Transformation and Mobility of Al Nanomaterials in the Environment

MARIE SKLODOWSKA-CURIE ACTIONS

Co-funding of regional, national and international programmes (COFUND)

DOC2AMU PROJECT 2017 CALL FOR APPLICATIONS

TRANSFORMATION AND MOBILITY OF AL NANOMATERIALS IN THE ENVIRONMENT

1. DESCRIPTION OF THE PHD THESIS PROJECT

(Up to 4 pages)

1.1 OBJECTIVES OF THE PROJECT BASED ON THE CURRENT STATE OF THE ART

Engineered aluminum nanoparticles have become a part of our everyday life. Aluminum (Al) oxides and (oxy)hydroxides are used in a wide range of industrial applications (pharmaceuticals, cosmetics, food, water treatment…) either in the form of the particle core or in the form of coating of other nano-sized objects. While a rapid library search reveals that synthesis and reactivity of nano-sized Al species are popular research fields, their environmental fate and/or potentially adverse effects have received only marginal attention. Just like any other chemical, the environmental reactivity, mobility and toxicity of nano-sized Al phases are controlled by their speciation, and especially their surface chemistry. Al is a known toxicant for over a century, but its toxicity is usually attributed to soluble species, and in particular the Al3+ monomer. In the early 1990s, it was demonstrated that a ca. 2 nm Al nanoparticle (i.e. aka Al13) exhibits toxic effects 60 times more severe than Al3+.1 In more recent years, it has been reported than Al oxides and (oxy)hydroxides, which are usually considered as non toxic, have detrimental effects when their size falls within the nano range.2

In a time where regulators must address concerns against nano-enabled products in general, it is important to provide a sound knowledge basis to be used by mechanism-driven predictive tools. In this vast endeavor, the present project aims at determining the mechanisms controlling the fate of Al based nanomaterials after their intended use. In this end-of-life stage, the aim is to characterize the fate of selected Al nano-phases in a wastewater treatment plant (WWTP) and the downstream natural environment. This project has been selected in the 2016 DOC2AMU call, but the chosen candidate did not respond to the invitation for the interview.

1.2 METHODOLOGY

To reach this goal, it is necessary to monitor the speciation of these Al compounds but also their spatial distribution, including in the food chain (algae, unicellular and higher organisms). Given the affinity between Al and organics, which are ubiquitous, the analytical tools used in this project need to be able to determine the Al and C speciation with the least amount of sample preparation. Nuclear magnetic resonance (NMR) is an element specific probe that is extremely valuable to provide a detailed speciation for both Al and C, and is perfectly suited to analyze nanoparticles and their coatings. In the present case, however, several challenges need to be met, mainly because it is conceptually necessary to monitor the Al nanophase in realistic environments. Besides standardized physical and chemical aging tests, the bio-physical-chemical alteration will be addressed using bio- reactors to simulate a WWTP situation, and mesocosm testing to simulate environmental aging, both of which are available. The analytical challenges are just as demanding owing to low concentration issues (which result in low sensitivity). In fact, while the "chemical resolution" of NMR is unparalleled, especially for low Z elements, its application to the speciation of environmentally relevant systems typically suffers from its inherent lack of sensitivity. This limitation is being lifted by recent advances in the so-called dynamic nuclear polarization (DNP) technique, which enhances nuclear magnetization through the microwave-driven transfer of electron spin polarization to nuclei via exogenous paramagnetic centers. DNP is currently revolutionizing NMR by providing huge sensitivity enhancements (up to 100-fold), hereby reducing the duration of NMR experiments from several years down to a few hours. As such, DNP NMR has become particularly efficient for unraveling the structure of surface species and core-shell particles.3 In addition, characterizing the fate and mobility of Al-nanomaterials also requires mapping their distribution within the different compartments of the system, including living organisms. While 3D X-ray imaging has the necessary spatial resolution, this absorption technique cannot unequivocally identify the underlying element. In this context, magnetic resonance imaging (MRI) could prove highly complementary because it is an element specific technique (i.e. 27Al imaging) with a resolution in the µm3 range that makes it ideal for investigating the aggregation state of Al nanomaterials. Therefore, an important outcome of the project will be the development DNP NMR and MRI methodologies to study the speciation and mapping of Al-nanomaterials in an environmentally significant context. 1. Shann J.R. and Bertsch P.M. (1993): Differential cultivar response to polynuclear hydroxo-aluminum complexes Soil Sci. Soc. Amer. J.: 57(1); 116-120 2. Park E.J., Lee G.H., Yoon C., Jeong U., Kim Y., Cho M.H. and Kim D.W. (2016): Biodistribution and toxicity of spherical aluminum oxide nanoparticles J. Appl. Toxicol.: 36(3); 424-433 3. Rossini, A. J.; Zagdoun, A.; Lelli, M.; Lesage, A.; Copéret, C.; Emsley, L., Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy. Acc. Chem. Res. 2013, 46, 1942-1951.

