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Titre : Electrochemical formation and transformation of corrosion products on carbon steel under cathodic protection in seawater	Année : 2013
Auteur(s) : Refait Ph. Jeannin M. Sabot R. Antony H. Pineau S. Abstract : Carbon steel coupons were permanently exposed to seawater in the low water zone of two French harbors for 5 years before to be subjected to cathodic protection (potential about 0.95 V vs. Ag/AgCl/seawater) for 1 year. The application of cathodic polarization to the previously unprotected coupons induced the transformation of GR(SO2 4 ) into GR(CO2 3 ). Other coupons were permanently protected by cathodic protection during the 6 years immersion. A thin film of green rust and mackinawite was observed on the steel surface. This film was covered by a thicker layer of calcareous deposits. 2013 Elsevier Ltd. All rights reserved. Elsevier - Corrosion Science 71 (2013) 32-36

Titre : Efficacy and environmental acceptability of two ballast water treatment chemicals and an alkylamine based-biocide	Année : 2010
Auteur(s) : La Carbona S. Viitasalo-Frösen S. Masson D. Sassi J. Pineau S. Lehtiniemi M. Corroler D. Abstract : Ship's ballast waters transport large numbers of organisms which may become invasive in coastal regions. One option to address this problem is the use of biocides as ballast water treatment (BWT). Ef?cacy and environmental acceptability of three commercial active substances (the BWT biocides Peraclean® Ocean and Seakleen®, and alkylamine-based biocide Mexel® 432/336) were tested against three bacteria species, two vegetative microalgae and one zooplanktonic larva, in 10 and 30 Practical Salinity Unit (PSU) waters. In both salinities, PeraClean® Ocean was the most effective biocide against bacteria causing N 90% mortality at 20 mg/l, compared with 50 mg/l for Mexel® 432/336 and N 500 mg/l for Seakleen®. Regarding zooplankton, Seakleen® was the most effective chemical causing 90% mortality in 24 h at concentrations b 6 mg/l (LC9024 h) in both salinities, compared with 23 and 26 mg/l for Mexel® 432/336 and 370 and 480 mg/l for PeraClean® Ocean in 10 and 30 PSU, respectively. Similar pattern of ef?cacy was obtained for microalgae in 30 PSU: effective concentrations inducing 50% growth inhibition in 4 days were ? 1.6 mg/l for Seakleen®, ? 10.1 mg/l for Mexel® 432/336 and ?30.9 mg/l for PeraClean® Ocean. Our work highlighted that treated waters displayed residual toxicity after 24 h still inducing mortality depending on the organism and biocide. However Mexel® 432/336 is the only biocide which had no impact on oyster larvae development at effective concentration. Altogether our data showed that Mexel® 432/336 was the only biocide displaying a broad spectrum ef?cacy in concentrations b 50 mg/l and not toxic for oyster larvae development at this concentration. However residual toxicity of treated waters for any organism should be taken into account in BWT systems utilising biocides. STOTEN-12286; No of Pages 9

Titre : Dynamics of bacterial consortia and Sulphate-Reducing Microorganisms associated to ALWC products in marine port structures	Année : 2010
Auteur(s) : Paisse S. Ghiglione JF. Gueune H. Marty F. Muyzer G. Quillet L. Abstract : European port authorities are commonly concerned by Accelerated Low Water Corrosion (ALWC) occurring in low water zone of steel port structures. High corrosion rates induced can shorten drastically service life of the structure or lead to failure. Solutions to mitigate this corrosion are available but still remains costly. The goal of the MICSIPE project (Microbiologically Induced Corrosion of Steel structures In Port Environment) is to develop risk assessment methods to predict and assess ALWC for industrial end users, combining microbiological, chemical and corrosion sciences approaches. Chemical process of corrosion has been already well documented. ALWC is microbiologically induced; but mechanisms and bacteria involved have not been entirely determined until now. In this context, we studied the abundance, activity and diversity of bacteria and particularly Sulphate-Reducing Microorganisms (SRM) in both suspected accelerated (ALWC) and normal (NLWC) low water corrosion products from a European port. ISME 13 – Microbes - Stewards of a changing planet – 22-27 August 2010 - Seattle, WA, USA

Titre : Biocorrosion – Corrosion Influencée ou Induite par les Micro-organismes	Année : 2010
Auteur(s) : Antony H. Gueune H. Poisson A. Abstract : A study performed in 1990-1993 estimated a minimum of 12-13% of European harbours affected by a particularly aggressive localized MIC phenomenon, called Accelerated Low Water Corrosion (ALWC) occurring at or below the low water zone of steel waterfront structures. ALWC is well recognized to affect harbours worldwide, causing drastic reductions of the service life of steel structures due to unusual high corrosion rates. Prevention and mitigation solutions exist, but are costly, while ALWC prediction has so far not been possible due to the lack of understanding of abiotic and biotic factors and of the mechanisms involved. Presence and potential implication of sulfate-reducing and other sulfur bacteria in ALWC has been reported in previous studies. However, the mechanisms and the characteristics of the biofilm- deposit complex involved in ALWC remain unclear. The objective of this study is to obtain a detailed characterization of ALWC biofilm- deposit complexes taken from one European harbour in order to propose interaction and corrosion mechanisms. Several samples of corroded and non-corroded zones were recently taken from a European harbour affected by ALWC since 20 years. These samples were studied using different analytical methods: (1) cultivation targeting for the first time almost all MIC associated-bacterial metabolic groups (sulfate-reducing bacteria (SRB), thiosulfate-reducing bacteria (TRB), thiosulfate-oxidizing bacteria (TOB), iron- oxidizing bacteria (IOB), iron-reducing bacteria (IRB), manganese-reducing bacteria (MnRB) and marine aerobic heterotrophic bacteria); (2) 16S rDNA PCR-DGGE fingerprinting methods, (3) microscopic methods (e.g. SEM) and (4) analytical methods to determine chemical composition (i.e. XRD, XRFS, and Raman spectrometry). All targeted bacterial groups could be enriched from samples originating from ALWC and from the reference sites confirming that the presence of specific metabolic groups is not an exclusive criterion for characterizing ALWC biofilm. However, IOB activities appeared to be higher in ALWC than in reference samples indicating a potential implication of this metabolic group, which was not yet considered in ALWC. Analysis of SRB and TRB enrichments indicated specific populations associated with ALWC. Analysis of the different layers of biofilm-deposit complexes indicated the presence of an oxygen gradient within the biofilm/deposit complexes. Green rust and iron sulfide detected with SRB in the inner layers of ALWC samples indicated the occurrence of SRB activities. Further results and their interpretation will be discussed in the future to improve ALWC diagnostics and prediction. The work was carried out with a financial grant from the Research Fund for Coal and Steel of the European Community (Project number: RFSR-CT-2008-00018). EUROCORR - Journée de l’Institut de soudure Date : 18 juin 2010

