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Platinum Biogeochemical Cycles in Coastal Environments Melina Abdou

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Platinum Biogeochemical Cycles in Coastal Environments Melina Abdou Platinum biogeochemical cycles in coastal environments Melina Abdou To cite this version: Melina Abdou. Platinum biogeochemical cycles in coastal environments. Ecotoxicology. Université de Bordeaux, 2018. English. NNT : 2018BORD0068. tel-01968069 HAL Id: tel-01968069 https://tel.archives-ouvertes.fr/tel-01968069 Submitted on 2 Jan 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THÈSE Présentée à L’UNIVERSITE DE BORDEAUX ECOLE DOCTORALE SCIENCES ET ENVIRONNEMENTS Par Mélina ABDOU POUR OBTENIR LE GRADE DE DOCTEUR Label de Doctorat Européen SPÉCIALITÉ: Géochimie et Écotoxicologie Cycles biogéochimiques du platine dans les environnements côtiers Sous la direction de Pr. Jörg SCHÄFER et la co-direction de Pr. Gérard BLANC Soutenue le 24 Mai 2018 Devant la commission d’examen formée de M. Miguel Caetano, Directeur de recherche, IPMA, Lisbonne, Portugal Rapporteur M. Sébastien Rauch, Professeur, Université de Chalmers, Göteborg, Suède Rapporteur M. Antonio Cobelo-García, Directeur de Recherche, IIM-CSIC, Vigo, Espagne Examinateur M. Thierry Corrège, Professeur, Université Bordeaux Président M. Jörg Schäfer, Professeur, Université Bordeaux Directeur M. Gérard Blanc, Professeur, Université Bordeaux Co-Directeur Mme Mary-Lou Tercier-Waeber, Ingénieur de recherche, Genève, Suisse Invitée - 2018 – Biogeochemical platinum cycles in coastal environments Platinum (Pt) is a Technology-Critical Element (TCE) and an emerging contaminant increasingly released into all Earth compartments, but its environmental occurrence, distribution, and dynamics are under- documented. The present research combines laboratory observations and field monitoring studies on Pt biogeochemistry in coastal systems (Atlantic Ocean and northwestern Mediterranean Sea), including its distribution between seawater, particles, and living organisms. Exposure experiments with oysters facing a wide range of exposure levels provide the first Pt accumulation kinetics in marine bivalves, supporting uptake of Pt from seawater in line with field observations. At environmentally- relevant Pt levels (50 and 100 ng.L -1 ), the positive linear relation between exposure and Pt accumulation in tissues justifies the use of oysters as integrative sentinels for seawater Pt contamination. At relatively high Pt levels (10,000 ng.L -1 ), deleterious physiological effects (e.g. increased oxidative stress and energetic stock mobilization) occurred in oysters. Field observations at contrasting sites have provided regional background Pt concentrations in seawater in the Atlantic and Mediterranean coasts (0.05 ng.L -1 and 0.08 ng.L -1 , respectively) and bioconcentration factors for phytoplankton (~ 10 4), and bivalves (oysters and mussels ~ 10 3). Spatial distribution of Pt levels in seawater, plankton and bivalves suggest higher contamination along the northwestern Mediterranean coast, especially in semi- enclosed, industrialized/urbanized systems (Toulon Bay and Genoa Harbor). Historical records in sediments (~ 1900 - 2010) and bivalves (1980 to present) from the Gironde watershed and the Toulon Bay showed past Pt contamination due to industrial (metallurgic, oil-refining, coal) activities, whereas the strong recent increase in Pt contamination originates from emerging Pt sources, e.g. car catalytic converters, hospital effluents, and sewage. High temporal resolution observation of Pt partitioning, together with environmental master variables (O 2, Salinity, Chl-a, nutrients etc.), suggests that in coastal systems, biogeochemical processes including phytoplankton production and degradation may play an important role in Pt behavior and fate. Keywords: Platinum, seawater, particles, bivalves, accumulation, distribution, contamination Cycles biogéochimiques du platine dans les environnements côtiers Le platine (Pt) est un élément technologique critique (ETC) et un contaminant émergent dans les compartiments environnementaux. Peu de données existent concernant ses concentrations, sa distribution et sa dynamique dans le milieu naturel. Ce travail combine des résultats d'expérimentation en laboratoire à des observations de terrain afin d'étudier la biogéochimie de Pt dans les systèmes côtiers (Océan Atlantique et Méditerranée). Une expérimentation exposant des huîtres à une large gamme de concentrations de Pt a produit les premières données de cinétique d’accumulation de Pt dans les bivalves marins et reflète l’assimilation de Pt constatée in situ . À des niveaux d’expositions réalistes (50 et 100 ng.L -1 ), la relation linéaire positive entre les niveaux d'exposition et celles des tissus justifie l'utilisation des huîtres comme sentinelles des niveaux de Pt dans l’eau de mer. À forts niveaux de Pt (10 000 ng.L -1 ), des effets délétères sur l’état physiologique des huîtres (e.g. augmentation du stress oxydatif et mobilisation du stock énergétique) sont observés. A partir d’études de terrain dans des sites contrastés les bruits de fond géochimiques régionaux dans l’eau de mer des côtes atlantique et méditerranéenne (0,05 ng.L -1 et 0,08 ng.L -1 respectivement) et les facteurs de bioconcentration dans le phytoplancton (~ 10 4) et dans les bivalves (huîtres et moules, ~ 10 3) ont été établis. La répartition spatiale des niveaux de Pt dans l’eau de mer, le plancton et les bivalves reflète une contamination plus élevée de la côte nord-ouest méditerranéenne, particulièrement dans les zones semi-fermées et fortement urbanisées / industrialisées (baie de Toulon et port de Gênes). Les enregistrements historiques dans les sédiments (~ 1900 - 2010) et dans les bivalves (1980 à aujourd’hui) en Gironde et dans la baie de Toulon ont montré une contamination ancienne de Pt liée aux activités industrielles (métallurgie, raffinage du pétrole, charbon), tandis que la forte augmentation récente provient de sources émergentes telles que les pots catalytiques, les rejets hospitaliers et les eaux usées. L’observation à haute résolution temporelle de la distribution de Pt entre la phase dissoute et particulaire et des paramètres environnementaux majeurs (O 2, salinité, Chl-a, nutriments etc.), suggèrent l’importance des processus biogéochimiques, comprenant la production et dégradation du phytoplancton, dans le comportement et le devenir du Pt en milieu côtier. Mots clés : Platine, eau de mer, particules, bivalves, accumulation, distribution, contamination This work was funded by the EU FP7 Ocean 2013.2 Project SCHeMA (Project-Grant Agreement 614002). This work has also greatly benefited from the support by the FEDER Aquitaine-1999-Z0061, the COST Action TD1407 and the University of Bordeaux IdEx mobility grant which is gratefully acknowledged. This work has benefited from the sample banks of (i) RNO/ROCCH Ifremer for which Jean- François Chiffoleau, Dominique Auger and Christophe Brach-Papa are greatly acknowledged, (ii) IRSN for which Sabine Charmasson and Franck Ginier are greatly acknowledged, (iii) PROTEE (CARTOCHIM Project) for which Cédric Garnier is particularly acknowledged. Remerciements / Acknowledgments I would like to greatly acknowledge Dr Miguel Caetano and Dr Sebastien Rauch for accepting to review the present work. Merci aux autres membres du jury, particulièrement à Thierry Corrège pour avoir accepté de le présider. Merci à mon directeur de thèse et mentor, Jörg Schäfer. Je te remercie pour m’avoir donné l’opportunité d’intégrer l’équipe, pour m’avoir fait contribuer à des opportunités uniques durant la thèse: partir en conférence à l’étranger, collaborer avec des partenaires internationaux, participer à de nombreuses campagnes de terrain... Merci pour m’avoir appris toutes ces précieuses connaissances et pour m’avoir soutenue durant ces années. Merci pour avoir suscité, dans mon travail et au quotidien, rigueur et exigence, j’espère avoir fourni un travail à la hauteur. J’espère également que ce n’est qu’une étape d’une plus longue collaboration. Je remercie mon co-directeur de thèse Gérard Blanc. Vous m’avez permis d’intégrer l’équipe et avez été présent lorsque j’en avais besoin. Merci pour vos conseils et pour nos échanges tant scientifiques que sur tout autre sujet. Je remercie chaleureusement Alexandra Coynel. Merci également pour m’avoir pleinement intégrée dans l’équipe. Mais par-dessus tout, merci d’avoir pris soin du bon déroulement de ma thèse, en particulier sur le plan technique. Tu as fait en sorte que je puisse mener à bien mes expérimentations et terminer sereinement ma thèse. J’ai pleine conscience du dévouement dont tu as fait preuve pour nous préserver des soucis rencontrés récemment et t’en remercie mille fois. Merci à Lionel Dutruch. Lionel tu m’a aussi très vite permis de faire partie de l’équipe. Je te remercie pour beaucoup de raisons mais si il fallait en garder deux: je te remercie pour m’avoir aidé dans toutes mes manips de laboratoire et avoir répondu à toutes mes questions, et je te remercie pour avoir fait toujours preuve d’un chaleureux accueil lors de mes nombreuses sollicitations. Je remercie Cécile Bossy. Cécile, en premier lieu, c’est pour ta bienveillance que je t’exprime
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