1.3 WORK PLAN

The work to be accomplished within this project consist of two main phases: application of the DNP NMR and MRI to model system to determine detection limits, examine specific spectral features and develop adequate data acquisition sequences. The materials will be commercial aluminum nanophases used in industry (nanoboehmite, nanobayerite, PCBA…) included in simple abiotic (e.g. sand, polysaccharide gels) and biotic matrices (e.g.model organisms such E. Coli, P. Brassicacaerum, Aribidopsis roots). The PhD candidate will also use this phase to familiarize himself/herself with the DNP and MRI techniques that are usually not part of a typical university curriculum.

The second phase will examine the aging of actual products during and after the use phase of these products and the furhter development of Al DNP NMR and MRI to take into account the specificity of natural samples. At this point, the nano-enabled materials will be chosen among off-the-shelf cosmetics and water treament coagulation agents. This phase is subdivided into two parts: abiotic and biotic monitoring of the aging and (bio)distribution of the Al nanophases. Abiotic aging includes abrasion and weathering of the products using standardized protocols when avaible; bio-physico- chemical aging includes bio-reactor and mesocosm testing to simulate environmental aging. All these tests are long term experimentation (as an example, to complete a mesocosm testing with its data treament a minimum of 4 months is necessary) and consequently will represent the majority of the time.

Month 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36

Bibliography

Training DNP and MRI

Test on model systems

Actual products abiotic test

Actual products biotic test

Writing thesis manuscript

1.4 SUPERVISORS AND RESEARCH GROUPS DESCRIPTION

Main supervisor for this PhD project is Armand MASION (CNRS research director) from the InterFast (Interfaces and Transfer) research group at the CEREGE (UM 34 AMU/CNRS/IRD/Collège de France). The group has ca. 10 permanent staff involved in research regarding the environmental impacts of nanotechnolgies. Intrumentation to determined particle size, charge, and chemistry is available on-

site, as well as as 2D XRF and micro- and nano- Xray tomography equipment and a complete mesocosm facility. Additionally the group has access to synchrotron based tools (EXAFS, XANES, SAXS) and bio-reactors.

Co-supervisor is Stéphane VIEL (AMU Professor, Junior Member of the Institut Universitaire de France). He leads the NMR group of the Institut de Chimie Radicalaire (UMR 7273 AMU/CNRS, Director: Dr. Didier GIGMES) within the SACS research team managed by Pr. Laurence CHARLES. The NMR group is composed of 4 permanent staff members and develops research activities at the interface of analytical chemistry and molecular spectroscopy. In particular, this group develops and applies novel nuclear magnetic resonance (NMR) methodologies, both in the liquid and in the solid state, to investigate the structure and dynamics of complex molecules and materials. The group has access to a full range of on-site NMR spectrometers, from 400 to 600 MHz (1H nuclear Larmor frequency), and benefits from a privileged access to state-of-the-art dynamic nuclear polarisation (DNP) solid-state NMR instrumentation via the Bruker Biospin R&D centre located in Wissemborug (France).

Use of the on-site instrumentation and lab supplies are funded by other current research proposals Additional funding is applied for at the Amidex foundation and at the Labex Serenade.

2. 3I DIMENSIONS AND OTHER ASPECTS OF THE PROJECT

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2.1 INTERDISCIPLINARY DIMENSION

The supervisors of this PhD project have strong backgrounds in environmental and chemical science, respectively. This interdisciplinary aspect is important because accurate determination of the speciation and environmental fate (including toxic effects) of Al nanomaterials heavily relies on state- of-the-art spectroscopic and imaging tools, which puts this project at the interface between environmental science, physical chemistry, and biology. The history of successful collaboration of the two research teams is based on their complementary expertise and has resulted in 9 joint publications, 7 of which regarding the fate of nanomaterials (red numbers in the appendix). The team at the CEREGE will lead the experimentation regarding the transformation of the Al nanomaterials throughout the life cycle. The team at the ICR will lead all NMR developments and experiments.

2.2 INTERSECTORAL DIMENSION: The Pôle Eau, i.e. the Water Competitiveness Cluster, is the intersectorial partner for this PhD project. It consists of water treatment specialists from the academic and industrial sectors. Waste water treatment plants are a sink for many Al nanomaterials (costemics, pharmaceuticals). Additionally this industry still uses Al nanophases in drinking water processes. The expertise and guidance of these professionals wil be invaluable for design meaning bio-reactor experiments. Pr Nicolas Roche is a member of the Pôle Eau and has accepted to become a member of the PhD advisory committee. A secondary intersectorial partner is Bruker. As previously mentioned, the PhD work will rely on advanced DNP NMR and MRI experiments. This will require the candidate to interact with Bruker BioSpin (one of the main industrial manufacturers of NMR and micro-MRI instrumentation in the world) in order to adapt existing DNP NMR and MRI technologies to the specific needs of nanomaterial speciation and imaging, through training internships at their R&D facilities (located in France, Germany, and Switzerland).

