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Use of the 34S/32S isotopic ratio for the study of the bioorigin of the sulfur phases located in the corrosion product layer of iron or low alloy-steel samples corroded in anoxic conditions

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HAL Id: cea-02332799

https://hal-cea.archives-ouvertes.fr/cea-02332799

Submitted on 25 Oct 2019

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Use of the 34S/32S isotopic ratio for the study of the

bioorigin of the sulfur phases located in the corrosion

product layer of iron or low alloy-steel samples corroded

in anoxic conditions

Sophie Grousset, Alexandre Dauzères, Didier Crusset, Valérie Deydier,

Yannick Linard, Laurent Urios, Smail Mostefaoui, Nicolas Nuns, Muriel

Bouttemy, Arnaud Etcheberry, et al.

To cite this version:

Sophie Grousset, Alexandre Dauzères, Didier Crusset, Valérie Deydier, Yannick Linard, et al.. Use of the 34S/32S isotopic ratio for the study of the bioorigin of the sulfur phases located in the corrosion product layer of iron or low alloy-steel samples corroded in anoxic conditions. Eurocorr 2016, Sep 2016, Montpellier, France. �cea-02332799�

(2)

Use of the 34S

P

2S isotopie ratio for the study of the bioorigin of the sulfur phases located in the corrosion product layer of iron or low alloy-steel samples corroded in anoxie

conditions

Sophie GROUSSETI,2,3, Alexandre DAUZERES2 Didier CRUSSET3, Valérie DEYDIER3,

Yanruck LINARD3, Laurent URJOS4

, SmaiI MOSTEFAOUI5, Nicolas NUNS6, Muriel BOUITEMy7 Amaud ETCHEBERRy7, Philippe DILLMANNl, Florence MERCIER-

BIONl, Delphine NEFFl

l NIMBE/LAPA, CENCNRS. UMRJ685, CEA Saclay, 91 191 GifsurYvctte, France

2lRSN, PRP-DGElSRTG/Lm S, B.1'.17. 92262 Fontenay-aux-Roses, France

l ANDRA Direction de la recherche ct développement, 1-7 Ille Jean Monnet, 92298 Châtenay-Malabry, France 'IPREM-EEM, UMR 5254, Université de Pau el dt!S Pays de l'Adour, 64013 Pau Cedex, France

j lMPMC-COSMO, Museum National d'Histoire Naturelle, 75231 Paris Cedex OS, France 6lJlstÏlut M.E, Chevreul. Université de Lille, CNRS, 59650 Villeneuve d' Ascq Cedex, France 'ILV, In.stitut Lavoisier de Versailles UMR CNRS-UVSQ 8180. 78000 Versailles, France

The presence ofSulfate-Reducing Bacteria (SRB) may influence the corrosion rate offerrous objects by inducing iron sulfides precipitation [1]. The same phases are formed by biotic or abiotic ways. An analytic method for detecting bacterial interventions in corrosion pro cesses is required. Yet, biotic iron sulfides are supposed to be depleted in heavy isotopes of sulfur relative to the starting sulfate [2].

The aim ofthis study is to set-up a methodology based on 34S/32S isotopic ratio determination to evidence the origin of sulfides in the corrosion product layers of "long term systems":

ferrous archaeological samples studied as analogues oflong-term corrosion of nuclear waste package and steel samples issued from anoxic corrosion experiments in contact with

claystone. In paraUel "model systems", iron coupons corroded in anaerobiosis with or without SRB, are studied to compare the sulfur isotopic fractionation resulting from a bacterial or an inorganic sulfide source.

Complementary techniques were used to characterize the sulfur-bearing compounds in the samples: FESEM-EDS for their distribution, I-l-Raman and nano-Auger spectroscopy for the nature of phases. Then, the 34S/32S isotopic ratio was detennÏned by NanoSIM.S and compared to the one of the sulfates from the surrounding solution. As a result, d34Ssultàte_sulfide reaches values of ~ 10 %0 to ~60 %0.

[1] H.A. Videla and al., Int. Biodeterior. Biodegrad. 63 (2009) 896-900.

[2] M.S. Sim and al., Science. 333 (2011) 74-77.

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