Το Εθνικό Θαλάσσιο Πάρκο Ζακύνθου περιλαμβάνει τη θαλάσσια έκταση και τις νησίδες του Κόλπου του Λαγανά, τις παραλίες ωοτοκίας της θαλάσσιας χελώνας Caretta caretta (Γέρακας, Δάφνη, Σεκάνια, Καλαμάκι, Ανατολικός Λαγανάς και Μαραθονήσι) και μια ζώνη γης, που περιβάλλει αυτές, τον υγρότοπο της Λίμνης Κερίου και τις Νήσους Στροφάδες. Ιδρύθηκε με κύριο σκοπό τη διατήρηση και την προστασία των σημαντικότερων παραλιών ωοτοκίας στη Μεσόγειο της θαλάσσιας χελώνας Caretta caretta και του θαλάσσιου και χερσαίου χώρου που τις περιβάλλει. Η συνολική έκταση της χερσαίας περιοχής του Ε.Θ.Π.Ζ. είναι περίπου 45km². Η περιοχή μελέτης περιλαμβάνει το σύνολο σχεδόν της χερσαίας έκτασής του (εκτός από τις νήσους Στροφάδες), μέρος της οποίας συγκαταλέγεται στο έργο οικοτόπων, Φύση 2000, στην Ελλάδα (Κωδικός Περιοχής: GR 2210002). Η χλωρίδα της χερσαίας περιοχής του Εθνικού Θαλάσσιου Πάρκου Ζακύνθου είχε μελετηθεί κατά το παρελθόν στα πλαίσια της Ειδικής Περιβαλλοντικής Μελέτης για τον κόλπο του Λαγανά (ΥΠΕΧΩΔΕ, 1997), όπου καταγράφηκαν 173 taxa. Επιπροσθέτως, έρευνες που αφορούν στη καταγραφή της χλωρίδας της Ζακύνθου και αναφέρονται λιγότερο ή περισσότερο και σε περιοχές που απαρτίζουν το Ε.Θ.Π.Ζ αποτελούν οι εργασίες των Margot & Reuter (1839 & 1841), Bornmüller (1928) και Ronniger (1941), στις οποίες αναφέρονται 150 φυτικά taxa. Εφόσον, τα τελευταία χρόνια, δεν υπάρχει μια ολοκληρωμένη εργασία, θεωρήθηκε σκόπιμη η πλήρης καταγραφή της χλωρίδας της συγκεκριμένης προστατευόμενης περιοχής με τη συλλογή φυτικών δειγμάτων από κάθε τύπο οικοτόπου. Επιπρόσθετα, ολόκληρη η Ζάκυνθος χαρακτηρίζεται από πλούσια χλωρίδα και βλάστηση, ενώ χαρακτηριστικό είναι το γεγονός ότι απαντώνται σε αυτήν 34 ελληνικά ενδημικά φυτικά taxa, εκ των οποίων τα τέσσερα (Asperula naufraga, Limonium phitosianum, Limonium zacynthium και Micromeria browiczii) αποτελούν αποκλειστικά ενδημικά taxa της νήσου. Έτσι, θεωρήθηκε χρήσιμη η βίο-παρακολούθηση αυτών των taxa, προκειμένου να αξιολογήσουμε την κατάσταση διατήρησής τους με τη χρήση των νέων κριτηρίων της IUCN (2012). Η βίο-παρακολούθηση πραγματοποιήθηκε στα τρία από τα τέσσερα taxa, λόγω μη έγκαιρου εντοπισμού του είδους Asperula naufraga, με την κατάλληλη τοποθέτηση μόνιμων δειγματοληπτικών επιφανειών 25m² για κάθε taxon και τη μελέτη της χωρικής τους κατανομής και της αναπαραγωγικής βιολογίας τους. Σύμφωνα με τα αποτελέσματα, η χλωρίδα του Εθνικού Θαλάσσιου Πάρκου Ζακύνθου συνίσταται από 559 taxa, από τα οποία τα 236 αποτελούν νέες αναφορές για την περιοχή μελέτης. Οι οικογένειες με την υψηλότερη α ποικιλότητα είναι κατά σειρά οι Asteraceae (72 taxa), Fabaceae (67 taxa) και Poaceae (42 taxa), γεγονός που αντικατοπτρίζει την επικρατούσα κατάσταση στον ελληνικό χώρο. Επιπλέον, αναδείχτηκε ο έντονος μεσογειακός χαρακτήρας της χλωρίδας της υπό εξέταση περιοχής με την κυριαρχία των θεροφύτων στο βιολογικό φάσμα και των μεσογειακών στοιχείων στο χωρολογικό φάσμα. Ωστόσο, το μεγάλο ποσοστό συμμετοχής των κοσμοπολιτικών-υποκοσμοπολιτικών στοιχείων και των αλλόχθονων taxa στην χλωρίδα της περιοχής, υποδεικνύει την έντονη ανθρωπογενή επίδραση που φαίνεται να έχει ενταθεί κατά τα τελευταία χρόνια. Τέλος, καταγράφηκαν 12 ελληνικά ενδημικά taxa στην περιοχή, από τα οποία τα δύο (Limonium phitosianum και Limonium zacynthium) αποτελούν αποκλειστικά ενδημικά taxa για τη Ζάκυνθο. Η παρακολούθηση του είδους Micromeria browiczii καθόρισε το εύρος εξάπλωσής του (ΕΟΟ) στα 117km² και την έκταση κάλυψης στα 1,6 km². Το μέγεθος του πληθυσμού του εκτιμήθηκε στα 5.250 άτομα, ενώ η ΣΑΕ του είδους είναι πολύ χαμηλή (30%). Το Limonium zacynthium έχει εύρος εξάπλωσης 171,3 km² και έκταση κάλυψης 0,3 km². Το μέγεθος του πληθυσμού του εκτιμήθηκε στα 1.168 άτομα και η ΣΑΕ του είδους βρέθηκε αρκετά υψηλή (64,2%). Τέλος, το Limonium phitosianum έχει εύρος εξάπλωσης 93,5 km² και έκταση κάλυψης 0,17 km². Το μέγεθος του πληθυσμού εκτιμήθηκε στα 2.470 άτομα και η ΣΑΕ βρέθηκε πολύ υψηλή (79,1%). Βάσει των διαθέσιμων στοιχείων και τα τρία είδη κατατάσσονται στην κατηγορία Κρισίμως Κινδινεύον (CR) (IUCN, 2012), κυρίως λόγω της περιορισμένης χωρικής τους κατανομής, ωστόσο η αύξηση των σειρών δεδομένων σε θέματα παρακολούθησης αποτελεί απαραίτητο στοιχείο για να διαφανεί η τάση του πληθυσμού κάθε είδους και για την ανάλυση της βιωσιμότητας των πληθυσμών τους σε μεταγενέστερο στάδιο. / The National Marine Park of Zakynthos (N.M.P.Z.) includes the marine area and islands of the Bay of Laganas, nesting beaches of the sea turtle Caretta caretta (Gerakas, Daphne, Secania, Kalamaki, Laganas and Marathonisi East) and a belt land that surrounds them, the wetland of Keri Lake and the Strophadia Islands The founding of this National Marine Park began with the fundamental purpose of conservation and protection of important nesting beaches of the Mediterranean sea turtle Caretta caretta and the marine and terrestrial space surrounding them. The total land area of Marine Park is approximately 45km ². The study area includes almost the entire land area (excluding Strophadia Islands). A part of this area is included in the project of network Natura 2000 in Greece (Region Code: GR 2210002). The flora of the land area of the National Marine Park of Zakynthos had been studied previously in the context of the Special Environmental Study for the Laganas Gulf (Ministry of Environment, 1997) and had recorded 173 taxa. In addition, the work of Margot & Reuter (1839 & 1841), Bornmüller (1928) and Ronniger (1941 ), which listed 212 plant taxa, constitute a previous research related to the flora of Zakynthos and also referred in areas of the N.M.P.Z. Since, in recent years, there was no comprehensive work, it was considered appropriate to fully record the flora of the protected area by collecting plant samples from each habitat type. Additionally, the entire Zakynthos is characterized by a rich flora and vegetation, while it is important the fact that 34 Greek endemic plant taxa occur in this region, four of them (Asperula naufraga, Limonium phitosianum, Limonium zacynthium and Micromeria browiczii) are exclusively endemic taxa of island. Thus, the bio-monitoring