(Does the project answer one of the SRI-S3 objectives?)

2.2 INTERNATIONAL DIMENSION:

The PhD candidate will study the transformation and mobility of Al nanomaterials in the environment. The project will be conducted within the framework of the Labex SERENADE (15 partners including 2 industrial partners) and will benefit from its international ties, and especially the CEINT network (USA), for very large scale mesocosm testing.

3. RECENT PUBLICATIONS

Main supervisor's team selected publications (past 5 years) • Barton, L.E., Auffan, M., Durenkamp, M., McGrath, S., Bottero, J-Y., Wiesner, M-R., 2015. Monte Carlo simulations of the transformation and removal of Ag, TiO2, and ZnO nanoparticles in wastewater treatment and land application of biosolids, Science of the Total Environment, 511, 535-543, • Barton, L.E., Barton, L.E., Auffan, Olivi, L., Bottero, J-Y., Wiesner, M-R., 2015. Heteoaggregation, transformation and fate of CeO2 nanoparticles in wastewater treatment. Environmental Pollution, 203, 122-129, • Bossa, N., Chaurand, P., Vicente, J., Borschneck, D., Levard, C., Aguerre-Chariol, O., Rose, J., 2015. Micro and nano X-ray computed-tomography : a step forward in the characterization of the pore network of a leached cement paste, Cement and Concrete Research, 67, 138-147, • Tella, M., Auffan M., Brousset L., Morel, E., Proux, O., Chanéac, C., Angeletti, B., Pailles C., Artells, E., Santaella C., Rose J., Thiery A., Bottero J-Y., 2015. Chronic dosing of a simulated pond ecosystem in indoor aquatic mesocosms : fate and transport of CeO2 nanoparticles. Environmental Science Nano, http://dx.doi.org/10.1039/c5en00092k • Barton, L. E., Therezien, M., Auffan, M., Bottero, J.-Y., Wiesner, M. R., 2014. Theory and Methodology for Determining Nanoparticle Affinity for Heteroaggregation in Environmental Matrices Using Batch Measurements. Environmental Engineering Science, 31, 421–427, • Tella, M., Auffan M., Brousset L., Issartel J., Kieffer I., Pailles C., Morel E., Santaella C., Angeletti B., Artells E., Rose J., Thiery A., Bottero J-Y., 2014. Transfer, Transformation, and Impacts of Ceria Nanomaterials in 2 Aquatic Mesocosms Simulating a Pond Ecosystem. Environmental Science and Technology, 48, 9004-9013, • Artells, E., Issartel, J., Auffan, M., Borschneck, D., Thill, D., Tella, M., Brousset, L., Rose, J., Bottero, J- Y., Thiéry, A., 2013. Exposure to cerium dioxide nanoparticles differently affect swimming performance and survival in two daphnid species, PlosOne 8(8) : e71260,

Co-supervisor's team selected publications (past 5 years) • Mollica, G.; Dekhil, M.; Ziarelli, F.; Thureau, P.; Viel, S., Quantitative structural constraints for organic powders at natural abundance using dynamic nuclear polarization solid-state NMR spectroscopy. Angew. Chem. Int. Ed. 2015, 54, 6028-6031 • Ziarelli, F.; Casciola, M.; Pica, M.; Donnadio, A.; Aussenac, F.; Sauvee, C.; Capitani, D.; Viel, S., Dynamic nuclear polarisation NMR of nanosized zirconium phosphate polymer fillers. Chem. Commun. 2014, 50 (70), 10137-10139 • Thureau, P.; Mollica, G.; Ziarelli, F.; Viel, S., Solid-State 1H NMR Studies of Homonuclear Dipolar Couplings. In Annu. Rep. NMR Spectrosc., Graham, A. W., Ed. Academic Press: 2014; Vol. 82, pp 217- 249 • Le, D.; Casano, G.; Phan, T. N. T.; Ziarelli, F.; Ouari, O.; Aussenac, F.; Thureau, P.; Mollica, G.; Gigmes, D.; Tordo, P.; Viel, S., Optimizing sample preparation methods for dynamic nuclear polarization solid-state NMR of synthetic polymers. Macromolecules 2014, 47, 3909-3916

