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1. In Vitro Co-Exposure to CeO2 Nanomaterials from Diesel Engine Exhaust and Benzo(a)Pyrene Induces Additive DNA Damage in Sperm and Cumulus Cells but Not in Oocytes

Author: Martina Cotena, Mélanie Auffan, Virginie Tassistro, Noémie Resseguier, Jérôme Rose, and Jeanne Perrin
Subjects: genotoxicity, nanomaterials, polycyclic aromatic hydrocarbons, germ cells, additivity, cocktail, Chemistry, QD1-999
Abstract: Benzo(a)pyrene (BaP) is a recognized reprotoxic compound and the most widely investigated polycyclic aromatic hydrocarbon in ambient air; it is widespread by the incomplete combustion of fossil fuels along with cerium dioxide nanomaterials (CeO2 NMs), which are used in nano-based diesel additives to decrease the emission of toxic compounds and to increase fuel economy. The toxicity of CeO2 NMs on reproductive organs and cells has also been shown. However, the effect of the combined interactions of BaP and CeO2 NMs on reproduction has not been investigated. Herein, human and rat gametes were exposed in vitro to combusted CeO2 NMs or BaP or CeO2 NMs and BaP in combination. CeO2 NMs were burned at 850 °C prior to mimicking their release after combustion in a diesel engine. We demonstrated significantly higher amounts of DNA damage after exposure to combusted CeO2 NMs (1 µg·L−1) or BaP (1.13 µmol·L−1) in all cell types considered compared to unexposed cells. Co-exposure to the CeO2 NMs-BaP mixture induced additive DNA damage in sperm and cumulus cells, whereas no additive effect was observed in rat oocytes. This result could be related to the structural protection of the oocyte by cumulus cells and to the oocyte’s efficient system to repair DNA damage compared to that of cumulus and sperm cells.
Published: 2021
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2. CeO2 Nanomaterials from Diesel Engine Exhaust Induce DNA Damage and Oxidative Stress in Human and Rat Sperm In Vitro

Author: Martina Cotena, Mélanie Auffan, Stéphane Robert, Virginie Tassistro, Noémie Resseguier, Jérôme Rose, and Jeanne Perrin
Subjects: nanoparticles, DNA damage, Oxidative stress, reproductive toxicity, combustion, ageing, Chemistry, QD1-999
Abstract: Cerium dioxide nanomaterials (CeO2 NMs) are widely used in nano-based diesel additives to decrease the emission of toxic compounds, but they have been shown to increase the emission of ultrafine particles as well as the amount of released Ce. The Organization for Economic Cooperation and Development included CeO2 NMs in the priority list of nanomaterials that require urgent evaluation, and the potential hazard of aged CeO2 NM exposure remains unexplored. Herein, human and rat sperm cells were exposed in vitro to a CeO2 NM-based diesel additive (called EnviroxTM), burned at 850 °C to mimic its release after combustion in a diesel engine. We demonstrated significant DNA damage after in vitro exposure to the lowest tested concentration (1 µg·L−1) using the alkaline comet assay (ACA). We also showed a significant increase in oxidative stress in human sperm after in vitro exposure to 1 µg·L−1 aged CeO2 NMs evaluated by the H2DCF-DA probe. Electron microscopy showed no internalization of aged CeO2 NMs in human sperm but an affinity for the head plasma membrane. The results obtained in this study provide some insight on the complex cellular mechanisms by which aged CeO2 NMs could exert in vitro biological effects on human spermatozoa and generate ROS.
Published: 2020
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3. Stealth Biocompatible Si-Based Nanoparticles for Biomedical Applications

Author: Wei Liu, Arnaud Chaix, Magali Gary-Bobo, Bernard Angeletti, Armand Masion, Afitz Da Silva, Morgane Daurat, Laure Lichon, Marcel Garcia, Alain Morère, Khaled El Cheikh, Jean-Olivier Durand, Frédérique Cunin, and Mélanie Auffan
Subjects: porous silicon nanoparticle, surface functionalization, PEG, mannose, stealth properties, biodegradation kinetic, biocompatibility, Chemistry, QD1-999
Abstract: A challenge regarding the design of nanocarriers for drug delivery is to prevent their recognition by the immune system. To improve the blood residence time and prevent their capture by organs, nanoparticles can be designed with stealth properties using polymeric coating. In this study, we focused on the influence of surface modification with polyethylene glycol and/or mannose on the stealth behavior of porous silicon nanoparticles (pSiNP, ~200 nm). In vivo biodistribution of pSiNPs formulations were evaluated in mice 5 h after intravenous injection. Results indicated that the distribution in the organs was surface functionalization-dependent. Pristine pSiNPs and PEGylated pSiNPs were distributed mainly in the liver and spleen, while mannose-functionalized pSiNPs escaped capture by the spleen, and had higher blood retention. The most efficient stealth behavior was observed with PEGylated pSiNPs anchored with mannose that were the most excreted in urine at 5 h. The biodegradation kinetics evaluated in vitro were in agreement with these in vivo observations. The biocompatibility of the pristine and functionalized pSiNPs was confirmed in vitro on human cell lines and in vivo by cytotoxic and systemic inflammation investigations, respectively. With their biocompatibility, biodegradability, and stealth properties, the pSiNPs functionalized with mannose and PEG show promising potential for biomedical applications.
Published: 2017
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4. Cytotoxicity and genotoxicity of lanthanides for Vicia faba L. are mediated by their chemical speciation in different exposure media

Author: Ana Romero-Freire, Mélanie Auffan, Laure Giamberini, Jan E. Groenenberg, Sylvie Cotelle, V González, Hao Qiu, Laboratoire Interdisciplinaire des Environnements Continentaux (LIEC), Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Terre et Environnement de Lorraine (OTELo), Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Universidad de Granada (UGR), Wageningen University and Research [Wageningen] (WUR), Shanghai Jiao Tong University [Shanghai], Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and Universidad de Granada = University of Granada (UGR)
Subjects: Environmental Engineering, Mitotic index, Bodemscheikunde en Chemische Bodemkwaliteit, 010504 meteorology & atmospheric sciences, Gadolinium, Phosphate, 010501 environmental sciences, Lutetium, medicine.disease_cause, Ecotoxicology, 01 natural sciences, Lanthanoid Series Elements, Plant Roots, chemistry.chemical_compound, Toxicity Tests, medicine, Environmental Chemistry, Waste Management and Disposal, Rare earth elements, 0105 earth and related environmental sciences, Cerium, Pollution, Vicia faba, chemistry, Distilled water, Toxicity, Composition (visual arts), [SDV.TOX.ECO]Life Sciences [q-bio]/Toxicology/Ecotoxicology, [SDE.BE]Environmental Sciences/Biodiversity and Ecology, Genotoxicity, Soil Chemistry and Chemical Soil Quality, Nuclear chemistry, DNA Damage
Abstract: International audience; A comprehensive study of the toxicity of lanthanides (LN) in relation to the media composition will enhance the prediction of their potential adverse effects for living organisms. Here we examined the effect of different media on the V. faba root elongation and on the cytotoxic (mitotic index) and the genotoxic (micronucleated cell number) effects from toxicity tests with Ce, Gd and Lu (100, 800 and 6400 μg L −1). Three different exposure media were selected: the standard Hoagland media (SH); an alternative SH, without phosphates (SH-P); and distilled water (DW). In the SH no cyto-genotoxic effects were observed and even, for low LN content, potential root elongation stimulation was reported. The absence of toxic effects was explained by a drastic decrease of the total dissolved LN concentration due to the presence of phosphates causing LN precipitation. In SH-P, LN remained largely soluble and inhibition of root elongation was observed mainly for the highest treatments. While in the tests done in DW, toxic effects were obtained for all treatments. Our results showed that in absence of phosphorous, LN appear mainly as free form and complexed in carbonates and sulphates, and can cause toxic effects, whereas toxicity is not expected when phosphorous is available in aquatic media. The highest LN root contents were observed for the tests using distilled water, possibly due to the absence of competition by Ca 2+ for uptake. The present work demonstrated that media composition has a great impact in assessing the ecotoxicology of lanthanides.
Published: 2021
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5. CeO2 Nanomaterials from Diesel Engine Exhaust Induce DNA Damage and Oxidative Stress in Human and Rat Sperm In Vitro

Author: Jeanne Perrin, Stéphane Robert, Noémie Resseguier, Jérôme Rose, Virginie Tassistro, Mélanie Auffan, Martina Cotena, Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Centre National de la Recherche Scientifique (CNRS)-Institut de recherche pour le développement [IRD] : UMR237-Aix Marseille Université (AMU)-Avignon Université (AU), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS), Duke University [Durham], Centre recherche en CardioVasculaire et Nutrition = Center for CardioVascular and Nutrition research (C2VN), Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Aix Marseille Université (AMU), Hôpital de la Timone [CHU - APHM] (TIMONE), Hôpital de la Conception [CHU - APHM] (LA CONCEPTION), ANR-11-IDEX-0007-02/10-LABX-0064,Imust,Institut for Multiscale Science and Technology : from Fundamental Physics and Chemistry to Engineering in New Material and Processes and Ecotechnologies(2011), ANR-11-IDEX-0001-02/11-IDEX-0001,AMIDEX,AMIDEX(2011), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Department of Civil and Environmental Engineering [Durham] (CEE), Plateforme AMUTICYT [Marseille], Aix Marseille Université (AMU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Aix Marseille Université (AMU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), AMIDEXH2020UNIV-AMUCNRsECCOREV n° 3098, ANR-11-IDEX-0001,Amidex,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), ANR-11-IDEX-0007,Avenir L.S.E.,PROJET AVENIR LYON SAINT-ETIENNE(2011), European Project: 713750,H2020,H2020-MSCA-COFUND-2015,DOC2AMU(2016), Aix Marseille Université (AMU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), ANR: 11-IDEX-0001,AMIDEX,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)
Subjects: reproductive toxicity, DNA damage, NMs life cycle, General Chemical Engineering, media_common.quotation_subject, 010501 environmental sciences, Diesel engine, medicine.disease_cause, 01 natural sciences, Article, lcsh:Chemistry, 03 medical and health sciences, Diesel fuel, medicine, General Materials Science, Internalization, 030304 developmental biology, 0105 earth and related environmental sciences, media_common, [SDV.EE.SANT]Life Sciences [q-bio]/Ecology, environment/Health, 0303 health sciences, Chemistry, Sperm, In vitro, 3. Good health, lcsh:QD1-999, 13. Climate action, Oxidative stress, ageing, [SDE]Environmental Sciences, Biophysics, nanoparticles, Reproductive toxicity, combustion
Abstract: Cerium dioxide nanomaterials (CeO2 NMs) are widely used in nano-based diesel additives to decrease the emission of toxic compounds, but they have been shown to increase the emission of ultrafine particles as well as the amount of released Ce. The Organization for Economic Cooperation and Development included CeO2 NMs in the priority list of nanomaterials that require urgent evaluation, and the potential hazard of aged CeO2 NM exposure remains unexplored. Herein, human and rat sperm cells were exposed in vitro to a CeO2 NM-based diesel additive (called EnviroxTM), burned at 850 &deg, C to mimic its release after combustion in a diesel engine. We demonstrated significant DNA damage after in vitro exposure to the lowest tested concentration (1 &micro, g&middot, L&minus, 1) using the alkaline comet assay (ACA). We also showed a significant increase in oxidative stress in human sperm after in vitro exposure to 1 &micro, 1 aged CeO2 NMs evaluated by the H2DCF-DA probe. Electron microscopy showed no internalization of aged CeO2 NMs in human sperm but an affinity for the head plasma membrane. The results obtained in this study provide some insight on the complex cellular mechanisms by which aged CeO2 NMs could exert in vitro biological effects on human spermatozoa and generate ROS.
Published: 2020
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6. Anthropogenic Release and Distribution of Titanium Dioxide Particles in a River Downstream of a Nanomaterial Manufacturer Industrial Site

Author: Jérôme Rose, Nelly Guéniche, Andrea Campos, Olivier Aguerre-Chariol, Daniel Borschneck, Bernard Angeletti, Mélanie Auffan, Danielle L. Slomberg, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Duke University [Durham], Fédération Sciences Chimiques Marseille (FSCM), Institut National de l'Environnement Industriel et des Risques (INERIS), Centre National de la Recherche Scientifique (CNRS)European CommissionFrench Agency for the Environmental and Energetic Management (ADEME) - 2015 CORTEA call1581C0027, ANR-11-IDEX-0001,Amidex,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), and ANR-11-LABX-0064,SERENADE,Vers une conception de nanomatériaux innovants, durables et sûrs(2011)
Subjects: Anatase, 010504 meteorology & atmospheric sciences, manufactured TiO 2 nanomaterials, environmental exposure, 010501 environmental sciences, 01 natural sciences, Industrial waste, anthropogenic emission, chemistry.chemical_compound, lcsh:Environmental sciences, 0105 earth and related environmental sciences, General Environmental Science, lcsh:GE1-350, river ecosystem, sediment accumulation, aggregation, Sediment, Environmental exposure, Particulates, manufactured TiO2 nanomaterials, 6. Clean water, chemistry, 13. Climate action, Rutile, Environmental chemistry, Titanium dioxide, [SDE]Environmental Sciences, Environmental science, Sewage treatment
Abstract: International audience; Several industries manufacture and process large quantities of engineered nanomaterials, thus increasing the potential for their environmental release during waste management and disposal. Herein, we quantified the release and spatial distribution of titanium dioxide nanomaterials (TiO2 NMs) emitted from an industrial waste stream that flows into a nearby river. Two sampling campaigns were carried out on the river in fall 2017 and spring 2018 at selected sites upstream and downstream of the Industrial Effluent and an urban wastewater treatment plant (WWTP). Significant Ti accumulation was detected in the sediments at the Industrial Effluent and WWTP sites for both fall and spring samples, with measured Ti concentrations of 75–193 mg Ti/kg reaching 21–55× that of the local background upstream. X-ray diffraction analysis confirmed the anatase and rutile mineralogy of the inputs. River surface waters were filtered on-site to distinguish between particulate (>0.20 μm), colloidal (0.02–0.20 μm), and dissolved and/or small nanoparticulate (NP) (0.20 μm), and that the particles sediment rapidly near the emission source and accumulate in the sediment.
Published: 2020
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7. A sub-individual multilevel approach for an integrative assessment of CuO nanoparticle effects on Corbicula fluminea *