of these taxa was considered useful, in order to evaluate their conservation status using the new criteria of IUCN (2012). The bio-monitoring took place in three of the four taxa, due to the failure in time of localization and identification of the species Asperula naufraga. Permanent sample surfaces had been placed with proper placement. These surfaces were 25m ² for each taxon and we studied their spatial distribution and their reproductive biology. According to the results of this study in the National Marine Park, the flora of this area consists of 559 taxa. 236 of these taxa are new records for the study area. The families with the highest diversity in order are Asteraceae (72 taxa), Fabaceae (67 taxa) and Poaceae (42 taxa), reflecting the status of Greek area. Moreover, the strong Mediterranean character of flora of this area designated with the dominance of therophytes in the biological spectrum and the dominance of Mediterranean elements in chorological spectrum. However, the large proportion of cosmopolitan, semi-cosmopolitan elements and alien taxa in the flora of our area indicates a strong anthropogenic influence which seems to have increased in recent years. Finally, there are 12 Greek endemic taxa in the area, two of them (Limonium phitosianum and Limonium zacynthium) are exclusively endemic for Zakynthos. By monitoring Micromeria browiczii, the extent of occurrence (EOO) estimated 117km ² and the area of occupancy (AOO) 1,6 km ². Population size was estimated at 5.250 mature individuals, while the R.R.S. (Relative Reproductive Success) of the species was very low (30%). EOO of Limonium zacynthium is 171,3 km ² and AOO is 0,3 km². The population size was estimated at 1.168 mature individuals and the R.R.S. of the species was found quite high (64.2%). Finally, Limonium phitosianum has EOO 93,5 km ² and AOO 0,17 km ². The size of the population was estimated at 2.470 mature individuals and R.R.S. was found very high (79.1%). Based on the available data, these three species classified as Critical endangered (CR) (IUCN, 2012), mainly because of their limited spatial distribution. However, the increase of datasets in monitoring is an essential element to indicate the trend of population of each species and to analyze the viability of their populations at a later stage.

Les hydrocarbures aromatiques polycycliques (HAP) sont des polluants organiques persistants (POP) émis par les activités humaines suite à la combustion incomplète de la matière organique (industrie, chauffage, trafic routier...). En raison de leur faible taux de dégradation, de leur toxicité, de leur capacité à être transportés sur de longues distances et de leur bioaccumulation dans la matière organique, les HAP font l'objet d'une surveillance atmosphérique (directive cadre européenne 96/62/CE du 27 septembre 1996). Les bryophytes, plus communément appelées mousses, sont utilisées depuis une trentaine d'années pour la biosurveillance de la qualité de l'air. Leurs caractéristiques biologiques font de ces plantes terrestres d'excellents bioaccumulateurs des dépôts de polluants atmosphériques. Cependant, elles ont été peu utilisées pour la biosurveillance des HAP et pour des échelles spatiales et temporelles très limitées. Dans ce contexte, la thèse a pour objectif de valider l'utilisation de bryophytes comme outils pour la biosurveillance des retombées atmosphériques de HAP à différentes échelles spatio-temporelles. La première phase de ce travail a consisté en un développement analytique afin de valider l'analyse des HAP par chromatographie liquide associée à une détection par fluorescence (CLHP-FLD), l'extraction liquide-liquide des HAP contenus dans les dépôts totaux et l'extraction par liquide pressurisé (PLE) des HAP contenus dans les mousses. Cette dernière a été optimisée, grâce à la réalisation d'un plan d'expériences, et a été complétée par des tests de purification par extraction sur phase solide (SPE). Des études de terrain ont ensuite été réalisées afin d'évaluer les tendances temporelles à l'échelle saisonnière, annuelle et historique, ainsi que les tendances spatiales à l'échelle locale et régionale, des teneurs en HAP dans les mousses. Une étude menée sur des mousses d'herbier prélevées dans le Parc Naturel de Bertiz (Navarre, Espagne) entre 1879 et 2007 a permis d'identifier les sources historiques d'émission des HAP. Les bryophytes apparaissent comme de bons « témoins » de la contamination atmosphérique du passé. Une étude annuelle (2010-2011) de biosurveillance active menée à Bertiz a permis ensuite d'observer des tendances saisonnières des teneurs en HAP dans les mousses Hylocomium splendens (Hedw.) Schimp., liées aux variations des émissions atmosphériques et des conditions météorologiques, en particulier des précipitations. De plus, l'étude annuelle a révélé un fractionnement lors de l'accumulation par les mousses des HAP contenus dans les dépôts totaux, qui résulte d'une affinité des HAP pour les dépôts liée à leur solubilité et d'une affinité des HAP pour le végétal liée à leur propriété lipophile (KOW). Ainsi, le suivi des flux atmosphériques de HAP dans les dépôts totaux ne permet pas de prévoir a priori les teneurs de HAP dans les écosystèmes. Enfin, une analyse multivariée de la distribution spatiale des teneurs en HAP dans l'espèce Hypnum cupressiforme Hedw. prélevée en Espagne (Navarre), France (Île-de-France) et Suisse (Plateau Suisse et région de Bâle) a permis de caractériser les sources de contamination atmosphériques des régions étudiées et l'influence de paramètres environnementaux tels que l'altitude et la pluviométrie. / Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants (POPs) emitted by human activities during incomplete combustion of organic matter (industry, domestic heating, road traffic…). Due to their low degradation rates, toxicity, long-range transport and bioaccumulation in organic matter, PAHs are monitored in the atmosphere (Council Directive 96/62/EC of 27 September 1996). Bryophytes, more commonly called mosses, have been used during the past three decades for