• Ouari, O.; Phan, T.; Ziarelli, F.; Casano, G.; Aussenac, F.; Thureau, P.; Gigmes, D.; Tordo, P.; Viel, S., Improved Structural Elucidation of Synthetic Polymers by Dynamic Nuclear Polarization Solid-State NMR Spectroscopy. ACS Macro Lett. 2013, 2 (8), 715-719 • Mollica, G.; Madhu, P. K.; Ziarelli, F.; Thevand, A.; Thureau, P.; Viel, S., Towards measurement of homonuclear dipolar couplings in H-1 solid-state NMR: recoupling with a rotor-synchronized decoupling scheme. Phys. Chem. Chem. Phys. 2012, 14 (13), 4359-4364 • Thureau, P.; Ziarelli, F.; Thevand, A.; Martin, R. W.; Farmer, P. J.; Viel, S.; Mollica, G., Probing the Motional Behavior of Eumelanin and Pheomelanin with Solid-State NMR Spectroscopy: New Insights into the Pigment Properties. Chemistry-a European Journal 2012, 18 (34), 10689-10700) •

4. EXPECTED PROFILE OF THE CANDIDATE

The candidate should have a strong background in physical-chemistry and chemistry and a working knowledge in environmental science and/or geosciences. Experience in NMR spectroscopy is strongly desired. He/she needs to have excellent English communication skills (oral and written) and the ability to work as an active member of in a multi-site, multi-disciplinary team. Basic knowledge in the French language is not required but would be appreciated.

5. SUPERVISORS’ PROFILES

MAIN SUPERVISOR Dr. Armand MASION (CNRS Research Director) • PhD 1993, ENSG-INPL (Nancy, France); HDR 1999 U. Paul Cezanne (Marseille, France); • 82 Publications, 15 book chapters, 1 patent, 62 invited conferences, >250 talks, H index 29 • Coordination of 4 international and 10 national research programs (+active participation in >50 programs) • Supervision activity summary Post doc: 4 PhD: 16 (4 as major advisor, 5 as co-major advisor, 8 associate advisor) Graduate Students: ca. 30 International degrees: 4 • Details of Doctoral Supervision (as director and co-director only). The exhaustive list of co- authored publications is reported in the appendix. - Astride Vilgé-Ritter. Doctorat Université d'Aix-Marseille III, 1994-1997. "Etude des mécanismes d'élimination de la matière organique des eaux de surface par coagulation-floculation à l'aide de sels d'aluminium ou de fer." Currently: R&D specialist TERRIS Corp., France - Emmanuel Doelsch. Doctorat Université d'Aix-Marseille III, 1997-2000. "Compléxation, nucléation et mécanismes de croissance des associations Fe(II)-Si et Fe(III)-Si." Currently: Research Director CIRAD, France - Mohamed Ennahali. Doctorat Université d'Aix-Marseille III, 2004-2007. "Stabilisation des nanoparticules dans les suspensions liquides de polissage mécano-chimique" Currently : Program Manager SOLVAY Corp. Belgium. - Clément Levard. Doctorat Université d'Aix-Marseille III, 2005-2008. "Nanoparticules naturelles : imogolites et allophanes. Structure, mécanismes de croissance et capacité de rétention des éléments traces métalliques" Currently: Research Scientist CNRS, France - Laetitia ElBeze. Doctorat Université d'Aix-Marseille III, 2005-2008. "Identification de traceurs permettant d’étudier les problèmes d’homogénéité entre bitume vieilli et bitume neuf d’apport" Currently: Administrator, Ministère de l'Enviornnement, France - Marwen Rabhi. Doctorat Université d'Aix-Marseille III, 2005-2008. "Caractérisation et Contrôle Optique In Situ des Slurries. Suspensions Colloïdales de nanoparticules" Currently: Reseach Scientist IRSN, FRance

- Fabrice Cuoq. Thèse de Doctorat Aix-Marseille Université, 2009-2012 "Mise au point de nouveau matériaux réactifs pour le traitement des eaux par coagulation-floculation" Currently: R&D specialist SABIC Corp., Netherlands - Naresh Kumar. Doctorat Aix-Marseille Université, 2010-2013. "Nano to granular sized zero valent iron for groundwater remediation: Physico-chemical and biological mechanisms". Currently: Post-Doc Stanford Univ. Stanford, USA - Astrid Avellan. Doctorat Aix-Marseille Université 2012-2015"Les imogolites comme modèle d’étude de l’écotoxicité des nanoparticules" Currently: Post-Doc Carnegie Mellon Univ, Pittsburgh, USA.

