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<p>This doctoral research comparatively assesses the biogeochemical properties of suspended aquatic flocs through a integrated field-laboratory approach; providing new insight into the linkages among floc associated bacteria, floc-reactive solid phases and trace metal uptake.</p> <p>Results show flocs to possess a distinct geochemistry, microbiology and composition from bed sedimentary materials in close proximity (III-oxyhydroxide minerals (FeOOH); resulting in localized floc-Fe-mineral precipitates and enhanced reactivity. Further, the Fe-enrichment of floc and of floc bio-mineral constituents in turn provides an important and novel lens through which to examine how environmental microbial communities, microbial metabolism and Fe^III/Fe^IIredox transformations interact. The results were the discovery of floc-hosted, Fe^III/II-redox cycling bacterial consortia across diverse oxygenated (O₂^Sat.=1-103%) aquatic systems, which were not predicted to sustain bacterial Fe-metabolism. Both environmental<em> </em>and experimentally-developed consortial aggregates constituted multiple genera of aero-intolerant Fe^III-reducing and Fe^II-oxidizing bacteria together with oxygen consuming organotrophic species. These findings highlight that the implementation of geochemical thermodynamic constraints alone as a guide to investigating and interpreting microbe-geosphere interactions may not accurately capture processes occurring <em>in situ.</em></p> <p><em> </em> Seasonal investigation of microbial Fe^III/II-redox transformations highlighted the interdependence of floc Fe-redox cycling consortia members, revealing that cold conditions and a turnover in putative Fe-reducing community membership extinguishes the potential for coupled Fe-redox cycling by wintertime floc bacteria. Further, the observed summer-winter seasonal turnover of <em>in situ</em> floc community membership corresponded with an overall shift from dominant Fe to S redox cycling bacterial communities. This significantly impacted observable floc Fe and TE (Cd, Pb) geochemistry, resulting in a shift in floc associated Fe-phases from dominantly Fe^(III)_(s) to Fe^(II)_(s), and, in turn, corresponded to a large decrease of TE uptake by flocs under ice.</p> / Doctor of Science (PhD)

O Reservatório do Rio Grande faz parte do Complexo Billings, apesar de ser separado do Corpo Central pela barragem Anchieta. Esse reservatório está localizado na Região Metropolitana de São Paulo e é aproveitado para usos múltiplos, incluindo abastecimento público, recreação, lazer e corpo receptor de dejetos industriais e domésticos. No presente trabalho, foi estudada a coluna d’água de 6 pontos de coleta ao longo desse reservatório, em duas excursões a campo, uma em março e outra em outubro de 2004. Foram feitas medições de pH, temperatura, condutividade elétrica, oxigênio dissolvido (OD), transparência da coluna d’água, material em suspensão, sólidos totais, clorofila a, feoftina e compostos nitrogenados. Os dados foram tratados estatisticamente por meio de análise multivariada não paramétrica tipo PCA. Durante o mês de março, houve estratificação térmica, de pH e de condutividade elétrica. No mês de outubro houve maiores concentrações de clorofila a e menor transparência do disco de Secchi. O Índice de Estado Trófico, calculado a partir da clorofila a e a partir da profundidade do disco de Secchi, revelaram um ambiente meso a eutrófico. Foram registrados teores de NH4+, OD e clorofila a referentes a classes de uso menos nobres, de acordo com a Resolução CONAMA n° 357 de 17/03/2005. A análise estatística mostrou que os dois primeiros eixos explicam 55% da variância dos dados. O nitrogênio total e o pH são as variáveis que mais contribuem para compor os eixos 1 e 2, respectivamente, refletindo a importância do estado trófico para a caracterização do reservatório e a carga de esgoto que o corpo d’água recebe. Os pontos de amostragem se segregaram de acordo com a data de coleta, sem demonstrar padrão no sentido montante-jusante. O Reservatório do Rio Grande, Complexo Billings, está localizado na Região Metropolitana de São Paulo, e é um importante local de recreação e de onde é extraída água para o abastecimento de cidades da Grande São Paulo. Os sedimentos lacustres são um reservatório concentrado de contaminantes, dentre os quais se destacam os metais-traço. Esses metais podem ser incorporados à biota, acumulados e transferidos ao longo da rede trófica (bioacumulação e biomagnificação) ou permanecer biologicamente indisponíveis na forma de complexos insolúveis ou muito estáveis e refratários. Em ambiente anóxido, o sulfeto pode controlar a disponibilidade de íons metálicos livre, pois reage com os metais para formar um sal insolúvel potencialmente não biodisponível. Neste trabalho, foi utilizado método de extração ácida fraca a frio para a determinação dos Sulfetos Volatilizáveis por Acidificação (SVA) e dos íons metálicos extraídos