biomonitoring air quality. Because of their biological characteristics, these terrestrial plants are excellent bioaccumulators of airborne pollutants. However, few studies concern PAH biomonitoring and they are usually restricted to studies limited in time and space. In this context, the thesis aims to validate bryophytes as tools for biomonitoring atmospheric deposition of PAHs on various space-time scales. The first step of this work consisted in developing the analytical procedures in order to validate PAH analysis by liquid chromatography associated with fluorescence detection (HPLC-FLD), liquid-liquid extraction of PAHs from bulk deposition and pressurized liquid extraction (PLE) of PAHs from mosses. The latter was optimized with a factorial design and was completed by purification tests with solid phase extraction (SPE). Field studies were then carried out to evaluate temporal trends of PAH levels in mosses at seasonal, annual and historical scales, as well as spatial trends, at local and regional scales. A study undertaken on herbarium mosses sampled in Bertiz Natural Park (Navarra, Spain) between 1879 and 2007 leaded to the identification of PAH historical emission sources. Bryophytes appear as excellent “witnesses” of the past atmospheric contamination. An annual biomonitoring study (2010-2011) at Bertiz showed seasonal trends of PAH content in mosses Hylocomium splendens (Hedw.) Schimp., which are related to variations of PAH emissions and weather conditions, particularly precipitations. Moreover, the annual study revealed a fractionation of PAHs while they are transferred from total deposition to the mosses, as the affinity of PAHs for deposition samples was related with their solubility and their affinity for the plant was related to their lipophilic property (KOW). Thus, monitoring PAH fluxes in total deposition does not give an a priori estimation of PAH contents in the ecosystems. Finally, multivariate analysis of the spatial distribution of PAHs in the species Hypnum cupressiforme Hedw. sampled in Spain (Navarra), France (Île-de-France) and Switzerland (Swiss Plateau and Basel area) leaded to the characterization of the atmospheric contamination sources in the different areas and the influence of environmental parameters such as elevation and pluviometry.

O tolueno e o xileno são substâncias presentes, ao lado de outras, em vários produtos, entre eles as tintas, tíneres e colas, provocando exposição combinada dos trabalhadores a diversas substâncias químicas. Assim, foi objetivo deste trabalho desenvolver um método simples, rápido e confiável de cromatografia em fase gasosa que permitisse análise simultânea do ácido hipúrico (AH) e ácido metil-hipúrico (AMH) em urina, bioindicadores de dose interna utilizados na monitorização da exposição ocupacional ao tolueno e xileno respectivamente. Após extração líquido-líquido e derivação com trimetilfenilamôneo, foi realizada análise cromatográfica em coluna capilar 100% polidimetilsiloxano, usando-se o ácido heptadecanóico como padrão interno. Foram avaliados 69 trabalhadores que manipulavam tintas em atividades de repintura de veículos e 31 trabalhadores não-expostos (controle). O método mostrou-se linear entre 0,1 (limite de quantificação) e 5,0 g/L para o AH e 0,2 (limite de quantificação) e 5 g/L para o AMH. A recuperação média foi de 81 % e a inexatidão de aproximadamente - 8,0% (bias) para ambos os analitos. Os coeficientes de variação médios para as concentrações de 0,5; 2,0 e 4,0 g/L foram, para a precisão intra-ensaio, de 3,5% para o AH e de 3,7% para o AMH, e para a interensaio, de 10,5% para o AH e de 10,7% para o AMH. Os analitos permaneceram estáveis em até 3 ciclos de congelamento/descongelamento das amostras de urina. O valor médio obtido nas amostras de trabalhadores expostos foi de 0,55 g/g de creatinina (mediana = 0,36 g/g de creatinina). Apesar de diferença estatisticamente significativa (teste t Student, p ≤ 0,05) ter sido observada entre os valores médios de AH nos trabalhadores expostos e nos do grupo controle, esta diferença não foi detectada quando analisou-se as medianas. O hábito de fumar e de ingerir bebidas alcoólicas também não mostrou alterar significativamente a excreção dos bioindicadores no grupo avaliado. / Toluene and the xylene, among others substances, are solvents used in several products, such as inks, thiners and glues, and are responsible for mixed exposure in workers. Thus, the aim of this work was to develop a simple, fast and reliable gas chromatographic method to allow the simultaneous detection and quantitation of hippuric acid (HA) and methylhippuric acid (MHA) in urine, which are internai dose bioindicators in the monitoring of occupational exposure to toluene and the xylene, respectively. After liquid-liquid extraction and derivation with trimethylphenylammonium, the chromatographic analysis was accomplished using capillary column 100% methylsiloxane, and heptadecanoic acid as internai standard. 69 workers exposed to inks in activities such as vehicles painting and 31 nonexposed workers were evaluated. The method showed linearity range between 0,1 (quantitation limit) and 5,0 g/L for HA and 0,2 (quantitation limit) and 5 g/L for MHA. The recovery was 81 % and the inaccuracy of approximately - 8,0% (bias) for both analytes. The mean variation . coefficients for the concentrations of 0,5; 2,0 and 4,0 g/L were, for the intraassay precision, of 3,5% for HA and of 3,7% for MHA, and for the inter assay, 10,5% for HA and 10,7% for MHA. The analytes were stable for 3 freezing cycles of the urine samples. The medium value obtained in the exposed workers\' samples was of 0,55 creatinina g/g (medium = 0,36 creatinina g/g). In spite of the observed statistical significant differences (test t Student, p ≤ 0,05) among the medium values of HA in the exposed workers and the control groups, this difference was not detected when it was analyzed the respective median values. Smoking and drinking alcoholic beverages habits did not significantly alter the excretion of these bioindicators in the studied group.