Author: Mélanie Auffan, Vanessa Koehlé-Divo, Catherine Mouneyrac, Bénédicte Sohm, Daniele Pauly, Laure Giamberini, Sandrine Pain-Devin, Justine Flayac, Simon Devin, Laboratoire Interdisciplinaire des Environnements Continentaux (LIEC), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Mer, molécules et santé EA 2160 (MMS), Le Mans Université (UM)-Université de Nantes - UFR des Sciences Pharmaceutiques et Biologiques, Université de Nantes (UN)-Université de Nantes (UN), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Terre et Environnement de Lorraine (OTELo), Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Université de Nantes - UFR des Sciences Pharmaceutiques et Biologiques, Université de Nantes (UN)-Université de Nantes (UN)-Le Mans Université (UM)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), French National Research Agency (ANR) [ANR-3-CESA-0014/NANOSALT], CPER Lorraine-ZAM (Contrat Projet Etat Region Lorraine, Zone Atelier Moselle) Région Grand-Est, Centre National de la Recherche Scientifique (CNRS), French Research ministry, Institut Ecologie et Environnement (INEE), Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Terre et Environnement de Lorraine (OTELo), Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Le Mans Université (UM)-Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Université de Nantes - UFR des Sciences Pharmaceutiques et Biologiques, Region Grand-Est, Centre National de la Recherche Scientifique (CNRS)European Commission, Ministry of Research, France, and ANR-13-CESA-0014,nanoSALT,Nanomatériaux à travers un gradient de salinité: exposition et effets ecotoxicologiques au cours de leur cycle de vie (production, utilisation, fin de vie)(2013)
Subjects: Thioredoxin Reductase 1, Antioxidant, 010504 meteorology & atmospheric sciences, Copper oxide nanoparticles (CuO NP), Biochemical effects, Health, Toxicology and Mutagenesis, medicine.medical_treatment, Defence mechanisms, Metal Nanoparticles, Fresh Water, 010501 environmental sciences, Toxicology, 01 natural sciences, Antioxidants, Gene expression, medicine, Animals, Corbicula fluminea, Gene, Corbicula, 0105 earth and related environmental sciences, Filtration rate, Glutathione Peroxidase, biology, Chemistry, Superoxide Dismutase, Bivalve, General Medicine, Metabolism, biology.organism_classification, Catalase, Pollution, [SDE.ES]Environmental Sciences/Environmental and Society, Hsp70, Biochemistry, Molecular Response, [SDE]Environmental Sciences, Cats, Copper, Water Pollutants, Chemical
Abstract: International audience; Because they are widely used, copper oxide nanoparticles (CuO NPs) are likely to enter the aquatic environment and then reach the sediment. We have examined the effect of CuO NPs in the freshwater endobenthic bivalve Corbicula fluminea. Some previous studies have investigated effects at biochemical and physiological levels, but molecular endpoints are still poorly studied despite they are sensitive in early detection of NPs effect. In the present study, we have investigated short-term effects (96 h) of CuO NP (12, 30 nm; 0, 20 and 100 mg/L) using molecular endpoints as well as more conventional biochemical and physiological markers. The expression of antioxidant (CuZnSOD, MnSOD, Cat, Se-GPx, Trxr) and antitoxic (GST-Pi, HSP70, MT, Pgp, MRP1) related genes was measured at the mRNA level while anti-oxidant (SOD, TAC) and antitoxic (GST, ACP) defenses, energetic reserves and metabolism (ETS, Tri, LDH), and cellular damages (LPO) were assessed using a biochemical approach. The filtration rate measured at 96 h provided information at the physiological scale. Gene expression and filtration rate were responsive to CuO NPs but the effects differed according to the NP size. The results suggest that defense mechanisms may have been set up following 30 nm-NP exposure. The response to 12 nm-NP was lower but still showed that exposure to 12 nm-NP led to activation of cellular elimination mechanisms. The lowering of the filtration rate may have protected the organisms from the contamination. However, this raised the question of further repercussions on organism biology. Together, the results (i) indicate that CuO NP may exert effects at different levels even after a short-term exposure and (ii) point out the precocity of molecular response.
Published: 2019
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8. The influence of salinity on the fate and behavior of silver standardized nanomaterial and toxicity effects in the estuarine bivalveScrobicularia plana

Author: Mélanie Auffan, Clément Levard, Jérôme Labille, Catherine Mouneyrac, Hanane Perrein-Ettajani, Carole Bertrand, Laure Giamberini, Christophe Pagnout, Amélie Châtel, Simon Devin, Laurence Poirier, and Aurore Zalouk-Vergnoux
Subjects: 0106 biological sciences, geography, geography.geographical_feature_category, biology, Chemistry, 010604 marine biology & hydrobiology, Health, Toxicology and Mutagenesis, media_common.quotation_subject, Estuary, 010501 environmental sciences, biology.organism_classification, Bivalvia, 01 natural sciences, Salinity, Speciation, Ultrafiltration (renal), Bioaccumulation, Environmental chemistry, Toxicity, Environmental Chemistry, Scrobicularia plana, 0105 earth and related environmental sciences, media_common
Abstract: Because of their antibacterial properties, silver (Ag) engineered nanomaterials are included in many products. The present study used a standardized Ag nanomaterial (NM-300K, 20 nm) supplied with a stabilizing agent. The aim was to investigate the behavior of Ag nanomaterial in an estuarine-like medium at 2 salinities (15 psu and 30 psu). Uptake as well as sublethal effects of Ag nanomaterial (10 μg Ag/L), its stabilizing agent, and AgNO3 (10 μg Ag/L) were assessed in the clam Scrobicularia plana, after 7 d of exposure. The release of soluble Ag from Ag nanomaterial in the experimental media was quantified by using diffusive gradient in thin films and ultrafiltration. A multibiomarker approach was employed to reveal responses of clams at subindividual and individual levels. The bioaccumulation of Ag was significantly greater at 15 psu versus 30 psu, which could be explained by differences in Ag speciation. In conclusion, the present study showed different impacts of Ag nanomaterial that were not always explained by the release of Ag ions in clams at both salinities; such impacts were particularly characterized by induction of oxidative stress, cell damage, and impairment of energetic levels. Burrowing of clams was affected by the stabilizing agent depending on the salinity tested, with stronger effects at 15 psu. Finally, the present study highlighted salinity-dependent changes in the physiology of estuarine bivalves. Environ Toxicol Chem 2016;35:2550-2561. © 2016 SETAC.
Published: 2016
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9. Phytoavailability of silver at predicted environmental concentrations: does the initial ionic or nanoparticulate form matter?

Author: Philippe Ortet, Mohamed Barakat, Mélanie Montes, Clément Levard, Mélanie Auffan, Claire Chevassus-Rosset, Catherine Santaella, Emmanuel Doelsch, Clément Layet, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), International Consortium for the Environmental Implications of Nanotechnology (ICEINT), Laboratoire d'Ecologie Microbienne de la Rhizosphère et d'Environnements Extrêmes (LEMIRE), Institut de Biosciences et Biotechnologies d'Aix-Marseille (ex-IBEB) (BIAM), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Ecosystèmes continentaux et risques environnementaux (ECCOREV), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Duke University [Durham], Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad), Département Performances des systèmes de production et de transformation tropicaux (Cirad-PERSYST), ANR-11-IDEX-0001-02/11-IDEX-0001,AMIDEX,AMIDEX(2011), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Recyclage et risque (UPR Recyclage et risque), French Environment and Energy Management Agency (ADEME), Labex SERENADE, Excellence Initiative of Aix-Marseille University - A*MIDEX, a French 'Investissements d'Avenir' program, through its associated Labex SERENADE project, INSU (CNRS), CNRS, ANR-11-IDEX-0001,Amidex,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: P33 - Chimie et physique du sol, Materials Science (miscellaneous), F60 - Physiologie et biochimie végétale, [SDE.MCG]Environmental Sciences/Global Changes, Argent, Nanoparticle, Ionic bonding, 02 engineering and technology, 010501 environmental sciences, 01 natural sciences, chemistry.chemical_compound, Flux (metallurgy), Organic matter, 0105 earth and related environmental sciences, General Environmental Science, chemistry.chemical_classification, biology, Chemistry, Soil classification, 021001 nanoscience & nanotechnology, biology.organism_classification, [SDE.ES]Environmental Sciences/Environmental and Society, Physiologie végétale, Soil water, Carbonate, 0210 nano-technology, Festuca arundinacea, Nuclear chemistry
Abstract: International audience; Silver phytoavailability in exposure scenarios close to predicted environmental concentrations (PEC) has rarely been studied. The ISO-standardized RHIZOtest, based on a root mat technique, was used to expose tall fescue (Festuca arundinacea) to silver at a concentration close to 0.0015 mg kg −1 and 100 times higher (0.15 mg kg −1) than PEC in soils (the PEC of Ag nanoparticulate in the soil range from 6 × 10 −6 to 1.4 × 10 −3 mg kg −1). Silver was supplied in the form of nanoparticles with organic (PVP) or inorganic (SiO 2) coating, or as dissolved Ag (AgNO 3), in different soil types, with contrasting properties, including pH, cationic exchange capacity, and carbonate, organic matter, and clay contents. The Ag concentration was quantified in plant roots and leaves and in soil solutions using ICP-MS spectrometry. Multivariate analyses showed that the form of Ag, nanoparticulate or ionic, had no impact on either the flux or the translocation of Ag in plants (p-value > 0.05). At a silver concentration close to PEC, Ag phytoavailability from Ag NPs or AgNO 3 was indistinguishable from that of geogenic Ag. At 100× PEC, the type of soil, mainly clay and carbonate contents , controlled the Ag flux. While both decreased Ag in soil solution, clays and carbonates showed antagonistic actions in modulating the Ag flux. We hypothesize that proton root exudation locally dissolves car-bonates and releases phytoavailable Ag, while immobilizing Ag on the edges of clays.
Published: 2019
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10. Redox Reactivity of Cerium Oxide Nanoparticles Induces the Formation of Disulfide Bridges in Thiol-Containing Biomolecules

Author: Françoise Rollin-Genetet, Caroline Seidel, Ester Artells, Mélanie Auffan, Alain Thiéry, Claude Vidaud, Service de Biochimie et Toxicologie Nucléaire (SBTN), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: Inorganic chemistry, Metal Nanoparticles, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Toxicology, 01 natural sciences, Redox, Metal, Animals, Reactivity (chemistry), Cysteine, Disulfides, Sulfhydryl Compounds, chemistry.chemical_classification, Chemistry, Circular Dichroism, Biomolecule, Cerium, General Medicine, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, Liver, Catalytic oxidation, visual_art, [SDE]Environmental Sciences, visual_art.visual_art_medium, Thiol, Rabbits, 0210 nano-technology, Oxidation-Reduction
Abstract: International audience; The redox state of disulfide bonds is implicated in many redox control systems, such as the cysteine cystine couple. Among proteins, ubiquitous cysteine-rich metallothioneins possess thiolate metal binding groups susceptible to metal exchange in detoxification processes. CeO2 NPs are commonly used in various industrial applications due to their redox properties. These redox properties that enable dual oxidation states (Ce(IV)/Ce(III)) to exist at their surface may act as oxidants for biomolecules. The interaction among metallothioneins, cysteine, and CeO2 NPs was investigated through various biophysical approaches to shed light on the potential effects of the Ce4+/Ce3+ redox system on the thiol groups of these biomolecules. The possible reaction mechanisms include the formation of a disulfide bridge/Ce(III) complex resulting from the interaction between Ce(IV) and the thiol groups, leading to metal unloading from the MTs, depending on their metal content and cluster type. The formation of stable Ce3+ disulfide complexes has been demonstrated via their fluorescence properties. This work provides the first evidence of thiol concentration-dependent catalytic oxidation mechanisms between pristine CeO2 NPs and thiol-containing biomolecules.
Published: 2015
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11. Non-linear release dynamics for a CeO2 nanomaterial embedded in a protective wood stain, due to matrix photo-degradation

Author: Mélanie Auffan, Perrine Chaurand, Jérôme Labille, Jérôme Rose, Nathan Bossa, Isabelle Kieffer, Bernard Angeletti, Jean-Yves Bottero, Lorette Scifo, Armand Masion, Astrid Avellan, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), BM30B/FAME, European Synchrotron Radiation Facility (ESRF), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), European Synchroton Radiation Facility [Grenoble] (ESRF), TECNALIA Foundation, 'Excellence Initiative' of Aix-Marseille University A*MIDEX, a French 'Investissements d'Avenir' program, through its associated Labex SERENADE [ANR-11-LABX-0064], European Project: 604305,EC:FP7:NMP,FP7-NMP-2013-LARGE-7,SUN(2013), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: Polymer nanocomposite, Health, Toxicology and Mutagenesis, Weathering, 02 engineering and technology, 010501 environmental sciences, Toxicology, 01 natural sciences, Stain, Irradiation, Photodegradation, Photo-degradation, 0105 earth and related environmental sciences, Nanocomposite, Chemistry, Polymer nanocomposites, General Medicine, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Aging of nanomaterials, Pollution, Wood stain, Engineered nanomaterials (ENM) release, Chemical engineering, 13. Climate action, Acrylic stain, [SDE]Environmental Sciences, Leaching (metallurgy), 0210 nano-technology
Abstract: International audience; The release of CeO2-bearing residues during the weathering of an acrylic stain enriched with CeO2 nanomaterial designed for wood protection (Nanobyk brand additive) was studied under two different scenarios: (i) a standard 12-weeks weathering protocol in climate chamber, that combined condensation, water spraying and UV–visible irradiation and (ii) an alternative accelerated 2-weeks leaching batch assay relying on the same weathering factors (water and UV), but with a higher intensity of radiation and immersion phases. Similar Ce released amounts were evidenced for both scenarios following two phases: one related to the removal of loosely bound material with a relatively limited release, and the other resulting from the degradation of the stain, where major release occurred. A non-linear evolution of the release with the UV dose was evidenced for the second phase. No stabilization of Ce emissions was reached at the end of the experiments. The two weathering tests led to different estimates of long-term Ce releases, and different degradations of the stain. Finally, the photo-degradations of the nanocomposite, the pure acrylic stains and the Nanobyk additive were compared. The incorporation of Nanobyk into the acrylic matrix significantly modified the response of the acrylic stain to weathering.
Published: 2018
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12. Very low concentration of cerium dioxide nanoparticles induce DNA damage, but no loss of vitality, in human spermatozoa

Author: Jeanne Perrin, I. Sari-Minodier, Lise Preaubert, Mélanie Auffan, Jérôme Rose, Virginie Tassistro, Blandine Courbiere, Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Service de Gynécologie et Obstétrique [Marseille], Hôpital de la Conception [CHU - APHM] (LA CONCEPTION), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Hôpital de la Conception [CHU - APHM] (LA CONCEPTION ), Centre National de la Recherche Scientifique (CNRS)-Institut de recherche pour le développement [IRD] : UMR237-Aix Marseille Université (AMU)-Avignon Université (AU), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: 0301 basic medicine, Male, DNA damage, Cell Survival, media_common.quotation_subject, chemistry.chemical_element, Metal Nanoparticles, Human spermatozoa, 010501 environmental sciences, Environment, Toxicology, medicine.disease_cause, 01 natural sciences, Cerium dioxide nanoparticles, 03 medical and health sciences, chemistry.chemical_compound, Microscopy, Electron, Transmission, medicine, Humans, Internalization, Comet assay, 0105 earth and related environmental sciences, media_common, [SDV.EE.SANT]Life Sciences [q-bio]/Ecology, environment/Health, General Medicine, Cerium, Spermatozoa, In vitro, 030104 developmental biology, chemistry, [SDV.TOX]Life Sciences [q-bio]/Toxicology, Biophysics, Reproductive toxicity, DNA, Genotoxicity
Abstract: International audience; Cerium dioxide nanoparticles (CeO 2 NP) are widely used for industrial purposes, as in diesel, paint, wood stain and as potential therapeutic applications. The Organization for Economic Cooperation and Development included CeO 2 NP in the priority list of nanomaterials requiring urgent evaluation. As metal nanoparticles can cross the blood-testis barrier, CeO 2 NP could interact with spermatozoa. The genotoxicity of CeO 2 NP was demonstrated in vitro on human cell lines and mouse gametes. However, the effects of CeO 2 NP on human spermatozoa DNA remain unknown. We showed significant DNA damage induced in vitro by CeO 2 NP on human spermatozoa using Comet assay. The genotoxicity was inversely proportional to the concentration (0.01 to 10 mg·L −1). TEM showed no internalization of CeO 2 NP into the spermatozoa. This study shows for the first time that in vitro exposure to very low concentrations of cerium dioxide nanoparticles can induce significant DNA damage in human spermatozoa. These results add new and important insights regarding the reproductive toxicity of priority nanomaterials, which require urgent evaluation.
Published: 2018
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13. Evidence that Soil Properties and Organic Coating Drive the Phytoavailability of Cerium Oxide Nanoparticles