simultaneamente (MES). SVA foi quantificado por espectrofotometria visível, enquanto Cd, Cu, Ni, Pb, Cr e Zn por ICP-AES. Matéria orgânica (MO) e a porcentagem de silte e argila, fases importantes na complexação de metais, também foram quantificadas. Os resultados foram comparados com valores-guias de qualidade de sedimento sugeridos pela USEPA (relação molar &#8721; MES-SVA) e pelo Conselho Canadense do Ministério do Meio Ambiente (CCME) e também com Valores de Referência Regionais (VRR) estabelecidos para a Bacia do Alto-Tietê. Os resultados mostraram haver excesso de sulfeto em relação aos teores de metais, o que indica um baixo potencial tóxico. Houve um aumento do teor de SVA da ordem de 100 vezes do ponto 4 (montante) ao ponto 26 (jusante). No entanto, as concentrações de metais foram superiores ao VRR, especialmente Cu (102,7 vezes maior), Cd (46,2 vezes) e Pb (12,5 vezes). Também foram registradas concentrações maiores que as sugeridas pelo CCME (9,3; 8,3 e 2,9 vezes maior para Cu, Pb e Cd, respectivamente). À exceção do Zn, todos os metais analisados apresentaram incremento no sentido montante-jusante. A análise estatística tipo PCA demonstrou que a variação dos dados de metais possui correlação com a variação de MO, ao invés de SVA, o que sugere a importância da MO no controle da biodisponibilidade de metais. / The Rio Grande branch is a part of Billings Complex and is isolated from the central body by Anchieta Dam. This reservoir is located in São Paulo Metropolitan Region and has multiple uses, including water supply, recreation, leisure, receptor of domestic and industrial wastewater. At the present work, the water column was studied in 6 stations along the reservoir, in two different days (one in March and the other in October, 2004). We measured pH, temperature, electric conductivity, dissolved oxygen (DO), transparence of water column, suspended material, total solid, chlorophyll a, feoftin, nitrogenated substances. The data was treated by means of a PCA, a multivariate non-parametric analysis. During March, the water column was stratified because of temperature, pH and electric conductivity. During October, there were higher chlorophyll a concentrations and lower transparence. Trofic State Index was calculated from chlorophyll a and from Secchi disc data, and showed a meso to eutrofic environment. Some NH4+, DO and chlorophyll a concentrations are those of classes designated for less noble uses according to Brazilian law CONAMA n° 357 of 17/03/2005. The statistical analysis showed that the first two axis where responsible for 55% of the total data variance. Total nitrogen and pH were the variables that contributed most for the composition of axis 1 and 2. This reflects the importance of trofic state for the reservoir’s characteristics. The stations were segregated according to the sampling date, with no high-low direction pattern. Rio Grande reservoir, Billings Complex, is located in São Paulo Metropolitan Region. It is an important recreation place from where water is extracted in order to supply cities nearby. Lacustrine sediments are concentrated pool for chemicals, among which are trace metals. These metals may be taken up by organisms, accumulated by them and transferred along the food web (bioaccumulation and biomagnification) or may remain biologically unavailable as insoluble, stable and refractory complexes. In anoxic environments, sulfide may be responsible for metal free ion availability control, since it reacts with metal ions and forms an insoluble salt, potentially not bioavailable. At the present work, it was used a weak-acid extraction method for the acid volatile sulfide (AVS) and the simultaneously extracted metals (SEM) determination. Cd, Cu, Ni, Pb, Cr and Zn were quantified by means of an ICP-AES and AVS by means of visible spectrophotometer. Organic matter (OM) and clay-silt percentiles, important phases for metal complexation, were also measured. Results were compared to sediment quality guidelines suggested by USEPA (&#8721; MES-SVA molar relation) and by Canadian Council of Ministers of Environment (CCME) as well by Regional Reference Values (RRV) established for the Alto-Tietê basin. There was an increase of AVS concentration of 100 folds from station 4 (near the riverine region) to station 26 (near the dam). Results showed excess of sulfide compared with metals, what means a low toxic potential. On the other hand, metal concentrations were above RRV, specially Cu (102,7 times greater), Cd (46,2 times greater) and Pb (12,5 times greater). There were also concentrations greater than values suggested by CCME (9,3; 8,3 and 2,9 times greater for Cu, Pb and Cd, respectively). Excepted by Zn, all metals showed increasing patterns from upper to lower regions of the reservoir. PCA statistical analysis demonstrated that the metal data variation has a correlation with OM variation, instead with AVS, and suggests the importance of OM in controlling metal bioavailability in the studied system.