O crescimento no número de hortas urbanas em todo o mundo tem desempenhado um papel importante no fortalecimento de sistemas alimentares urbanos mais sustentáveis. Embora as hortas urbanas ofereçam múltiplos benefícios à sociedade, ainda não é claro em até que medida os vegetais cultivados são contaminados pela absorção de elementos químicos e compostos orgânicos provenientes de deposições atmosféricas, levantando questões sobre o quão seguro é o cultivo de alimentos em metrópoles superlativas. Esta tese foi elaborada com o objetivo de avaliar a influência da poluição do ar em vegetais folhosos cultivados em hortas urbanas na cidade de São Paulo. Foram quantificadas as concentrações de 17 elementos químicos (relacionados ao tráfego veicular e à biologia vegetal) e 16 hidrocarbonetos aromáticos policíclicos (HPAs) absorvidos nas folhas da Brassica oleracea var. acephala (couve) e Tetragonia tetragonioides (Pall.) Kuntze (espinafre). Para verificar a correlação entre os elementos químicos encontrados nos espinafres/couves e os presentes no material particulado atmosférico foram expostos simultaneamente aos vegetais exemplares de Tillandsia usneoides L. (Bromeliaceae). Além disso, utilizamos dois métodos de biomonitoramento: as frequências de micronúcleos em tétrades de Tradescantia pallida (Rose) Hunt. cv. \"Purpurea\" Boom (Trad-MCN) como um indicador de curto prazo de resposta genotóxica à poluição atmosférica, e também o uso de cascas de árvores para quantificar a acumulação de elementos químicos relacionados ao tráfego veicular a longo prazo nas regiões circundantes das hortas. Análises multivariadas foram utilizadas para correlacionar as concentrações elementares, os resultados de biomonitoramento e as características do ambiente urbano local, como variáveis meteorológicas, tráfego e obstáculos verticais adjacentes aos jardins. Encontramos diferenças significativas nas concentrações elementares dos vegetais nas diferentes hortas comunitárias. Essas diferenças foram relacionadas ao tráfego veicular, obstáculos verticais e clima local. As concentrações de Pb e Cd em ambos os vegetais excederam os valores-limite para o consumo após 60 dias de exposição. Observou-se uma forte correlação entre a concentração de elementos relacionados ao tráfego nos vegetais e nos exemplares de Tillandsia usneoides L.. A frequência de Trad-MCN apresentou uma correlação significativa com as variáveis de tráfego e elementos químicos relacionados à ressuspensão de poeira (road dust) e emissão por escape veicular depositados nas cascas de árvores. Foram observadas associações negativas entre Trad-MCN e a distância de vias de tráfego veicular intenso, bem como a presença de obstáculos verticais no entorno das hortas. As concentrações de Mn/Zn presentes nas cascas de árvores foram associadas com o aumento de Trad-MCN. Os níveis de HPAs em ambos os vegetais nos períodos de 45 dias foram < 1 ug kg-1. A poluição do ar proveniente do tráfego veicular influencia diretamente a absorção de elementos químicos em vegetais folhosos e as concentrações desses elementos podem exceder os valores recomendados para o consumo humano / Urban vegetable gardens have steadily increased worldwide playing a significant role in the strengthening of sustainable urban food systems. Although urban gardens provide multiple benefits to society, the extent to which vegetables are contaminated by the absorption of chemical elements and compounds derived from atmospheric deposition is unclear raising questions about how safe is the cultivation of foods in superlative metropolises. This thesis was designed to evaluate the influence of air pollution on leafy vegetables cultivated in gardens of São Paulo, Brazil. We quantified the concentrations of 17 elements (traffic-related and those essential to plant biology) and 16 polycyclic aromatic hydrocarbons (PAHs) absorbed in the edible tissues of Brassica oleracea var. acephala (collard greens) and Tetragonia tetragonioides (Pall.) Kuntze (spinach). In addition, to verify a correlation between the chemical elements found in collard greens/spinach and those from air pollution particles, we simultaneously exposed specimens of the air plant Tillandsia usneoides L. (Bromeliaceae). Also, we evaluated the use of two biomonitoring methods: the micronuclei frequencies for early tetrads of Tradescantia pallida (Rose) Hunt. cv. \"Purpurea\" Boom (hereafter, Trad-MCN) as a short-term indicator of genotoxic response and tree barks to quantify the accumulation of traffic-related chemical elements as a long-term biomarker of air pollution in urban gardens. Multivariate analysis was used to correlate the elemental concentrations, biomonitoring results and the characteristics of the local urban environment, such as weather variables, traffic burden and vertical obstacles adjacent to the gardens. We found significant differences in the elemental concentrations of the vegetables in the different community gardens. These differences were related to the vehicular traffic, vertical obstacles and local weather. Pb and Cd concentrations in both vegetables exceeded the limit values for consumption after 60 days of exposure. A strong correlation was observed between the concentration of traffic-related elements in vegetables and in Tillandsia usneoides L. The frequency of Trad-MCN had a significant correlation with traffic variables and chemical elements related to road dust and tailpipe emissions deposited in tree barks. Negative associations between Trad-MCN and both the distance through traffic and the presence of vertical obstacles were observed in the vegetable gardens. The Mn and Zn concentration in tree barks were associated with increased Trad-MCN. The levels of PAHs in both vegetables over 45-day periods were < 1 ug kg-1. Air pollution exerts a direct influence in the absorption of urban particles, which may reach levels above the recommended values for consumption