Author: Blanche Collin, Samuel Legros, Philippe Ortet, Olivier Proux, Isabelle Kieffer, Catherine Santaella, Mélanie Montes, Matthieu Bravin, Mélanie Auffan, Jean-Louis Hazemann, Mohamed Barakat, Claire Chevassus-Rosset, Emmanuel Doelsch, Bernard Angeletti, Clément Layet, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Institut de Biosciences et Biotechnologies d'Aix-Marseille (ex-IBEB) (BIAM), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Ecologie Microbienne de la Rhizosphère et d'Environnements Extrêmes (LEMIRE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Recyclage et risque (UPR Recyclage et risque), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad), Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Matériaux, Rayonnements, Structure (MRS), Institut Néel (NEEL), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Matériaux, Rayonnements, Structure (NEEL - MRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Recyclage et risque (Cirad-Persyst-UPR 78 Recyclage et risque), Département Performances des systèmes de production et de transformation tropicaux (Cirad-PERSYST), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)-Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad), Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), MRS - Matériaux, Rayonnements, Structure, and Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)
Subjects: Cerium oxide, Nanoparticle, 02 engineering and technology, Phytochimie, 010501 environmental sciences, Plant Roots, 01 natural sciences, Soil, Solanum lycopersicum, Coating, Sol sableux, Soil Pollutants, Nanotechnologie, Sol argileux, media_common, 2. Zero hunger, chemistry.chemical_classification, biology, Cerium, 021001 nanoscience & nanotechnology, Pollution, Environmental chemistry, [SDE]Environmental Sciences, 0210 nano-technology, P02 - Pollution, P33 - Chimie et physique du sol, Relation plante sol, media_common.quotation_subject, Inorganic chemistry, chemistry.chemical_element, Festuca arundinacea, engineering.material, Poaceae, complex mixtures, Environmental Chemistry, Organic matter, Propriété physicochimique du sol, Technique analytique, 0105 earth and related environmental sciences, General Chemistry, 15. Life on land, biology.organism_classification, chemistry, Soil water, engineering, Nanoparticles
Abstract: International audience; The ISO-standardized RHIZOtest is used here for the first time to decipher how plant species, soil properties, and physical chemical properties of the nanoparticles and their transformation regulate the phytoavailability of nanoparticles. Two plants, tomato and fescue, were exposed to two soils with contrasted properties: a sandy soil poor in organic matter and a clay soil rich in organic matter, both contaminated with 1, 15, and 50 mg-kg(-1) of dissolved Ce-2(SO4)(3), bare and citrate coated CeO2 nanoparticles. All the results demonstrate that two antagonistic soil properties controlled Ce uptake. The clay fraction enhanced the retention of the CeO2 nanoparticles and hence reduced Ce uptake, whereas the organic matter content enhanced Ce uptake. Moreover, in the soil poor in organic matter, the organic citrate coating significantly enhanced the phytoavailability of the cerium by forming smaller aggregates thereby facilitating the transport of nanoparticles to the roots. By getting rid, of the dissimilarities between the root systems of the different plants and the normalizing the surfaces exposed to nanoparticles, the RHIZOtest demonstrated that the species of plant did not drive the phytoavailability, and provided evidence for soil plant transfers at concentrations lower than those usually cited in the literature and closer to predicted environmental concentrations.
Published: 2017
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14. Effect of field site hydrogeochemical conditions on the corrosion of milled zerovalent iron particles and their dechlorination efficiency

Author: Vesna Micic Batka, Stephan Wagner, Mélanie Auffan, Frank von der Kammer, Thilo Hofmann, Doris Schmid, Olivier Proux, Daniel Borschneck, Milica Velimirovic, Luca Carniato, Universität Wien, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Delft University of Technology (TU Delft), Helmholtz Centre for Environmental Research (UFZ), Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Helmholtz Zentrum für Umweltforschung = Helmholtz Centre for Environmental Research (UFZ), Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: Apparent corrosion rate, Environmental Engineering, Hydrogen, Groundwater remediation, Inorganic chemistry, Maghemite, chemistry.chemical_element, 02 engineering and technology, 010501 environmental sciences, engineering.material, 01 natural sciences, Corrosion, Milled zero valent iron, chemistry.chemical_compound, Degradation, Adsorption, Environmental Chemistry, Hydrogeochemistry, Waste Management and Disposal, Dissolution, 0105 earth and related environmental sciences, Magnetite, Zerovalent iron, Structural changes, [SDE.IE]Environmental Sciences/Environmental Engineering, 021001 nanoscience & nanotechnology, Pollution, 6. Clean water, chemistry, 13. Climate action, engineering, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other
Abstract: International audience; Milled zerovalent iron (milled ZVI) particles have been recognized as a promising agent for groundwater remediation because of (1) their high reactivity with chlorinated aliphatic hydrocarbons, organochlorine pesticides, organic dyes, and a number of inorganic contaminants, and (2) a possible greater persistance than the more extensively investigated nanoscale zerovalent iron. We have used laboratory-scale batch degradation experiments to investigate the effect that hydrogeochemical conditions have on the corrosion of milled ZVI and on its ability to degrade trichloroethene (TCE). The observed pseudo first-order degradation rate constants indicated that the degradation of TCE by milled ZVI is affected by groundwater chemistry. The apparent corrosion rates of milled ZVI particles were of the same order of magnitude for hydrogeochemical conditions representative for two contaminated field sites (133–140 mmol kg− 1 day− 1, indicating a milled ZVI life-time of 128–135 days). Sulfate enhances milled ZVI reactivity by removing passivating iron oxides and hydroxides from the Fe0 surface, thus increasing the number of reactive sites available. The organic matter content of 1.69% in the aquifer material tends to suppress the formation of iron corrosion precipitates. Results from scanning electron microscopy, X-ray diffraction, and iron K-edge X-ray adsorption spectroscopy suggest that the corrosion mechanisms involve the partial dissolution of particles followed by the formation and surface precipitation of magnetite and/or maghemite. Numerical corrosion modeling revealed that fitting iron corrosion rates and hydrogen inhibitory terms to hydrogen and pH measurements in batch reactors can reduce the life-time of milled ZVI particles by a factor of 1.2 to 1.7.
Published: 2017
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15. Biological Fate of Fe3O4 Core-Shell Mesoporous Silica Nanoparticles Depending on Particle Surface Chemistry

Author: Jean-Marie Devoisselle, Wei Liu, Joséphine Lai-Kee-Him, Yannick Guari, Mélanie Auffan, Afitz Da Silva, Magali Gary-Bobo, Estelle Rascol, Morgane Daurat, Patrick Bron, Bernard Angeletti, Clarence Charnay, Marie Maynadier, Christophe Dorandeu, Joël Chopineau, Marcel Garcia, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), NanoMedSyn (NMS), Centre de Biochimie Structurale [Montpellier] (CBS), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Nîmes (UNIMES), Institut Charles Gerhardt, Université Montpellier 2 - Sciences et Techniques ( UM2 ), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] ( IBMM ), Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université de Montpellier ( UM ) -Centre National de la Recherche Scientifique ( CNRS ), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier ( ICGM ICMMM ), Université Montpellier 1 ( UM1 ) -Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université de Montpellier ( UM ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de recherche en cancérologie de Montpellier ( IRCM ), Université Montpellier 1 ( UM1 ) -CRLCC Val d'Aurelle - Paul Lamarque-Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Université de Montpellier ( UM ), Centre de Biochimie Structurale [Montpellier] ( CBS ), Institut National de la Santé et de la Recherche Médicale ( INSERM ) -Université de Montpellier ( UM ) -Centre National de la Recherche Scientifique ( CNRS ), Interactions cellulaires et moléculaires ( ICM ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -IFR140-Centre National de la Recherche Scientifique ( CNRS ), Centre européen de recherche et d'enseignement de géosciences de l'environnement ( CEREGE ), Centre National de la Recherche Scientifique ( CNRS ) -Institut de Recherche pour le Développement ( IRD ) -Aix Marseille Université ( AMU ) -Collège de France ( CdF ) -Institut National de la Recherche Agronomique ( INRA ) -Institut national des sciences de l'Univers ( INSU - CNRS ), School of Computer [Chine], National University of Defense Technology [Changsha], Chimie moléculaire et organisation du solide ( CMOS ), Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Centre National de la Recherche Scientifique ( CNRS ), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), NanoMedSyn, Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Institut National de la Santé et de la Recherche Médicale (INSERM), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), and Beaussier, Catherine
Subjects: safety, General Chemical Engineering, Nanoparticle, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, Nanotechnology, nanoparticles, surface coating, cell-membrane interactions, biodistribution, 02 engineering and technology, Polyethylene glycol, 010402 general chemistry, 01 natural sciences, Article, Cell membrane, chemistry.chemical_compound, PEG ratio, medicine, General Materials Science, [INFO.INFO-BT]Computer Science [cs]/Biotechnology, Lipid bilayer, Chemistry, technology, industry, and agriculture, Mesoporous silica, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surface coating, [INFO.INFO-BT] Computer Science [cs]/Biotechnology, medicine.anatomical_structure, Membrane, Chemical engineering, [SDU.STU] Sciences of the Universe [physics]/Earth Sciences, 0210 nano-technology, [ INFO.INFO-BT ] Computer Science [cs]/Biotechnology
Abstract: International audience; The biological fate of nanoparticles (NPs) for biomedical applications is highly dependent of their size and charge, their aggregation state and their surface chemistry. The chemical composition of the NPs surface influences their stability in biological fluids, their interaction with proteins, and their attraction to the cell membranes. In this work, core-shell magnetic mesoporous silica nanoparticles (Fe 3 O 4 @MSN), that are considered as potential theranostic candidates, are coated with polyethylene glycol (PEG) or 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayer. Their biological fate is studied in comparison to the native NPs. The physicochemical properties of these three types of NPs and their suspension behavior in different media are investigated. The attraction to a membrane model is also evaluated using a supported lipid bilayer. The surface composition of NPs strongly influences their dispersion in biological fluids mimics, protein binding and their interaction with cell membrane. While none of these types of NPs is found to be toxic on mice four days after intravenous injection of a dose of 40 mg kg 1 of NPs, their surface coating nature influences the in vivo biodistribution. Importantly, NP coated with DMPC exhibit a strong accumulation in liver and a very low accumulation in lung in comparison with nude or PEG ones.
Published: 2017
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16. Theory and Methodology for Determining Nanoparticle Affinity for Heteroaggregation in Environmental Matrices Using Batch Measurements

Author: Mathieu Therezien, Jean-Yves Bottero, Lauren E. Barton, Mélanie Auffan, Mark R. Wiesner, Duke University [Durham], Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: inorganic chemicals, exposure assessment, education, Oxide, Nanoparticle, Suspension (chemistry), Metal, chemistry.chemical_compound, mental disorders, medicine, activated sludge, Environmental Chemistry, Waste Management and Disposal, Dissolution, health care economics and organizations, surface and interfaces, Chromatography, Polyvinylpyrrolidone, Chemistry, technology, industry, and agriculture, respiratory system, Pollution, Partition coefficient, Activated sludge, Chemical engineering, visual_art, [SDE]Environmental Sciences, visual_art.visual_art_medium, nanoparticles, medicine.drug
Abstract: International audience; In this study, we present a method for determining the relative affinity of nanoparticles (NPs) for an ensemble of other particles in a complex, heterogeneous suspension. We evaluated this method for NPs heteroaggregating with suspended solids present in activated sludge. A relationship was derived between the heterogeneous affinity coefficient, alpha, and measurements over time of the distribution coefficient, gamma, of NPs measured in supernatant versus those removed by heteroaggregation and subsequent settling. Application of this method, which uses a mathematical relationship to determine alpha from experimentally measured gamma values, to a series of metal and metal oxide NPs heteroaggregated with activated sludge indicated a relative affinity in the order of pristine CeO2, TiO2 NPs, and ZnO NPs > Ag(0) NPs surface-modified with polyvinylpyrrolidone (PVP) > citrate-functionalized CeO2 NP > Ag(0) NPs surface-modified with gum arabic. This trend in relative affinity followed the observed trend in removal such that higher affinity corresponded to higher removals of NPs. Values of alpha were calculated from measured relative affinities using average diameter and concentration of the activated sludge particles. The value calculated for PVP-stabilized Ag(0) NPs was comparable to a value previously reported for the attachment of these same NPs to a biofilm. Calculations also yielded size dependence of alpha in the case of the two Ag(0) evaluated that may be linked to NP dissolution.
Published: 2014
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17. Long-term aging of a CeO2 based nanocomposite used for wood protection

Author: Mélanie Auffan, Jérôme Rose, Fabio Ziarelli, Jérôme Labille, Wei Liu, Jean-Yves Bottero, Christophe Geantet, Armand Masion, Marie-Ange Diot, Luca Olivi, Perrine Chaurand, Olivier Proux, RAFFINAGE (RAFFINAGE), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Health, Toxicology and Mutagenesis, UV filter, 02 engineering and technology, 010501 environmental sciences, Toxicology, 01 natural sciences, Citric Acid, Nanocomposites, Nanomaterials, Desorption, Weather, 0105 earth and related environmental sciences, Nanocomposite, Chemistry, Cerium, [CHIM.CATA]Chemical Sciences/Catalysis, General Medicine, Carbon-13 NMR, 021001 nanoscience & nanotechnology, Wood, [SDE.ES]Environmental Sciences/Environmental and Society, Pollution, XANES, Chemical engineering, 13. Climate action, Sunlight, Degradation (geology), Chemical stability, 0210 nano-technology
Abstract: RAFFINAGE+CGE; A multi-scale methodology was used to characterize the long-term behavior and chemical stability of a CeO2-based nanocomposite used as UV filter in wood stains. ATR-FTIR and C-13 NMR demonstrated that the citrate coated chelates with Ce(IV) through its central carboxyl- and its alpha-hydroxyl- groups at the surface of the unaged nanocomposite. After 42 days under artificial daylight, the citrate completely disappeared and small amount of degradation products remained attached to the surface even after 112 days. Moreover, the release/desorption of the citrate layer led to a surface reorganization of the nano-sized CeO2 core observed by XANES (Ce L-3-edge). Such a surface and structural transformation of the commercialized nanocomposite could have implications in term of fate, transport, and potential impacts towards the environment. (C) 2014 Elsevier Ltd. All rights reserved.
Published: 2014
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18. Aged TiO2-Based Nanocomposite Used in Sunscreens Produces Singlet Oxygen under Long-Wave UV and Sensitizes Escherichia coli to Cadmium

Author: Catherine Santaella, Bruno Allainmat, France Simonet, Corinne Chanéac, Jérome Labille, Mélanie Auffan, Jérome Rose, Wafa Achouak, Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Ultraviolet Rays, Radical, Membrane lipids, chemistry.chemical_element, medicine.disease_cause, Photochemistry, Nanocomposites, chemistry.chemical_compound, Escherichia coli, medicine, Environmental Chemistry, Sensitization, Titanium, Cadmium, Singlet Oxygen, Hydroxyl Radical, Singlet oxygen, Mutagenesis, Electron Spin Resonance Spectroscopy, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, [SDE.ES]Environmental Sciences/Environmental and Society, Oxidative Stress, medicine.anatomical_structure, chemistry, 13. Climate action, Microscopy, Electron, Scanning, Reactive Oxygen Species, Sunscreening Agents, Oxidative stress
Abstract: +FSI; TiO2-based nanocomposite (NC) are widely used as invisible UV protectant in cosmetics. These nanomaterials (NMs) end in the environment as altered materials. We have investigated the properties of T-Lite SF, a TiO2-NC used as sunscreen, after weathering in water and under light. We have examined the formation of ROS and their consequences on cell physiology of Escherichia coli. Our results show that aged-T-Lite SF produced singlet oxygen under low intensity long wave UV and formed hydroxyl radicals at high intensity. Despite the production of these ROS, T-Lite SF had neither effect on the viability of E. coli nor on mutant impaired in oxidative stress, did not induce mutagenesis and did not impair the integrity of membrane lipids, thus seemed safe to bacteria. However, when pre-exposed to T-Lite SF under low intensity UV, cells turned out to be more sensitive to cadmium, a priority pollutant widely disseminated in soil and surface waters. This effect was not a Trojan horse: sensitization of cells was dependent on the formation of singlet oxygen. These results provide a basis for caution, especially on NMs that have no straight environmental toxicity. It is crucial to anticipate indirect and combined effects of environmental pollutants and NMs.
Published: 2014
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19. Stealth Biocompatible Si-Based Nanoparticles for Biomedical Applications