Shelf seas represent an important source of iron (Fe) to the open ocean. Additionally, shelf seas are highly productive environments which contribute to atmospheric carbon dioxide drawdown and support large fisheries. The work presented in this thesis describes the seasonal cycle of Fe in the Celtic and Hebridean Shelf Seas, and determines the physico-chemical speciation of Fe supplied from oxic margins. The results from repeated field surveys of the central Celtic Sea showed a nutrient type seasonal cycling of dissolved Fe (< 0.2 µm; dFe), which is surprising in a particle rich shelf system, suggesting a balance of scavenging and remineralisation processes. Coincident drawdown of dFe and nitrate (NO3-) was observed during the phytoplankton spring bloom. During the bloom, preferential drawdown of soluble Fe (< 0.02 µm; sFe) over colloidal Fe (0.02-0.2 µm; cFe) indicated greater bioavailability of the soluble fraction. Throughout summer stratification, it is known that NO3- is drawn down to < 0.02 µM in surface waters. This study revealed that both dFe and labile particulate Fe (LpFe) were also seasonally drawn down to < 0.2 nM. Consequently, it is hypothesised that the availability of Fe seasonally co-limits primary production in this region. At depth both dFe and NO3- concentrations increased from spring to autumn, indicating that remineralisation is an important process governing the seasonal cycling of dFe in the central Celtic Sea. In spring, summer and autumn, distinctive intermediate nepheloid layers (INL) were observed emanating from the Celtic Sea shelf slope. The INLs were associated with elevated concentrations of dFe (up to 3.25 ± 0.16 nM) and particulate Fe (up to 315 ± 1.8 nM) indicating that they are a persistent conduit for the supply of Fe to the open ocean. Typically > 15% of particulate Fe was labile and 60-90% of dFe was in the colloidal fraction. Despite being < 50 km from the 200 m isobath, the concentration of dFe was < 0.1 nM in surface waters at several stations. Broadly, the concentration of nutrients in surface waters described an oligotrophic environment where co-limitation between multiple nutrients, including Fe, appears likely. Over the Hebridean shelf break, residual surface NO3- concentrations (5.27 ± 0.79 µM) and very low concentrations of dFe (0.09 ± 0.04 nM) were observed during autumn, implying seasonal Fe limitation. The dFe:NO3- ratio observed is attributed to sub-optimal vertical supply of Fe relative to NO3- from sub-surface waters. In contrast to the shelf break, surface water in coastal regions contained elevated dFe concentrations (1.73 ± 1.16 nM) alongside low NO3-. Seasonal Fe limitation is known to occur in the Irminger and Iceland Basins; therefore, the Hebridean shelf break likely represents the eastern extent of sub-Arctic Atlantic seasonal Fe limitation, thus indicating that the associated weakening of the biological carbon pump exists over a wider region of the sub-Arctic Atlantic than previously recognised. These key findings demonstrate that the availability of Fe to phytoplankton may seasonally reach limiting levels in temperate shelf waters and that oxic margins persistently supply Fe dominated by colloidal and particulate fractions to the ocean.

