Innovative chemical and biological tools for the evaluation of the efficiency of wastewater advanced treatments and sludge treatments
Introduction. The general objective of the ECHIBIOTEB research program (“Innovating tools for sampling, chemical and biological analyses for the diagnostic of wastewater advanced treatments and sludge treatments”, 2011-2014, financed by the French National Research Agency, coordinated by Irstea) is to use innovative and complementary tools to better assess the efficiency of wastewater advanced treatments and sludge treatments. To achieve this goal, various strategies were combined: chemical analysis of a large panel of selected priority and emerging contaminants, non-target chemical analysis, in vitro and in vivo biological analysis and integrative samplers. Through various examples, our presentation will focus on the interest and also the limit of these tools to evaluate the efficiency of wastewater advanced treatments and sludge treatments. The chemical and biological tools tested in the program. -Chemical analysis of targeted contaminants: 14 traces metal and 170 organic molecules belonging to pharmaceuticals, oestrogenic hormones, alkylphenols (AkP), Endocrine Disruptor Compounds (EDC), Polycyclic Aromatic Hydrocarbons (PAH), pesticides, PolyChloroBiphenyl (PCB) and PolyBrominated DiphenylEthers (PBDE) were selected. According to their physico-chemical properties, they are measured in the dissolved phase of water and/or in sludge samples. After extractions by methods such as Solid Phase Extraction or Solid Phase MicroExtraction (SPME) for waters, and Accelerated Solvent Extraction or microwave extraction for sludge, molecules are analysed by gas (GC) or liquid phase chromatography (LC) coupled with single or tandem mass spectrometry. In fine, the aim is to select the relevant compounds to characterize such water and sludge treatment processes. -Non-target chemical analysis: Various instrumental strategies such as GC-2D-MS/TOF (two-dimensional gas phase chromatography coupled to Time Of Flight mass spectrometer), SPME-GC/TOF, HRMS/TOF (High Resolution Mass Spectrometry) are applied to identify new organic contaminants or degradation products. -In vitro and in vivo biological analysis: they are used to link the presence of contaminants to their effects on biological receptors (in vitro assays) or on living organisms (in vivo assays). Receptors studied by in vitro bioassays are estrogen, androgen, glucocorticoid, thyroid and dioxin receptors. Cytotoxicity and genotoxicity are also evaluated. In vivo bioassays are performed either in laboratory on effluents, fresh sludge samples and sludge eluates, or in a modified in situ approach with wastewaters deviated and flow controlled. In vivo laboratory bioassays include aquatic and terrestrial tests: bacteria (acute toxicity, Microtox®), micro-algae (growth), rotifers (reproduction), micro-crustaceans (reproduction) and plants (root elongation and early growth). In vivo modified in situ bioassays are realised on gasteropod (survival, growth, reproduction), crustacean (survival, alimentation rate, reproduction), insect (survival, growth) and fish embryos (survival, hatching, developmental abnormalities). -Integratives samplers: POCIS (Polar Organic Chemical Integrative Sampler) and SPMD (Semi-Permeable Membrane Device), dedicated to water sampling of hydrophilic and hydrophobic organic molecules respectively, are used to increase the samples representativeness1. Their use are combined with target and non target chemical analysis and with in vitro biological tests. -Effect directed analysis (EDA): whose principle is based on a combination of biotesting (by in vitro bioassays), fractionation procedure and chemical analytical methods. The toxic response guide the chemical fractionation and identification of compound responsible for the observed toxic effects. -Interaction of Dissolved Organic Matter (DOM) with micropollutants: the influence of the DOM onto toxicity and bioavailability of contaminants is studied through fast and small microplate tests, based on inhibitive competition of fluorescence. Sampling campaigns. From March 2011 to October 2012, 13 sampling campaigns (10 for water and 3 for sludge) were conducted. Water campaigns were organized either on a short (1 day) or on a long period (1 month). During short campaigns, chemical analysis of targeted contaminants, non-target chemical analysis, in vitro bioassays, in vivo bioassays praticed in laboratory and DOM tests were implemented. During long campaigns, every ECHIBIOTEB tools were used, including integrative samplers and in vivo in