hydrological characteristics) (Zhang et al., 1996; Doherty et al., 2000; Karouna-Renier and Sparling, 2001; Yuan et al., 2001; Rothwell et al., 2010).
Source, distribution and dispersion pattern characterization of heavy metals and PAHs in sediments of the estuaries and continental shelf of the Basque Autonomous Region (southeastern Bay of Biscay).
Irati Legorburu Artola PhD Thesis, 2014
DEPARTMENT OF APPLIED CHEMISTRY. UNIVERSITY OF THE BASQUE COUNTRY.
AUTORIZACION DEL DIRECTOR DE TESIS PARA SU PRESENTACION
Dr. Ibon Galparsoro Iza con N.I.F. 34104032T como Director de la Tesis Doctoral: “Source, distribution and dispersion pattern characterization of heavy metals and PAHs in sediments of the estuaries and continental shelf of the Basque Autonomous Region (southeastern Bay of Biscay)” realizada en el Departamento de Química Aplicada por la Doctoranda Doña Irati Legorburu Artola, autorizo la presentación de la citada Tesis Doctoral, dado que reúne las condiciones necesarias para su defensa.
En Pasaia a 24 de Junio de 2014
EL DIRECTOR DE LA TESIS
Fdo.: Ibon Galparsoro Iza
AUTORIZACION DE LA DIRECTORA DE TESIS PARA SU PRESENTACION
Dra. Joana Larreta Astola con N.I.F. 78884542Q como Directora de la Tesis Doctoral: “Source, distribution and dispersion pattern characterization of heavy metals and PAHs in sediments of the estuaries and continental shelf of the Basque Autonomous Region (southeastern Bay of Biscay)” realizada en el Departamento de Química Aplicada por la Doctoranda Doña Irati Legorburu Artola, autorizo la presentación de la citada Tesis Doctoral, dado que reúne las condiciones necesarias para su defensa.
En Pasaia a 24 de Junio de 2014
LA DIRECTORA DE LA TESIS
Fdo. Joana Larreta Astola
AUTORIZACION DE LA PONENTE DE TESIS PARA SU PRESENTACION
Dra. Esmeralda Millán Martín como Ponente de la Tesis Doctoral: “Source, distribution and dispersion pattern characterization of heavy metals and PAHs in sediments of the estuaries and continental shelf of the Basque Autonomous Region (southeastern Bay of Biscay)” realizada en el Departamento de Química Aplicada por la Doctoranda Doña Irati Legorburu Artola, y dirigida por el Dr. Ibon Galparsoro Iza y la Dra. Joana Larreta Astola autorizo la presentación de la citada Tesis Doctoral, dado que reúne las condiciones necesarias para su defensa.
En Donostia a
de
de 2014
LA PONENTE DE LA TESIS
Fdo. Esmeralda Millán Martín
CONFORMIDAD DEL DEPARTAMENTO
El Consejo del Departamento de Química Aplicada, en reunión celebrada el día
de
de 2014 ha acordado dar la
conformidad a la admisión a trámite de presentación de la Tesis Doctoral titulada: “Source, distribution and dispersion pattern characterization of heavy metals and PAHs in sediments of the estuaries and continental shelf of the Basque Autonomous Region (southeastern Bay of Biscay)” dirigida por el Dr. Ibon Galparsoro Iza y la Dra. Joana Larreta Astola y presentada por Doña Irati Legorburu Artola ante este Departamento. En Donostia a
de
de 2014
Vº Bº DIRECTORA DEL DEPARTAMENTO
SECRETARIO DEL DEPARTAMENTO
Fdo. Rosa García Arrona
Fdo. Jose Manuel Seco Botana
ACTA DE GRADO DE DOCTOR O DOCTORA ACTA DE DEFENSA DE TESIS DOCTORAL DOCTORANDA DOÑA Irati Legorburu Artola. TITULO DE LA TESIS: “Source, distribution and dispersion pattern characterization of heavy metals and PAHs in sediments of the estuaries and continental shelf of the Basque Autonomous Region (southeastern Bay of Biscay)”. El Tribunal designado por la Comisión de Postgrado de la UPV/EHU para calificar la Tesis Doctoral arriba indicada y reunido en el día de la fecha, una vez efectuada la defensa por el/la doctorando/a y contestadas las objeciones y/o sugerencias que se le han formulado, ha otorgado por___________________la calificación de: unanimidad ó mayoría
SOBRESALIENTE / NOTABLE / APROBADO / NO APTO Idioma/s de defensa (en caso de más de un idioma, especificar porcentaje defendido en cada idioma): ______________________________________________________
En
a
de
de 2014
EL/LA PRESIDENTE/A,
EL/LA SECRETARIO/A,
Fdo.:
Fdo.:
Dr/a: ____________________
Dr/a:______________________
VOCAL 1º,
VOCAL 2º,
VOCAL 3º,
Fdo.:
Fdo.:
Fdo.:
Dr/a:
Dr/a:
Dr/a:
LA DOCTORANDA, Fdo. Irati Legorburu Artola.