Les potentiels de nouveaux moyens d’investigation en sciences de l’environnement, tel que la géochimie des isotopes stables du Cu et du Zn et l’étude de la spéciation des éléments en trace métalliques (ETM) par titrage acidimétrique sont évalués dans le cadre de trois cas d’études, faisant intervenir des matériaux de matrices et de concentrations en ETM variables. Afin de mettre en évidence de très subtiles variations des compositions isotopiques du Cu et du Zn dans les matériaux particulaires variablement pollués, une attention particulière à été voué à la mise au point des méthodes de séparation chimique et d’analyse par MC-ICP-MS. La méthodologie analytique a été développée afin d’exploiter tout les avantages techniques offerts par le spectromètre de masse à l’ULB. Différents modes d’introduction (plasma humide vs plasma sec (Aridus/DSN), d’acquisition des mesures (mode statique ou dynamique) de correction du biais de masse (dopage au Cu, au Zn et au Ga; correction SSBM, SSBC et EEN)ont été évaluées, pour leurs effets sur la précision et la reproductibilité des mesures. D’autres travaux ont permis de quantifier les effets des interférences spectrales et non spectrales par les éléments de la matrice (Ti, Cr, Co,Fe, Ba, Si, Na, Mg et Ca) et par le rapport dopant/analyte en vue de comprendre les sources d’inexactitudes des mesures isotopiques et d’y remédier. Les données isotopiques acquises sur des minerais, sur des (plaques de) dépôts atmosphériques (usine Pb-Zn Metaleurop de Noyelles-Godault), sur des sédiments et des matières en suspension (estuaire de l’Escaut et mer du Nord), révèlent des variations significatives des compositions isotopiques du cuivre et du zinc. Dans l’estuaire de l’Escaut, les variations temporelles (carotte non perturbée, enregistrant la sédimentation sur 30 ans) et spatiales (matières en suspension échantillonnées sur 100 km, selon le profil de salinité) sont caractérisées par des signatures isotopiques en Zn anticorrélées à celle du Cu. Les données peuvent permettre de distinguer le fond géochimique naturel (le « réservoir naturel »), les pollutions diffuses (le « réservoir anthropique commun »- intégrant de multiples sources de contamination en provenance du bassin versant) et certaines pollutions ponctuelles associées à la métallurgie du Zn. Alors que les procédés utilisés en métallurgie sont eux,capable de produire des signatures isotopiques très fractionnées en Zn, ni la diagenèse précoce dans les sédiments, ni les gradients physicochimiques développés lors du mélange des eaux continentales et marines ne sont capables d’affecter significativement la signature isotopique du Cu et du Zn en phase particulaire. Dans de tels milieux, les signatures isotopiques en Cu et Zn (ainsi que celles en Pb) semblent n’être contrôlées que par le mélange conservatif entre le « réservoir naturel » et le « réservoir anthropique commun ». Les données en elles-mêmes constituent la seule base de données isotopiques en Cu, Zn, Pb dans des matériaux particulaires anthropisés estuariens et marins jamais produite à ce jour. Elles permettent de prédire que la signature isotopique en Cu du « réservoir naturel » devrait être légèrement plus enrichie en isotopes lourds que celle du réservoir « anthropique commun » (par analogie au Zn). Si la géochimie isotopique du Cu et du Zn a le potentiel de distinguer différentes sources de pollution, l’évaluation des risques liés à ces pollutions doit tenir compte des formes chimiques des ETM, typiquement mises en évidences par les méthodes d’extraction sélectives (séquentielles, dont le protocole BCR). La méthode alternative proposée pour l’étude de la spéciation, plus versatile (capable de mettre en évidence des phases non prédéfinies et applicable à une variété de matrices plus large) est capable de surmonter plusieurs limitations (dont les problèmes de sélectivité liées au mauvais contrôle de l’acidité du milieu réactionnel) caractéristiques des méthodes traditionnelles. Appliquée à des sédiments marins/estuariens et des sols, la méthode de titrage acidimétrique s’est révélée capable de quantifier les proportions relatives des phases acido-solubles (principal problème des méthodes d’extraction sélectives), ce qui permet d’établir univoquement la spéciation des éléments qui leurs sont associés, d’évaluer la réactivité des ETM vis-à-vis du pH, mais aussi d’évaluer la sélectivité des protocoles d’extraction séquentielle « BCR » et « Tessier ». La méthode de titrage acidimétrique apporte également des informations importantes sur la géochimie des éléments majeurs dans l’estuaire de l’Escaut et met en évidence les particularités minéralogiques des sols pollués en comparaison aux sédiments. Les études de cas démontrent que ces nouvelles techniques ont des applications dans le domaine de la géochimie de l’environnement, mais peuvent également être vouées, sur le moyen/long terme à une utilisation sortant du cadre des sciences exactes. En effet, l’identification/ discrimination des sources de pollutions et l’évaluation des risques de remobilisation des polluants métalliques font partie des nombreuses questions posées par la société aux scientifiques de l’environnement.

