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Metal Pollution in Estuaries and High Altitude Mountains: Geographical Distribution, Evolution in Time and Toxicological Implications

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Metal Pollution in Estuaries and High Altitude Mountains: Geographical Distribution, Evolution in Time and Toxicological Implications METAL POLLUTION IN ESTUARIES AND HIGH ALTITUDE MOUNTAINS: GEOGRAPHICAL DISTRIBUTION, EVOLUTION IN TIME AND TOXICOLOGICAL IMPLICATIONS AZIBAR RODRIGUEZ IRURETAGOIENA November 2015 METAL POLLUTION IN ESTUARIES AND HIGH ALTITUDE MOUNTAINS: GEOGRAPHICAL DISTRIBUTION, EVOLUTION IN TIME AND TOXICOLOGICAL IMPLICATIONS This PhD Thesis has been developed in the Department of Analytical Chemistry from the University of the Basque Country (Faculty of Science and Technology, Leioa, Spain) Azibar Rodriguez Iruretagoiena Leioa, NOVEMBER 2015 (c)2015 AZIBAR RODRIGUEZ IRURETAGOIENA ESKERRAK Lau urtetan zehar egindako lana laburbiltzen duen tesia entregatzeko ordu batzuk besterik ez dira falta. Nire kasuan, hilabete batzuk gehiago behar izan ditut tesi liburua amaitzeko, baina badirudi heldu dela azkenean eguna. Iritsi da, eta orain, ondo pentsatuta, atzera begiratu eta denbora zeinen azkar pasatzen den konturatzen zara. Lau urte luze hauetan denetarik gertatu dela esan dezaket eta orri apur hauek ez dira dena laburbiltzeko nahikoa izango. Gertatutakoak aparte utzita, (beste liburu bat idatzi beharko nukeelako pasatako momentuak kontatzeko) lau urte hauetan ia egunero ikusi ditudan lankideez arituko naiz. Ziurrenik baten bat ahaztuko dut, baina denok betirako gogoan izango zaituztedala jakin dezazuen nahi dut, nahiz eta lerro hauetan ez agertu. Lehenik ea behin nire tesi zuzendari izandakoekin hasiko naiz, Alberto eta Silviarekin hain zuzen. Silvia, egia esan beti izan ditugu gure hika mikak, askotan elkarrekin haserretzera eraman gaituztenak, biok nahiko burugogorrak baikara. Hika mika horietako batean, zure bulegoan inoiz ahaztuko ez dudan esaldia esan zenidan: “¡Parece que predico al desierto! ”. Bina zuk ondo dakizunez, oso momentu alaiak ere izan ditugu, bai laginketetan zein egunerokoan, oso pertsona zarelako eta hori nabaritzen zaizu. Alberto, zurekin ere denetarik pasa dut, baina egia esan, askoz ugariagoak izan dira momentu oso onak txarrak baino. Hori bai, momentu txarra, bakarra izan arren, betirako geratuko zait markatuta, jende askori kontatu izan diodan bezala. Mintegiko nominazioak zirela eta, hori gertatu eta pare bat egun beranduago zure bulegora deitu ninduzun. Zure aurrean jesarri nintzen eta begirada batez esan zenidan “hau ez dadila berriro gertatu, hurrengoan ni arduratuko naiz zutaz eta”. Nahikoa izan nuen horrekin. Baina elkarrekin pasatako egunak hortxe, nire oroitzapenean betirako egongo direla ziur nago. Asko eta asko dira momentu horiek: Pirinioetan Iratiko basoan eta lakuetan egindako laginketak, zenbait egun dutxatu gabe pasata autokarabanan lo egindako gauak, Aridaneren etxean ohe berean lo egin genuen gau hura, perretxikotan pasatako uneak edota jatetxe onetan afaltzen edo bazkaltzen janariaz disfrutatzen igarotakoak… esan bezala momentu eder asko zurekin Alberto. Leioako mintegira pasako naiz orain. Leioako mintegian pasatako eta inoiz ahaztuko ez dudan asteetako bat nominazio aste hura izan zen. Ez dut ondo gogoratzen noiz izan ziren, baina bai Josean eta biok mintegian bata bestearen aurrean jesarrita geundela. Jendeak ezin zuela lanik egin esan eta Luis Angelek mintegiko norbait botatzea proposatu zuen. Nominazio aste horren ondorioz, Sandra eta ni kanporatu gintuzten. Egia esan, horrek mintegiko egoera baretzeko balio izan zuen, nahiz eta aste pare batez tentsio handiko egunak pasatu genituen. Mintegiko jendearen txanda orain. Asko izan zarete lau urte hauetan egunero ikusi zaituztedanak. Bekili, Mireli, Arnatza eta Itsaski, zuekin egin dut barre gehien eta beti horrela izango dela ziur nago. Hala ez badirudi ere, oso garrantzitsuak izan zarete niretzako unibertsitatean, egunero bertara joatea eramangarriago egiten zenutelako, elkarrekin oso momentu onak pasa ditugulako. Ainara, zuk ere asko lagundu didazu urte hauetan eta elkarrekin denetarik pasa dugu: laginketa egunak, nire kotxean kantaldiak, askotan zirikatu izan zaitut baita ere, laborategiko elkarlana… eskerrik asko zuri ere hor egoteagatik. Julene eta Leticia, zuekin ere momentu oso on asko ditut, hirugarren mailako ingurumen zientziak ikasten elkartu ginenetik gainera, urte asko elkarrekin eta oraindik ere oso gustura zuekin beti. Nikole, Ane, Oscar, Leire Kortazar eta Mijangos, Haizea, Laura, Olaia, Nerea, Oier, Pati, Oihana, Naiara, Maitane, Ailette, Jone, Asier, Josu, Ibone, Nagore, Olivia, Maite eta Hector, zuei ere mila esker. Lau urte hauetako egun asko konpartitu ditugu eta momentu oso onak pasa ere. Esandakoa, norbait ez badut aipatu barkatu nazala, izena agian bai, baina berekin bizitakoa ez dut sekula ahaztuko. Eta orain los “VIP-s”!!! “toca callar un momento porque