situ bioassays. Moreover, global parametres like phosphorus, nitrate, pH and suspended particles were controlled in order to give an indication on the operational conditions of the treatment studied. The treatments used for advanced (or tertiary) water treatments were adsorbants like Granular Activated Carbon (GAC), zeolites or expanded clay, and advanced oxidation processes (AOP) like ozone (O3), ozone peroxide (H2O2), UV/H2O2 , O3 + GAC, and polishing pond ; they were studied in full scale or large scale pilot design, located at the outlet of secondary biological treatments. For sludge treatments, solar dryer, compost and reed-bed filter were tested. First results. - Chemical analysis of targeted contaminants: For most of the compounds and whatever the type of treatment, targeted analysis showed a significant reduction in contaminant concentration in the dissolved phase of water after treatment. Pharmaceuticals concentrations, as example, were reduced in effluents about 100 times lower than in influents. The evaluation and discussion on removal rates are presented in a parallel study (ARMISTIQ research program) and detailed in the abstract “Occurrence of selected micropollutants in treated wastewater and removal with optimised tertiary treatments”. In our presentation, we will discuss on the pertinence of these compounds and more precisely on the selection of a shorter list of targeted compounds to characterize water and sludge treatment processes. -Non-target chemical analysis of 3 different sludge samples allowed to obtain a list of 190 molecules of interest, among which some nitrogen heterocyclic compounds as potential new contaminants. Further investigations are needed, especially combining chemical with biological analysis (EDA), to determine which compounds among these 190 would be the most relevant to be considered for water or sludge treatment characterization. -With in vitro biological analysis, an oestrogenic activity was detected in the aqueous influent of various advanced treatments, whereas it was poorly or not detected in the effluent. Compounds responsible for this toxic activity seem to be efficiently removed by GAC. Moreover, low PAH-like activity was detected in aqueous influent and effluent of wastewater tertiary treament in link to the low PAH concentrations measured in water samples. No dioxin-like or thyroid activity was detected in wastewaters. Genotoxic and cytotoxic activities were detected in some aqueous influents. Genotoxicity was no longer detected in effluents whereas cytotoxic activites are still detected at significant level in the ozone effluent. -With in vivo biological tests, low toxicity was measured in situ and in the laboratory before and after the studied treatment (O3+GAC and O3). Nevertheless, the size of the Japanese Medaka larvae and the hatching efficiency were reduced before those advanced treatments. Regarding the reproduction of Ceriodaphnia dubia, atypical dose-response curves were observed before the O3+GAC treatment showing inhibitory effects at low concentrations and reproduction rates significantly higher than the control at high concentrations. No difference was observed on the sludge toxicity before and after the solar dryer. On the contrary, the composting of sludge reduces the toxicity of the samples in terrestrials tests and tests performed on sludge water extracts, Furthermore, the root elongation test on oat in contact with fresh sludge sample seems suitable for routine analyses because of this simplicity and fastness. -The use of POCIS as integrative samplers allowed us to detect and quantify more -blockers, as an example, than with grab sampling. Nevertheless, the decrease of -blockers concentrations after advanced water treatment is in the same order of magnitude with grab and passive sampling. Compared to grab sampling, POCIS allowed to detect 7 more pharmaceuticals in influent of tertiary treatments and 4 more in effluents. The detection of a greater number of compounds thanks to integrative samplers (i.e. concentration effect) should be helpful to explain some toxicity results.
(pp. 48, 25/06/2026)
UR MALY, IRSTEA, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, INERIS, ESE, UP11, CNRS
Usages et qualité sur un territoire ostréicole
Ce rapport présente les résultats issus de recherches menées sur le Bassin d'Arcachon dans le cadre du projet de recherche OSQUAR, financé par la région Aquitaine. Il s'agit plus particulièrement du rapport du volet 2 du projet, qui mobilisait SHS et sciences du milieu sur la question des usages sur le territoire du Bassin d'Arcachon en lien avec la qualité du milieu.