Author: Laure Lichon, Armand Masion, Marcel Garcia, Magali Gary-Bobo, Mélanie Auffan, Alain Morère, Morgane Daurat, Bernard Angeletti, Khaled El Cheikh, Arnaud Chaix, Frédérique Cunin, Wei Liu, Jean-Olivier Durand, Afitz Da Silva, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), School of Computer [Chine], National University of Defense Technology [Changsha], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier ( ICGM ICMMM ), Université Montpellier 1 ( UM1 ) -Université Montpellier 2 - Sciences et Techniques ( UM2 ) -Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université de Montpellier ( UM ) -Centre National de la Recherche Scientifique ( CNRS ), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] ( IBMM ), Ecole Nationale Supérieure de Chimie de Montpellier ( ENSCM ) -Université de Montpellier ( UM ) -Centre National de la Recherche Scientifique ( CNRS ), Centre européen de recherche et d'enseignement de géosciences de l'environnement ( CEREGE ), Centre National de la Recherche Scientifique ( CNRS ) -Institut de Recherche pour le Développement ( IRD ) -Aix Marseille Université ( AMU ) -Collège de France ( CdF ) -Institut National de la Recherche Agronomique ( INRA ) -Institut national des sciences de l'Univers ( INSU - CNRS ), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)
Subjects: Materials science, Biocompatibility, General Chemical Engineering, Nanoparticle, Nanotechnology, 02 engineering and technology, Polyethylene glycol, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, porous silicon nanoparticle, surface functionalization, PEG, mannose, stealth properties, biodegradation kinetic, biocompatibility, 010402 general chemistry, 01 natural sciences, Article, lcsh:Chemistry, [ SDE ] Environmental Sciences, chemistry.chemical_compound, In vivo, PEG ratio, General Materials Science, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [SDV.SP.PG]Life Sciences [q-bio]/Pharmaceutical sciences/Galenic pharmacology, lcsh:QD1-999, chemistry, Drug delivery, Surface modification, Nanocarriers, 0210 nano-technology
Abstract: International audience; A challenge regarding the design of nanocarriers for drug delivery is to prevent their recognition by the immune system. To improve the blood residence time and prevent their capture by organs, nanoparticles can be designed with stealth properties using polymeric coating. In this study, we focused on the influence of surface modification with polyethylene glycol and/or mannose on the stealth behavior of porous silicon nanoparticles (pSiNP, similar to 200 nm). In vivo biodistribution of pSiNPs formulations were evaluated in mice 5 h after intravenous injection. Results indicated that the distribution in the organs was surface functionalization-dependent. Pristine pSiNPs and PEGylated pSiNPs were distributed mainly in the liver and spleen, while mannose-functionalized pSiNPs escaped capture by the spleen, and had higher blood retention. The most efficient stealth behavior was observed with PEGylated pSiNPs anchored with mannose that were the most excreted in urine at 5 h. The biodegradation kinetics evaluated in vitro were in agreement with these in vivo observations. The biocompatibility of the pristine and functionalized pSiNPs was confirmed in vitro on human cell lines and in vivo by cytotoxic and systemic inflammation investigations, respectively. With their biocompatibility, biodegradability, and stealth properties, the pSiNPs functionalized with mannose and PEG show promising potential for biomedical applications.
Published: 2017
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20. High-Energy Resolution Fluorescence Detected X-Ray Absorption Spectroscopy: A Powerful New Structural Tool in Environmental Biogeochemistry Sciences

Author: Eric Lahera, Jérôme Rose, Isabelle Kieffer, Elena F. Bazarkina, Denis Testemale, Mohammed Irar, Mélanie Auffan, Jean-Louis Hazemann, William Del Net, Marie Tella, Sara A. Thomas, Antonio Aguilar-Tapia, Alain Prat, Olivier Proux, Mauro Rovezzi, Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), MRS - Matériaux, Rayonnements, Structure, Institut Néel (NEEL), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF), Department of Civil and Environmental Engineering [Evanston], Northwestern University [Evanston], Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), X'Press - X'Press, Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), ANR-07-NANO-027-NanoSurf,ANR-07-NANO-027-NanoSurf, ANR-10-NANO-0006,MESONNET,Utilisation de mésocosmes terrestres et aquatiques en réseau pour l'évaluation du risque associé à la dispersion de nanoparticules manufacturées(2010), ANR-10-LABX-0056/10-LABX-0056,OSUG@2020,Innovative strategies for observing and modelling natural systems(2010), ANR-10-EQPX-0027/10-EQPX-0027,EcoX,Ligne de lumière microfocus et très haute dilution à l’ESRF pour les sciences de l’environnement(2010), Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Matériaux, Rayonnements, Structure (NEEL - MRS), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), X'Press : diffraction et hautes pressions (NEEL - X'Press), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), ANR-07-NANO-0027,NANOSURF,Corrélation entre l'effet de taille nanométrique et l'énergie de surface, Impact sur la structure et la réactivité de la surface.(2007), ANR-10-LABX-0056,OSUG@2020,Innovative strategies for observing and modelling natural systems(2010), ANR-10-EQPX-0027,EcoX,Ligne de lumière microfocus et très haute dilution à l'ESRF pour les sciences de l'environnement(2010), Matériaux, Rayonnements, Structure (MRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), X'Press (X'Press), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: Environmental Engineering, Absorption spectroscopy, Analytical chemistry, trace elements, 02 engineering and technology, 010501 environmental sciences, Management, Monitoring, Policy and Law, 01 natural sciences, HERFD, high resolution spectroscopy, [PHYS.PHYS.PHYS-INS-DET]Physics [physics]/Physics [physics]/Instrumentation and Detectors [physics.ins-det], Spectroscopy, Absorption (electromagnetic radiation), Waste Management and Disposal, 0105 earth and related environmental sciences, Water Science and Technology, X-ray absorption spectroscopy, Ecology, Extended X-ray absorption fine structure, Spectrometer, Chemistry, [SDE.IE]Environmental Sciences/Environmental Engineering, Resolution (electron density), 021001 nanoscience & nanotechnology, Pollution, XANES, EXAFS, X-Ray Absorption Spectroscopy, 13. Climate action, 0210 nano-technology, Environmental Monitoring
Abstract: International audience; The study of the speciation of highly diluted elements by X-ray absorption spectroscopy (XAS) is extremely challenging, especially in environmental biogeochemistry sciences. Here we present an innovative synchrotron spectroscopy technique: high-energy resolution fluorescence detected XAS (HERFD-XAS). With this approach, measurement of the XAS signal in fluorescence mode using a crystal analyzer spectrometer with a ~1-eV energy resolution helps to overcome restrictions on sample concentrations that can be typically measured with a solid-state detector. We briefly describe the method, from both an instrumental and spectroscopic point of view, and emphasize the effects of energy resolution on the XAS measurements. We then illustrate the positive impact of this technique in terms of detection limit with two examples dealing with Ce in ecologically relevant organisms and with Hg species in natural environments. The sharp and well-marked features of the HERFD–X-ray absorption near-edge structure spectra obtained enable us to determine unambiguously and with greater precision the speciation of the probed elements. This is a major technological advance, with strong benefits for the study of highly diluted elements using XAS. It also opens new possibilities to explore the speciation of a target chemical element at natural concentration levels, which is critical in the fields of environmental and biogeochemistry sciences.
Published: 2017
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21. Is There a Trojan-Horse Effect during Magnetic Nanoparticles and Metalloid Cocontamination of Human Dermal Fibroblasts?

Author: Laila Benameur, Jérôme Rose, Olivier Proux, Jean-Yves Bottero, Mélanie Auffan, Corinne Chanéac, Wei Liu, Alain Botta, Armand Masion, Fabio Ziarelli, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), équipe FAME, Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), International Consortium for the Environmental Implications of Nanotechnology (iCEINT), Aix en Provence, France, Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Stereochemistry, Metal Nanoparticles, Nanoparticle, 02 engineering and technology, 010501 environmental sciences, 01 natural sciences, Arsenic, Adsorption, Desorption, Zeta potential, Humans, Environmental Chemistry, Surface charge, Magnetite Nanoparticles, Cytotoxicity, Cells, Cultured, Metalloids, Skin, 0105 earth and related environmental sciences, chemistry.chemical_classification, Chemistry, General Chemistry, Fibroblasts, 021001 nanoscience & nanotechnology, Culture Media, [SDE]Environmental Sciences, Biophysics, Thiol, Thermodynamics, Magnetic nanoparticles, 0210 nano-technology
Abstract: International audience; This study investigates the issue of nanoparticles/pollutants cocontamination. By combining viability assays, physicochemical and structural analysis (to probe the As speciation and valence), we assessed how gamma Fe2O3 nanoparticles can affect the cytotoxicity, the intra- and extracellular speciation of As(III). Human dermal fibroblasts were contaminated with gamma Fe2O3 nanoparticles and As(III) considering two scenarios: (i) a simultaneous coinjection of the nanoparticles and As, and (ii) an injection of the I: nanoparticles after 24 h of As adsorption in water. In both scenarios, we did not notice significant changes on the nanoparticles surface charge (zeta potential similar to -10 mV) nor hydrodynamic diameters (similar to 9.50 nm) after 24 h. We demonstrated that the coinjection of gamma Fe2O3 nanoparticles and As in the cellular media strongly affects the complexation of the intracellular As with thiol groups. This significantly increases at low doses the cytotoxicity of the As nonadsorbed at the surface of the nanoparticles. However, once As is adsorbed at the surface the desorption is very weak in the culture medium. This fraction of As strongly adsorbed at the surface is significantly less cytotoxic than As itself. On the basis of our data and the thermodynamics, we demonstrated that any disturbance of the biotransformation mechanisms by the nanoparticles (i.e., surface complexation of thiol groups with the iron atoms) is likely to be responsible for the increase of the As adverse effects at low doses.
Published: 2012
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22. Remote Biodegradation of Ge–Imogolite Nanotubes Controlled by the Iron Homeostasis of Pseudomonas brassicacearum

Author: Marie Bertrand, Armand Masion, Jérôme Rose, Mélanie Auffan, Clément Levard, Wafa Achouak, Astrid Avellan, Catherine Santaella, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Laboratoire d'Ecologie Microbienne de la Rhizosphère et d'Environnements Extrêmes (LEMIRE), Institut de Biosciences et Biotechnologies d'Aix-Marseille (ex-IBEB) (BIAM), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Nanotube, Iron, Imogolite, Nanotechnology, 010501 environmental sciences, Bacterial growth, 010402 general chemistry, medicine.disease_cause, 01 natural sciences, Pseudomonas, medicine, Homeostasis, Environmental Chemistry, 0105 earth and related environmental sciences, chemistry.chemical_classification, Reactive oxygen species, Nanotubes, biology, Chemistry, General Chemistry, Biodegradation, biology.organism_classification, 0104 chemical sciences, Biodegradation, Environmental, Chemical engineering, 13. Climate action, Toxicity, [SDE]Environmental Sciences, Pseudomonas brassicacearum, Oxidative stress
Abstract: PMID: 27347687; International audience; The toxicity of high-aspect-ratio nanomaterials (HARNs) is often associated with oxidative stress. The essential nutrient Fe may also be responsible of oxidative stress through the production of reactive oxygen species. In the present study, it has been examined to what extent adding Fenton reaction promoting Fe impacted the toxicity of an alumino-germanate model HARN. Structural addition of only 0.95% wt Fe to Ge–imogolite not only alleviated the toxicity observed in the case of Fe-free nanotubes but also stimulated bacterial growth. This was attributed to the metabolization of siderophore-mobilized Fe from the nanotube structure. This was evidenced by the regulation of the homeostasis-monitoring intracellular Fe levels. This was accompanied by a biodegradation of the nanotubes approaching 40%, whereas the Fe-free nanomaterial remained nearly untouched.
Published: 2016
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23. DNA damage and oxidative stress induced by CeO2 nanoparticles in human dermal fibroblasts: Evidence of a clastogenic effect as a mechanism of genotoxicity

Author: Virginie Tassistro, Mélanie Auffan, Jérôme Rose, Sylvia Pietri, Laila Benameur, Wei Liu, Mathieu Cassien, Jean-Yves Bottero, Pierre Stocker, Marcel Culcasi, Hidayat Rahmouni, Alain Botta, Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Centre National de la Recherche Scientifique (CNRS)-Institut de recherche pour le développement [IRD] : UMR237-Aix Marseille Université (AMU)-Avignon Université (AU), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Surface Properties, DNA damage, [SDV]Life Sciences [q-bio], Primary Cell Culture, Biomedical Engineering, free radicals, Biology, Toxicology, medicine.disease_cause, Lipid peroxidation, chemistry.chemical_compound, glutathione status, medicine, Humans, [CHIM]Chemical Sciences, Colloids, Particle Size, Hydrogen peroxide, Cells, Cultured, Skin, Genetics, Cerium, Glutathione, Fibroblasts, nanoceria, Oxidative Stress, chemistry, Catalase, Micronucleus test, Biophysics, biology.protein, Nanoparticles, nanogenotoxicity, Cytokinesis-blocked micronucleus assay, Genotoxicity, Oxidative stress, DNA Damage, Mutagens
Abstract: The broad range of applications of cerium oxide (CeO2) nanoparticles (nano-CeO2) has attracted industrial interest, resulting in greater exposures to humans and environmental systems in the coming years. Their health effects and potential biological impacts need to be determined for risk assessment. The aims of this study were to gain insights into the molecular mechanisms underlying the genotoxic effects of nano-CeO2 in relation with their physicochemical properties. Primary human dermal fibroblasts were exposed to environmentally relevant doses of nano-CeO2 (mean diameter, 7 nm; dose range, 6 x10-5–6x10-3 g/l corresponding to a concentration range of 0.22–22 mM) and DNA damages at the chromosome level were evaluated by genetic toxicology tests and compared to that induced in cells exposed to micro- CeO2 particles (mean diameter, 320 nm) under the same conditions. For this purpose, cytokinesis-blocked micronucleus assay in association with immunofluorescence staining of centromere protein A in micronuclei were used to distinguish between induction of structural or numerical chromosome changes (i.e. clastogenicity or aneuploidy). The results provide the first evidence of a genotoxic effect of nano-CeO2, (while not significant with micro-CeO2) by a clastogenic mechanism. The implication of oxidative mechanisms in this genotoxic effect was investigated by (i) assessing the impact of catalase, a hydrogen peroxide inhibitor, and (ii) by measuring lipid peroxidation and glutathione status and their reversal by application of N-acetylcysteine, a precusor of glutathione synthesis in cells. The data are consistent with the implication of free radical-related mechanisms in the nano-CeO2-induced clastogenic effect, that can be modulated by inhibition of cellular hydrogen peroxide release.
Published: 2015
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24. Monte Carlo simulations of the transformation and removal of Ag, TiO2, and ZnO nanoparticles in wastewater treatment and land application of biosolids

Author: Lauren E. Barton, Mark Durenkamp, Jean-Yves Bottero, Mark R. Wiesner, Mélanie Auffan, Steve P. McGrath, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Duke University [Durham], Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Silver, Environmental Engineering, Biosolids, Metal Nanoparticles, Nanoparticle, Wastewater treatment, Wastewater, Waste Disposal, Fluid, Nanomaterials, Exposure, Environmental Chemistry, Monte Carlo modeling, Waste Management and Disposal, Effluent, Titanium, Chemistry, Nanopartides, Agriculture, Pollution, 6. Clean water, Waste treatment, Models, Chemical, Environmental chemistry, [SDE]Environmental Sciences, Nanoparticles, Water treatment, Sewage treatment, Zinc Oxide, Monte Carlo Method
Abstract: International audience; The use of nano-enabled materials in industry and consumer products is increasing rapidly and with it, the more imperative it becomes to understand the consequences of such materials entering the environment during production, use or disposal. The novel properties of engineered nanomaterials (ENMs) that make them desirable for commercial applications also present the possibility of impacting aquatic and terrestrial environments in ways that may differ from materials in bulk format. Modeling techniques are needed to proactively predict the environmental fate and transport of nanomaterials. A model for nanopartide (NP) separation and transformation in water treatment was parameterized for three metal and metal-oxide NPs. Functional assays to determine NP specific distribution and transformation were used to parameterize the model and obtain environmentally relevant concentrations of NPs and transformation byproducts leaving WWTPs in effluent and biosolids. All three NPs were predicted to associate >90% with the solid phase indicating significant accumulation in the biosolids. High rates of transformation for ZnO and Ag NPs resulted in similar to 97% transformation of the NPs that enter the plant despite differences in transformation rate in aerobic versus anaerobic environments. Due to high insolubility and negligible redox transformation, the only process predicted to impact TiO2 NP fate and transport in WWTPs was distribution between the solid and liquid phases. Subsequent investigation of ZnO NP species fate and transport when land applied in biosolids indicated that steady state concentrations of ZnO phases would likely be achieved after approximately 150 days under loading conditions of biosolids typical in current practice. (C) 2014 Elsevier B.V. All rights reserved.
Published: 2015
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25. Chronic dosing of a simulated pond ecosystem in indoor aquatic mesocosms: fate and transport of CeO2 nanoparticles