Titre : Aluminium accumulation in mussel Mytilus edulis: laboratory investigation	Année : 2009
Auteur(s) : Mao A. Caplat Ch. Mahaut ML. Pineau S. Barillier D. Abstract : Non disponible SETAC Europe 19th Annual Meeting, 31 May – 4 June 2009, Götegorg, Sweden

Titre : Comportement des aciers inoxydables exposés en milieu marin	Année : 2009
Auteur(s) : Antony H. Abstract : Non disponible lundi de la mécanique - CETIM

Titre : Installation véhiculant ou stockant de l'eau - Matériaux & Corrosion	Année : 2009
Auteur(s) : Antony H. Abstract : Non disponible USIDO

Titre : Formation of the Fe(II-III) hydroxysulphate green rust during marine corrosion of steel associated to molecular detection of dissimilatory sulfite-reductase	Année : 2008
Auteur(s) : Pineau S. Sabot R. Quillet L. Jeannin M. Caplat Ch. Dupont-Morral I. Refait Ph. Abstract : Accelerated corrosion phenomena of carbon steel constantly immersed in seawater could be simulated in situ via a galvanic coupling of samples with steel port structures. Three harbours located on different seas and various conditions of immersion were considered so as to study the eventual correlation between dissimilatory sulphite-reductase genes and suplhate-containing corrosion products. In each case, after 6 or 12 months, the rust layers proved to be made of an inner black layer, close to steel surface, and an orange outer layer. Scanning electron microscopy, chemical analyses by inductively coupled plasma/atomic emission spectroscopy, X-ray diffraction and micro-Raman spectroscopy were used to obtain a detailed characterisation of these layers. The inner one proved to be mainly composed of iron sulphides FeS and Fe(II-III) hydroxysulphate green rust GR(SO42-), the outer one one of Fe(III) oxyhydroxides, with lepido-sulphate reduction by micro-organisms, was applied for the first time to rust layers. This detection was positive in most cases, especially for the inner part of the rust layers. This demonstrates that sulphate reducing bacteria are associated to GR(SO42-) inside the rust layers, sulphate reducing bacteria and/or thiosulphate reducing bacteria. © 2007 Elsevier Ltd. All rights reserved. Corrosion Science, 50 (2008), p. 1099-1111

Titre : Process and Efficiency of In Situ Experimentation for Accelerated Corrosion Studies, in French Marine Ports	Année : 2008
Auteur(s) : Pineau S. Lefèvre Y. Dupont-Morral I. Marsset B. Scherrer P. Auzeby C. Bénaïssa B. Abstract : Non disponible Material Performance, October 2008, p. 2-6

Titre : The study of relationship between diversity of bacterial biofilms and marine corrosion of carbon steel in harbour environments	Année : 2008
Auteur(s) : Pineau S. Ghiglione JF. Quillet L. Caplat Ch. Refait Ph. Abstract : Here is reported investigation aimed to elucidate relationship between accelerated marine corrosion of carbon steel and community structure of bacterial biofilms associated with corrosion products. The study was conducted in three different French coastal regions (English Channel, Atlantic Ocean and Mediterranean Sea). SEM-EDX, ICP-AES, XRD and micro-Raman spectrometry revealed stratification of corrosion products based on iron oxidation state, regardless of geographical location. Molecular biology techniques and standard cultivation methods demonstrated that bacteria in corrosion products were abundant and highly diverse. Moreover, corrosion products contained many species of diatoms and multicellular organisms. Characterisation of cultivable bacteria and culture-independent molecular fingerprinting method (CE-SSCP) revealed more than 20 bacterial ribotypes in the deposits. Molecular detection of sulphate-reducing bacteria (SRB) was carried out using dissimilatory sulfite-reductase gene (dsrAB) and 16S rDNA probes specific for six SRB sub-groups. The results of microbiological analysis demonstrated that the composition and diversity of bacterial populations associated with corrosion products are determined by the chemistry of different regions, i.e. steel surface, corrosion product surface and green rust / oxy-hydroxide interface, without clear stratification. Moreover, the study confirmed that, irrespective of the site investigated, bacterial species detected in corrosion products differed from the ones present in bulk water, thus emphasising the importance of biofilm sampling when investigating corrosion failures. In view of the obtained results, the role of green rust as sulphate reservoir, the localised acidification induced by biogenically produced sulphur, the plausible role of extracellular polymeric substances in connecting bacterial cells and mineral corrosion products and the impact of multicellular organisms on the corrosion product stability are discussed. 14th International Congress on Marine Corrosion and Fouling July 27-31, 2008 Kobe, Japan

Titre : Biofilm et matériaux : je t’aime moi non plus ». XIème colloque du Groupe Français de Bioélectrochimie	Année : 2008
Auteur(s) : Pineau S. Abstract : A une époque où la tendance serait à la stérilisation généralisée, les biofilms sont souvent une source de problèmes sanitaires et industriels, liés à des effets toxiques mais également à des impacts sur les infrastructures (modification des propriétés de surface ou corrosion par exemple). Ces communautés biologiques, de l’échelle micrométrique à centimétrique selon la thématique (biofilms bactériens ou évolution en macro-biofilms pluricellulaires), présentent une affinité toute particulière pour la plupart des matériaux, métalliques ou non. Il s’agit donc d’un processus normal, naturel et généralement bénéfique d’un point de vue écologique. Néanmoins, bien que les matériaux soient conçus pour résister à un environnement donné, les micro-organismes viennent fréquemment perturber le sommeil des gestionnaires de ces structures. Difficiles à modéliser, à prédire et à maîtriser, que ce soit pour l’expérimentation scientifique ou pour le suivi industriel, ces interactions entre biofilms et matériaux concernent tous les domaines de compétences mais principalement la science des matériaux, la microbiologie et l’électrochimie. Cette communication pluridisciplinaire, parfois laborieuse, offre de nombreuses perspectives de recherche. Une partie de cette problématique est illustrée par des exemples issus de cas industriels, particulièrement en eau de mer, où la distinction des frontières minéral/organique et bénéfique/préjudiciable est discutée. Lacanau-Océan, 29 septembre - 2 octobre 2008