O ambiente costeiro tem sido fortemente alterado em função de múltiplos impactos ambientais decorrentes das atividades antrópicas, como por exemplo, o escoamento de esgoto proveniente de áreas urbanas, a liberação de inúmeros produtos químicos das indústrias, a agricultura e o fluxo de embarcações, que podem acarretar vazamentos acidentais de petróleo e derivados, combustíveis e outros produtos transportados por via marítima. Neste contexto, um dos meios para avaliação da contaminação ambiental causada por essas substâncias potencialmente tóxicas em água do mar é a monitoração por meio de diferentes espécies de bivalves, que tem sido utilizada por diversos pesquisadores, do Brasil e do exterior. No que se refere aos moluscos bivalves, particularmente os mexilhões, o seu uso no biomonitoramento da contaminação marinha deve-se principalmente à sua ampla distribuição geográfica, hábito séssil e habilidade de concentrar metais tóxicos em até 102 - 105 vezes em relação às concentrações detectadas na água. No presente trabalho, foi empregado o biomonitoramento passivo com o uso do molusco bivalve Perna perna com relação aos elementos Br, Cl, K, Mg, Mn e V. Foram escolhidos estes elementos uma vez que eles podem ser determinados pelo método de INAA (Análise por Ativação com Nêutrons Instrumental), por meio da irradiação curta o que proporciona análises mais rápidas e também por serem importantes do ponto de vista nutricional ou ambiental. O objetivo do presente trabalho foi avaliar os teores de Br, Cl, K, Mg, Mn e V em amostras de mexilhões Perna perna (Linnaeus, 1758: Mollusca, Bivalvia) coletados em regiões costeiras de São Paulo sujeitas à contaminação antrópica (Ponta de Itaipu e Ilha das Palmas, em Santos), comparando os valores obtidos nos sítios possivelmente impactados com os valores do sítio controle situado na Praia da Cocanha, em Caraguatatuba. Os pontos de coleta no litoral de São Paulo estão localizados nas regiões geográficas 23º 37 S 45º 24 W (Caraguatatuba) e 23º 57\' S - 46º 20\' W (Santos). A coleta dos organismos foi realizada em todas as estações do ano, com início na primavera de 2008 e término no inverno de 2009. As amostras coletadas foram limpas, trituradas, homogeneizadas e secas por meio da liofilização para posterior INAA. O procedimento de INAA consistiu em irradiar alíquotas das amostras obtidas na forma de pó em invólucros de polietileno no reator nuclear IEA R1 do IPEN/CNEN - SP juntamente com padrões sintéticos de elementos. O tempo de irradiação no reator foi de 8 a 10 s e sob o fluxo de nêutrons térmicos de 6,6 x 1012 n cm-2 s-1. As concentrações dos elementos foram calculadas pelo método comparativo. O procedimento de INAA foi validado com relação à exatidão e precisão, por meio das análises dos materiais de referência certificados NIST SRM 1566b Oyster Tissue e NIST SRM 2876 Mussel Tissue. Os resultados destes materiais de referência certificados indicaram uma boa qualidade dos resultados com relação à precisão e exatidão. As faixas das concentrações (em base seca) dos elementos obtidos nos mexilhões coletados em Santos e na Praia da Cocanha para as quatro estações do ano foram de: 173,80 a 358,99 mg kg-1 para Br; 45658 ± 1811 a 109166 ± 824 mg kg-1 para Cl; 7043 ± 856 a 12506 ± 675 mg kg-1 para K; 2774 ± 211 a 5691 ± 717 mg kg-1 para Mg; 7,01 ± 0,30 a 29,74 ± 3,32 mg kg-1 para Mn e 0,77 ± 0,02 a 3,43 ± 0,28 mg kg-1 para V. Foi estudada a variação sazonal e espacial das concentrações desses elementos e também foram comparados esses resultados com valores da literatura. A partir dos resultados obtidos pode - se concluir que os mexilhões da espécie Perna perna, podem ser utilizados como biomonitores da contaminação marinha. / The coastal environment has been heavily altered by multiple environmental impacts of human activities, such as disposal of sewage from urban areas, the release of numerous chemical industries, agriculture and the flow of vessels, which can lead to accidental spills of oil and oil products, fuels and other products transported by sea. In this context, a means of determining concentrations of these potentially toxic substances in the sea water is the biomonitoring by means of different types of bivalves, which have been used by various researchers, in Brazil and other countries. With regard to bivalve mollusks, particularly mussels, their use in monitoring the marine contamination is mainly due to their wide geographic distribution, sessile habit and ability to concentrate toxic metals to 102-105 times in relation to the concentrations detected in water. In the present study, we employed the passive biomonitoring using the Perna perna bivalve mollusk with respect to the elements Br, Cl, K, Mg, Mn and V. These elements were chosen since they can be determined by INAA method (Instrumental Neutron Activation Analysis), by means of short irradiation which provides faster analyzes and also due to their importance from the standpoint of environmental or nutritional studies. The aim of this study was to evaluate the content of Br, Cl, K, Mg, Mn and V in samples of Perna perna mussels (Linnaeus, 1758: Mollusca, Bivalvia) collected in coastal regions of São Paulo subject to anthropogenic contamination (Ponta de Itaipu and Palmas Island, in Santos), comparing the values obtained in sites potentially impacted with the values of the control site in Praia da Cocanha, in Caraguatatuba. The collection points located in São Paulo coast are located in the geographical areas 23º 37\'S - 45° 24\' W (Caraguatatuba) and 23º 57\'S - 46º 20\' W (Santos). The collection of organisms was performed in all seasons of the year, beginning in spring 2008 and ending in winter 2009. The samples were cleaned, crushed, homogenized and dried by lyophilization for further analysis by INAA. The INAA procedure consisted of irradiating aliquots of the samples obtained in powder form in polyethylene envelopes in the nuclear research reactor IEA - R1 of IPEN / CNEN - SP together with synthetic standards of elements. The irradiation time in the reactor was 8 to 10 s under the thermal neutron flux of 6.6 x 1012 n cm-2 s-1. The concentrations of the elements were calculated using the comparative method. The INAA procedure was validated with respect to accuracy and precision, through the analysis of certified reference materials NIST SRM 1566b Oyster Tissue and NIST SRM 2876 Mussel Tissue. The results of these certified reference materials indicated good quality of results with respect to precision and accuracy. The ranges of concentrations (dry basis weight) of the elements obtained in mussels collected in Santos and Praia da Cocanha for the four seasons of the year were: 173.80 to 358.99 mg kg-1 for Br; 45658 ± 1811 to 109166 ± 824 mg kg-1 for Cl; 7043 ± 856 to 12506 ± 675 mg kg-1 for K; 2774 ± 211 to 5691 ± 717 mg kg-1 for Mg; 7.01 ± 0.30 to 29.74 ± 3.32 mg kg-1 for Mn and 0.77 ± 0.02 to 3.43 ± 0.28 mg kg-1 for V. The seasonal and spatial variations of the concentrations of these elements were studied and the values compared to the literature. From the results obtained it can be concluded that the species of Perna perna mussels, can be used as biomonitors of marine contamination.