CO-SUPERVISOR

Prof. Stéphane VIEL (Aix-Marseille University Professor)

Short description: After a B. S. from Juniata College (PA, USA) in 1998, Prof. Stéphane VIEL (40 years old) graduated from an engineering school (HEI, Lille) and obtained a M.S. from the University of Lille in 1999. He then performed his National Service as a Cooperation Scientist at the Centro Nazionale delle Ricerche in Rome (Italy). In 2004, he obtained a PhD in collaboration between University of Molise (Italy) and Paul Cézanne University (France). He became assistant professor at Aix-Marseille University in 2006 and got his Research Habilitation in 2009. Since 2012, he is head of the NMR group of the ICR. In 2013, he was invited for 3 months by La Sapienza University in Rome, and he obtained a full-time CNRS delegation (renewed in 2014). He was promoted Full Professor in 2014. He is the recipient of several awards including the Young Researcher Award (City of Marseille) in 2008, the 4- year Scientific Excellence Award (PES) in 2009 and 2013, the A*MIDEX ‘Rising Star’ award in 2013, and he was recently nominated Junior member of the Institut Universitaire de France (2015-20). At the interface between analytical chemistry and molecular spectroscopy, his research activities aim at designing and applying novel NMR methodologies to study the structure and dynamics of organic molecules and materials, both in the liquid and in the solid state (including with the use of dynamic nuclear polarization). This has led to 76 publications (h = 21) in peer-reviewed journals (mean impact factor > 4.5) and 25 invited lectures (RESEARCHERID: F-7030-2014). Since 2012, he is in charge of the NMR research group (4 staff members, 1 PhD student) of the Institut de Chimie Radicalaire.

Supervision activity summary : Post doc: 2 PhD: 6 (4 as co-major advisor, 2 associate advisor) Graduate Students: ca. 10 International degrees: 3

PhD supervision activity:

Myriam DEKHIL (2013-2016) – Bourse MESR (co-major advisor: Dr. P. Thureau) “Développements méthodologiques en RMN du solide pour la mesure de distances internucléaires en phase solide” (3 scientific publications) Currently: Laboratory manager, MICHELIN (Clermont Ferrand, France)

Caroline BARRERE (2008-2011) – Bourse MRT (co-major advisor: Prof. L. Charles) “Développements méthodologiques en Spectrométrie de Masse et RMN pour l’analyse de copolymères à blocs” (3 scientific publications) This PhD thesis has received 2 Scientific Excellence Award in 2012: one from AMU and another from the French Chemical Society (Analytical chemistry division)

Currently: Laboratory manager, TOTAL (Gonfreville, France)

Rémi GIORDANENGO (2007-2010) – Bourse CIFRE, société ARKEMA (co-major advisor: Prof. L. Charles) “Développements méthodologiques en Spectrométrie de Masse et RMN pour l’étude de la microstructure de copolymers” (6 scientific publications) Currently: NMR service manager, R&D centre RHODIA (Aubervillers, France) This PhD thesis has received the French Society of Mass Spectrometry Award in 2010.

Caroline CARRARA (2006-2009) – Bourse MRT (co-major advisor: Prof. S. Caldarelli) “Développements méthodologiques en RMN Chromatographique : application à l’étude de l’activité des silanols résiduels” (3 scientific publications) Currently: R&D laboratory, Société EXPIRIS (Marignane, France)

Michaël MAZARIN (2005-2008) – Bourse MRT (associate advisor) “L’ionisation MALDI des polymères synthétiques en spectrométrie de masse” (6 scientific publications) Currently: Product Manager, TOTAL (Solaize, France)

Pierre THUREAU (2003-2006) – Bourse MRT (associate advisor) “RMN DOSY : comparaison des méthodes de traitement et application à l’étude de l’échange chimique” (4 scientific publications) Currently: Assistant Professor (HDR) at AMU