(pp. 273, 25/06/2026)
UR ADBX, IRSTEA, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
Hydrological variability of major French rivers over recent decades, assessed from gauging station and GRACE observations
This study was carried out in the framework of the Surface Water and Ocean Topography (SWOT) programme of the French National Centre of Space Studies (CNES). Based on discharge measurements and Gravity Recovery and Climate Experiment (GRACE) determination of total water storage (TWS), we have investigated the hydrological variability of the main French drainage basins (Seine, Loire, Garonne and Rhône) using a wavelet approach (continuous wavelet analyses and wavelet coherence analyses). The results of this analysis have shown a coherence ranging between 82% and 90% for TWS and discharge, thus demonstrating the potential use of TWS for characterization of the hydrological variability of French rivers. Strong coherence between the four basin discharges (between 73% and 92%) and between their associated TWS data (from 82% to 98%) suggested a common external influence on hydrological variability. To determine this influence, we investigated the relationship between hydrological variability and the North Atlantic Oscillation (NAO), considered as an index of prevailing climate in Europe. Basin discharges show strong coherence with NAO, ranging between 64% and 72% over the period 1959–2010. The coherence between NAO and TWS was 62% to 67% for 2003–2009. This is similar to the coherence between NAO and basin discharges detected for the same period. According to these results, strong influence of the NAO was clearly observed on the TWS and discharges of the major French river basins.
(Hydrological Sciences Journal. vol. 59, n° 0262-6667, pp. 1844 - 1855, 25/06/2026)
M2C, UNICAEN, NU, INSU - CNRS, UNIROUEN, NU, CNRS, LEGOS, IRD, UT3, Comue de Toulouse, INSU - CNRS, CNES, CNRS, IRD, UPVD, AU, UR, UM, UG, UA, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
Influence of organic matter from urban effluents on trace metal speciation and bioavailability in river under strong urban pressure
In aquatic systems, dissolved organic matter (DOM) constitutes a key component of the carbon cycle controlling the transport, speciation, bioavailability, and toxicity of trace metals. In this work, we study the spatiotemporal variability of the MO in terms of both quality and quantity from upstream to downstream the Parisian conurbation. Urban discharges which are the main source of allochthonous organic matter into the Seine at low-water periods were also investigated. The DOM collected was fractionated according to polarity criteria into five fractions: hydrophobic, transphilic, hydrophilic acid, hydrophilic basic, and hydrophilic neutral. Due to urban discharges, a strong enrichment in the hydrophilic (HPI) fraction was observed for downstream sites. This hydrophilic fraction presented stronger binding capacities for copper than hydrophobic fraction from less urbanized site (upstream from Paris) and Suwannee river fulvic acid (SRFA). Furthermore, biotests highlighted a significant copper bioavailability decrease in presence of hydrophilic DOM. \textcopyright 2013 Zhejiang University Press and Springer Science+Business Media Dordrecht. All rights are reserved.