Titre : Carbonate and sulphate green rusts – Mechanisms of oxidation and reduction	Année : 2008
Auteur(s) : Antony H. Legrand L. Chaussé A. Abstract : The oxidation and reduction of carbonate, GR(CO3), and sulphate, GR(SO4), green rusts (GR) have been studied through electrochemical techniques, electrochemical quartz crystal microbalance (EQCM), FTIR, XRD and SEM. The used samples were made of thin films electrodeposited on gold substrate. The results from the present work, from our previous studies and from literature were compiled in order to establish a general scheme for the formation and transformation pathways involving carbonate or sulphate green rusts. Depending on experimental conditions, two routes of redox transformations occur. The first one corresponds to reaction via solution and leads to the formation of ferric products such as goethite or lepidocrocite (oxidation) or to the release of FeII ions into the solution (reduction) with soluble FeII–FeIII complexes acting as intermediate species. The second way is solid-state reaction that involve conversion of lattice Fe2+ into Fe3+ and deprotonation of OH groups in octahedra sheets (solid-state oxidation) or conversion of lattice Fe3+ into Fe2+ and protonation of OH groups (solid-state reduction). The solid-state oxidation implies the complete transformation of GR(CO3) or GR(SO4) to ferric oxyhydroxycarbonate exGRc-Fe(III) or ferric oxyhydroxysulphate exGRs-Fe(III), for which the following formulas can be proposed, FeIII 6(OH)(12-2y)(O)(2+y)(H2O)(y)(CO3) or FeIII 6(OH)(12-2z)(O)(2+z)(H2O)(6+z)(SO4) with 0 <=y or z<=2. The solid-state reduction gives ferrous hydroxycarbonate exGRc-Fe(II) or ferrous hydroxysulphate exGRs-Fe(II), which may have the following chemical formulas, [FeII 6(OH)10(H2O)2]·[CO3, 2H2O] or [FeII 6(OH)10(H2O)2]·[SO4, 8H2O]. Electrochimica Acta, Volume 53, 2008, Pages 7146-7156

Titre : Study of FeII/FeIII ratio in thin films of carbonate or sulphate green rusts obtained by potentiostatic electrosynthesis	Année : 2008
Auteur(s) : Antony H. Labrit A. Rouchaud JC. Legrand L. Chaussé A. Abstract : Thin films of carbonate or sulphate green rusts were synthesised from potentiostatic oxidation of solutions containing ferrous species and bicarbonate or sulphate ions at slightly alkaline pHs and ambient temperature. The thin films were characterised by means of electrochemical quartz crystal microbalance, scanning electron microscopy, X-ray diffraction and infrared reflection–absorption spectroscopy. The composition of carbonate or sulphate green rusts was studied through chemical titration, inductively coupled plasma-optical emission spectroscopy (ICP-OES) and gravimetry and is as follows: [FeII (2R)FeIII 2(OH)(4R'2R'+6)(H2O)(2R'-2)]2R'+·[R'CO3, (2R-{3 or 4}R' + 2)·H2O]2R'- and [FeII (2R)FeIII 2(OH)(4R?2R''+6)(H2O)(2R''-2)]2R''+·[R''SO4, (4R-4R' + 4)·H2O]2R''- FeII/FeIII ratio R depends on the concentration of soluble ferrous species that are located at electrode surface during the potentiostatic synthesis and increases as the potential is made more negative. R-values are in the ?2–2.5 range for carbonate green rust, and in the ~2–2.2 range for sulphate green rust. The obtained R'- and R''-values are 1–1.3 and 1.1–1.4 for carbonate and sulphate green rusts, respectively. The present study excludes the existence of green rusts with FeII/FeIII ratio, R, lower than 2. The R-values lower than 2 that are found in some studies might relate to mixtures of the green rust and its solid-state oxidation product exGR-Fe(III) (ferric oxyhydroxycarbonate or ferric oxyhydroxysulphate) rather than to pure green rust. Electrochimica Acta, Volume 53, 2008, Pages 7146-7156

Titre : Experimental evidence of the evolution of the oxide barrier layer during corrosion of low alloyed steels	Année : 2008
Auteur(s) : Martin F. Antony H. Bataillon Ch. Abstract : In the framework of the study of corrosion of nuclear waste packages in geological disposal conditions, a general corrosion modelling has been suggested to predict their long term behaviour. This corrosion model (Diffusion Poisson Coupled Model) associated to the code CALIPSO is able to describe the iron release in Fe(II) and Fe(III) cations at the external interface, as well as the iron and electrons fluxes across the system. Introduction of the oxygen flux will be the next step in the modelling because it is responsible for the formation of the oxide barrier layer. In order to bring entrance data for this model, a non destructive method has been developed to estimate the thickness of the oxide layer. This method is based on the EDS analysis. Combining ex situ gravimetry measures and the measured oxide layer thicknesses gives an estimation of the Fe released in solution function of immersion time. The first results obtained on a pre-oxidised Armco Fe sample (thus covered by an oxide layer of a definite thickness) in a deaerated Tris buffered solution are presented. These preliminary observations show that both outer and inner interfaces move towards the metal bulk with immersion time (see figure), which confirms the growth/dissolution mechanisms at the inner and outer interfaces described in the PDM. Moreover, the corrosion rate decreases to reach a quasi-stationary state. This is materialised by a nearly constant thickness of the oxide film for long times. Eurocorr

Titre : Marine corrosion: a widespread, underestimated and poorly understood phenomenon	Année : 2007
Auteur(s) : Daret J. Pineau S. Braisaz T. Abstract : Seawater is a universal fluid – it is the medium where oceanographic moorings, ships, harbour installations and offshore platforms spend their life. Seawater is also widely used in industrial applications: for cooling and for use against fire in ships and platforms, and in coastal installations such as refineries, chemical/petrochemical plants, desalination plants and power stations. By nature, seawater is very corrosive to metallic materials; it contains, for example, dissolved oxygen, micro-organisms, and high concentrations of chloride ions and other chemical species deleterious to the integrity of metallic materials, such as hydrogen sulphide and ammonia compounds. Therefore, when designing any equipment or industrial plant that will be in contact with seawater, it is important to know about, and to take into account, the behaviour of metallic materials in seawater. It is also absolutely essential to evaluate the effects not only of corrosion, but also the environmental effects of measures taken to counteract it. Ocean Challenge, Vol. 15; No. 1, p. 38-43

Titre : Sulfate reducing microorganisms: microorganisms implicated in heavy metals speciation and biocorrosion process in coastal and estuarial environments	Année : 2007
Auteur(s) : Quillet L. Leloup J. Boust D. Popova M. Lafite R. Ouddane B. Pineau S. Ghiglione JF. Petit F. Abstract : Non disponible Annual conference of Universidad Católica de Chile, Santiago du Chili, 19 juillet 2007

Titre : Corrosion deposits in natural seawater: a habitat with constant mineral organization and high micro-organisms diversity	Année : 2007
Auteur(s) : Pineau S. Ghiglione JF. Refait Ph. Sabot R. Jeannin M. Caplat Ch. Dupont-Morral I. Abstract : Investigations into chemistry and microbiology of deposits formed during marine corrosion processes on surfaces of carbon steel are scarce. During the last decade a small number of in situ studies, mainly related to accelerate corrosion reported in harbour environments, has been carried out in Europe, Australia and Asia. Specific corrosion products, such as iron-sulphides in black liquid localized in the internal layer (steel side) or magnetite and iron oxy-hydroxides in external layer (seawater side), were found across the thickness of the deposit. However, the formation and the type of minerals, e.g. iron sulphide species and green rusts were not clearly identified. In this study, the structural organization and the composition of corrosion deposits formed on steel piling structures in three French ports in the English Channel, Atlantic Ocean and Mediterranean Sea have been determined. Spatial distribution of corrosion products did not differ between the three sites and it was strongly correlated with steel corrosion behaviour in saline electrolyte. The weight of the inorganic (mineral) fraction in corrosion products was frequently less than 50% (w/v) of the total weight; the other fraction being composed of water, organic compounds and micro-organisms. Bacterial diversity in the deposit was investigated using cultivable and molecular fingerprinting methods. High abundance and diversity was found in the three sites, with slight differences between surface and interface layers. The results indicate that corrosion deposits can be regarded as habitats with constant mineral fraction and stratification dependent on and following iron oxidation state. The composition and diversity of bacterial populations associated with corrosion products are determined by the chemistry of different regions, i.e. steel surface, deposit surface and green rust / oxy-hydroxide interface without clear stratification. The study confirmed that bacterial species detected in corrosion products differed from the ones present in bulk water, thus emphasising the importance of biofilm sampling when investigating corrosion failures. International conference on biocorrosion of materials (Biocorys 2007), 11-14 June 2007, Paris