As zonas costeiras são áreas complexas que contemplam ambientes terrestres e marinhos que, além de possuírem enorme riqueza ambiental, também são áreas atrativas aos seres humanos por oferecer alimentos, lazer, negócios, transporte, entre outros. Algumas dificuldades de gerenciamento ocorrem pela complexidade, conflito de interesses e pelo fato de não haver padronização no levantamento de dados e disponibilização para a comunidade científica, órgãos públicos, etc. O uso de geotecnologias pode auxiliar na organização, padronização e compartilhamento destas informações em Atlas Web além de apoiar no planejamento e tomada de decisão pois agregam, em um único ambiente, diversos dados provenientes de fontes distintas. A construção de um modelo de dados espacial voltado à área ambiental, para ser utilizada em Infraestrutura de Dados Espaciais (IDE) é exemplificada a partir da modelagem de um bioindicador, Macrobentos, de qualidade de sedimentos. Este trabalho apresenta as etapas necessárias para a construção de modelo de dados espacial de Macrobentos e emprega a Região Metropolitana da Baixada Santista como referência, além de ilustrar e discutir as principais dificuldades para organizar os dados não padronizados. Conclui-se que a estruturação do conhecimento quando se trabalha com dados ambientais em um modelo é essencial para sua posterior integração em IDE. Constatou-se no processo de modelagem que questões metodológicas relativas ao processo de coleta podem dificultar ou até mesmo inviabilizar a integração de dados provenientes de diferentes estudos. A construção de um modelo de dados espacial e sua posterior publicação via Geoportal, como o apresentado neste estudo, poderá ser utilizado como referência para novas pesquisas com objetivos semelhantes. / Coastal zones are complex areas that include marine and terrestrial environments. Besides its huge environmental importance, they also attract humans because they provide food, recreation, business, transportation, among others. Some difficulties to manage these areas are related with their complexity, diversity of interests and the absence of standardization to collect and share data to scientific community, public agencies, among others. The use of geo-technologies can be used in the organization, standardization and sharing of this information through Atlas Web and assists planning and decision making issues because it aggregates different files from distinct sources. The construction of a spatial database integrating the environmental business, to be used on Spatial Data Infrastructure (SDI) is illustrated by a bioindicator, Macrobenthos, that indicates the quality of the sediments. This research shows the required steps to build Macrobenthos spatial database based on Santos Metropolitan Region as a reference. Besides, it tries to illustrate the problems related to organize non standardized data. It can be concluded, when working with environmental data, that the structuring of knowledge in a conceptual model is essential for their subsequent integration into the SDI. During the modeling process it can be noticed that methodological issues related to the collection process may obstruct or make impracticable the data integration from different studies of the same area. The development of a database model and its subsequent publication in a Geoportal can be used as a reference for further research with similar goals.

Submitted by (edna.saturno@ufrpe.br) on 2017-02-14T14:20:14Z No. of bitstreams: 1 Ivo Thadeu Lira Mendonca.pdf: 906790 bytes, checksum: 20a8319a942fd0ff9acd8bcc2c266f8c (MD5) / Made available in DSpace on 2017-02-14T14:20:14Z (GMT). No. of bitstreams: 1 Ivo Thadeu Lira Mendonca.pdf: 906790 bytes, checksum: 20a8319a942fd0ff9acd8bcc2c266f8c (MD5) Previous issue date: 2009-02-18 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Opportunist species increase their population in detriment to others that previously participated in the assemblage, changing the ecosystem structure. Such changes can be used as ecological tools in pollutant sources monitoring, because they corroborate in the description of alterations of aquatic ecosystem trophic state. Therfore, this study aimed at surveying and characterizing the planktonic algae species of Boa Esperança Hydroelectric reservoir – PI/MA, Brazil, along its extension in different seasonal periods. Four quarterly surveys were carried out, between July 2006 and April 2007, in 17 sampling stations. The biological material was obtained through vertical tows along the euphotic zone. Algae ecological strategies and associations were defined and biotic indexes applied. 189 taxons were identified, distributed among Chlorophyta (94), Bacillariophyta (41), Cyanophyta (30), Euglenophyta (13), Dinophyta (4), Chrysophyta (3), Cryptophyta (3) and Xantophyta (1). The diversities and densities showed temporal differences, although tended to be longitudinally similar. The highest diversity was found in October 2006, 4,3 bit×org-1, in BOA 04, and the lowest was found in July 2006, 0,6 bit×org-1, in BOA 17, due the density of Aulacoseira granulata. The highest density was recorded in January 2007, 114,8×103 org×L-1, in BOA 17, and the lowest in April 2007, 1,4×103 org×L-1, in BOA 02. During the study, Cyanophyta and Aulacoseira granulata (Bacillariophyta) were the algal division and the species that presented the highest densities, respectively. The indexes indicated that the environment was, predominantly, mesotrophic during the year sessions. / Espécies oportunistas aumentam sua população em detrimento de outras que, outrora participavam da comunidade, mudando a estrutura populacional. Mudanças nessa estrutura podem ser utilizadas como ferramentas ecológicas em monitoramento de fontes poluidoras, pois corroboram na descrição de alterações do estado trófico em ecossistemas aquáticos. Sendo assim, objetivou-se inventariar e caracterizar