Understanding the impact of silver as an emerging contaminant in the Ibaizabal and Gironde estuaries Ane Rementeria Ugalde To cite this version: Ane Rementeria Ugalde. Understanding the impact of silver as an emerging contaminant in the Ibaizabal and Gironde estuaries. Geochemistry. Université de Bordeaux, 2016. English. NNT : 2016BORD0443. tel-01552293 HAL Id: tel-01552293 https://tel.archives-ouvertes.fr/tel-01552293 Submitted on 2 Jul 2017 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 EN COTUTELLE PRÉSENTÉE POUR OBTENIR LE GRADE DE DOCTEUR DE L’UNIVERSITÉ DE BORDEAUX ET DE L’UNIVERSITÉ DU PAYS BASQUE ÉCOLE DOCTORALE SCIENCES et ENVIRONNEMENTS ÉCOLE DOCTORALE DE L’UNIVERSITÉ DU PAYS BASQUE SPÉCIALITÉ GÉOCHIMIE et ÉCOTOXICOLOGIE Par Ane REMENTERIA UGALDE UNDERSTANDING THE IMPACT OF SILVER AS AN EMERGING CONTAMINANT IN THE IBAIZABAL AND GIRONDE ESTUARIES Sous la direction de Pr. Jörg SCHÄFER (Université de Bordeaux) et de PhD. Beñat ZALDIBAR (Université du Pays Basque) Soutenue le 16-12-2016 Membres du jury : M.SOTO LOPEZ, Manu Universidad del País Vasco Président M. HYLLAND, Ketil Universitetet i Oslo Rapporteur Mme. KALOYIANNI, Martha Aristotle University of Thessaloniki Rapporteur Mme. GORBI, Stefania Università Politecnica delle Marche Examinateur Mme. COYNEL, Alexandra Université de Bordeaux Examinateur Mme. TORREBLANCA TAMARIT, Amparo Universitat de València Examinateur Mme/M. ZORITA AGUIRRE, Izaskun Azti Tecnalia Examinateur Titre : COMPRÉHENSION DE L’IMPACT DE L’ARGENT COMME CONTAMINANT ÉMERGENT DANS LES ESTUAIRES D’IBAIZABAL ET DE LA GIRONDE Résumé : Les estuaires ont été soumis à une forte pression humaine qui a entraîné la présence de polluants dans leurs eaux et sédiments, par exemple les métaux traces. Les estuaires du Golfe de Gascogne n’en sont pas une exception et les estuaires d’Ibaizabal et de la Gironde sont bien connus pour avoir des concentrations élevées de métaux. Dans ce contexte, les programmes de surveillance de l’environnement se sont appuyés sur l’utilisation des moules et des huîtres comme espèces sentinelles, car les analyses chimiques et biologiques de leurs tissus permettent d’évaluer l’état général de santé de leur environnement. Dans le but d’acquérir une meilleure compréhension des interactions entre la bioaccumulation et des effets toxiques du cuivre (Cu) et de l’argent (Ag) dans les huîtres Crassostrea gigas , ainsi que l’influence de facteurs environnementaux, le présent travail présente une étude de terrain et trois expériences de laboratoire. Parmi les résultats obtenus, on peut souligner que : (I) même si les huîtres et les moules peuvent indiquer correctement l’état de santé des estuaires du Golfe de Gascogne, une accumulation clairement plus élevée de métaux se produit dans les huîtres que dans les moules, (II) la voie d’exposition (directe ou alimentaire) induit des réponses de différentes intensités dans les huîtres, (iii) la toxicité de l’Ag est renforcée par la présence accrue de Cu dans les huîtres et (IV) la salinité a un faible effet sur la toxicité des métaux dans les huîtres. Mots clés : Huîtres, estuaires, argent, cuivre, biomarqueurs Title: UNDERSTANDING THE IMPACT OF SILVER AS AN EMERGING CONTAMINANT IN THE IBAIZABAL AND GIRONDE ESTUARIES Abstract: Estuaries have been subjected to a high human pressure which has led to the presence of pollutants in their waters and sediments including trace metals. The estuaries in the Bay of Biscay do not constitute an exception of this situation and the Ibaizabal and Gironde Estuaries are both very well known for having high metal concentrations in different compartments. In this context, environmental health monitoring programmes have relied on the use of mussels and oysters as sentinel organisms because chemical and biological analyses of their tissues allow assessing the general health status of their surrounding environment. The present work aims at acquiring a deeper understanding of the interactions between bioaccumulation and the toxic effects of copper (Cu) and silver (Ag) in oysters Crassostrea gigas , as well as the effects that environmental factors may have on them, For this, one field study and three laboratory experiments have been carried out. Among the most relevant results obtained it can be highlighted that: (I) both oysters and mussels are useful to properly indicate the health status of estuaries of the Bay of Biscay, yet higher accumulation of metals occurs in oysters than in mussels, (II) the intake pathway (water column and/or food) induces different