(. vol. 9789400756342, pp. 517--521, 25/06/2026)
LEESU, UPEM, ENPC, UPEC UP12, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, UR HBAN, IRSTEA, CEREVE, ENPC, UPEC UP12
Polychlorinated Biphenyls, Polybrominated Diphenyl Ethers, and Phthalates in Roach from the Seine River Basin (France): Impact of Densely Urbanized Areas
Endocrine disruptors (EDs) from three chemical classes—polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and phthalates—were investigated in the Seine River and one tributary, the Orge River, upstream and downstream of urban areas. The impact of urban areas was characterized by a concentration increase of all compounds in the Seine River and for phthalates and PBDEs in the Orge River. In the Seine River, from upstream (Marnay) to downstream (Triel) of urban areas, water concentration increases were greater for diethylhexyl phthalate (DEHP) (6 times, p < 0.05) and ∑tri-hexa BDE (5 times [p < 0.05]) than for ∑7PCBi (2.6 times). Simultaneously, sediments displayed a strong accumulation of contaminants downstream and compared with upstream values, their concentrations increased greatly: 202-fold for DEHP, 69-fold for BDE209, 25-fold for ∑tri-hexa-BDE, and 11-fold for ∑7PCBi. Variations of fish ED concentrations gave an indication of their habitat contamination increase observed downstream of densely urbanized areas of the Seine River, especially for PBDEs (∑tri-hexa-PBDEs = 14-fold increase ≤15.7 ± 6.9 ng g−1 dry weight [dw; p < 0.001]) and for PCBs (∑7PCBi eightfold increase ≤211 ± 55 ng g−1 dw [p < 0.01]). PCA results highlighted relationships between the different ED classes. A correlation (p < 0.05) was observed between PCB and PBDE fish concentrations, suggesting common sources and similar absorption mechanisms. For PCBs, which were poorly biodegraded, the bioaccumulation factor was strongly correlated (p < 0.001) to molecular hydrophobicity, whereas for PBDEs a negative correlation (p < 0.05) was observed related active debromination processes. This multichemical study investigates for the first time the occurrence of a wide range of EDs in roach, which was chosen as a sentinel species for this survey of surface water contamination.
(Archives of Environmental Contamination and Toxicology. vol. 66, n° 0090-4341, pp. 41-57, 25/06/2026)
SISYPHE, UPMC, EPHE, PSL, PSL, CNRS, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS
A note about the critical bandwidth for a kernel density estimator with the uniform kernel
Among available bandwidths for kernel density estimators, the critical bandwidth is a data-driven one, which satisfies a constraint on the number of modes of the estimated density. When using a random bandwidth, it is of particular interest to show that it goes toward 0 in probability when the sample size goes to infinity. Such a property is important to prove satisfying asymptotic results about the corresponding kernel density estimator. It is shown here that this property is not true for the uniform kernel.
(17/12/2012)
IMB, UB, Bordeaux INP, CNRS, CQFD, IMB, UB, Bordeaux INP, CNRS, Inria, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, LMBA, UBS, UBO EPE, CNRS
High-resolution architecture of a polygonal fault interval inferred from geomodel applied to 3D seismic data from the Gjallar Ridge, Vøring Basin, Offshore Norway
3D seismic data located in the Gjallar Ridge (Vøring Basin, offshore Norway) reveals a closely-spaced polygonal fault system affecting more than 800 m of homogeneous mud-dominated Quaternary and Tertiary sequences. As some faults reach the modern seafloor, they represent an active polygonal fault system at present day. Even if the processes remain unclear and are still under debate, it is generally agreed that the initiation of polygonal faults is the result of shallow burial dewatering of fine-grained unconsolidated sediments by volumetric compaction. 3D seismic data are commonly interpreted by propagating horizons automatically and by picking faults manually. However, in the case of polygonal fault intervals, this approach is time consuming due to the huge number of faults and because automatic propagation can be misleading. In this study, we applied a new technique of 3D seismic interpretation based on a sequential stratigraphy analysis, using the new PaleoScan© software (Eliis Company). It allowed us to build a 3D geological model computing more than 300 horizons within the faulted intervals. We then used the coherency attribute, depicting anomalies in the shape of seismic waveform like faults, in order to constrain a possible link between fault distribution and stratigraphic levels. Our approach allows fault throws to be calculated in milliseconds on any polygonal fault plane. The result shows that fault segments have been reactivated by dip-linkage. Distribution of faults depends on mechanical units, intervals characterized by different petrophysical properties, which are independent from lithological and diagenetic changes. According to these results, we propose a model showing the evolution of polygonal fault intervals in which faulting stages are separated by a quiescence phase during burial. A first tier of polygonal faults is initiated at a specific depth, according to the Cam-clay model. Then, following a period of quiescence during which mud-rich sediments continued to accumulate, new fault segments are initiated above the first mechanical unit and within this undeformed interval. New nucleated faults then connect downward to pre-existing underlying polygonal fault system, thus progressively increasing the thickness of the faulted interval.
(Marine Geology. vol. 332-334, n° 0025-3227, pp. 134-161, 01/12/2012)
UAG, INSU - CNRS, UM, CNRS, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, NOC, Géosciences Montpellier, UAG, INSU - CNRS, UM, CNRS, UiO, LPG, UA, UN UFR ST, UN, INSU - CNRS, CNRS
Early mid-Holocene SST variability and surface-ocean water balance in the southwest Pacific
[1] We present early mid-Holocene records of Sr/Ca,δ18O and δ18Osw from marine archives collected in Vanuatu: two Porites sp. corals (6.7–6.5 ka BP) and a Tridacna maxima giant clam (6.2–6.0 ka BP). Sr/Ca, δ18O, and δ18Osw were used as proxies for sea surface temperature (SST) and sea surface salinity (SSS). The fossil geochemical records were compared to modern Porites sp. and T. maxima records. Reconstructed mean SSTs from the two fossil Porites sp.and from the modern coral are similar, implying that the Western Pacific Warm Pool (WPWP)' southern edge had reached its modern location by 6.7–6.5 ka BP. The post-glacial SST rise in the Southwest Pacific was thus completed by the early mid-Holocene. The two early mid-Holocene corals and the giant clam recorded saltier conditions than modern related to 1) a decoupling between the precipitation regime and the SPCZ due to a northerly position of this climatic feature and 2) an increase of the moisture transport to the extra-tropics, driven by a strengthened or extended Hadley cell. The longest δ18O coral profile displays an El Niño Southern Oscillation (ENSO) signal reduced by 20–30% compared to the period 1928–1992, in concordance with the reduced ENSO variability observed in the Pacific area during the first half of the Holocene. However, the decoupling between the SPCZ and the precipitation regime may have also contributed to the weak ENSO signal recorded in the early mid-Holocene coral δ18O profile.
(Paleoceanography. vol. 27, n° 0883-8305, 01/12/2012)
PALEOPROXUS, LOCEAN, IPSL, ENS-PSL, UVSQ, UPMC, CEA, INSU - CNRS, X, CNES, CNRS, MNHN, IRD, UPMC, INSU - CNRS, CNRS, EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, LEGOS, IRD, UT3, Comue de Toulouse, INSU - CNRS, CNES, CNRS, LOCEAN, IPSL, ENS-PSL, PSL, UVSQ, UPMC, CEA, INSU - CNRS, X, IP Paris, CNES, CNRS, MNHN, IRD, UPMC, INSU - CNRS, CNRS
In situ study of short-term variations of redox species chemistry in intertidal permeable sediments of the Arcachon lagoon
(Hydrobiologia. vol. 699, n° 0018-8158, pp. 69-84, 01/12/2012)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS, LPG-ANGERS, LPG, UA, UN UFR ST, UN, INSU - CNRS, CNRS
Seagrass burial by dredged sediments: Benthic community alteration, secondary production loss, biotic index reaction and recovery possibility
In 2005, dredging activities in Arcachon Bay (France) led in burying 320,000m(2) of Zostera noltii intertidal seagrass. Recovery by macrobenthos and seagrass was monitored. Six months after works, seagrass was absent and macrobenthos drastically different from surrounding vegetated stations. Rapidly and due to sediment dispersal, disposal area was divided into a sandflat with a specific benthic community which maintained its difference until the end of the survey (2010), and a mudflat where associated fauna became similar to those in adjacent seagrass. Macrobenthic community needs 3years to recover while seagrass needs 5years to recover in the station impacted by mud. The secondary production loss due to works was low. In this naturally carbon enriched system, univariate biotic indices did not perform well to detect seagrass destruction and recovery. Multivariate index MISS gave more relevant conclusions and a simplified version was tested with success, at this local scale.
(Marine Pollution Bulletin. vol. 64, n° 0025-326X, pp. 2340-2350, 01/11/2012)
EPOC, EPHE, PSL, UB, INSU - CNRS, CNRS