PhD Thesis
Source, distribution and dispersion pattern characterization of heavy metals and PAHs in sediments of the estuaries and continental shelf of the Basque Autonomous Region (southeastern Bay of Biscay).
Presented by Irati Legorburu
Thesis supervisors Dr. Ibon Galparsoro Dr. Joana Larreta
Department of Applied Chemistry Year 2014
Zapatak erantzi ditut, lokarriak askatuz, oinutsik belarraren laztanak nabaritu nahi ditudalako, nire azalean. Egurraren beroa, harriaren hotza. Oinutsik-Kashbad
Eskerrik asko! Lehenik eta behin Tesi honetan zuzendari moduan jardun diren Ibon Galparsoro eta Joana Larretari eskerrak eman nahi nizkieke beren aholku eta laguntzagatik. Eskerrak zuri bereziki, Ibon, hasi nintzen lehenengo egunetik emandako laguntza eta irakatsitako guztiagatik. Germán, Luis y Ángel, gracias por vuestra gran ayuda y consejos, sin ellos esta Tesis no habría sido posible. A Victor, porque las conversaciones que hemos tenido (incluyendo alguna master class), siempre me han dado que pensar y ayudado a ver las cosas desde puntos de vista diferentes. Oihana, edozein duda edo zeozer behar izan dudanean beti aurpegi onez erantzuteagatik (animo, zuri ere gutxi falta zaizu eta!). Urteetan zehar laginak hartzen eta analizatzen ibili den jende guztiari, zuen lanarengatik ez balitz, nik ezingo bainuen nerea aurrera atera. Esmeralda, gracias por tu ayuda y facilitarnos todos los trámites. Tesi hau burutzeko datuak edota finantzaketa ahalbidetu dituzten erakunde eta proiektuei: Iñaki Goenaga - Zentru Teknologikoen Fundazioa (IG-ZTF); AZTITecnalia; Uraren Euskal Agentzia; Eusko Jaurlaritzako Ingurumen, Lurralde Plangintza, Nekazaritza eta Arrantza Saila; Gipuzkoako Foru Aldundia; Añarbeko Urak S.A; Eusko Jaurlaritzako Portu Zuzendaritza; European MESMA project (Monitoring and Evaluation of Spatially Managed Areas: 7th Framework Programme, Grant Agreement no: 226661); MESHAtlantic project (Mapping European Seabed Habitats for a Better Marine Management in the Atlantic Area. Atlantic Area Transnational Cooperation Programme 2007-2013 of the European Regional Development Fund). Urte guzti hauetan bekadun gelan eta hortik kanpo inguruan izan ditudanei ere eskerrak eman nahi dizkiet. Naro, Nerea G., Mari eta Manel, hasi nintzenean lekutan ikusten zen zuek zineten puntua, baina azkenean iritsi da!!! Denbora luzean lagun izan ditudan Albitsu, Stefani, Johnny, Nerea L., Iker, Maitane, Kat, Nagore C., Iñaki, Urangius, Jorge, Carlos, Lohitzune, Nekane, Aizko, Mireia, Eva… Nola ez, Berregi, Mikel, Deniz, Xiker, Julien, Luis, Irene, Marivi eta Naiara, segi horren jator! Baina bereziki, Nat (eskerrak “pack”-ean joan garen…), Marta, Maialen, Ganix eta Eneko (nere hilehori gogokoenak!), Irati, Imanol eta Nagore Z., kantuak dioen