response intensities in oysters (III) the toxicity of Ag is enhanced in the presence of Cu in oysters and (IV) salinity has a low effect on the toxicity of both metals in oysters. Keywords: Oysters, estuaries, silver, copper, biomarkers Unité de recherche TGM Research Group, UMR 5805 EPOC, Environnements et Paléoenvironnements Océaniques et Continentaux, Université de Bordeaux CBET Research Group, Dept. Zoology and Animal Cell Biology. Sci and Technol Fac and Research Centre for Experimental Marine Biology and Biotechnology (PiE, University of the Basque Country) FUNDING The University of the Basque Country (UPV/EHU) through the grant for performing the PhD thesis in cotutelle between the University of the Basque Country (UPV/EHU) and the University of Bordeaux. Basque Government through a grant to the Consolidated Research Group “Cell Biology in Environmental Toxicology” (GIC07/26-IT-393-07, 2007-2012 and GIC12/149-IT-810-13, 2013-2018). University of the Basque Country by means of a grant to the Unit Formation and Research “Ecosystem Health Protection” (UFI11/37, 2011-2014). Spanish Government through a research project CTM2012-40203-C02-01 (MINECO). La Région Aquitaine, and the FEDER Aquitaine for financial support for analytical equipment. ACKNOWLEDGMENTS I wish to thank, ° Prof. Jörg Schäfer and Dr. Beñat Zaldibar my PhD supervisors for giving me the chance to carry out this thesis work. For their effort, advices and help. ° Prof. Ionan Marigómez and Prof. Manu Soto director and deputy director of PiE for gently admitting me in the Plentzia Marine Station (PiE) and allowed me to perform the experimentations. ° Prof. Miren Cajaraville, head of Cell Biology in Environmental Toxicology (CBET) research group, UPV/EHU, for giving the opportunity of joining her team. EXTENDED ABSTRACT Estuarine environments have provided humans food sources and the capacity to exchange goods with the rest of the world through navigation since ancient times. In consequence, many historical main human settlements have occurred around estuaries, leading to their degradation by the modification of their natural functioning and also by increased pollutant inputs due to various anthropogenic sources. In the last centuries, estuaries have become major sites for waste disposal and European estuaries are not an exception. Nowadays, many European estuaries show recovery processes mainly as a result of the general decline on industrial activities and the increased environmental awareness of the society, which has led to the implementation of new policies and regulations. Within the Bay of Biscay two estuaries could be considered as good examples of these recovery processes: the Ibaizabal (Bilbao, Basque Country, Spain) and the Gironde (South-Western France) Estuaries. Despite all the improvements that both estuaries have undergone, pollutant concentrations are still relevant in their waters and sediments. Among the pollutants present in the mentioned compartments (water and sediments), metallic pollution is of special relevance for the scientific community and environmental managers. In fact, metals can exert toxicity effects on aquatic biota at very low exposure levels and they can bioaccumulate or biomagnify through the food chain, potentially affecting both aquatic environmental and human health. Among the different metals showing anomalies in estuaries silver (Ag) and copper (Cu) are of special interest. Silver is regarded as a very toxic element for aquatic biota, particularly in its ionic form Ag +, whereas Cu, is an essential element for living organisms but also toxic once certain exposure levels have been surpassed. These two elements have been extensively used by humans since ancient periods and nowadays they share to some extent similar pollution sources. Mining and metallurgy have been the classical pollution sources for Ag whereas more recently (during the last decades of the XX th century) main Ag inputs have been related to photographic and electronic industries and also to Ag uses in hospitals. In fact, Ag has been considered as a good tracer for urban pollution during several decades. Nowadays, additional Ag inputs into the environment also originate from domestic and urban wastewaters, being increasingly related with the use of Ag nanoparticles in textiles and personal care products due to the bactericidal properties of Ag. Furthermore, Ag-iodide (AgI) is also used in agriculture to prevent hail storms through networks of cloud seeding devices. In the case of Cu, classical