APPENDIX

Selected joint-publications between the teams at the CEREGE and the ICR 1. Lenoble V., Garnier C., Masion A., Ziarelli F. and Garnier J.M. (2008): Combination of 13C/113Cd NMR, potentiometry, and voltammetry in characterizing the interactions between Cd and two models of the main components of soil organic matter. Anal. Bioanal. Chem.: 390(2); 749-757. 2. Labille J., Masion A., Ziarelli F., Rose J., Brant J., Villieras F., Pelletier M., Borschneck D., Wiesner M.R. and Bottero J.Y. (2009): Hydration and dispersion of C-60 in aqueous systems: The nature of water-Fullerene interactions. Langmuir: 25(19); 11232-11235. 3. Levard C., Masion A., Rose J., Doelsch E., Borschneck D., Dominici C., Ziarelli F. and Bottero J.Y. (2009): Synthesis of Imogolite fibers from decimolar concentration at low temperature and ambient pressure: A promising route for inexpensive nanotubes. J. Am. Chem. Soc.: 131(7); 17080-17081. 4. Auffan M., Pedeutour M., Rose J., Masion A., Ziarelli F., Borschneck D., Chaneac C., Botta C., Chaurand P., Labille J. and Bottero J.Y. (2010): Surface structural degradation of TiO2-based nanomaterial used in cosmetics Environ. Sci. Technol.: 44(7); 2689-2694. 5. Levard C., Rose J., Thill A., Masion A., Doelsch E., Maillet P., Spalla O., Olivi L., Cognigni A., Ziarelli F. and Bottero J.Y. (2010): Formation and growth mechanisms of imogolite-like aluminogermanate nanotubes. Chem. Mater.: 22(8); 2466-2473. 6. Levard C., Masion A., Rose J., Doelsch E., Borschneck D., Olivi L., Chaurand P., Dominici C., Ziarelli F., Thill A., Maillet P. and Bottero J.Y. (2011): Synthesis of Ge-imogolite: influence of the hydrolysis ratio on the structure of the nanotubes. Phys. Chem. Chem. Phys.: 13; 14516-14522. 7. Auffan M., Rose J., Proux O., Masion A., Lui W., Benameur L., Ziarelli F., Botta A., Chaneac C. and Bottero J.Y. (2012): Is there a Trojan horse effect during magnetic nanoparticles and metalloid co-contamination of human dermal fibroblasts ? Environ. Sci. Technol.: 46(19); 10789-10796. 8. Cuoq F., Masion A., Labille J., Rose J., Ziarelli F., Prelot B. and Bottero J.Y. (2013): Preparation of amino- functionalized silica in aqueous conditions. Appl. Surf. Sci.: 266; 155-160.

9. Auffan M., Masion A., Labille J., Diot M.A., Liu W., Olivi L., Proux O., Ziarelli F., Chaurand P., Geantet C., Bottero J.Y. and Rose J. (2014): Long-term aging of a CeO2 based nanocomposite used for wood protection. Environ. Pollut.: 188; 1-7.

Main supervisor’s papers co-authored with supervised PhD students (names in boldface)

• Peer reviewed journal articles

1. Avellan A., Auffan M., Masion A., Levard C., Bertrand M., Rose J., Santaella C. and Achouak W. (2016): Remote Biodegradation of Ge-Imogolite Nanotubes Controlled by the Iron Homeostasis of Pseudomonas brassicacearum Environ. Sci. Technol.: 50(14); 7791-7798 2. Avellan A., Levard C., Chaneac C., Borschneck D., Onofri F.R.A., Rose J. and Masion A. (2016): Accelerated microwave assisted synthesis of alumino-germanate imogolites nanotubes RSC Adv.: 6(109); 108146-108150. 3. Avellan A., Levard C., Kumar N., Rose J., Olivi L., Thill A., Chaurand P., Borschneck D. and Masion A. (2014): Structural incorporation of iron into Ge–imogolite nanotubes: a promising step for innovative nanomaterials. RSC Adv.: 4; 49827-49830. 4. Avellan A., Levard C., Rose J., Auffan M., Bertrand M., Olivi L., Santaella C., Achouak W. and Masion A. (2016): Influence of structural defects of Ge-imogolite nanotubes on their toxicity towards Pseudomonas brassicacearum Environmental Science-Nano: 3(4); 839-846 5. Bottero J.Y., Auffan M., Borschnek D., Chaurand P., Labille J., Levard C., Masion A., Tella M., Rose J. and Wiesner M.R. (2015): Nanotechnology, global development in the frame of environmental risk forecasting. A necessity of interdisciplinary researches. C. R. Geosci.: 347(1); 35-42.