bezela, “zuentzat ere nire begirunea, besarkada beroena”: egunero hor egoteagatik; hain lagun onak izateagatik; pasatako momentu on, haserrealdi eta eroaldiengatik; elkarrekin egindako barre, mimimi, bidai, “pato jan”, dantza eta tontakeri guztiengatik; katana zorroztuta mantentzen laguntzeagatik (baita gordetzen ere)… ESKERRIK ASKO! Ama, aita, Oihana, Mikel eta osaba-izebei, batzutan ni aguantatzea errexa izan ez den arren, nekatuta eta urduri ikusi nauzuenean emandako animoengatik. Zuetako batzuk ia nik adina sufritu duzue Tesi hau, baina lixto, bukatu da! Kuadrilako lagunei, nerekin izandako pazientziagatik (Mol, Berro, nahi dezutenian mariskada!). Nere “euskaltzain” partikularrei: zalantza non? Ima eta Borja, han! Ziurrenik lerro hauetan norbait aipatzea ahaztu zaidan arren, ESKERRIK ASKO DENOI!
Publications The results from different works carried out during the development of this Thesis have led to a series of publications in different peer-reviewed journals. Some of them represent the main core of the present Thesis; others have served to give context to the followed lines of work. A number of them have already been published and others are submitted for publication. They are listed below in chronological order: Galparsoro, I., Liria, P., Legorburu, I., Ruiz-Minguela, P., Pérez, G., Marqúes, J., Torre-Enciso, Y., González, M., 2008. Atlas de energía del oleaje en la costa vasca. La planificación espacial marina como herramienta en la selección de zonas adecuadas para la instalación de captadores. Revista de Investigación Marina 8, 11. Galparsoro, I., Borja, A., Legorburu, I., Hernández, C., Chust, G., Liria, P., Uriarte, A., 2010. Morphological characteristics of the Basque continental shelf (Bay of Biscay, northern Spain); their implications for Integrated Coastal Zone Management. Geomorphology 118 (3-4), 314-329. Pascual, M., Borja, A., Vanden Eede, S., Deneudt, K., Vincx, M., Galparsoro, I., Legorburu, I., 2011. Marine biological valuation mapping of the Basque continental shelf (Bay of Biscay), within the context of marine spatial planning. Estuarine, Coastal and Shelf Science 95 (1), 186-198. Galparsoro, I., Liria, P., Legorburu, I., Bald, J., Chust, G., Ruiz-Minguela, P., Pérez, G., Marqúes, J., Torre-Enciso, Y., González, M., Borja, A., 2012. A marine spatial planning approach to select suitable areas for installing wave energy converters on the Basque continental shelf (Bay of Biscay). Coastal Management 40, 1-19. Galparsoro, I., Borja, A., Rodríguez, J. G., Muxika, I., Pascual, M., Legorburu, I., 2012. Rocky reef and sedimentary habitats within the continental shelf of the southeastern Bay of Biscay. In: Harris, P. T., Baker, E. K. (Eds.), Insights into Seafloor Geomorphology as Benthic Habitat: GeoHAB Atlas of Seafloor Geomorphic Features and Benthic Habitats. Elsevier, pp. 493-507.