Titre : Biocorrosion des matériaux métalliques	Année : 2007
Auteur(s) : Pineau S. Abstract : Non disponible Journée membres Institut de Soudure, Corrosion des aciers. 22 mars 2007, Villepinte

Titre : Etude des communautés bactériennes associées au complexe dépôt de corrosion / biofilm en eau de mer	Année : 2007
Auteur(s) : Pineau S. Ghiglione JF. Quillet L. Dupont-Morral I. Janvier M. Abstract : L’acier au carbone, principal matériau utilisé dans la construction des ouvrages maritimes engendre, au cours des processus de corrosion en environnement marin, la formation d’un dépôt composé de produits minéraux, organiques et de micro-organismes, conduisant à le qualifier de « complexe dépôt de corrosion / biofilm ». Ces travaux présentent une étude exploratoire des communautés bactériennes, à partir d’une expérimentation réalisée sur trois sites portuaires français. Des portiques d’essai ont été installés dans différentes zones d’immersion en Manche (Le Havre), en Atlantique (Nantes-St-Nazaire) et en Méditerranée (Marseille). Des méthodes métallographiques, physico-chimiques, microbiologiques et de biologie moléculaire ont été réalisées à partir des biofilms formés sur ces échantillons d’acier, après 6 et 12 mois d’expérimentation. Un dénombrement de la flore totale a été réalisé par épifluorescence (environ 8.108 bactéries.g-1 de dépôt humide). L’analyse de la fraction cultivable a été effectuée sur milieu non sélectif Marine Agar (environ 4.106 UFC.g-1), représentant en moyenne seulement 0,5 % de la biomasse totale. 1040 souches ont été isolées au cours de ces travaux. Après amplification PCR de l’ADNr 16S et discrimination des produits PCR par la technique RFLP, 102 souches ont été séquencées, démontrant une importante diversité avec plus de 39 espèces bactériennes différentes (dominance de gamma-proteobacteria et de Bacilli). La structure de ces communautés bactériennes a également été étudiée via des analyses d’empreinte moléculaire (CE-SSCP) qui ont permit de mettre en évidence l’effet sélectif des dépôts de corrosion sur le développement bactérien (nombre de ribotypes dans les dépôts inférieur à l’eau de mer environnante). La structure des communautés varie d’un site d’essai à un autre mais reste relativement constante entre 6 et 12 mois d’essai. Une importante activité sulfurogène a été mise en évidence dans ces échantillons par PCR directe et Nested-PCR. D’une part, la détection moléculaire des six sous-groupes de bactéries sulfato-réductrices (BSR) a révélé une dominance des genres Desulfobulbus et Desulfovibrio. D’autre part, l’utilisation d’amorces spécifiques de la sulfite-réductase dissimilatrice (dsrAB) a confirmé la présence de BSR. Ces travaux mettent en évidence une diversité bactérienne très importante au sein d’un environnement minéral inexploré et confirme le rôle prépondérant de la flore sulfurogène dans ce type d’habitat. Société Française de Microbiologie, 30 mai – 1 juin 2007, Nantes

Titre : Electrochemical study of indoor atmospheric corrosion layers formed on ancient iron artefacts	Année : 2007
Auteur(s) : Antony H. Perrin S. Dillmann Ph. Legrand L. Chaussé A. Abstract : Several indoor atmospheric corrosion layers (0–800 years old) were selected from different localisations in France. Each sample was scrapped from its iron substrate. The resulting powder was mixed with graphite in appropriate proportions and the mixture was pressed onto a stainless steel grid to constitute a composite electrode. The electrochemical responses of the different samples were recorded under galvanostatic regulation, in a near-neutral pH-buffered NaCl solution at 25 °C. The E–t reduction curves allowed the determination of two characteristic parameters, E?/2, the potential value obtained at half the transition time, and Q?, the coulombic charge obtained at the end of the reduction. The diminution of E?/2 and Q? with the age of the corrosion layer showed that the “reduction reactivity” decreases with time, suggesting a progressive stabilisation of the corrosion layer. In a second part of the work, we synthesised several common ferric or ferrous/ferric products (goethite, lepidocrocite, magnetite, maghemite, ferrihydrite) and compared their reduction responses (product alone or mixture of 2 or 3 products) to those of corrosion samples. Electrochimica Acta

Titre : Étude électrochimique de couches de corrosion d'objets archéologiques formées en corrosion atmosphérique	Année : 2007
Auteur(s) : Antony H. Monnier J. Perrin S. Dillmann Ph. Legrand L. Chaussé A. Abstract : La dégradation des matériaux à base de fer en corrosion atmosphérique est un phénomène bien connue qui peut avoir des conséquences importantes, particulièrement dans le cas du stockage/entreposage de déchets radioactifs. La prédiction à long terme de la corrosion atmosphérique sous abri d’aciers entrant dans la constitution des fûts ou systèmes destinés à l’entreposage et au stockage de déchets fait appel à un modèle mécaniste basé sur des hypothèses qui doivent être validées par des données expérimentales [1,2]. Ainsi une des hypothèses fortes du modèle proposé par le CEA qui suppose la réduction de constituants de la couche de corrosion lors de l’une des étapes du cycle de corrosion atmosphérique est à valider. Au cours de cette étape dite période humide (formation d’un film électrolytique à la surface du matériau) les constituants de la couche de corrosion sont susceptibles de jouer le rôle d’accepteur d’électron. Les fers anciens ou objets archéologiques constituent des sources de données intéressantes pour alimenter les modèles prédictifs de corrosion car ils ont été au contact d’un environnement agressif pendant plusieurs centaines d’année. Afin de valider l’une des hypothèses du modèle, une étude électrochimique sur des poudres de rouille issues d’objets archéologiques (0-800 ans) a été réalisée. Un mélange homogène poudre – graphite compacté sur grille de platine collectrice de courant constitue une électrode composite parfaitement adaptée à une étude électrochimique. La réponse électrochimique sous imposition de courant de ces électrodes est obtenue en milieu NaCl à pH neutre et à température ambiante. A partir de ces réponses, deux paramètres, Et/2, valeur du potentiel obtenue à demi-réaction de réduction et Qt, quantité d’électricité mise en jeu au cours du processus de réduction peuvent être déterminés. La diminution de ces deux paramètres en fonction de l’âge de l’échantillon de fers anciens est observée et montre une diminution de la réactivité des produits constituants la couche de rouille en fonction de l’âge. Dans une seconde partie sera présenté le comportement électrochimique de produits synthétiques ferriques les plus couramment rencontré dans une couche de rouille (goethite, lepidocrocite, magnetite, maghemite, ferrihydrite), ainsi que la réponse électrochimique de mélange de ces composés. JE