6. Cuoq F., Masion A., Labille J., Rose J., Ziarelli F., Prelot B. and Bottero J.Y. (2013): Preparation of amino-functionalized silica in aqueous conditions. Appl. Surf. Sci.: 266; 155-160. 7. Doelsch E., Auffan M., Bottero J.Y., Chaurand P., Legros S., Levard C., Masion A. and Rose J. (2011): Déchets et nanomatériaux : valorisation, dépollution, impacts environnementaux et toxicologiques. Actualite Chimique: 356-357; 91-96. 8. Doelsch E., Basile-Doelsch I., Rose J., Masion A., Borschneck D., Hazemann J.L., Saint-Macary H. and Bottero J.Y. (2006): New combination of EXAFS spectroscopy and density fractionation for the speciation of chromium within an andosol. Environ. Sci. Technol.: 40(24); 7602-7608. 9. Doelsch E., Masion A., Cazevieille P. and Condom N. (2009): Spectroscopic characterization of organic matter of a soil and vinasse mixture during aerobic and anaerobic incubation. Waste Management: 29(6); 1929-1935. 10. Doelsch E., Masion A., Moussard G., Chevassus-Rosset C. and Wojciechowicz O. (2010): Impact of pig slurry and green waste compost application on heavy metal exchangeable fractions in tropical soils Geoderma: 155(3-4); 390-400. 11. Doelsch E., Masion A., Rose J., Stone W.E.E., Bottero J.Y. and Bertsch P.M. (2003): Chemistry and structure of colloids obtained by hydrolysis of Fe(III) in the presence of SiO4 ligands. Colloids Surfaces A: Physicochem. Eng. Aspects: 217; 121-128. 12. Doelsch E., Rose J., Masion A., Bottero J.Y., Nahon D. and Bertsch P.M. (2000): Speciation and crystal chemistry of iron(III) chloride hydrolyzed in the presence of SiO4 ligands. 1. An Fe K-edge EXAFS study. Langmuir: 16(10); 4726-4731. 13. Doelsch E., Rose J., Masion A., Bottero J.Y., Nahon D. and Bertsch P.M. (2002): Hydrolysis of iron(II) chloride in anoxic conditions and influence of SiO4 ligands. Langmuir: 18; 4292-4299. 14. Doelsch E., Stone W.E.E., Petit S., Masion A., Rose J., Bottero J.Y. and Nahon D. (2001): Speciation and crystal chemistry of Fe(III) chloride hydrolyzed in the presence of SiO4 ligands. 2. Characterization of Si- Fe aggregates by FTIR and 29Si solid state NMR. Langmuir: 17(5); 1399-1405. 15. Elbeze L., Rose J., Mouillet V., Farcas F., Masion A., Chaurand P. and Bottero J.Y. (2012): Location and Evolution of the speciation of Vanadium in bitumen and model of reclaimed bituminous mixes during ageing: can Vanadium serve as a tracer of the aged and fresh parts of the reclaimed asphalt pavement mixture? Fuel: 102; 423-430. 16. Guigues S., Bravin M.N., Garnier C., Masion A., Chevassus-Rosset C., Cazevieille P. and Doelsch E. (2016): Involvement of nitrogen functional groups in high-affinity copper binding in tomato and wheat root apoplasts: spectroscopic and thermodynamic evidence Metallomics: 8(3); 366-376 17. Guigues S., Bravin M.N., Garnier C., Masion A. and Doelsch E. (2014): Isolated cell walls exhibit cation binding properties distinct from those of plant roots. Plant Soil: 381(1-2); 367-379. 18. Kumar N., Omoregie E.O., Rose J., Masion A., Lloyd J.R., Diels L. and Bastiaens L. (2014): Inhibition of sulfate reducing bacteria in aquifer sediment by iron nanoparticles. Wat. Res.: 51; 64-72. 19. Legros S., Chaurand P., Rose J., Masion A., Briois V., Ferrasse J.H., Saint-Macary H., Bottero J.Y. and Doelsch E. (2010): Investigation of Copper speciation in pig slurry by a multitechnique approach. Environ. Sci. Technol.: 44(18); 6926–6932. 20. Legros S., Doelsch E., Masion A., Rose J., Borschneck D., Proux O., Hazemann J.L., Saint-Macary H. and Bottero J.Y. (2010): Combining size fractionation, scanning electron microscopy, and X-ray absorption spectroscopy to probe Zinc speciation in pig slurry. J. Environ. Qual.: 39(2); 531-540. 21. Levard C., Doelsch E., Basile-Doelsch I., Abidin Z., Miche H., Masion A., Rose J., Borschneck D. and Bottero J.Y. (2012): Structure and distribution of allophanes, imogolite and proto-imogolite in volcanic soils. Geoderma: 183-184; 100-108. 22. Levard C., Doelsch E., Rose J., Masion A., Basile-Doelsch I., Proux O., Hazemann J.L., Borschneck D. and Bottero J.Y. (2009): Role of natural nanoparticles on the speciation of Ni in andosols of la Reunion. Geochim. Cosmochim. Acta: 73(16); 4750-4760 23. Levard C., Masion A., Rose J., Doelsch E., Borschneck D., Dominici C., Ziarelli F. and Bottero J.Y. (2009): Synthesis of Imogolite fibers from decimolar concentration at low temperature and ambient pressure: A promising route for inexpensive nanotubes. J. Am. Chem. Soc.: 131(7); 17080-17081. 24. Levard C., Masion A., Rose J., Doelsch E., Borschneck D., Olivi L., Chaurand P., Dominici C., Ziarelli F., Thill A., Maillet P. and Bottero J.Y. (2011): Synthesis of Ge-imogolite: influence of the hydrolysis ratio on the structure of the nanotubes. Phys. Chem. Chem. Phys.: 13; 14516-14522.