Legorburu, I., Rodríguez, J. G., Borja, Á., Menchaca, I., Solaun, O., Valencia, V., Galparsoro, I., Larreta, J., 2013. Source characterization and spatio-temporal evolution of the metal pollution in the sediments of the Basque estuaries (Bay of Biscay). Marine Pollution Bulletin 66 (1-2), 25-38. Legorburu, I., Galparsoro, I., Larreta, J., Rodríguez, J. G., Borja, A., 2013. Spatial distribution of metal accumulation areas in the continental shelf of the Basque Country (Bay of Biscay): A GIS-based approach. Estuarine, Coastal and Shelf Science 134, 162-173. Legorburu, I., Rodríguez, J. G., Valencia, V., Solaun, O., Borja, A., Millán, E., Galparsoro, I., Larreta, J., 2014. Source and spatial distribution of polycyclic aromatic hydrocarbons in coastal sediments of the Basque Country (Bay of Biscay). Chemistry and Ecology, doi: 10.1080/02757540.2014.894990. Legorburu, I., Ferrer, L., Galparsoro, I., Larreta., J., submitted. Distribution of riverborne particulate Pb in the Basque continental shelf (Bay of Biscay). Environmental Earth Sciences. Solaun, O., Rodríguez, J. G., Borja, A., Larreta, J., Legorburu, I., Valencia, V., In Preparation. Source characterization, and mid-term spatial and temporal distribution of polycyclic aromatic hydrocarbons in molluscs along the Basque coast (northern Spain).
Contents Figure list .......................................................................................................................... 1 Table list ........................................................................................................................... 7 Acronyms ......................................................................................................................... 9 Laburpena ....................................................................................................................... 13 Summary......................................................................................................................... 21 Introduction .................................................................................................................... 29 Objectives ....................................................................................................................... 39 Material and Methods ..................................................................................................... 43 Results ............................................................................................................................ 59 Chapter 1. Source characterization and spatio-temporal evolution of the metal pollution in estuarine sediments ...........................................................................63 Chapter 2. Spatial distribution of metal accumulation areas on the continental shelf of the Basque Country .......................................................................................... 93 Chapter 3. Sources and spatial distribution of Polycyclic Aromatic Hydrocarbons in coastal sediments ............................................................................................ 115 Chapter 4. Distribution of river-borne particulate Pb in the Basque continental shelf..................................................................................................................... 141 General Discussion ....................................................................................................... 169 Conclusions .................................................................................................................. 189 References .................................................................................................................... 195 Annex I ......................................................................................................................... 219 Annex II ........................................................................................................................ 235
Figure list
Figure list Introduction Fig. I1. Examples of point and diffuse sources .............................................................. 31 Fig. I2. Human activities and infrastructures exerting pressures in Basque estuaries and coastal marine water bodies .............................................................................. 33
Material and Methods Fig. M1. Study area and sampling locations in Basque estuaries and continental shelf, within the Bay of Biscay................................................................................ 46 Fig. M2. Basque continental shelf: (a) bathymetry; and (b) 5m resolution shaded relief model.. ............................................................................................................ 54 Fig. M3. Example of georeferenced data combination in a GIS environment ............... 55 Fig. M4. Conceptual model representing the steps followed during the development of the present Thesis ................................................................................................ 56
Results Chapter 1 Fig. 1.1. (a) Study area and sampling locations in Basque estuaries, within the Bay of Biscay. Examples of different sampling approaches are also shown for the Oiartzun estuary; (b) sampling points under the Littoral Water Quality Monitoring and Control Network (LQM); and (c) sampling points of the intensive sediment characterization survey ............................................................ .67 Fig. 1.2. (a) Redundancy Analysis (RDA) biplot of the relationship between heavy metal concentration in sediments and environmental variables. (b) Partition of the variation explained by two groups of environmental variables obtained by partial RDA ............................................................................................................. 78 Fig. 1.3. Organic matter content in surficial sediments of different systems. Deba estuary: (a) 2000 and (b) 2011; Oiartzun estuary: (c) 2000 and (d) 2011; and Urola estuary: (e) 2000 and (f) 2011 ....................................................................... 83 Fig. 1.4. Heavy metal stock variations in surficial sediments: (a) Zn in Oiartzun estuary; (b) Cr in Ibaizabal estuary; (c) Hg in Deba estuary; (d) Cd in Urola estuary; and (e) Cu in Urumea estuary .................................................................... 84 Fig. 1.5. Fine sediment (