Author: Olivier Proux, Ester Artells, Marie Tella, E. Morel, Christine Paillès, Alain Thiéry, Jérôme Rose, Mélanie Auffan, Bernard Angeletti, Jean-Yves Bottero, Corinne Chanéac, Catherine Santaella, Lenka Brousset, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Avignon Université (AU), Aix Marseille Université (AMU), Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Centre National de la Recherche Scientifique (CNRS)-Institut de recherche pour le développement [IRD] : UMR237-Aix Marseille Université (AMU)-Avignon Université (AU), Institut de Recherche pour le Développement (IRD), Fédération Nationale des Agriculteurs Multiplicateurs de Semences (FNAMS), Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF)-Centre National de la Recherche Scientifique (CNRS), International Institute of Earthquake Engineering and Seismology, inconnu, Inconnu, CNRS, French ANR [ANR-10-NANO-0006/MESONNET], ``Investissements d'Avenir' French Government program of the French National Research Agency (ANR) through the A*MIDEX project [ANR-11-LABX-0064, ANR-11-IDEX-0001-02], Labex OSUG [ANR-10-LABX-0056], FP7 project NANoREG (a common European approach to the regulatory testing of manufactured nanomaterials, European Commission) [310584], OSU-Institut pytheas, ANR-11-IDEX-0001-02/11-IDEX-0001,AMIDEX,AMIDEX(2011), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC), ANR-11-IDEX-0001,Amidex,INITIATIVE D'EXCELLENCE AIX MARSEILLE UNIVERSITE(2011), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Planorbarius corneus, biology, Chemistry, Materials Science (miscellaneous), Aquatic ecosystem, Eudiaptomus, fungi, technology, industry, and agriculture, Sediment, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010501 environmental sciences, Plankton, 021001 nanoscience & nanotechnology, biology.organism_classification, 01 natural sciences, Mesocosm, Water column, Benthic zone, Environmental chemistry, 0210 nano-technology, 0105 earth and related environmental sciences, General Environmental Science
Abstract: International audience; Indoor aquatic mesocosms were designed to mimic pond ecosystems contaminated by a continuous point-source discharge of cerium oxide nanoparticles (CeO2-NPs). Bare and citrate-coated CeO2-NPs exhibited different chemical and colloidal behaviors in the aquatic mesocosms. Bare CeO2-NPs were chemically stable but quickly homo-aggregated and settled out of the water column. Citrate-coated NPs both homo-and hetero-aggregated but only after the several days required to degrade the citrate coating. While they were more stable as a colloidal suspension, coated CeO2-NPs dissolved faster due to surface complexation with citrate, which resulted in the release of dissolved Ce into the water column. The different distributions over time between water/sediment or dissolved/particulate forms of Ce controlled the availability of Ce to benthic grazers (mollusk Planorbarius corneus) and planktonic filter feeders (copepod Eudiaptomus vulgaris).
Published: 2015
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26. Heteroaggregation, transformation and fate of CeO2 nanoparticles in wastewater treatment

Author: Mélanie Auffan, Luca Olivi, Jean-Yves Bottero, Mark R. Wiesner, Lauren E. Barton, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Elettra Sincrotrone Trieste, Duke University [Durham], Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA)
Subjects: inorganic chemicals, Biosolids, Health, Toxicology and Mutagenesis, education, Nanoparticle, CeO2 nanoparticles, 02 engineering and technology, Wastewater treatment, 010501 environmental sciences, Toxicology, 01 natural sciences, Exposure modeling, Transformation, Effluent, health care economics and organizations, 0105 earth and related environmental sciences, Chemistry, technology, industry, and agriculture, General Medicine, 021001 nanoscience & nanotechnology, Pollution, 6. Clean water, Partition coefficient, Waste treatment, Wastewater, 13. Climate action, Environmental chemistry, [SDE]Environmental Sciences, Sewage treatment, Water treatment, 0210 nano-technology
Abstract: International audience; Wastewater Treatment Plants (WWTPs) are a key pathway by which nanoparticles (NPs) enter the environment following release from NP-enabled products. This work considers the fate and exposure of CeO2 NPs in WWTPs in a two-step process of heteroaggregation with bacteria followed by the subsequent reduction of Ce(IV) to Ce(III). Measurements of NP association with solids in sludge were combined with experimental estimates of reduction rate constants for CeO2 NPs in Monte Carlo simulations to predict the concentrations and speciation of Ce in WWTP effluents and biosolids. Experiments indicated preferential accumulation of CeO2 NPs in biosolids where reductive transformation would occur. Surface functionalization was observed to impact both the distribution coefficient and the rates of transformation. The relative affinity of CeO2 NPs for bacterial suspensions in sludge appears to explain differences in the observed rates of Ce reduction for the two types of CeO2 NPs studied. (C) 2015 Elsevier Ltd. All rights reserved.
Published: 2015
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27. A new approach for the oocyte genotoxicity assay: adaptation of comet assay on mouse cumulus-oocyte complexes

Author: Blandine Courbiere, Thierry Orsière, Virginie Tassistro, Jeanne Perrin, Mélanie Auffan, F. Greco, Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Service de Gynécologie et Obstétrique [Marseille], Hôpital de la Conception [CHU - APHM] (LA CONCEPTION), Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Hôpital de la Conception [CHU - APHM] (LA CONCEPTION ), Centre National de la Recherche Scientifique (CNRS)-Institut de recherche pour le développement [IRD] : UMR237-Aix Marseille Université (AMU)-Avignon Université (AU), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: cumulus-oocyte complexes, DNA damage, Somatic cell, media_common.quotation_subject, Metal Nanoparticles, Biology, medicine.disease_cause, Mice, chemistry.chemical_compound, In vivo, comet assay, medicine, Animals, Hydrogen peroxide, oocyte, Ovulation, media_common, Genetics, Cumulus Cells, General Veterinary, genotoxicity, Cerium, Hydrogen Peroxide, Oocyte, Cell biology, Comet assay, medicine.anatomical_structure, chemistry, [SDE]Environmental Sciences, Oocytes, Female, Animal Science and Zoology, environment, Genotoxicity, DNA Damage, Mutagens
Abstract: Conventional genotoxicity tests are technically difficult to apply to oocytes, and results obtained on somatic cells cannot be extrapolated to gametes. We have previously described a comet assay (original–CA) on denuded mouse oocytes, but, in vivo, oocytes are not isolated from their surrounding follicular cells. Our objective was to develop a comet assay on cumulus–oocyte complexes (COC–CA) for a more physiological approach to study the genotoxicity of environmental factors on oocytes. For COC–CA, whole COC were exposed directly to exogenous agents after ovulation and removal from oviducts. Three conditions were studied: a negative control group, and two positive control groups, one of which was exposed to hydrogen peroxide (H2O2) and the other group was incubated with cerium dioxide nanoparticles (CeO2 NPs). With both tests, DNA damage was significant in the presence of both H2O2 and CeO2 NPs compared with the negative control. COC–CA offers an interesting tool for assaying the genotoxicity of environmental agents towards germinal cells. Furthermore, COC–CA is less time-consuming and simplifies the protocol of the original–CA, because COC-CA is easier to perform without the washing-out procedure.
Published: 2015
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28. Salinity-dependent silver nanoparticle uptake and transformation by Atlantic killifish (Fundulus heteroclitus) embryos

Author: Jérôme Rose, Richard T. Di Giulio, Olivier Proux, Wei Liu, M. C. Arnold, Mélanie Auffan, Jean-Yves Bottero, Perrine Chaurand, Barbara Fayard, Cole W. Matson, Mark R. Wiesner, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), International Consortium for the Environmental Implications of Nanotechnology iCEINT, Europôle de l'Arbois, 13545 Aix en Provence, Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), European Synchrotron Radiation Facility (ESRF), Duke University [Durham], Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: In situ, Silver, media_common.quotation_subject, Sodium, Biomedical Engineering, chemistry.chemical_element, Sodium Chloride, 010501 environmental sciences, Toxicology, 01 natural sciences, Silver nanoparticle, salinity, 03 medical and health sciences, Adsorption, Fundulidae, Animals, 030304 developmental biology, 0105 earth and related environmental sciences, media_common, 0303 health sciences, biology, Ecology, Chorion, biology.organism_classification, Fundulus, Salinity, Speciation, Membrane, chemistry, speciation, embryonic structures, [SDE]Environmental Sciences, estuarine, Nanoparticles, nanomaterial, Nuclear chemistry
Abstract: International audience; We assessed the biodistribution and in situ speciation of sub-lethal concentrations of citrate-coated silver nanoparticles and dissolved silver within Fundulus heteroclitus embryos. Using a thorough physico-chemical characterization, we studied the role of salinity on both uptake and in situ speciation. The Ag uptake or adsorption on the chorion was reduced by 2.3-fold for Ag NPs, and 2.9-fold for AgNO3 in estuarine water (10 parts per thousand ASW) compared to deionized water (0 parts per thousand ASW). Between 58% and 85% of the silver was localized on/in the chorion and formed patches between 20 and 80 mu m. More than a physical barrier, the chorion was found to be a chemically reactive membrane controlling the in situ speciation of silver. A strong complexation of the Cit-Ag NPs with the thiolated groups of proteins or enzymes of the chorion was responsible for the oxidation of 48 +/- 5% of the Ag-0 into Ag-(I)-S species at 0 parts per thousand ASW. However, at 10 parts per thousand ASW, the presence of Cl- ions at the surface of Ag NPs slow down this oxidation. For the dissolved silver, we observed that in deionized water 69 +/- 7% of Ag+ taken up by the chorion was complexed by the thiolated molecules while the others 30 +/- 3% were reduced into Ag-0 likely via interaction with the hemiacetal-reducing ends of polysaccharides of the chorion.
Published: 2014
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29. The Transformation of Pristine and Citrate-Functionalized CeO2 Nanoparticles in a Laboratory Scale Aerobic Activated Sludge Reactor

Author: Jean-Yves Bottero, Daniel Borschneck, Marie Bertrand, Mélanie Auffan, Catherine Santaella, Luca Olivi, Mark R. Wiesner, Nicolas Roche, Mohamed Barakat, Lauren E. Barton, Armand Masion, Department of Civil and Environmental Engineering [Durham] (CEE), Duke University [Durham], Center for the Environmental Implications of Nanotechnology, Duke University, International Consortium for the Environmental Implications of Nanotechnology (ICEINT), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Laboratoire d'Ecologie Microbienne de la Rhizosphère et d'Environnements Extrêmes (LEMIRE), Institut de Biosciences et Biotechnologies d'Aix-Marseille (ex-IBEB) (BIAM), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Elettra Sincrotrone Trieste, Laboratoire de Mécanique, Modélisation et Procédés Propres (M2P2), Centre National de la Recherche Scientifique (CNRS)-École Centrale de Marseille (ECM)-Aix Marseille Université (AMU), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU)-Direction de Recherche Fondamentale (CEA) (DRF (CEA))
Subjects: Biosolids, Engineered nanomaterials, Wastewater, Laboratory scale, Citric Acid, Water Purification, Bioreactors, Phase (matter), Environmental Chemistry, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Effluent, Biotransformation, Bacteria, Sewage, Waste management, Chemistry, [SDE.IE]Environmental Sciences/Environmental Engineering, Cerium, General Chemistry, 6. Clean water, Kinetics, X-Ray Absorption Spectroscopy, Activated sludge, Environmental chemistry, Nanoparticles, Sewage treatment, Ceo2 nanoparticles, Laboratories
Abstract: International audience; Engineered nanomaterials (ENMs) are used to enhance the properties of many manufactured products and technologies. Increased use of ENMs will inevitably lead to their release into the environment. An important route of exposure is through the waste stream, where ENMs will enter wastewater treatment plants (WWTPs), undergo transformations, and be discharged with treated effluent or biosolids. To better understand the fate of a common ENM in WWTPs, experiments with laboratory-scale activated sludge reactors and pristine and citrate-functionalized CeO2 nanoparticles (NPs) were conducted. Greater than 90% of the CeO2 introduced was observed to associate with biosolids. This association was accompanied by reduction of the Ce(IV) NPs to Ce(III). After 5 weeks in the reactor, 44 ± 4% reduction was observed for the pristine NPs and 31 ± 3% for the citrate-functionalized NPs, illustrating surface functionality dependence. Thermodynamic arguments suggest that the likely Ce(III) phase generated would be Ce2S3. This study indicates that the majority of CeO2 NPs (>90% by mass) entering WWTPs will be associated with the solid phase, and a significant portion will be present as Ce(III). At maximum, 10% of the CeO2 will remain in the effluent and be discharged as a Ce(IV) phase, governed by cerianite (CeO2).
Published: 2014
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30. Two-Photon Excitation of Porphyrin-Functionalized Porous Silicon Nanoparticles for Photodynamic Therapy

Author: Jean-Olivier Durand, Marie Maynadier, Audrey Gallud, Marcel Garcia, Vincent Hugues, Elise Bouffard, Philippe Maillard, Mireille Blanchard-Desce, Emilie Secret, Céline Frochot, Alain Morère, Frédérique Cunin, Khaled El Cheikh, Michael J. Sailor, Mélanie Auffan, Magali Gary-Bobo, Olivier Mongin, Arnaud Chaix, Nathalie Marcotte, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Network Centric (NC), TRT - THALES RESEARCH & TECHNOLOGY, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Conception, synthèse et vectorisation de biomolécules. (CSVB), Université Paris Descartes - Paris 5 (UPD5)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Curie [Paris], Chimie et Photonique Moléculaires (CPM), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Dept Chem & Biochem UC San Diego, University of California [San Diego] (UC San Diego), University of California-University of California, Institut de recherche en cancérologie de Montpellier (IRCM - U896 Inserm - UM1), CRLCC Val d'Aurelle - Paul Lamarque-Université de Montpellier (UM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Montpellier 1 (UM1), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Réactions et Génie des Procédés (LRGP), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Université Paris Descartes - Paris 5 (UPD5)-Institut Curie [Paris]-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry and Biochemistry [Univ California San Diego] (Chemistry - UC San Diego), University of California (UC)-University of California (UC), Université Montpellier 1 (UM1)-CRLCC Val d'Aurelle - Paul Lamarque-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université de Montpellier (UM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Institut Curie-Centre National de la Recherche Scientifique (CNRS)-Université Paris Descartes - Paris 5 (UPD5), Univ Calif San Diego, Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)
Subjects: Silicon, Porphyrins, Materials science, Infrared Rays, medicine.medical_treatment, Nanoparticle, Biocompatible Materials, Photodynamic therapy, 02 engineering and technology, 010402 general chemistry, Porous silicon, Endocytosis, Photochemistry, 01 natural sciences, chemistry.chemical_compound, Two-photon excitation microscopy, medicine, Humans, [CHIM]Chemical Sciences, General Materials Science, Nir laser, ComputingMilieux_MISCELLANEOUS, Photons, Microscopy, Confocal, Photosensitizing Agents, Cell Death, Mechanical Engineering, technology, industry, and agriculture, equipment and supplies, 021001 nanoscience & nanotechnology, Porphyrin, 0104 chemical sciences, 3. Good health, Microscopy, Fluorescence, Photochemotherapy, chemistry, Mechanics of Materials, MCF-7 Cells, Nanoparticles, 0210 nano-technology, Mannose, Porosity, Excitation
Abstract: Porous silicon nanoparticles (pSiNPs) act as a sensitizer for the 2-photon excitation of a pendant porphyrin using NIR laser light, for imaging and photodynamic therapy. Mannose-functionalized pSiNPs can be vectorized to MCF-7 human breast cancer cells through a mannose receptor-mediated endocytosis mechanism to provide a 3-fold enhancement of the 2-photon PDT effect.
Published: 2014
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31. Environmental release, fate and ecotoxicological effects of manufactured ceria nanomaterials