viene gorda”. Nos lo hemos pasado terrible no, lo siguiente!!! Me acuerdo que el primero que vino a hablarme uno de mis primeros día en el laboratorio fue Jousi. No hizo más que llegar, no nos conocíamos de nada y ya se lio ya, de risas desde el primer momento. Qué casualidad, que además salgo ese finde, le veo en el Galeón y se armó la que se armó que perdí hasta la txapela que me acuerdo que iba disfrazado de Olentzero, ahí ya se vio que íbamos a hacer gordas juntos Jous. No voy a dar la chapita aquí pero podemos escribir uno, dos o tres libros. Los otros dos, Arriskatu y Julianzas, grandes desde el primer momento aunque a ti Julianzas te costó bastante más, menos mal que empezamos a hacer woks rápido y se fue soltando la cosa. Con el paso de los días ibas a casa hasta a las 00:00 de la noche, el Julen que conocí empezó a cambiar y ya no cogía ni pronto el autobuya en Moyus. Arriskatu, un grande en toda regla con el que he hablado casi más de fútbol que con mi entrenador. El pesado que siempre tiene calor eso sí. Siempre en la calle y pasando frío por tu culpa y jodiendo los woks porque un día tuviste cagalerita. Momento para la historia el día de sin camisa en el bar de Manchester que ya no me acuerdo como se llama y que alguno de nosotros (no voy a decir quién pero creo que está bastante claro Josean) salió volando ayudado por el segurata. Hemos hecho grandes viajes juntos la verdad, que me encantaría que siguiéramos haciendo por lo menos una vez al año, porque está amistad que empezó en la Universidad no la vamos a perder nunca. También es verdad que hemos tenido momento malos en los que incluso no queríais aceptarme como VIP, pero al final el río siempre vuelve a su cauce y sé que nos quedan gordas juntos. Azkenik, eskerrik asko nire lagun asko eta askori eguna joan eta eguna etorri elkarrekin baikaude eta elkarrekin pasatako momentuak oso lagungarri dira baita lanerako ere. Askok ez duzue ideiarik ere lau urte hauetan zertan aritu naizen, baina beti esan izan duzue ez dudala ezer ere egiten eta denbora pasan nagoela unibertsitatean. Beti esan izan dizuedan bezala hitz egitea debalde da. Arduratu zaitezte zuen ingurua garbi edukitzeaz ;). Aita eta ama, zuek ere berdin. Ez dakizue zer egiten egon naizen lau urte hauetan, baina egia dena, biok asko maite zaituztedala da egunero elkarrekin gaudelako eta sarritan “a golpes” ibili arren, zuen laguntza eta konfiantza beti daukat hortxe. Momentu txar askotatik irteten laguntzen didazue eta beti bezala, oso momentu onak pasatzen ditugu elkarrekin. Eskerrik asko bihotzez!!! PREFACE Environmental pollution is considered by the European Environment Agency, United States Environmental Protection Agency (US-EPA) and World Health Organization (WHO) one of the greatest problems that the world is facing nowadays. All the environmental compartments are more and more affected due to an endless increase in human activity. The life style that human beings are carrying out produces noise, light and chemical pollution that seriously threatens the quality of air, water and soil. The uncontrolled release of chemicals to the environment results in concentrations of those chemicals significantly higher than the background values considered as “natural”. Above certain threshold limits, the presence of those chemicals provokes toxic effects in the organisms living around. The term “contamination” is related to the presence of “high” (above the natural background values) concentrations of substances in the environment, whereas the term “pollution” refers to the introduction of harmful substances (with toxicological implications) into the environment. This differentiation is not of general use in the scientific community, but it is rather widely accepted. Amongst others, some metals and metalloids are chemicals able to cause serious problems to the environment. The anthropogenic inputs of metals and metalloids to the environment have grown constantly since the industrial revolution. Their most important features, and the main reason of being of high concern, are non-degradability and persistence in the environment. Furthermore, some metals and metalloids are highly toxic and their toxicity highly depends on their concentration and speciation in each specific compartment. In addition, the speciation of a metal or metalloid is influenced by the physical and chemical characteristics of the medium where it is present. Natural water bodies are one of the compartments more seriously affected by metal/metalloid contamination/pollution. In words of the World Health Organisation (WHO) “water is essential for life”. The amount of fresh water in earth is limited, and its quality is under constant pressure. Preserving the quality of fresh water is important for drinking-water supply, food production and recreational use. The quality of continental (lakes, rivers and underground water), oceanic and transitional waters is nowadays threatened by the direct
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