi à être un guide de découverte de la technique pour les personnes désireuses de voir ce que peut apporter l’analyse non ciblée, mais également un guide de bonnes pratiques pour celles et ceux qui acquièrent ou qui analysent des données issues de ces techniques.
(TSM. Techniques Sciences Méthodes – Génie urbain, génie rural, n° 0299-7258, pp. 43-54, 01/06/2021)
BRGM, LHN, ANSES, LEESU, ENPC, UPEC UP12, VERI, UB, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, CIRSEE, ISA, UCBL, INC-CNRS, CNRS, UNILIM, PEIRENE, GEIST, UNILIM, INERIS, LCE, AMU, INC-CNRS, CNRS, RiverLy, INRAE
Uptake and effects of graphene oxide nanomaterials alone and in combination with polycyclic aromatic hydrocarbons in zebrafish
Because of its surface characteristics, once in the aquatic environment, graphene could act as a carrier of pollutants, such as polycyclic aromatic hydrocarbons (PAHs), to aquatic organisms. In this study we aimed to (1) assess the capacity of graphene oxide (GO) to sorb PAHs and (2) to evaluate the toxicity of GO alone and in combination with PAHs on zebrafish embryos and adults. GO showed a high sorption capacity for benzo(a)pyrene (B(a)P) (98% of B(a)P sorbed from a nominal concentration of 100 μg/L) and for other PAHs of the water accommodated fraction (WAF) of a naphthenic North Sea crude oil, depending on their log Kow (95.7% of phenanthrene, 84.4% of fluorene and 51.5% of acenaphthene). In embryos exposed to different GO nanomaterials alone and with PAHs, no significant mortality was recorded for any treatment. Nevertheless, malformation rate increased significantly in embryos exposed to the highest concentrations (5 or 10 mg/L) of GO and reduced GO (rGO) alone and with sorbed B(a)P (GO-B(a)P). On the other hand, adults were exposed for 21 days to 2 mg/L of GO, GO-B(a)P and GO co-exposed with WAF (GO + WAF) and to 100 μg/L B(a)P. Fish exposed to GO presented GO in the intestine lumen and liver vacuolisation. Transcription level of genes related to cell cycle regulation and oxidative stress was not altered, but the slight up-regulation of cyp1a measured in fish exposed to B(a)P for 3 days resulted in a significantly increased EROD activity. Fish exposed to GO-B(a)P and to B(a)P for 3 days and to GO + WAF for 21 days showed significantly higher catalase activity in the gills than control fish. Significantly lower acetylcholinesterase activity, indicating neurotoxic effects, was also observed in all fish treated for 21 days. Results demonstrated the capacity of GO to carry PAHs and to exert sublethal effects in zebrafish.
(Science of the Total Environment. vol. 775, n° 0048-9697, pp. 145669, 01/06/2021)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, UPV / EHU
Etude des effets interactifs d’un produit virucide et de la lumière artificielle sur les biofilms aquatiques en milieu urbain
(31/05/2021)
UR EABX, INRAE, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, UQAM, INRS
Approche multi-descripteurs pour le suivi des effets interactifs d’un biocide et de la lumière sur les biofilms de rivières
(27/05/2021)
UR EABX, INRAE, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, UQAM, INRS
Evaporation process of linalool droplet at high relative humidity using acoustic levitation
(25/05/2021)
ISM, UB, INC-CNRS, CNRS, LPTC, UB, CNRS, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
A realistic Greenland ice sheet and surrounding glaciers and ice caps melting in a coupled climate model
Greenland ice sheet experienced an intensive melting in the last century, especially in the 1920s and over the last decades. The supplementary input into the ocean could disrupt the freshwater budget of the North Atlantic. Simultaneously, some signs of a recent weakening of the Atlantic Meridional Overturning Circulation (AMOC) have been reported. In order to better understand the possible impact of the increasing melting on the North Atlantic circulation, salinity and temperature trends, we construct an observation-based estimate of the freshwater fluxes spanning from 1840 to 2014. The estimate is based on runoff fluxes coming from Greenland ice sheet and surrounding glaciers and ice caps. Input from iceberg melting is also included and spatially distributed over the North Atlantic following an observed climatology. We force a set of historical simulations of the IPSL-CM6A-LR coupled climate model with this reconstruction from 1920 to 2014. The ten-member ensemble mean displays freshened and cooled waters around Greenland, which spread in the subpolar gyre, and then towards the subtropical gyre and the Nordic Seas. Over the whole period, the convection is reduced in the Labrador and Nordic Seas, while it is slightly enhanced in the Irminger Sea, and the AMOC is weakened by 0.32±0.35 Sv at 26∘ N. The multi-decadal trend of the North Atlantic surface temperature obtained with the additional freshwater forcing is slightly closer to observations than in standard historical simulations, although the two trends are only different at the 90% confidence level. Slight improvement of the Root Mean Square Error with respect to observations in the subpolar gyre region suggests that part of the surface temperature variability over the recent decades may have been forced by the release of freshwater from Greenland and surrounding regions since the 1920s. Finally, we highlight that the AMOC decrease due to Greenland melting remains modest in these simulations and can only explain a very small amount of the 3±1 Sv weakening suggested in a recent study.
(Climate Dynamics. vol. 57, n° 0930-7575, pp. 2467-2489, 24/05/2021)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, LOCEAN-VARCLIM, LOCEAN, MNHN, IRD, INSU - CNRS, SU, CNRS, IPSL (FR_636), ENS-PSL, UVSQ, CEA, INSU - CNRS, X, CNES, SU, CNRS, UPCité, LOCEAN-NEMO R&D, LOCEAN, MNHN, IRD, INSU - CNRS, SU, CNRS, IPSL (FR_636), ENS-PSL, UVSQ, CEA, INSU - CNRS, X, CNES, SU, CNRS, UPCité, IRD, SHOM, IFREMER, CNRS
Dispersive characteristics of non-linear waves propagating and breaking over a mildly sloping laboratory beach
The dispersive characteristics of unidirectional irregular waves propagating and breaking over a mildly sloping beach are examined using a highly-resolved laboratory dataset. Cross-spectral analyses are used to determine the cross-shore evolution of (single-valued) dominant wavenumber κ and phase velocity c spectra, and lead to the identification of four different regimes of propagation: I - a linear regime where short waves mostly propagate as free components; II - a shoaling regime where non-linear effects at high harmonics are significant but primary components follow the linear wave dispersion relation; III - a shoaling regime near the mean breaking point location, where amplitude dispersion effects at primary components are important; IV - a surf zone regime, where all components propagate slightly faster than non-dispersive shallow water waves. Bispectral analyses performed onshore of the shoaling region show that the presence of forced energy at high harmonics, which originate from non-linear interactions between triads of frequencies, are responsible for the deviations of wavenumber and phase velocity spectral estimates from predictions by the linear dispersion relation, confirming the findings from previous field-based studies. A Boussinesq approximation of the non-linear energy exchanges between triads is then used to quantify the relative amount of forced energy at high harmonics and explain the differences in dispersion properties observed in the shoaling region between broad and narrow-band spectra. Larger relative amounts of forced energy at high frequencies, which suggest more efficient non-linear energy transfers, are found to be associated with larger deviations of dominant κ and c from predictions by the linear dispersion relation.
(Coastal Engineering. vol. 167, n° 0378-3839, pp. 103917, 21/05/2021)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, LEGI, CNRS, Fédération OSUG, UGA, Grenoble INP, UGA