Author: Arturo A. Keller, Jamie R. Lead, Jason C. White, Claus Svendsen, Andrew C. Johnson, Blanche Collin, Ruth C. Merrifield, Inder Kaur, Xingmao Ma, Anastasiya Lazareva, Mélanie Auffan, Jason M. Unrine, Centre Régional de Lutte contre le cancer Georges-François Leclerc [Dijon] (UNICANCER/CRLCC-CGFL), UNICANCER, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), NERC Centre for Ecology and Hydrology, Natural Environment Research Council (NERC), Institute of Arctic and Alpine Research (INSTAAR), University of Colorado [Boulder], Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Centre Régional de Lutte contre le cancer - Centre Georges-François Leclerc (CRLCC - CGFL), Université de Bourgogne (UB)-Centre National de la Recherche Scientifique (CNRS), Centre Régional de Lutte contre le cancer - Centre Georges-François Leclerc ( CRLCC - CGFL ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Centre européen de recherche et d'enseignement de géosciences de l'environnement ( CEREGE ), Centre National de la Recherche Scientifique ( CNRS ) -Institut de Recherche pour le Développement ( IRD ) -Aix Marseille Université ( AMU ) -Collège de France ( CdF ) -Institut National de la Recherche Agronomique ( INRA ) -Institut national des sciences de l'Univers ( INSU - CNRS ), NERC - Centre for Ecology and Hydrology, Institute of Arctic and Alpine Research ( INSTAAR ), University of Colorado Boulder [Boulder], Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), and Institute of Arctic Alpine Research [University of Colorado Boulder] (INSTAAR)
Subjects: Materials science, Future studies, Materials Science (miscellaneous), Environmental media, 02 engineering and technology, 010501 environmental sciences, 021001 nanoscience & nanotechnology, 01 natural sciences, 6. Clean water, Aquatic organisms, [ SDE ] Environmental Sciences, Toxicology, Chemistry, 13. Climate action, Environmental protection, [SDE]Environmental Sciences, Ecological risk, 0210 nano-technology, Chronic toxicity, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences, General Environmental Science
Abstract: Recent interest in the environmental fate and effects of manufactured CeO2 nanomaterials (nanoceria) has stemmed from its expanded use for a variety of applications including fuel additives, catalytic converters, chemical and mechanical planarization media and other uses. This has led to a wave of publications on the toxicological effects of nanoceria in ecological receptor species, but only limited information is available on possible environmental releases, concentrations in environmental media, or environmental transformations. In this paper, we make initial estimates of likely environmental releases and exposure concentrations in soils and water and compare them to published toxicity values. Insufficient information was available to estimate aquatic exposures, but we estimated inputs to a hypothetical wastewater treatment plant that could result in effluent concentrations that would result in acute toxicity to the most sensitive aquatic organisms tested so far, cyanobacteria. The purpose of this exercise is to identify which areas are lacking in data to perform either regional or site specific ecological risk assessments. While estimates can be made for releases from use as a diesel fuel additive, and predicted toxicity is low in most terrestrial species tested to date, estimates for releases from other uses are difficult at this stage. We recommend that future studies focus on environmentally realistic exposures that take into account potential environmental transformations of the nanoceria surface as well as chronic toxicity studies in benthic aquatic organisms, soil invertebrates and microorgansims.
Published: 2014
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32. Molecular Insights of Oxidation Process of Iron Nanoparticles: Spectroscopic, Magnetic, and Microscopic Evidence

Author: Daniel Borschneck, Naresh Kumar, Delphine Kaifas, Michael Jublot, Laure Malleret, Luca Olivi, Jean-Yves Bottero, Petr Kvapil, Pierre Doumenq, Jérôme Gattacceca, Jérôme Rose, Mélanie Auffan, Universiteit Antwerpen = University of Antwerpen [Antwerpen], Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Department of Earth, Atmospheric and Planetary Sciences [MIT, Cambridge] (EAPS), Massachusetts Institute of Technology (MIT), International Consortium for the Environmental Implications of Nanotechnology iCEINT, Europôle de l'Arbois, 13545 Aix en Provence, Elettra Sincrotrone Trieste, Laboratoire Chimie de l'environnement (LCE), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universiteit Antwerpen [Antwerpen], Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: Iron, Inorganic chemistry, Analytical chemistry, Iron oxide, Nanoparticle, Maghemite, Metal Nanoparticles, engineering.material, Ferric Compounds, Metal, chemistry.chemical_compound, Magnetics, Microscopy, Electron, Transmission, X-Ray Diffraction, Environmental Chemistry, Energy filtered transmission electron microscopy, Nanotechnology, High-resolution transmission electron microscopy, X-ray absorption spectroscopy, Chemistry, Oxides, General Chemistry, Trichloroethylene, X-Ray Absorption Spectroscopy, 13. Climate action, visual_art, [SDE]Environmental Sciences, engineering, visual_art.visual_art_medium, Oxidation-Reduction, Water Pollutants, Chemical, Superparamagnetism
Abstract: International audience; Oxidation behavior of nano-Fe-0 particles in an anoxic environment was determined using different state-of-the-art analytical approaches, including high resolution transmission electron microscopy (HR-TEM) combined with energy filtered transmission electron microscopy (EFTEM), X-ray absorption spectroscopy (XAS), and magnetic measurements. Oxidation in controlled experiments was compared in standard double distilled (DD) water, DD water spiked with trichloroethene (TCE), and TCE contaminated site water. Using HR-TEM and EFTEM, we observed a surface oxide layer (similar to 3 nm) formed immediately after the particles were exposed to water. XAS analysis followed the dynamic change in total metallic iron concentration and iron oxide concentration for the experimental duration of 35 days. The metallic iron concentration in nano-Fe-0 particles exposed to water, was similar to 40% after 35 days; in contrast, the samples containing TCE were reduced to similar to 15% and even to nil in the case of TCE contaminated site water, suggesting that the contaminants enhance the oxidation of nano-Fe0. Frequency dependence measurements confirmed the formation of superparamagnetic particles in the system. Overall, our results suggest that nano-Fe0 oxidized via the Fe-0 - Fe(OH)(2) - Fe3O4 - (gamma-Fe2O3) route and the formation of superparamagnetic maghemite nanoparticles due to disruption of the surface oxide layer.
Published: 2014
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33. Role of molting on the biodistribution of CeO2 nanoparticles within Daphnia pulex

Author: Mélanie Auffan, Alain Thiéry, Christine Paillès, Jean-Yves Bottero, Jérôme Rose, Delphine Bertin, Christian Dominici, Perrine Chaurand, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Spectropôle - Aix Marseille Université (AMU SPEC), Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Centre National de la Recherche Scientifique (CNRS)-Institut de recherche pour le développement [IRD] : UMR237-Aix Marseille Université (AMU)-Avignon Université (AU), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), and Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS)
Subjects: Environmental Engineering, Cuticle, 0211 other engineering and technologies, Uptake, Chitin, 02 engineering and technology, 010501 environmental sciences, Biology, Molting, Ecotoxicology, 01 natural sciences, Daphnia pulex, Toxicology, chemistry.chemical_compound, Ingestion, Animals, Nanotechnology, Tissue Distribution, Waste Management and Disposal, 0105 earth and related environmental sciences, Water Science and Technology, Civil and Structural Engineering, Nanomaterials, 021110 strategic, defence & security studies, Ecological Modeling, Water, Cerium, biology.organism_classification, Pollution, Gastrointestinal Tract, Chlorella, Pulex, chemistry, Daphnia, Exuviation, [SDE]Environmental Sciences, Biophysics, Nanoparticles, Moulting, Environmental Monitoring
Abstract: International audience; As all arthropods, microcrustaceans shed their chitinous exoskeleton (cuticule, peritrophic membrane) to develop and grow. While the molting is the most crucial stage in their life cycle, it remains poorly investigated in term of pollutant biodistribution within the organisms. In this paper, we used optical, electronic, and X ray-based microscopies to study the uptake and release of CeO2 nanoparticles by/from Daphnia pulex over a molting stage. We measured that D. pulex molts every 59 +/- 21 h (confidence interval) with growth rates about 1.1 or 1.8 gm per stage as a function of the pieces measured. Ingestion via food chain was the main route of CeO2 nanoparticles uptake by D. pulex. The presence of algae during the exposure to nanoparticles (sub-lethal doses) enhanced by a factor of 3 the dry weight concentration of Ce on the whole D. pulex. Nanoparticles were localized in the gut content, in direct contact with the peritrophic membrane, and on the cuticle. Interestingly, the depuration (24 h with Chlorella pseudomonas) was not efficient to remove the nanoparticles from the organisms. From 40% to 100% (depending on the feeding regime during exposure) of the CeO2 taken up by D. pulex is not release after the depuration process. However, we demonstrated for the first time that the shedding of the chitinous exoskeleton was the crucial mechanism governing the released of CeO2 nanoparticles regardless of the feeding regime during exposure. (C) 2013 Elsevier Ltd. All rights reserved.
Published: 2013
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34. Protein corona formation for nanomaterials and proteins of a similar size: hard or soft corona?

Author: Claude Vidaud, Jérôme Rose, Mélanie Auffan, Jean-Yves Bottero, Sophie Plantevin, Wei Liu, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Service de Biochimie et Toxicologie Nucléaire (SBTN), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Circular dichroism, Macromolecular Substances, Surface Properties, Size-exclusion chromatography, education, Molecular Conformation, Nanoparticle, Protein Corona, 02 engineering and technology, Plasma protein binding, 010402 general chemistry, 01 natural sciences, Adsorption, Materials Testing, General Materials Science, Particle Size, Bovine serum albumin, Binding Sites, Chromatography, biology, Chemistry, technology, industry, and agriculture, Proteins, 021001 nanoscience & nanotechnology, Nanostructures, 0104 chemical sciences, [SDE]Environmental Sciences, Biophysics, biology.protein, Surface modification, Crystallization, 0210 nano-technology, Protein Binding
Abstract: International audience; Nanoparticles (NPs) entering a biological fluid undergo surface modification due to dynamic, physicochemical interactions with biological components, especially proteins. In this work we used complementary bio-physico-chemical approaches to characterize the effects of interactions between CeO2 NPs, immunoglobulins (IgGs) and bovine serum albumin (BSA) of a similar size on protein structural evolution as well as formation of (hetero-) aggregates. Using circular dichroism we showed that IgGs and BSA underwent significant structural changes after interaction with NPs. The NPs and protein-NPs were observed after size exclusion chromatography, highlighting the fact that few aggregates were stable enough to pass this mild separation step. X-ray absorption spectroscopy suggested that the surface chemistry of NPs was not affected by these proteins, also implying weak interactions. Competitive experiments revealed that, while the serum was more concentrated for BSA, IgG-NP aggregates were more stable. Altogether, our results indicate that, under our experimental conditions, the formation of a ``protein corona'' is an unstable and reversible mechanism. This indicates that, when NPs and proteins are similar in size, the adsorption concept (i.e. protein corona concept) cannot be applied to model the NP-protein interaction, and a heteroaggregation model is more appropriate.
Published: 2013
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35. Influence of the Length of Imogolite-Like Nanotubes on Their Cytotoxicity and Genotoxicity toward Human Dermal Cells

Author: Daniel Borschneck, Antoine Thill, Alain Botta, Jérôme Rose, Florence Chaspoul, Perrine Chaurand, Mélanie Auffan, Michel De Méo, Wei Liu, Jean-Yves Bottero, Philippe Gallice, Carole Di Giorgio, Armand Masion, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Institut méditerranéen de biodiversité et d'écologie marine et continentale (IMBE), Avignon Université (AU)-Aix Marseille Université (AMU)-Institut de recherche pour le développement [IRD] : UMR237-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), International Consortium for the Environmental Implications of Nanotechnology (iCEINT), Aix en Provence, France, Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Stereochemistry, Cell Survival, Nanoparticle, Imogolite, 02 engineering and technology, 010402 general chemistry, Toxicology, medicine.disease_cause, 01 natural sciences, Structure-Activity Relationship, medicine, Humans, DNA Breaks, Double-Stranded, Particle Size, Cytotoxicity, Chemical composition, Cells, Cultured, Nanotubes, Dose-Response Relationship, Drug, Chemistry, Small-angle X-ray scattering, Scattering, Germanium, General Medicine, Fibroblasts, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Cell culture, [SDE]Environmental Sciences, 0210 nano-technology, Genotoxicity, Nuclear chemistry, Aluminum, DNA Damage
Abstract: International audience; Physical-chemical parameters such as purity, structure, chemistry, length, and aspect ratio of nanoparticles (NPs) are linked to their toxicity. Here, synthetic imogolite-like nanotubes with a set chemical composition but various sizes and shapes were used as models to investigate the influence of these physical parameters on the cyto- and genotoxicity and cellular uptake of NPs. The NPs were characterized using X-ray diffraction (XRD), small angle X-ray scattering (SAXS), and atomic force microscopy (AFM). Imogolite precursors (PR, ca. 5 nm curved platelets), as well as short tubes (ST, ca. 6 nm) and long tubes (LT, ca. 50 am), remained stable in the cell culture medium. Internalization into human fibroblasts was observed only for the small particles PR and ST. None of the tested particles induced a significant cytotoxicity up to a concentration of 10(-1) mg.mL(-1). However, small sized NPs (PR and ST) were found to be genotoxic at very low concentration 10(-6) mg.mL(-1), while LT particles exhibited a weak genotoxicity. Our results indicate that small size NPs (PR, ST) were able to induce primary lesions of DNA at very low concentrations and that this DNA damage was exclusively induced by oxidative stress. The higher aspect ratio LT particles exhibited a weaker genotoxicity, where oxidative stress is a minor factor, and the likely involvement of other mechanisms Moreover, a relationship among cell uptake, particle aspect ratio, and DNA damage of NPs was observed.
Published: 2012
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36. Early-stage precipitation kinetics of zinc sulfide nanoclusters forming in the presence of cysteine

Author: Boris L. T. Lau, Armand Masion, Andreas Gondikas, Heileen Hsu-Kim, Mélanie Auffan, Department of Civil and Environmental Engineering [Durham] (CEE), Duke University [Durham], Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA)
Subjects: Metal sulfide, Inorganic chemistry, Nanoparticle, 02 engineering and technology, 010501 environmental sciences, 01 natural sciences, Nanoclusters, Metal, chemistry.chemical_compound, Dynamic light scattering, Geochemistry and Petrology, 0105 earth and related environmental sciences, Natural organic matter, Small-angle X-ray scattering, Precipitation (chemistry), Geology, SAXS, 021001 nanoscience & nanotechnology, Zinc sulfide, EXAFS, chemistry, 13. Climate action, Cluster, visual_art, [SDE]Environmental Sciences, visual_art.visual_art_medium, 0210 nano-technology, Cysteine
Abstract: International audience; Nanoparticulate metal sulfides such as ZnS are important for the speciation of pollutant metals in sediments, wastewater effluent, and other sulfidic environments. In these settings, particles of ZnS are formed in the presence of natural organic acids such as humic substances, proteins and other biomolecules that will interfere with cluster growth and aggregation kinetics. Thiol-containing organics such as cysteine are capable of adsorbing to clusters and nanoparticles of metal sulfides as they precipitate from solution. The thiols induce electrostatic repulsive forces at particle interfaces resulting in slow aggregation rates. The aim of this work was to investigate how cysteine influences the nucleation and growth rate of ZnS during early stages (less than one day) of precipitation. Results from time-resolved small angle X-ray scattering and dynamic light scattering confirmed that cysteine altered the ZnS precipitation process by decreasing aggregation rates of polynuclear ZnS clusters (smallest size
Published: 2012
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37. Antimicrobial effects of commercial silver nanoparticles are attenuated in natural streamwater and sediment