Titre : Comportement des rouilles vertes carbonatées et sulfatées	Année : 2007
Auteur(s) : Antony H. Legrand L. Chaussé A. Abstract : Les rouilles vertes (RV) sont des composés hydroxydes doubles lamellaires de formule générale [FeII (1-x)FeIII x(OH)2]x+.[x/nAn-.mH2O]x- (avec An- : CO3 2-, SO4 2-, Cl-…). Elles interviennent dans les processus de corrosion des aciers [1], le cycle biogéochimique du fer [2] et peuvent être utilisés comme composés actifs dans certains procédés de dépollution [3]. Le caractère ferreux-ferrique qu’elles présentent, leur confère potentiellement le double rôle de donneur et d’accepteur d’électrons et les positionne, par conséquent, au centre des processus d’oxydoréduction impliquant l’élément fer. La littérature comporte quelques études du comportement en oxydation des rouilles vertes ; ces études concernent principalement des suspensions mises en aération, et les résultats reportés indiquent la possibilité d’obtenir différents composés ferriques finaux selon les conditions expérimentales, ce qui semble suggérer l’intervention de différents mécanismes. En revanche, aucune étude sur le comportement en réduction n’était reportée, vraisemblablement du fait de la difficulté à imposer des conditions de réduction à ces suspensions. Nous utilisons au laboratoire, des films minces de composés purs, synthétisés par voie électrochimique ou chimique, sur divers substrats [4, 5]. Des électrodes ainsi constituées sont particulièrement bien adaptées pour l’étude des processus rédox ; en effet, une perturbation oxydante ou réductrice peut facilement être appliquée au composé par imposition d’un potentiel ou courant appropriés. De même, cette approche permet de coupler in-situ les mesures électrochimiques avec d’autres techniques d’analyse comme la microbalance à quartz et le microRaman. La présente communication reporte des résultats obtenus au cours d’études de l’oxydation et de la réduction de films minces de rouilles vertes carbonatée et sulfatée [6]. Les mesures gravimétriques in-situ ont été exploitées pour préciser la nature des transformations rédox (à l’état solide ou via la solution). Ces résultats ont été complétés par des analyses ex-situ par MEB, FTIR en mode réflection-absorption et DRX. A partir de nos travaux et des données déjà existantes dans la littérature, nous avons pu établir le schéma général des voies de transformation redox des rouilles vertes carbonatée et sulfatée. JE

Titre : Applications de la spectroscopie infrarouge a transformée de Fourier (IRTF) pour la caractérisaton de bactéries sulfurogènes présentes dans les biofilms marins	Année : 2006
Auteur(s) : Boudaud N. Pineau S. Amiel C. Mariey L. Travert J. Abstract : Non disponible Journées thématiques Biofilms 2006 BRGM Orléans, 14-15 Juin 2006

Titre : Electrochemical reduction of ferric corrosion products and evaluation of galvanic coupling with iron	Année : 2006
Auteur(s) : Lair V. Antony H. Legrand L. Chaussé A. Abstract : Ferric product powders were synthesised. The purity of each compound was controlled by FTIR and XRD analysis; the BET surface area and electrical conductivity were also reported. The galvanostatic electrochemical reduction of graphite/ferric product composite electrodes was investigated at 25 °C in mildly alkaline pH-buffered solutions containing chloride, sulphate or bicarbonate anions. The efficiency of the reduction process (FeIII-to-FeII reaction) was quantified by reporting the potential value obtained at half the transition time, Es/2, on the E–t transient, as a function of Qs, the coulombic charge obtained at the end of the reduction. The possibilities for a galvanic coupling to occur have been discussed based on the reduction efficiency plots and corrosion potential values of iron in the various media. © 2005 Elsevier Ltd. All rights reserved. Corrosion Sciences, Volume 48, Issue 8, Août 2006, Pages 2050-2063

Titre : Coupled electrochemical and gravimetric study of iron corrosion products	Année : 2006
Auteur(s) : Antony H. Legrand L. Chaussé A. Abstract : Understanding the transformation pathways that occur during the growth and evolution of a corrosion layer on steel is a hard challenge since it is difficult to clearly identify the contributions of each corrosion product and the influence of the iron substrate. Thin films of iron products deposited on inert conducting substrate are very appropriate for performing electrochemical measurements. Indeed, both oxidation and reduction behavior can be studied by imposing anodic or cathodic perturbations to the iron corrosion product. Moreover, the coupling of in-situ characterization methods is easily carried out. Procedures were developed to synthesize commonly-occurring iron corrosion products as thin films [1-3]. Once synthesized, the thin film was electrochemically studied through voltametry or chronopotentiometry. Quartz crystal microbalance was used in order to get insitu mass measurements during both the synthesis and the oxidation/reduction studies. Gravimetric measurements give information on dissolved and non-dissolved reduced quantities, providing details on transformation and allowing the establishment of reduction or oxidation classification. Concerning green rusts (mixed Fe(II)-Fe(III) hydroxides occurring as intermediates between iron and ferric oxyhydroxides), we could point out the possibility for solid-state oxidation or solid-state reduction [1], giving to these compounds a redox flexibility that may play a key role in the evolution of some corrosion layers. A reduction mechanism was proposed for the ferric oxihydroxide model, Lepidocrocite g-FeOOH [4]. Several ferric corrosion products (Ferrihydrite, Maghemite, …) were also studied. Complementary information was obtained from usual techniques (FTIR, SEM, XRD, …). EMCR

Titre : Electrochemical study of indoor atmospheric corrosion layers formed on ancient iron artefacts	Année : 2006
Auteur(s) : Antony H. Perrin S. Dillmann Ph. Legrand L. Chaussé A. Abstract : The degradation of iron-based materials by atmospheric corrosion is a well-know problem that may have incidence, especially for the storage of radioactive nuclear wastes. It is of importance to evaluate the damages due to this kind of corrosion within long time-periods. Atmospheric corrosion is thought to be a cycling process for which some parts of the corrosion layer may play a key role of electron acceptor during the wet periods. Studying atmospheric corrosion layers formed on ancient iron coupons provides helpful information on this phenomenon. Several indoor atmospheric corrosion layers (0-800 years old), were selected from different localizations in France. Each sample was scrapped from its iron substrate. The resulting powder was mixed with graphite in appropriate proportions and the mixture was pressed onto a stainless steel grid to constitute a composite electrode. The electrochemical responses of the different samples were recorded under galvanostatic regulation, in a nearneutral pH-buffered NaCl solution at 25°C. The E-t reduction curves allowed the determination of two characteristic parameters, Et / 2 , the potential value obtained at half the transition time, and Qt , the coulombic charge obtained at the end of the reduction. The diminution of Et / 2 and Qt with the age of the corrosion layer showed that the “reduction reactivity” decreases with time, suggesting a progressive stabilisation of the corrosion layer. In a second part of the work, we synthesised several common ferric or ferrous/ferric products (goethite, lepidocrocite, magnetite, maghemite, ferrihydrite) and compared their reduction responses (product alone or mixture of 2 or 3 products) to those of corrosion samples. EMCR