The Black Sea, with its oxic, suboxic and anoxic layers, provides a unique environment for studying how biological and geochemical processes affect the composition of particulate matter. The elemental composition of particles in the Black Sea is controlled by their origin and sources. Particles from rivers are dominated by aluminosilicate material that has compositions similar to the earth&rsquo / s crust. In general this material is relatively unreactive. Biological processes in the upper oxic and suboxic layers of the water column result in enrichments of elements which used as nutrients. Cu, Ba and Mo have been proposed as tracers for planktonic material and new production. Geochemical processes like manganese and iron recycling between oxidized and reduced forms, metal sulfide formation, and biogenic matter decomposition can have a large impact on the composition of particles in the suboxic and anoxic zones. The aim of this thesis was to study the composition of particles suspended in the water column of the Black Sea, in regional rivers draining into the Black Sea, and of particles deposited in these rivers and Black Sea sediments. The objectives were to determine the chemical composition and distribution of particles supplied by rivers and produced in the Black Sea, and compare with those particles buried in the sediments. The chemical distributions can help us to understand the biogeochemical processes taking place. The ultimate goal is to understand if there is a chemical signature that characterizes sediments deposited in anoxic basins that can be used to determine if ancient sedimentary rocks were deposited under such conditions. Water column filter samples were collected from the central western basin and along transects to the SW shelf regions during several research cruises of R/V Bilim and R/V Knorr in the Black Sea. Samples were taken by using both in situ large volume filtration systems and on deck vacuum filtration of discrete samples. River samples were collected by hand from the bank of four Turkish rivers and the Danube River. Sediment samples were obtained from 0 - 25 cm interval of a box core from the deep western basin. All samples were digested and analyzed by inductively coupled plasma - mass spectrometry and combination of atomic absorption (flame &amp / graphite furnace) instruments. The elements analyzed included Al, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Mo, Ag, Cd, Ba, Pb, and U. Great care was taken to avoid contamination and to obtain the highest level of precision and accuracy. The precision was typically about 5% for most elements. The accuracy, determined using standard reference materials, was also usually better than 5%. Another goal of this research was to determine the metal concentrations and best digestion methods using different types of filter materials. Blank filters were digested and analyzed and the analyses of various filter blanks are presented in the thesis. The analyses showed that the particulate matter data from Turkish Rivers were very similar to the composition of global average riverine particulate material and global average crust. The Danube River had elevated concentrations for some elements that were probably due to anthropogenic contamination. The Turkish river samples were closer to (but still higher than) the averages for the world&rsquo / s rivers but many elements in the Danube were much higher. These high values determined for major elements in the Danube samples strongly suggest considerable contamination of the Danube as compared to the Turkish Rivers. The Danube River samples were especially enriched in Pb, Zn, Ag, Cu, Cd, and Mn and slightly enriched with Cr and Ni. The first five elements, in particular, are well known indicators of pollution. The particulate matter in the water column of the Black Sea was influenced by lithogenic input from rivers, biological processes and geochemical processes. In order to examine the biogeochemical processes extensively, all the data were plotted as Metal/Al (Me/Al) ratios and compared with the ratios of the average crust and Turkish Rivers. Deviations were used to examine the anomalies due to biological and geochemical processes. In addition, the Al content of individual sample and the Me/Al ratio of crust or rivers were used to subtract the lithogenic component from the total composition. Enrichments due to biological processes were observed for Ba &gt / Fe &gt / Cr &gt / Mn &gt / Zn &gt / Ni &gt / Cu &gt / Mo &gt / V &gt / Co &gt / Cd &gt / U for the overall biogenic composition. Enrichments due to biology are most evident for Ba, Fe, Cr and Mn. This is a unique data set as there have been few previous analyses of biological enrichment for most of these elements. The results of particulate matter analyses showed that some elements including U, V, Cr, Ni, Cu, Co, Zn, Ba and Mo were enriched in the set of samples from the euphotic zone. Redox cycling in the suboxic zone was observed, as expected, for Mn and Fe, whose oxides play an important role in scavenging processes. The redox dependent processes in the suboxic &ndash / anoxic interface influence the vertical distribution of U, Ni, Co, Cu, Zn, Ba and possibly Mo, Cr and V. Elements influenced by sulfide formation in the anoxic layer are Fe, Cr, Ni, Co, Mo, and presumably Ag. The sediment data were also examined based on the same approaches. The elements Zn, Pb, U and Cd decreased with sediment depth over the top 5 cm suggesting that they were remobilized out of the sediments. In general the sediments from the Black Sea have Me/Al ratios very similar to local Turkish Rivers and average crust. There is no unique sediment signature (except possibly for Mo) indicating that these sediments were deposited under sulphidic conditions. This study does not support the hypothesis that the composition of ancient rocks can be used to characterize the environment of deposition.