25. Levard C., Rose J., Masion A., Doelsch E., Borschneck D., Olivi L., Dominici C., Grauby O., Woicik J.C. and Bottero J.Y. (2008): Synthesis of large quantities of single-walled aluminogermanate nanotube. J. Am. Chem. Soc.: 130(18); 5862-5863. 26. Levard C., Rose J., Thill A., Masion A., Doelsch E., Maillet P., Spalla O., Olivi L., Cognigni A., Ziarelli F. and Bottero J.Y. (2010): Formation and growth mechanisms of imogolite-like aluminogermanate nanotubes. Chem. Mater.: 22(8); 2466-2473. 27. Maillet P., Levard C., Larquet E., Mariet C., Spalla O., Menguy N., Masion A., Doelsch E., Rose J. and Thill A. (2010): Evidence of double-walled Al−Ge Imogolite-like nanotubes. A Cryo-TEM and SAXS investigation. J. Am. Chem. Soc.: 132(4); 1208-1209. 28. Maillet P., Levard C., Spalla O., Masion A., Rose J. and Thill A. (2011): Growth kinetic of single and double-walled aluminogermanate imogolite-like nanotubes: an experimental and modeling approach. Phys. Chem. Chem. Phys.: 13(7); 2682-2689. 29. Masion A., Doelsch E., Rose J., Moustier S., Bottero J.Y. and Bertsch P.M. (2001): Speciation and crystal chemistry of iron(III) chloride hydrolyzed in the presence of SiO4 ligands. 3. Semi-local scale structure of the aggregates. Langmuir: 17(16); 4753-4757. 30. Masion A., Vilgé-Ritter A., Rose J., Stone W.E.E., Teppen B.J., Rybacki D. and Bottero J.Y. (2000): Coagulation-flocculation of natural organic matter with Al salts: speciation and structure of the aggregates. Environ. Sci. Technol.: 34(15); 3242-3246. 31. Rabhi M., Masion A., Roze C., Dussouillez P. and Bottero J.Y. (2010): Optical size and concentration monitoring of slurries: comparison between measurements and Monte Carlo simulation. J. Instrum.: 5; P04002 04001-04014. 32. Rose J., Levard C., Masion A., Cortalezzi M.M., Barron A.R. and Wiesner M.R. (2009): Ceramic membranes formed from nanoparticles: an environmental technology. Actualite Chimique: 331; 36-40. 33. Vilgé-Ritter A., Masion A., Boulangé T., Rybacki D. and Bottero J.Y. (1999): Removal of NOM by coagulation-flocculation: a pyrolysis-GC-MS study. Environ. Sci. Technol.: 33(17); 3027-3032. 34. Vilgé-Ritter A., Rose J., Masion A., Bottero J.Y. and Lainé J.M. (1999): Chemistry and structure of aggregates formed with Fe salts and natural organic matter. Colloids Surfaces A: Physicochem. Eng. Aspects: 147(3); 297-308.

• Peer -reviewed book sections and conference proceedings

1. Rose J., Chaurand P., Borschneck D., Geitner N., Levard C., Masion A., Vidal V., Thill A., Brant J. and Montano M.D. (2016) Methods for structural and chemical characterization of Nanomaterials. In: Wiesner M.R. and Bottero J.Y. (eds) Environmental Nanotechnology: Applications and impacts of nanomaterials, Second Edition., vol. McGraw-Hill, New York, Chigaco, San Francisco, Athens, Lodnon, Madrid, Mexico City, Milan, New Dehli, Singapore, Sydney, Toronto, pp 57-104. 2. Masion A., Vilgé-Ritter A., Bertsch P.M. and Bottero J.Y. (1998) Liquid- and solid state speciation of Al(III) in the presence of organics: mechanisms of hydrolysis in model systems and natural samples. In: 16th World Congress of Soil Science, vol. ISSS, Montpellier, France, pp S22(161)161-164. 3. Vilgé A., Rose J., Masion A., Lainé J.M. and Bottero J.Y. (1997) Advanced coagulation of natural organic matter. Mechanism of interaction between NOM and Al and Fe. In: AWWA Annual Meeting, vol C. American Water Works Association, Atlanta GA (June 15-19), pp 403-412. 4. Vilgé-Ritter A., Masion A., Rose J. and Bottero J.Y. (1998) Mécanismes d'élimination de la matière organique naturelle des eaux de surface par coagulation-floculation à l'aide de sels d'aluminium ou de fer. In: Bersillon J.L., Bues M., Cases J.M. and Tosot J.P. eds) Colloque Eau 50, vol. ASGA, Nancy, France Oct 5-7, pp 125-130.

• Patent

1. Brevet 06 02464 (dépôt 21-03-2006) Michel G., Ennahali M., Bottero J.Y., Masion A. "Composition de Polissage mécano chimique, procédé de préparation et utilisation"