Author: Mélanie Auffan, Mark R. Wiesner, Benjamin P. Colman, Emily S. Bernhardt, Si-Yi Wang, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Department of Civil and Environmental Engineering [Durham] (CEE), Duke University [Durham], Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Geologic Sediments, Nutrient cycle, Silver, Health, Toxicology and Mutagenesis, Microorganism, Microbial Consortia, Microbial biomass, Metal Nanoparticles, 02 engineering and technology, 010501 environmental sciences, Management, Monitoring, Policy and Law, Environment, Toxicology, 01 natural sciences, Silver nanoparticle, chemistry.chemical_compound, Microbial respiration, Rivers, Respiration, Ecotoxicology, Biomass, 14. Life underwater, Enzyme activity, Sulfate, Incubation, 0105 earth and related environmental sciences, General Medicine, 021001 nanoscience & nanotechnology, Phosphate, 6. Clean water, chemistry, 13. Climate action, Environmental chemistry, [SDE]Environmental Sciences, Silver Nitrate, Silver nanoparticles, 0210 nano-technology
Abstract: International audience; Given the demonstrated antimicrobial properties of silver nanoparticles (AgNPs), and the key role that microorganisms play in performing critical ecosystem functions such as decomposition and nutrient cycling, there is growing concern that AgNP pollution may negatively impact ecosystems. We examined the response of streamwater and sediment microorganisms to commercially available 21 +/- A 17 nm AgNPs, and compared AgNP impacts to those of dissolved-Ag added as AgNO3. We show that in streamwater, AgNPs and AgNO3 decreased respiration in proportion to dissolved-Ag concentrations at the end of the incubation (r(2) = 0.78), while in sediment the only measurable effect of AgNPs was a 14 % decrease in sulfate concentration. This contrasts with the stronger effects of dissolved-Ag additions in both streamwater and sediment. In streamwater, addition of dissolved-Ag at a level equivalent to the lowest AgNP dose led to respiration below detection, a 55 % drop in phosphatase enzyme activity, and a 10-fold increase in phosphate concentration. In sediment, AgNO3 addition at a level equivalent to the highest AgNP addition led to a 34 % decrease in respiration, a 55 % increase in microbial biomass, and a shift in bacterial community composition. The results of this study suggest that, in similar freshwater environments, the short-term biological impacts of AgNPs on microbes are attenuated by the physical and chemical properties of streamwater and sediment.
Published: 2012
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38. Uptake of silver nanoparticles and toxicity to early life stages of Japanese medaka (Oryzias latipes): Effect of coating materials

Author: Ashutosh Chilkoti, Mark R. Wiesner, Appala Raju Badireddy, Stella M. Marinakos, Kevin W.H. Kwok, Jie Liu, Mélanie Auffan, David E. Hinton, Clay M. Nelson, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Department of Civil and Environmental Engineering [Durham] (CEE), Duke University [Durham], Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: Gills, Gill, Biodistribution, Embryo, Nonmammalian, Silver, food.ingredient, Hyperspectral imaging, Health, Toxicology and Mutagenesis, Oryzias, Metal Nanoparticles, 02 engineering and technology, 010501 environmental sciences, Aquatic Science, 01 natural sciences, Citric Acid, Silver nanoparticle, Excipients, Toxicology, Gum Arabic, food, Anti-Infective Agents, medicine, Animals, Tissue Distribution, 0105 earth and related environmental sciences, Nanomaterials, biology, Polyvinylpyrrolidone, Chemistry, Povidone, 021001 nanoscience & nanotechnology, biology.organism_classification, Antimicrobial, Eleutheroembryos, Larva, Toxicity, [SDE]Environmental Sciences, Silver Nitrate, Gum arabic, 0210 nano-technology, Water Pollutants, Chemical, medicine.drug, Nuclear chemistry
Abstract: International audience; Silver nanoparticles (AgNPs) with antimicrobial properties are perhaps the most deployed engineered nanomaterials in consumer products. Almost all AgNPs are coated with organic materials to enhance their dispersion in water. Contributions of coatings to the toxicity of NPs have received little attention. Studies using AgNPs with one of three different coating materials (citrate (Cit), gum arabic (GA), and polyvinylpyrrolidone (PVP)) showed significantly different toxicity. GA AgNP proved to be the most toxic, while PVP and Cit AgNP exhibited similar and lower toxicity. However, all AgNPs were about three to ten times less toxic than AgNO3 when their toxicities were compared on a mass-concentration basis. Evidence for NP-specific toxicity was observed with longer time for initiation of toxicity and increased incidence of resultant spinal flexure of medaka exposed to AgNPs, compared to AgNO3. Hyperspectral imaging of 6 mu m paraffin sections of fish exposed to AgNPs revealed AgNPs and their aggregates in tissues of fish. Gill distribution was ubiquitous, while small amounts were found in other organs, including the liver and brain. AgNPs were observed regularly in the gut lumen, but rarely in mural elements and mesentery. These results suggest that while ingestion was common, gills were the principal sites of AgNP uptake. In conclusion, AgNPs is a source of toxic Ag ions, while itself contribute partially to its toxicity to fish, and which interact with skin surface and were taken up via the gills. (C) 2012 Elsevier B.V. All rights reserved.
Published: 2012
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39. Intestinal toxicity evaluation of TiO2 degraded surface-treated nanoparticles: a combined physico-chemical and toxicogenomics approach in caco-2 cells

Author: Frédéric Bérenguer, Mélanie Auffan, Gérard Steinmetz, Matthieu Fisichella, Jérôme Rose, Odette Prat, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, media_common.quotation_subject, Health, Toxicology and Mutagenesis, Life cycle, lcsh:Industrial hygiene. Industrial welfare, Nanoparticle, Metal Nanoparticles, Nanotechnology, 02 engineering and technology, 010501 environmental sciences, degradation of nanomaterials, Cell morphology, Toxicology, 01 natural sciences, chemistry.chemical_compound, Surface-treated nanoparticles (STNPs), Coated Materials, Biocompatible, lcsh:RA1190-1270, Humans, Internalization, 0105 earth and related environmental sciences, media_common, lcsh:Toxicology. Poisons, chemistry.chemical_classification, Titanium, Reactive oxygen species, Toxicity, Aluminium hydroxide, Research, Nanoparticles (NPs), technology, industry, and agriculture, General Medicine, 021001 nanoscience & nanotechnology, Enterocytes, chemistry, [SDE]Environmental Sciences, Biophysics, Photocatalysis, Titanium dioxide, Environmental Pollutants, Gene expression, 0210 nano-technology, Toxicogenomics, lcsh:HD7260-7780.8
Abstract: Background Titanium dioxide (TiO2) nanoparticles (NPs) are widely used due to their specific properties, like UV filters in sunscreen. In that particular case TiO2 NPs are surface modified to avoid photocatalytic effects. These surface-treated nanoparticles (STNPs) spread in the environment and might release NPs as degradation residues. Indeed, degradation by the environment (exposure to UV, water and air contact …) will occur and could profoundly alter the physicochemical properties of STNPs such as chemistry, size, shape, surface structure and dispersion that are important parameters for toxicity. Although the toxicity of surface unmodified TiO2 NPs has been documented, nothing was done about degraded TiO2 STNPs which are the most likely to be encountered in environment. The superoxide production by aged STNPs suspensions was tested and compared to surface unmodified TiO2 NPs. We investigated the possible toxicity of commercialized STNPs, degraded by environmental conditions, on human intestinal epithelial cells. STNPs sizes and shape were characterized and viability tests were performed on Caco-2 cells exposed to STNPs. The exposed cells were imaged with SEM and STNPs internalization was researched by TEM. Gene expression microarray analyses were performed to look for potential changes in cellular functions. Results The production of reactive oxygen species was detected with surface unmodified TiO2 NPs but not with STNPs or their residues. Through three different toxicity assays, the STNPs tested, which have a strong tendency to aggregate in complex media, showed no toxic effect in Caco-2 cells after exposures to STNPs up to 100 μg/mL over 4 h, 24 h and 72 h. The cell morphology remained intact, attested by SEM, and internalization of STNPs was not seen by TEM. Moreover gene expression analysis using pangenomic oligomicroarrays (4x 44000 genes) did not show any change versus unexposed cells after exposure to 10 μg/ mL, which is much higher than potential environmental concentrations. Conclusions TiO2 STNPs, degraded or not, are not harmful to Caco-2 cells and are unlikely to penetrate the body via oral route. It is likely that the strong persistence of the aluminium hydroxide layer surrounding these nanoparticles protects the cells from a direct contact with the potentially phototoxic TiO2 core.
Published: 2012
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40. Physico-chemical Control over the Single- or Double-Wall Structure of Aluminogermanate Imogolite-like Nanotubes

Author: Mélanie Auffan, Luc Belloni, Perrine Chaurand, Antoine Thill, Béatrice Guiose, Olivier Spalla, Jérôme Rose, Perrine Maillet, Luca Olivi, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA)
Subjects: Models, Molecular, Nanotube, Morphology (linguistics), Double wall, Silicon, Surface Properties, chemistry.chemical_element, Nanotechnology, Germanium, Imogolite, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, Colloid and Surface Chemistry, Particle Size, Nanotubes, Molecular Structure, Chemistry, Physical, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemical engineering, chemistry, Aluminum Silicates, 0210 nano-technology, Chemical control, Aluminum
Abstract: International audience; It is known that silicon can be successfully replaced by germanium atoms in the synthesis of imogolite nanotubes, leading to shorter and larger AlGe nanotubes. Beside the change in morphology, two characteristics of the AlGe nanotube synthesis were recently discovered. AlGe imogolite nanotubes can be synthesized at much higher concentrations than AlSi imogolite. AlGe imogolite exists in the form of both single-walled (SW) and double-walled (DW) nanotubes, whereas DW AlSi imogolites have never been observed. In this article, we give details on the physicochemical control over the SW or DW AlGe imogolite structure. For some conditions, an almost 100% yield of SW or DW nanotubes is demonstrated. We propose a model for the formation of SW or DW AlGe imogolite, which also explains why DW AlSi imogolites or higher wall numbers for AlGe imogolite are not likely to be formed.
Published: 2012
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41. Physicochemical Properties of Nanoparticles in Relation with Toxicity

Author: Patrick M. Winter, Gregory M. Lanza, Samuel A. Wickline, Marc Madou, Chunlei Wang, Parag B. Deotare, Marko Loncar, Yoke Khin Yap, Jérôme Rose, Mélanie Auffan, Olivier Proux, Vincent Niviere, Jean-Yves Bottero, Zhong Lin Wang, Ying Liu, R. G. Polcawich, J. S. Pulskamp, R. M. Proie, Woo-Tae Park, Sergei V. Kalinin, Brian J. Rodriguez, Andrei L. Kholkin, Gang Logan Liu, Jao Lagemaat, Lorenzo Valdevit, John W. Hutchinson, Seajin Oh, Katja Tonisch, Enrica De Rosa, Joseph Fernandez-Moure, Ennio Tasciotti, Denis Gebauer, Brian E. O’Neill, King C. Li, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), International Consortium for the Environmental Implications of Nanotechnology (iCEINT), Aix en Provence, France, Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Brushan Bharat, Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG)
Subjects: Chemical engineering, Chemistry, [SDV.TOX]Life Sciences [q-bio]/Toxicology, Toxicity, Nanoparticle, 02 engineering and technology, 010501 environmental sciences, [SPI.NANO]Engineering Sciences [physics]/Micro and nanotechnologies/Microelectronics, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences
Abstract: International audience
Published: 2012
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42. Mechanism of Silver Nanoparticle Toxicity Is Dependent on Dissolved Silver and Surface Coating in Caenorhabditis elegans

Author: Jie Liu, Heileen Hsu-Kim, Xinyu Yang, Mélanie Auffan, Stella M. Marinakos, Joel N. Meyer, Andreas Gondikas, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: Silver, Surface Properties, Metal Nanoparticles, Nanotechnology, 02 engineering and technology, 010501 environmental sciences, engineering.material, 01 natural sciences, Silver nanoparticle, chemistry.chemical_compound, Coating, Animals, Environmental Chemistry, Chromans, Particle Size, Caenorhabditis elegans, Dissolution, Chelating Agents, 0105 earth and related environmental sciences, Ions, General Chemistry, 021001 nanoscience & nanotechnology, Acetylcysteine, Oxidative Stress, Surface coating, Monomer, chemistry, Ionic strength, Toxicity, [SDE]Environmental Sciences, engineering, Trolox, 0210 nano-technology, Gene Deletion, Nuclear chemistry
Abstract: International audience; The rapidly increasing use of silver nanoparticles (Ag NPs) in consumer products and medical applications has raised ecological and human health concerns. A key question for addressing these concerns is whether Ag NP toxicity is mechanistically unique to nanoparticulate silver, or if it is a result of the release of silver ions. Furthermore, since Ag NPs are produced in a large variety of monomer sizes and coatings, and since their physicochemical behavior depends on the media composition, it is important to understand how these variables modulate toxicity. We found that a lower ionic strength medium resulted in greater toxicity (measured as growth inhibition) of all tested Ag NPs to Caenorhabditis elegans and that both dissolved silver and coating influenced Ag NP toxicity. We found a linear correlation between Ag NP toxicity and dissolved silver, but no correlation between size and toxicity. We used three independent and complementary approaches to investigate the mechanisms of toxicity of differentially coated and sized Ag NPs: pharmacological (rescue with trolox and N-acetylcysteine), genetic (analysis of metal-sensitive and oxidative stress-sensitive mutants), and physicochemical (including analysis of dissolution of Ag NPs). Oxidative dissolution was limited in our experimental conditions (maximally 15% in 24 h) yet was key to the toxicity of most Ag NPs, highlighting a critical role for dissolved silver complexed with thiols in the toxicity of all tested Ag NPs. Some Ag NPs (typically less soluble due to size or coating) also acted via oxidative stress, an effect specific to nanoparticulate silver. However, in no case studied here was the toxicity of a Ag NP greater than would be predicted by complete dissolution of the same mass of silver as silver ions.
Published: 2012
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43. Filter-Feedling Bivalves Store and Biodeposit Colloidally Stable Gold Nanoparticles

Author: Peter J. Vikesland, Irvin R. Schultz, Matthew S. Hull, Jason Jones, Perrine Chaurand, Mélanie Auffan, Jérôme Rose, Jean-Yves Bottero, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: endocrine system, Nanoparticle, Metal Nanoparticles, Nanotechnology, 02 engineering and technology, Gold Colloid, 010501 environmental sciences, complex mixtures, 01 natural sciences, Feces, Environmental Chemistry, Animals, Particle Size, Biotransformation, 0105 earth and related environmental sciences, Chemistry, digestive, oral, and skin physiology, Spectrometry, X-Ray Emission, Serum Albumin, Bovine, General Chemistry, Feeding Behavior, 021001 nanoscience & nanotechnology, Bivalvia, Filter feeding, Colloidal gold, [SDE]Environmental Sciences, Cattle, 0210 nano-technology, Filtration, Environmental Monitoring
Abstract: International audience; Nanoparticles resistant to salt-induced aggregation are continually being developed for biomedical and industrial applications. Because of their colloidal stability these functionalized nanoparticles are anticipated to be persistent aquatic contaminants. Here, we show that Corbicula fluminea, a globally distributed clam that is a known sentinel of aquatic ecosystem contamination, can uptake and biodeposit bovine serum albumin (BSA) stabilized gold nanoparticles. Nanopartide clearance rates from suspension were dictated by diameter and concentration, with the largest particles cleared most quickly on a mass basis. Particle capture facilitates size-selective `biopurification' of particle suspensions with nanoscale resolution. Nanoparticles were retained either within the clam digestive tract or excreted in feces. Our results suggest that biotransformation and biodeposition will play a significant role in the fate and transport of persistent nanoparticles in aquatic systems.
Published: 2011
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44. TiO2-based nanoparticles released in water from commercialized sunscreens in a life-cycle perspective: Structures and quantities