as espécies de algas planctônicas do reservatório da Hidroelétrica de Boa Esperança, PI/MA, Brasil, ao longo de sua extensão e em diferentes períodos sazonais. Foram realizadas quatro coletas trimestrais, entre julho de 2006 e abril de 2007, em 17 estações amostrais. O material biológico foi obtido através de arrastos verticais ao longo da zona eufótica. Foram definidas as associações ecológicas e calculados índices bióticos. Foram identificados 189 táxons, distribuídos entre as Chlorophyta (94), Bacillariophyta (41), Cyanophyta (30), Euglenophyta (13), Dinophyta (4), Chrysophyta (3), Cryptophyta (3) e Xantophyta (1). As diversidades e densidades apresentaram diferenças entre os períodos de coleta, embora longitudinalmente tenham tendido à homogeneidade. A maior diversidade foi encontrada em outubro/06, 4,3 bit.org-1, em BOA 04, enquanto a menor em julho/06, 0,6 bit.org-1, em BOA 17, devido a densidade de Aulacoseira granulata. A maior densidade foi observada em janeiro/07, 114,8×103 org.L-1, em BOA 17, e a menor em abril/07, 1,4×103 org.L-1, em BOA. Durante o estudo, Cyanophyta e Aulacoseira granulata (Bacillariophyta) foram a divisão algal e a espécie que apresentaram as maiores densidades, respectivamente. Os índices aplicados indicaram que o ambiente encontra-se, predominantemente, mesotrófico nos diferentes períodos do ano.

Com o objetivo de avaliar o potencial bioindicador de Psidium guajava e Psidium cattleyanum para avaliação da qualidade do ar em área industrial no município de Canoas, Brasil, estas espécies foram expostas em monitoramento ativo em nove pontos de amostragem, sendo cinco internos e quatro externos a área de influência de uma área industrial e mais um ponto controle localizado no Campus do Vale da Universidade Federal do Rio Grande do Sul, distando 27 Km da área de estudo. Foram realizadas cinco exposições para P. guajava e quatro para P. cattleyanum que coincidiram com as estações de inverno (2005, 2006), primavera (2005), verão (2006) e outono (2006), durante o período de um ano e três meses de monitoramento. A exposição foi feita em estandes padronizados a um metro de altura do solo, com suplementação automática de água e proteção contra o excesso de radiação. Após cada três meses de exposição foram medidos o crescimento relativo em altura, a área foliar e a biomassa total, nas duas espécies expostas.Em P. cattleyanum foi analisado também a formação de ácido malonialdeído (MDA) nas folhas primárias e em P. guajava foi analisado a fotossíntese máxima e a eficiência carboxilativa in vivo, o teor de níquel e de enxofre em folhas secas, previamente lavadas. As medidas de crescimento, área foliar e biomassa não apresentaram diferença significativa em relação ao controle para as duas espécies, o que indica que não houve danos visíveis devido à poluição atmosférica. A formação de MDA mostrou diferença significativa na coleta de verão e inverno, em sua maioria, para os pontos internos. Os teores de enxofre apresentaram valores entre 0,15 e 0,41% ficando abaixo dos níveis basais paraplantas terrestres, observando-se diferenças significativas em relação ao ponto controle, para as coletas de verão e primavera, apenas para dois pontos internos. Os teores de níquel apresentaram valores entre 0,2 e 3 μg g-1, também ficando abaixo dos níveis basais para plantas terrestres, mas apresentaram diferenças significativas em relação ao ponto controle para todas as coletas. Os pontos que apresentaram diferenças para o teor de níquel em relação ao controle foram aqueles localizados internamente na área industrial a menos de 1,5 km da potencial fonte emissora de níquel, excetuando-se a coleta de verão onde a maioria dos pontos apresentou diferenças significativas em relação ao ponto controle. A fotossíntese máxima e a eficiência carboxilativa não apresentaram diferenças significativas em nenhuma coleta. / In order to evaluate the bioindicator potential of Psidium guajava and Psidium cattleyanum to air quality monitoring, these species were exposed in an industrial area in the city of Canoas, Brazil, in ten different sites, five inner, four outside of industrial area and one control site placed at Federal University of Rio Grande do Sul. The exposures coincident with the season of winter (2005, 2006), spring (2005), summer (2006) and fall (2006) amount five exposures for P. guajava, and four exposures for P. cattleyanum. The exposition was made in a standard frame 1,0 m above the ground, with automatic supply of water and protection to excessive radiation. After three moths of exposure it was assessed total biomass, leaf area and height relative growth rate for both species. For P. cattleyanum it was assesed the content of malondialdehyde (MDA) in leaves, and for P. guajava it was assessed the nickel and sulfur content, maximum photosynthesis and carboxilation efficiency.The evaluate of total biomass, leaf area, height relative growth rate did not show any significant differences for both species, that indicate did not occur visual damage due the air pollution. MDA showed significant differences in summer and winter, mostly for inner sites. The sulfur content showed values between 0,15 and 0,41 %, below the basal level for terrestrial plants and showed significant differences in relation of control for spring and summer for three inner sites. The values of Ni showed between 0,2 and 3 μg g-1 and they were below of basal level for terrestrial plants, but showed significant differences in relation to control site for all seasons. The inner sites that showed significant differences were placed about 1,5 km from potential source emission ofNi, except in the summer whose distribution of Ni values was higher and the most of the sites showed significant differences in relation to control site. The maximum photosynthesis and the carboxilation efficiency did not show significant differences in relation to control site.