Titre : Approches méthodologiques pour la caractérisation des populations dominantes de biofilms marins naturels, sur acier au carbone	Année : 2005
Auteur(s) : Pineau S. Janvier M. Cabassut G. Dupont-Morral I. Abstract : Non disponible 7ème forum de biodétérioration des matériaux, Ouistreham, 26-27 mai 2005

Titre : microbial diversity of marine biofilms from carbon steel in port environment: optimization of research approach in Accelerated Low Water Corrosion (ALWC) context	Année : 2005
Auteur(s) : Pineau S. Cabassut G. Dupont-Morral I. Janvier M. Abstract : The degradation of carbon steel structures, especially in the case of Accelerated Low Water Corrosion (ALWC) in port environment, can be induced by the presence of microorganisms, or the products of their metabolic activities including enzymes, exopolymers substances, organic and inorganic acids. Bacteria most frequently studied in Microbiologically Induced Corrosion (MIC) are mainly the Sulphate-Reducing Bacteria (SRB). To study bacterial consortia in MIC, a research program is purposed for in situ experimentation in three French ports. Carbon steel samples have been placed in several different configuration sites. New molecular technologies have been developed and used to investigate the composition of microbial communities. However, successful application of molecular techniques relies on effective recovery of nucleic acids from environmental samples. The objective of this study is to develop a rapid method to remove biofilm from marine samples and further a robust, simple and effective total DNA extraction protocol. We applied the molecular approach of PCR-amplified 16S rDNA fragments separated by Denaturing Gel Electrophoresis (DGGE) to analyze the microbial community. The comparison of DGGE patterns from different samples gives us information about similarities and differences in their community structures. This approach can be used to compare bacterial diversity from different sampling sites. This molecular approach is combined to classic microbiological methods (cultivable strains). 13th International Biodeterioration and Biodegradation Symposium, Madrid (Spain), 4-9 septembre 2005

Titre : Study of lepidocrocite electrochemical reduction in neutral and slightly alkaline solutions at 25°C	Année : 2005
Auteur(s) : Antony H. Legrand L. Maréchal L. Perrin S. Dillmann Ph. Chaussé A. Abstract : The electrochemical reduction of lepidocrocite ?-FeOOH was investigated at 25 °C in neutral or slightly alkaline solutions containing chloride, sulphate or bicarbonate anions by means of thin lepidocrocite film electrodeposited on inert gold substrate or graphite/lepidocrocite powder composite electrode. Electrochemical measurements were coupled to in situ electrochemical quartz crystal microbalance (EQCM) and ex situ SEM and FTIR analysis. The reduction of lepidocrocite occurs in all the electrolytes considered here. The initial reduction product is adsorbed ferrous ion, Feads2+. The desorption of Feads2+ is promoted as pH increases, leading to an increase of reduction depth. This promotion is related to the formation of secondary FeII-containing species, as revealed by SEM and FTIR. The comparison of ?-FeOOH reduction potentials and iron corrosion potentials let us state that the galvanic coupling is possible. Electrochimica Acta, Volume 51, Issue 4, 1 November 2005, Pages 745-753

Titre : Long term atmospheric corrosion mechanisms : characterization of ancient rust scales on archaeological iron artifacts	Année : 2005
Auteur(s) : Neff D. Reguer S. Dillmann Ph. Mirambet F. Bellot-Gurlet L. Antony H. Legrand L. Abstract : Non disponible Eurocorr

Titre : Etude du rapport FeII/FeIII dans les rouilles vertes carbonatée et sulfatée synthétisées par voie électrochimique	Année : 2005
Auteur(s) : Antony H. Rouchaud JC. Legrand L. Chassaing E. Chaussé A. Abstract : Non disponible JE

Titre : Etude du comportement électrochimique d’oxydes/hydroxydes de fer par microbalance à quartz	Année : 2005
Auteur(s) : Antony H. Legrand L. Chaussé A. Abstract : Non disponible JE

Titre : Impact de la protection cathodique sur l’activité corrosive de la flore sulfurogène	Année : 2004
Auteur(s) : Pineau S. Lefèvre Y. Dupont-Morral I. Abstract : Non disponible Matériaux et Techniques, spécial biodétérioration. N° 7-8-9 2004 p.38-43

Titre : Biofilm, biocorrosion and ALWC study in French port environment through in situ tests	Année : 2004
Auteur(s) : Pineau S. Marsset B. Bénard C. Martens L. Crouzillac J. Bénaïssa B. Abstract : Microbiologically Influenced Corrosion (MIC) of carbon steel construction is widely observed in port environment in tidal and immersion zone. In the case of low water zone of microorganisms in the Accelerated Low Water Corrosion (ALWC) phenomena the influence has been identified. Most French laboratories, industrials and ports cooperate in research programs to study the bacterial consortia of marine biofilm on carbon steel surface. This study is conducted in laboratory for the fundamental approaches, but the applied approach is conducted through in situ tests in port environment in Atlantic Ocean, English Channel and Mediterranean Sea. This experimental system is developed for investigations in tidal and low water zone, with and without cathodic protection (permanent, after pre-colonization, with failure simulation). The research objectives are: to develop analytic methods, to estimate the most dangerous biofilm consortia, to estimate some risk factors for corrosive metabolism, and to estimate a prevention plan for port authorities. Port and Terminal Technology – millennium conferences, Amsterdam

Titre : Inhibition of microbiologically influenced corrosion by cathodic protection in marine environment	Année : 2004
Auteur(s) : Pineau S. Braisaz T. Dupont-Morral I. Lefèvre Y. Abstract : Non disponible Eurocorr 2004, Nice

Titre : Microbially influenced corrosion : studies on Enterobacteria isolated from seawater environment and influence of toxic metals on bacterial biofilm and biocorrosion	Année : 2004
Auteur(s) : Bermond-Tilly D. Janvier M. Pineau S. Dupont-Morral I. Grimont PAD. Abstract : Non disponible Eurocorr 2004, Nice