Author: Daniel Borschneck, Hélène Miche, Jérôme Labille, Mélanie Auffan, Céline Botta, Jean-Yves Bottero, Martiane Cabié, Jérôme Rose, Armand Masion, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Spectropôle - Aix Marseille Université (AMU SPEC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), and Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA)
Subjects: Sunscreens, Aging, Health, Toxicology and Mutagenesis, Salt (chemistry), Nanoparticle, Fraction (chemistry), Nanotechnology, 02 engineering and technology, 010501 environmental sciences, Toxicology, 01 natural sciences, chemistry.chemical_compound, Water pollution, 0105 earth and related environmental sciences, chemistry.chemical_classification, Nanocomposite, Chemistry, General Medicine, 021001 nanoscience & nanotechnology, Nanomaterial, Pollution, Chemical engineering, 13. Climate action, Titanium dioxide, [SDE]Environmental Sciences, Seawater, 0210 nano-technology, Dispersion (chemistry)
Abstract: International audience; This work investigates the physical-chemical evolution during artificial aging in water of four commercialized sunscreens containing TiO2-based nanocomposites. Sunscreens were analyzed in terms of mineralogy and TiO2 concentration. The residues formed after aging were characterized in size, shape, chemistry and surface properties. The results showed that a significant fraction of nano-TiO2 residues was released from all sunscreens, despite their heterogeneous behaviors. A stable dispersion of submicronic aggregates of nanoparticles was generated, representing up to 38 w/w% of the amount of sunscreen, and containing up to 30% of the total nano-TiO2 initially present in the creams. The stability of the dispersion was tested as a function of salt concentration, revealing that in seawater conditions, a major part of these nano-TiO2 residues will aggregate and sediment. These results were put in perspective with consumption and life cycle of sunscreens to estimate the amount of nano-TiO2 potentially released into AQUATIC environment. (C) 2011 Elsevier Ltd. All rights reserved.
Published: 2011
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45. More than the Ions: The Effects of Silver Nanoparticles on Lolium multiflorum

Author: Mark R. Wiesner, Jie Liu, Mélanie Auffan, Benjamin Espinasse, Liyan Yin, Yingwen Cheng, Benjamin P. Colman, Jérôme Rose, Emily S. Bernhardt, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Silver, Metal Nanoparticles, 02 engineering and technology, 010501 environmental sciences, Root hair, 01 natural sciences, Plant Roots, Silver nanoparticle, chemistry.chemical_compound, Botany, medicine, Lolium, Environmental Chemistry, Soil Pollutants, Cell damage, 0105 earth and related environmental sciences, biology, Dose-Response Relationship, Drug, food and beverages, General Chemistry, Lolium multiflorum, 021001 nanoscience & nanotechnology, medicine.disease, biology.organism_classification, chemistry, Seedling, Shoot, Toxicity, [SDE]Environmental Sciences, Biophysics, Growth inhibition, 0210 nano-technology, Plant Shoots
Abstract: International audience; Silver nanoparticles (AgNPs) are increasingly used as antimicrobial additives in consumer products and may have adverse impacts on organisms when they inadvertently enter ecosystems. This study investigated the uptake and toxicity of AgNPs to the common grass, Lolium multiflorum. We found that root and shoot Ag content increased with increasing AgNP exposures. AgNPs inhibited seedling growth. While exposed to 40 mg L(-1) GA-coated AgNPs, seedlings failed to develop root hairs, had highly vacuolated and collapsed cortical cells and broken epidermis and rootcap. In contrast, seedlings exposed to identical concentrations of AgNO(3) or supernatants of ultracentrifuged AgNP solutions showed no such abnormalities. AgNP toxicity was influenced by total NP surface area with smaller AgNPs (6 nm) more strongly affecting growth than did similar concentrations of larger (25 nm) NPs for a given mass. Cysteine (which binds Ag(+)) mitigated the effects of AgNO(3) but did not reduce the toxicity of AgNP treatments. X-ray spectro-microscopy documented silver speciation within exposed roots and suggested that silver is oxidized within plant tissues. Collectively, this study suggests that growth inhibition and cell damage can be directly attributed either to the nanoparticles themselves or to the ability of AgNPs to deliver dissolved Ag to critical biotic receptors.
Published: 2011
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46. Manufactured metal and metal-oxide nanoparticles: Properties and perturbing mechanisms of their biological activity in ecosystems

Author: Jean-Yves Bottero, Jérôme Labille, Jérôme Rose, Mélanie Auffan, Catherine Mouneyrac, Antoine Thill, Corinne Chanéac, Céline Botta, Armand Masion, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Nanoparticle, Nanotechnology, Oxydo-reduction, 02 engineering and technology, Metal oxide nanoparticles, 010501 environmental sciences, 01 natural sciences, Ecosystems, Metal, Physical chemical, Surface properties, Ecosystem, 0105 earth and related environmental sciences, Global and Planetary Change, Exotoxicity, Chemistry, Biological activity, Oxides, 021001 nanoscience & nanotechnology, Chemical engineering, 13. Climate action, Metals, visual_art, [SDE]Environmental Sciences, visual_art.visual_art_medium, General Earth and Planetary Sciences, Nanoparticles, Manufactured nanoparticles, 0210 nano-technology, Dispersion (chemistry)
Abstract: International audience; The inorganic manufactured nanoparticles as TiO(2), Ag degrees, the iron oxides and CeO(2) are more and more present in various manufactured products and in the aqueous media (TiO(2)). Their dispersion in the ecosystems during their life cycle will be associated with interactions with biota (plants, bacteria, fishes). The present work shows strong relations between particular physical chemical properties of very small nanoparticles (size < 30 nm) and biological activity perturbations. It is shown that Ag degrees and CeO(2) act at very low concentrations. TiO(2) act via the ROS production due to their photo-reactivity. (C) 2011 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Published: 2011
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47. Reactivity at (nano)particle-water interfaces, redox processes, and arsenic transport in the environment

Author: Yuheng Wang, Laurent Charlet, Jérôme Rose, Guillaume Morin, Mélanie Auffan, Alejandro Fernandez-Martinez, André Burnol, Géochimie, Institut des Sciences de la Terre (ISTerre), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-PRES Université de Grenoble-Institut de recherche pour le développement [IRD] : UR219-Institut national des sciences de l'Univers (INSU - CNRS)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Université Joseph Fourier - Grenoble 1 (UJF)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-PRES Université de Grenoble-Institut de recherche pour le développement [IRD] : UR219-Institut national des sciences de l'Univers (INSU - CNRS)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Université Joseph Fourier - Grenoble 1 (UJF), Institut de minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-PRES Université de Grenoble-Institut de recherche pour le développement [IRD] : UR219-Institut national des sciences de l'Univers (INSU - CNRS)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Université Joseph Fourier - Grenoble 1 (UJF), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Partial financial support by IUF, ANDRA, AQUATRAIN and CALIBRE EU networks and by EC2CO CNRS/INSU program + by EC2CO-CYTRIX CNRS/INSU program, by ACI/FNS grant #3033, and by SESAME IdF grant #1775 + NSF grant CHE-0431425 (Stanford Molecular Environmental Science Institute)., Centre National de la Recherche Scientifique (CNRS)-PRES Université de Grenoble-Université Joseph Fourier - Grenoble 1 (UJF)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-PRES Université de Grenoble-Université Joseph Fourier - Grenoble 1 (UJF)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Centre National de la Recherche Scientifique (CNRS)-PRES Université de Grenoble-Université Joseph Fourier - Grenoble 1 (UJF)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry]), Université Joseph Fourier - Grenoble 1 (UJF)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-PRES Université de Grenoble-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-PRES Université de Grenoble-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris Diderot - Paris 7 (UPD7)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), and Université Joseph Fourier - Grenoble 1 (UJF)-Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-PRES Université de Grenoble-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)
Subjects: Bioavailability, Coprecipitation, Speciation, [SDE.MCG]Environmental Sciences/Global Changes, chemistry.chemical_element, Mineralogy, 010501 environmental sciences, Molecular dynamics, 010502 geochemistry & geophysics, 01 natural sciences, Redox, Arsenic, Molecular mechanism, chemistry.chemical_compound, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, Water treatment, [SDU.ENVI]Sciences of the Universe [physics]/Continental interfaces, environment, 0105 earth and related environmental sciences, Experimental artifacts, Global and Planetary Change, Sorption, Sulfur, 6. Clean water, Aquifers, chemistry, 13. Climate action, Environmental chemistry, Soil water, General Earth and Planetary Sciences, Carbonate, Adsorption, XAFS spectroscopy, [SDU.STU.MI]Sciences of the Universe [physics]/Earth Sciences/Mineralogy
Abstract: International audience; Massive deleterious impacts to human health are resulting from the use of arsenic-bearing groundwaters in South-East Asia deltas and elsewhere in the world for drinking, cooking and/or irrigation. In Bangladesh alone, a fifth of all deaths are linked to arsenicosis. In the natural and engineered subsurface environment, the fate of arsenic is, to a large extent, controlled by redox potential, pH, as well as total iron, sulfur and carbonate content, via sorption and coprecipitation on a variety of natural and engineered (nano)particles. In the present article, we address: (1) new insights in the sorption mechanisms of As on Fe(II) and Fe(III) nanophases recognized to play an important role in the microbial cycling of As and Fe; (2) artifacts often encountered in field and laboratory studies of As speciation due to the extreme redox sensitivity of the Fe-As-O-H phases; and (3) as a conclusion, the implications for water treatment. Indeed the specific reactivity of nanoparticles accounts not only for the As bioavailability within soils and aquifers, but also opens new avenues in water treatment.
Published: 2011
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48. Aging of TiO2 nanocomposites used in sunscreen. Dispersion and fate of the degradation products in aqueous environment

Author: Daniel Borschneck, Jinghuan Feng, Jean-Yves Bottero, Mélanie Auffan, Jérôme Labille, Magali Sammut, Jérôme Rose, Martiane Cabié, Céline Botta, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Spectropôle - Aix Marseille Université (AMU SPEC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Flocculation, Light, Health, Toxicology and Mutagenesis, Inorganic chemistry, 0211 other engineering and technologies, Aluminum Hydroxide, Electrophoretic Mobility Shift Assay, 02 engineering and technology, 010501 environmental sciences, Toxicology, 01 natural sciences, Nanocomposites, chemistry.chemical_compound, Colloid, Water Pollutants, Surface charge, Dimethylpolysiloxanes, [SDU.ENVI]Sciences of the Universe [physics]/Continental interfaces, environment, Dissolution, 0105 earth and related environmental sciences, Titanium, 021110 strategic, defence & security studies, Aqueous solution, Nanocomposite, Lasers, General Medicine, Pollution, [SDE.ES]Environmental Sciences/Environmental and Society, chemistry, Chemical engineering, 13. Climate action, Titanium dioxide, Dispersion stability, Sunscreening Agents, Water Pollutants, Chemical
Abstract: International audience; Aging in water of a TiO2-based nanocomposite used in sunscreen cosmetics has been studied as a function of light and time. It consisted initially in a TiO2 core, coated with Al(OH)(3) and polydimethylsiloxane (PDMS) layers. Size measurement, coating alteration, and surface charge were followed by laser diffraction, TEM/EDS, ICP-AES and electrophoretic mobility measurement. The nanocomposite rapidly underwent progressive dispersion in the aqueous phase, enabled by the dissolution of the PDMS layer. A stable suspension of colloidal byproducts from 50 to 700 nm in size was formed. Their positively charged Al(OH)(3) surface was evidenced with an isoelectric point around 7-8, controlling the dispersion stability. The critical coagulation concentrations measured with NaCl and CaCl2 was 2 x 10(-2) and 8 x 10(-3) M respectively. The presence of natural organic matter affected the colloidal stability according to the NOM/byproduct ratio. A 2 wt% ratio favored bridging flocculation, whereas a 20 wt% ratio induced sterical stabilization. (C) 2010 Elsevier Ltd. All rights reserved.
Published: 2010
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49. Intracellular uptake and associated toxicity of silver nanoparticles in Caenorhabditis elegans

Author: Elena A. Turner, Mark R. Wiesner, Stella M. Marinakos, Joel N. Meyer, Ashutosh Chilkoti, Appala Raju Badireddy, Christopher A. Lord, Mélanie Auffan, Xinyu Yang, Department of Civil and Environmental Engineering [Durham] (CEE), Duke University [Durham], Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA)
Subjects: Silver, Bioavailability, Health, Toxicology and Mutagenesis, Metal Nanoparticles, 02 engineering and technology, 010501 environmental sciences, Aquatic Science, medicine.disease_cause, 01 natural sciences, Silver nanoparticle, Toxicology, chemistry.chemical_compound, Aggregation, Anti-Infective Agents, medicine, Metallothionein, Animals, Caenorhabditis elegans, 0105 earth and related environmental sciences, biology, Povidone, 021001 nanoscience & nanotechnology, biology.organism_classification, Knockouts, chemistry, 13. Climate action, Oxidative stress, Toxicity, Environmental toxicology, [SDE]Environmental Sciences, Biophysics, Potassium, Environmental Pollutants, Growth inhibition, Silver nanoparticles, 0210 nano-technology, Intracellular
Abstract: International audience; Silver nanoparticles (AgNPs) are frequently used as antimicrobials. While the mechanism(s) by which AgNPs are toxic are unclear, their increasing use raises the concern that release into the environment could lead to environmental toxicity. We characterized the physicochemical behavior, uptake, toxicity (growth inhibition), and mechanism of toxicity of three AgNPs with different sizes and polyvinylpyrrolidone (PVP) or citrate coatings to the nematode Caenorhabditis elegans. We used wild-type (N2) C. elegans and strains expected to be sensitive to oxidative stress (nth-1, sod-2 and mev-1), genotoxins (xpa-1 and nth-1), and metals (mtl-2). Using traditional and novel analytical methods, we observed significant aggregation and extra-organismal dissolution of silver, organismal uptake and, in one case, transgenerational transfer of AgNPs. We also observed growth inhibition by all tested AgNPs at concentrations in the low mg/L levels. A metallothionein-deficient (mtl-2) strain was the only mutant tested that exhibited consistently greater AgNP sensitivity than wild-type. Although all tested AgNPs were internalized (passed cell membranes) in C. elegans, at least part of the toxicity observed was mediated by ionic silver. Finally, we describe a modified growth assay that permits differentiation between direct growth-inhibitory effects and indirect inhibition mediated by toxicity to the food source. (C) 2010 Elsevier B.V. All rights reserved.
Published: 2010
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50. Structural Degradation at the Surface of a TiO2-Based Nanomaterial Used in Cosmetics

Author: Jean-Yves Bottero, Jérôme Labille, Fabio Ziarelli, Céline Botta, Jérôme Rose, Mélanie Auffan, Maxime Pedeutour, Armand Masion, Daniel Borschneck, Perrine Chaurand, Corinne Chanéac, Centre européen de recherche et d'enseignement des géosciences de l'environnement (CEREGE), Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Collège de France (CdF)-Institut national des sciences de l'Univers (INSU - CNRS)-Aix Marseille Université (AMU)-Institut National de la Recherche Agronomique (INRA), Spectropôle - Aix Marseille Université (AMU SPEC), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie de la Matière Condensée de Paris (site Paris VI) (LCMCP (site Paris VI)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut national des sciences de l'Univers (INSU - CNRS)-Collège de France (CdF (institution))-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Silicon, Magnetic Resonance Spectroscopy, Nanostructure, Light, Surface Properties, Nanoparticle, chemistry.chemical_element, Aluminum Hydroxide, Cosmetics, 02 engineering and technology, 010501 environmental sciences, 01 natural sciences, Nanomaterials, chemistry.chemical_compound, Suspensions, Superoxides, Spectroscopy, Fourier Transform Infrared, Environmental Chemistry, Organic chemistry, Dimethylpolysiloxanes, 0105 earth and related environmental sciences, Titanium, Polydimethylsiloxane, Chemistry, Water, General Chemistry, Hydrogen-Ion Concentration, 021001 nanoscience & nanotechnology, Nanostructures, Titanium oxide, Chemical engineering, Ionic strength, [SDE]Environmental Sciences, 0210 nano-technology, Layer (electronics)
Abstract: International audience; A number of commercialized nanomaterials incorporate TiO2 nanoparticles. Studying their structural stability in media mimicking the environment or the conditions of use is crucial in understanding their potential eco-toxicological effects. We focused here on a hydrophobic TiO2 nanoparticle-based formulation used in cosmetics: T-Lite SF. It is composed of a TiO2 core, coated with two successive protective layers of Al(OH)(3), and polydimethylsiloxane. Soon after contact with water (pH = 5, low ionic strength), the T-Lite SF becomes hydrophilic and form aggregates. During this aging, 90%wt of the total Si of the organic layer is desorbed, and the PDMS remaining at the surface is oxidized. The Al(OH)(3) layer is also affected but remains sorbed at the surface. This remaining Al-based layer still protects from the production of superoxide ions from the photoactive/phototoxic TiO2 core in our experimental conditions.
Published: 2010
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