L’objectif de cette thèse est le diagnostic de l’état de santé de la lagune de Bizerte par une approche multi-marqueurs (chimique, biochimique et morphométrique) et multi-compartiments (sédiment et biote). Pour atteindre cet objectif, les modèles biologiques choisis sont la moule Mytilus galloprovincialis et le poisson gobie Zosterisessor ophiocephalus. Ces deux espèces sont largement répandues dans la lagune de Bizerte et la mer Méditerranée. Dans une première partie et afin d’estimer les niveaux de contamination de la lagune de Bizerte par les polluants organiques persistants (POPs), des analyses chimiques, granulométriques et minéralogiques (COT) de sédiments superficiels ont été réalisées. Par la suite la toxicité potentielle des sédiments a été évaluée par une batterie de bioessais. Dans une troisième partie la biodisponibilité et l’impact écotoxicologique des POPs étudiés ont été évalués par l’accumulation de ces contaminants au niveau des deux organismes indicateurs choisis et l’étude des réponses biologiques associées à travers quelques biomarqueurs tels que la catalase (CAT), l’acide thiobarbiturique (TBARS); l’Ethoxyrésorufine O-dééthylase (EROD); la glutathion-S-transférase (GST) et l'acétylcholinestérase (AChE). Les principaux résultats des analyses chimiques révèlent une contamination générale des sédiments et organismes étudiés par les POPs. Les niveaux de contamination sont fonction de l’espèce et de la station étudiée. La comparaison de nos valeurs avec les données de la littérature a montré que les niveaux de contamination de la lagune sont similaires ou légèrement inférieurs à ceux enregistrés dans des écosystèmes équivalents dans d’autres pays du monde. L’estimation de la toxicité des sédiments au moyen des valeurs guides sédimentaires (ERL, ERM, TEL et PEL) et trois tests biologiques (Microtox®, SOS-Chromotest® et test MELA) ont montré que les sédiments des stations du canal de Bizerte S1 et S3 représentent un danger accru pour les organismes aquatiques. Nos résultats ont montré que les biomarqueurs mesurés chez les deux espèces choisies sont des paramètres sensibles et inductibles permettant de qualifier l’état de santé des organismes et la qualité globale du milieu étudié. Les marqueurs morphométriques contrairement aux marqueurs biochimiques n’ont pas permis de discriminer les différents sites étudiés. Contrairement aux poissons, il a été démontré chez les moules que les facteurs abiotiques ont une influence sur les concentrations en POPs et les réponses des biomarqueurs.Au vu de l’ensemble de ces résultats, il apparaît que cette approche intégrative associant des mesures chimiques et écotoxicologiques représente un bon moyen pour évaluer la qualité de l’environnement notamment dans le cadre de programmes de biosurveillance. / The objective of this thesis was the diagnosis of the health status of the Bizerte lagoon using a multi-marker (chemical, biochemical and morphometric) and multi-compartment approach (sediment and biota). To achieve this objective, the selected biological models were the mussel Mytilus galloprovincialis and the goby fish Zosterisessor ophiocephalus. Both species are widespread in the Bizerte lagoon and the Mediterranean Sea. In a first part and in order to estimate the levels of contamination of the Bizerte lagoon, persistent organic pollutant (POPs), granulometric and mineralogical (TOC) analyses of surficial sediments were carried out. Afterwards, the potential toxicity of sediments was assessed by a battery of bioassays. In a the third part, bioavailability and ecotoxicological impact of POPs studied were assessed by bioaccumulation measurement in these two indicators species, and the study of biological responses associated through a battery of biomarkers such as catalase (CAT), thiobarbituric acid (TBARS); Ethoxyresorufin O-deethylase (EROD); glutathione-S-transferase (GST) and acetylcholinesterase (AChE). The main results of the chemical analyses show a general contamination of sediments and organisms studied by POPs. Contamination levels are dependent on the studied species and stations. Comparing our values with literature data, showed that the levels of contamination of the lagoon are similar or slightly lower than equivalent ecosystems in other parts of the world. Besides, the estimation of sediment toxicity, using sediment guideline values (ERL, ERM, TEL et PEL), as well as bioassays (Microtox®, SOS-Chromotest® and MELA test) showed that stations of canal of Bizerte S1 and S3 were associated with an increased hazard to aquatic organisms. Our results showed that biomarkers measured in both selected species are sensitive and inducible parameters, which allowed to characterize the health status of organisms and global quality of the studied environment. Biochemical but not morphometric markers allowed to discriminate the different studied sites according to chemical risk. Unlike fish, it has been demonstrated in mussels that abiotic factors influence the concentrations of POPs and biomarker responses.Obtained data suggest that integrative approach, combining chemical and ecotoxicological measurements, may represent a good way to asses the quality of the environment, particularly, in the context of biomonitoring programs.

Los estudios de biomonitorización con aves rapaces permiten evaluar el grado de contaminación ambiental y las consecuencias sobre la salud humana y ambiental. Los niveles de metales e insecticidas organoclorados en sangre de pollos de Búho real del sureste de España fueron en general bajos, siendo los niveles de plomo significativamente superiores en los individuos nacidos en una antigua zona minera. La enzima δ-ALAD es un biomarcador sensible de exposición y efecto a plomo en esta especie. El estudio de organoclorados y PBDEs en huevos no eclosionados sugiere cambios en la dieta o posibles focos de contaminación en la zona. El grosor de cáscara de huevo disminuyó conforme aumentaron las concentraciones de p,p’-DDE, alcanzando un porcentaje de disminución relacionada con declives poblacionales en aves a niveles de DDE superiores a 100 ng/g de peso de lípidos. El desarrollo de una nueva técnica permitió detectar residuos de rodenticidas en el 83% de las muestras de hígado. / Biomonitoring studies with raptor birds can be used to evaluate environmental pollution and consequencies to human and environmental health. Levels of metals and insecticides in blood of eagle owl chicks from Southeastern Spain were in general low, being lead levels significantly higher in individuals born in an ancient mining area. The enzime δ-ALAD is a sensitive biomarker of exposure and effect to lead in this species. The study of organochlorine and PBDEs in unhatched eggs suggests dietary shifts or pollutant sources. Eggshell thickness decreased with increasing p,p’-DDE, reaching a level related to population declines in birds when DDE levels exceded 100 ng/g lipid weight. The development of a new tecnique permited the detection of rodenticide residues in 83% of the liver samples.