Titre : Thin layers of iron corrosion products electrochemically deposited on inert substrates: synthesis and behaviour	Année : 2004
Auteur(s) : Peulon S. Antony H. Legrand L. Chaussé A. Abstract : The deterioration of iron-based materials due to corrosion is a well-known problem. A variety of corrosion products can be formed depending on the species present in the medium (soil, water, etc.). Understanding the transformation pathways during the evolution of a corrosion layer is a hard challenge since it is difficult to clearly identify the contributions of each corrosion product. That is why the development of electrodes with only one iron corrosion product deposited as thin layers on inert substrates (gold, silver) presents many advantages to carry out electrochemical studies. In this way, the present paper reports successful electrochemical synthesis of thin layers deposited on inert substrates (gold, silver) of commonly occurring iron corrosion products as siderite, green rusts incorporating carbonate or sulphate anions, magnetite and goethite. The films are characterised by usual ex-situ techniques: FTIR, SEM, and XRD. The study of the electrochemical behaviour of thin films of green rust deposited on silver illustrates the potential application of such electrodes. Electrochimica Acta, Volume 49, Issues 17-18, 30 July 2004, Pages 2891-2899

Titre : Electrochemical synthesis of lepidocrocite thin films on gold substrate—EQCM, IRRAS, SEM and XRD study	Année : 2004
Auteur(s) : Antony H. Peulon S. Legrand L. Chaussé A. Abstract : Lepidocrocite thin films have been electrochemically synthesised on polycrystalline Au substrates following two ways, direct synthesis and synthesis via green rust (GR). The direct synthesis consists in oxidising Fe(II) species in a 0.4 M NaCl/0.02 M Met-Imidazole/0.01 M FeCl2 solution at pH 7.5. The synthesis via GR consists in converting a green rust thin film into lepidocrocite thin film by galvanostatic oxidation. The thin films have been characterised by means of electrochemical quartz crystal microbalance, scanning electron microscopy, X-ray diffraction and infrared reflection–absorption spectroscopy. Electrochimica Acta, Volume 50, Issue 4, 15 December 2004, Pages 1015-1021

Titre : Electrochemical study of lepidocrocite reduction and redox cycling for the mechanistic modelling of atmospheric corrosion	Année : 2004
Auteur(s) : Antony H. Maréchal L. Legrand L. Chaussé A. Perrin S. Dillmann Ph. Abstract : Non disponible Science and Technology series, Ed ANDRA, Proceedings of the 2nd International Workshop, Eurocorr, Nice, September 2004

Titre : Utilisation de la microbalance à quartz pour l’étude des HDL de type rouille verte	Année : 2004
Auteur(s) : Antony H. Chassaing E. Chaussé A. Legrand L. Abstract : Non disponible GFECI

Titre : Synthèse électrochimique de film mince de rouille verte carbonatée	Année : 2004
Auteur(s) : Antony H. Legrand L. Chaussé A. Abstract : Non disponible GFECI

Titre : Electrochemical study of lepidocrocite reduction and redox cycling for the mechanistic modelling of atmospheric corrosion	Année : 2004
Auteur(s) : Antony H. Maréchal L. Legrand L. Chaussé A. Perrin S. Dillmann Ph. Abstract : Non disponible Eurocorr

Titre : Applications of thin layers of iron oxidation products for corrosion studies	Année : 2004
Auteur(s) : Antony H. Legrand L. Peulon S. Lair V. Chaussé A. Abstract : Non disponible Eurocorr

Titre : Electrochemical reduction of ferric corrosion products and evaluation of galvanic coupling with iron	Année : 2004
Auteur(s) : Lair V. Auzeby C. Legrand L. Chaussé A. Abstract : Non disponible Eurocorr

Titre : Généralités sur la biocorrosion	Année : 2003
Auteur(s) : Dupont-Morral I. Pineau S. Abstract : Non disponible Techniques de l’Ingénieur

Titre : Interrelationship between cathodic protection and microbiologically influenced corrosion in marine environment: brief-review and prospects	Année : 2003
Auteur(s) : Pineau S. Dupont-Morral I. Braisaz T. Abstract : Cathodic protection is widely used to prevent corrosion of steel constructions exposed to seawater. This protection causes a calcareous deposit as well as a biofilm formation. The Sulphate-Reducing Bacteria (SRB) and Thiosulphate-Reducing Bacteria (TRB) are involved in the steel biodegradation phenomena in marine environment. The surface colonization by these species under cathodic protection are described particularly for the TRB and with immersion periods of over 30 days. After a brief-review, preliminary studies explain the first results of our investigation in natural seawater and carbon steel during 4 to 8 weeks experiment. We have made experiments with natural strains of SRB/TRB, with monoculture of Desulfovibrio halophilus (SRB) and Dethiosulfovibrio peptidovorans (TRB), with potential a Cathodic Protection (CP) of –900 mV/SCE and –1000 mV/SCE and without CP. These results seem indicate that the effects of CP on the sulphide-producing bacteria metabolism is the reduction of their corrosive activity. Harbour Congress Proceeding, Antwerpen-Belgium, March-April 2003. Proceedings p.169-178

Titre : Impact de la protection cathodique sur l’activité corrosive de la flore sulfurogène	Année : 2003
Auteur(s) : Pineau S. Lefèvre Y. Dupont-Morral I. Abstract : La protection cathodique (PC) de l’acier au carbone en milieu marin est connue pour son effet inhibiteur vis-à-vis de la colonisation des genres bactériens aérobies [1]. En revanche, il a été démontré qu’un potentiel compris entre -900 mV/ECS et -1000 mV/ECS (généralement appliqué en zones portuaires françaises) est sans effet limitant vis-à-vis de la colonisation de la flore anaérobie de type sulfurogène telles que les Bactéries Sulfato-Réductrices (BSR) et Thiosulfato-Réductrices (BTR) [2][3][4][5]. Lors d’essais en laboratoire, il a été démontré que la rupture du système de PC accélère les phénomènes de biodétérioration, alors que ceux-ci semblent inhibés en temps normal [3][6]. Par conséquent, la PC modifierait le métabolisme bactérien et/ou l’action du produit du métabolisme bactérien. Plusieurs hypothèses sont émises, notamment le rôle de l’hydrogénase et l’inhibition de l’action des sulfures. 6ème forum de biodétérioration des matériaux, La Rochelle, 23-24 octobre 2003

Titre : formation du biofilm marin : conséquences et perspectives	Année : 2003
Auteur(s) : Pineau S. Abstract : Non disponible Séminaire VALOMER, pôle technologique de Bidart (Biarritz). 3-4 octobre 2003

Titre : Electrochemical deposition of thin films of green rusts 1 and 2 on inert gold substrate	Année : 2003
Auteur(s) : Peulon S. Legrand L. Antony H. Chaussé A. Abstract : Green rusts are layered Fe(II)–Fe(III) hydroxy-salts that play an important role in iron corrosion, soil chemistry, and environmental engineering. Successful electrochemical depositions of thin layers of green rusts incorporating anions such as carbonate or chloride (GRs1) or sulphate (GR2) on gold substrate are presented. As far as we know, it is the first time that such synthesis has been reported. The thin layers of green rusts were characterized by ex situ methods such as XRD, SEM, EDS and FTIR. This new way of synthesis allowed us to get green rust particles with sizes significantly larger than those obtained from the ways reported until now. Electrochemistry Communications, Volume 5, Issue 3, March 2003, Pages 208-213

Titre : Synthèse électrochimique et applications de films minces de composés HDL et rouilles vertes	Année : 2003
Auteur(s) : Legrand L. Antony H. Peulon S. Chaussé A. Abstract : Non disponible GFECI

Titre : Transformations rédox et phénomènes de passivation d’hydroxydes doubles lamellaires de type rouilles vertes	Année : 2003
Auteur(s) : Legrand L. Antony H. Alhajji E. Peulon S. Chaussé A. Abstract : Non disponible GFECI

Titre : Behavior of thin layers of green rusts electrochemically deposited on iron and inert substrates	Année : 2003
Auteur(s) : Antony H. Legrand L. Chaussé A. Peulon S. Abstract : The corrosion of iron is a well-know problem in many domains like environment, nuclear, … Even if anticorrosion solutions exist, it is practically impossible to avoid the formation of oxidation products, especially in the case of long-time contact of iron with corrosive media. The formation and structure of corrosion layers are often very complex because a variety of corrosion products can be formed, depending essentially on the species present in the medium (soil, water, …). Understanding the transformation pathways that occur during the growth and evolution of a corrosion layer is a hard challenge since it is difficult to clearly identify the contributions of each corrosion product and the influence of the iron substrate. Moreover, intermediate compounds like green rusts [1] or amorphous ferric phases, are particularly reactive and could induce local modifications that can result from redox or adsorption reactions with species present in the corrosive media . That is why the studies on the behavior of an oxidation product formed alone dependently and independently of iron or another compound are very interesting for many applications. In this case, it is possible to get a better understanding of the transformation or the stability of the compound and the relationships with its local environment (oxidant or reductive media), with the presence of inhibiting species like silicate or phosphate ions, … Moreover the interactivity of the product can be studied when it is in contact with very redox-active species like chromate, actinides, ….[2]. In this way, we studied the electrochemical synthesis of thin layers of iron corrosion products on iron and inert substrates (Au, Pt). Common corrosion products (goethite, siderite, magnetite,…) could be formed following this way of synthesis, as well as some intermediate products such as green rusts (GR1 and GR2), amorphous ferric phases, … In the case of green rusts and as far as we know, it is the first time that the synthesis of such thin layers has been reported on an inert substrate. Studying the corrosion product as a thin layer on a conducting substrate has many advantages compared to a powder or a suspension : (i) the manipulation of samples and their treatment (rinsing, drying) is generally easier, (ii) electrochemical measurements can be directly performed and coupled to in-situ techniques such as electrochemical quartz microbalance (EQCM), micro- Raman spectroscopy, (iii) ex-situ analyses (SEM, XPS, IRRAS) are more easily operated even if the amount of product is low. This presentation will be particularly focussed on the synthesis of thin layers of green rusts incorporating anions such as carbonate or chloride (GRs1) or sulphate (GR2) on iron, platinum or gold substrates, and on their electrochemical behavior. These compounds belong to the layered double hydroxides (LDH) group and have the general formula FeII (1-x)FeIII x(OH)2].[x/nAn-,mH2O]. They are intermediate products that may play an important role during the building and evolution of corrosion layers. The influence of parameters like concentration, pH temperature or potential on the synthesis will be detailed, as well as the characterization of the films by means of usual techniques such as FTIR, XRD, SEM, EDS … Figure 1 gives the SEM image of a carbonate green rust layer, showing large well-crystallized particles. Figure 2 illustrates the kind of information that can be obtained from a voltammetric study performed with a carbonate green rust (GRc) layer in contact with a solution of hydrogenocarbonate. The GRc-into-Fe(III)* solid-state oxidation is revealed by the anodic peak ; two cathodic peaks are observed on the reverse scan due to the progressive transformation of Fe(III)* into Fe(III) [3]. Such electrochemical measurements give information on the behavior of green rusts and on the transformation pathways involving these species. ECS

Titre : Influence de la protection cathodique, d’acier immergé en milieu marin, sur la vitesse de colonisation de la flore sulfurogène	Année : 2002
Auteur(s) : Pineau S. Dupont-Morral I. Abstract : Non disponible Matériau & Technique, spécial biodétérioration N°9-10 2002, p.23-29

Titre : Interactions entre la germination du dépôt calcomagnésien et la croissance de Desulfovibrio halophilus et Dethiosulfovibrio peptidovorans à la surface d’un acier carbone sous protection cathodique	Année : 2002
Auteur(s) : Dupont-Morral I. Pineau S. Ribot A. Abstract : Non disponible Colloque Matériaux 2002, Tours, 21-25 oct

Titre : Influence de la protection cathodique, d’acier immergé en milieu marin, sur la vitesse de colonisation de la flore sulfurogène	Année : 2002
Auteur(s) : Pineau S. Dupont-Morral I. Abstract : Non disponible 5ème forum de biodétérioration des matériaux (CEFRACOR/CNRS), Dourdan, 23-24 mai 2002

Titre : role of microorganisms on the formation of calcareous deposit resulted of cathodic protection applied in marine environment	Année : 2002
Auteur(s) : Dupont-Morral I. Pineau S. Dagbert C. Godard C. Galland J. Scherrer P. Baril JC. Bénaïssa B. Abstract : Non disponible Forum CEFRACOR Cathodic protection and associated coatings, Aix en Provence

Titre : Ballast water research in the french harbours : the bacteria and phytoplanctonic threats	Année : 2002
Auteur(s) : Masson D. Courtois O. Pineau S. Masson N. Abstract : Non disponible 11th International Conference on Aquatic Invasive Species. March 2002, Washington

Titre : Effet biocide du Mexel 432/0 sur les bactéries sulfato-réductrices marines naturelles fixées	Année : 2000
Auteur(s) : Dupont-Morral I. Makaroff M. Pineau S. Poisson A. Abstract : Cette étude fait suite à celle réalisée précédemment sur ce sujet. Les conclusions de cette dernière mettaient en évidence un bon pouvoir biocide et inhibiteur de la fixation des bactéries du Mexel 432/0. Mais cet effet ne durait pas dans le temps du fait d’un traitement unique. L’essai présenté a pour principal but le test d’un traitement appliqué périodiquement. L’étude est décomposée en deux étapes distinctes : - influence du pouvoir biocide du Mexel 432/0 sur les bactéries sulfato-réductrices (BSR) déjà fixées sur le matériau. Cette étape a pour objectif de mimer l’effet biocide du Mexel 432/0 sur un circuit d’eau de mer naturelle déjà contaminé par cette flore, - influence du Mexel 432/0 sur la fixation des BSR. Contrairement à l’étape précédente, l’étape 2 a pour objectif d’étudier la capacité du Mexel 432/0 à empêcher la colonisation d’un matériau “propre” par les BSR. Forum CEFRACOR biodétérioration des matériaux, Toulouse