The West Pacific Warm Pool (WPWP) plays an important role in the global heat budget and global hydrologic cycle, so knowledge about its past variability would improve our understanding of global climate. Variations in WPWP precipitation are most notable during El Niño-Southern Oscillation events, when climate changes in the tropical Pacific impact rainfall not only in the WPWP, but around the globe. The stalagmite records presented in this dissertation provide centennial-to-millennial-scale constraints of WPWP precipitation during three distinct climatic periods: the Last Glacial Maximum (LGM), the last deglaciation, and the Holocene. In Chapter 2, the methodologies associated with the generation of U/Th-based absolute ages for the stalagmites are presented. In the final age models for the stalagmites, dates younger than 11,000 years have absolute errors of ±400 years or less, and dates older than 11,000 years have a relative error of ±2%. Stalagmite-specific 230Th/232Th ratios, calculated using isochrons, are used to correct for the presence of unsupported 230Th in a stalagmite at the time of formation. Hiatuses in the record are identified using a combination of optical properties, high 232Th concentrations, and extrapolation from adjacent U/Th dates. In Chapter 3, stalagmite oxygen isotopic composition (d18O) records from N. Borneo are presented which reveal millennial-scale rainfall changes that occurred in response to changes in global climate boundary conditions, radiative forcing, and abrupt climate changes. The stalagmite d18O records detect little change in inferred precipitation between the LGM and the present, although significant uncertainties are associated with the impact of the Sunda Shelf on rainfall d18O during the LGM. A millennial-scale drying in N. Borneo, inferred from an increase in stalagmite d18O, peaks at ~16.5ka coeval with timing of Heinrich event 1, possibly related to a southward movement of the Intertropical Convergence Zone (ITCZ). An inferred precipitation maximum (stalagmite d18O minimum) during the mid-Holocene in N. Borneo supports La Niña-like conditions and/or a southward migration of the ITCZ over the course of the Holocene as likely mechanisms for the observed millennial-scale trends. In Chapter 4, stalagmite Mg/Ca, Sr/Ca, and d13C records reflect hydrologic changes in the overlying karst system that are linked to a combination of rainfall variability and cave micro-environmental effects. Dripwater and stalagmite geochemistry suggest that prior calcite precipitation is a mechanism which alters dripwater geochemistry in slow, stalagmite-forming drips in N. Borneo. Stalagmite Mg/Ca ratios and d13C records suggest that the LGM climate in N. Borneo was drier and that ecosystem carbon cycling may have responded to the drier conditions. Large amplitude decadal- to centennial-scale variability in stalagmite Mg/Ca, Sr/Ca and d13C during the deglaciation may be linked to deglacial abrupt climate change events.

La prise de conscience grandissante de la contamination des cours d'eau a entraîné l'établissement de réglementations de plus en plus strictes concernant les rejets urbains et la fixation d'objectifs de qualité à atteindre pour les milieux aquatiques. Cependant, l'échantillonnage ponctuel reste une limite importante dans l'estimation des flux de contaminants, et le besoin de suivis en continu est présent dans le milieu naturel et dans les réseaux d'assainissement urbains. Cette étude porte sur la quantification de la part des rejets urbains de l'agglomération grenobloise dans les flux totaux de matières en suspension (MES), nutriments (azote, phosphore), carbone organique et éléments traces métalliques (ETM) du milieu récepteur Isère (une rivière alpine). Ce travail s'est appuyé sur un réseau de mesures en continu de débits (Q) et de MES (par turbidimétrie) à l'amont et à l'aval de l'agglomération et sur une sonde spectrométrique à l'amont, associé à des campagnes de prélèvements réguliers et renforcés pendant les épisodes de crues. Des campagnes de mesures détaillées sur les principaux sous bassins du réseau d'assainissement ont été réalisées durant la période d'étude dans le cadre du schéma directeur d'assainissement de l'agglomération grenobloise. Le croisement de ces deux approches a permis de confronter les variations spatio-temporelles des MES, nutriments, carbone organique et ETM du réseau et du milieu récepteur en 2011 et 2012. Les flux sur ces deux années ont été établis afin de déterminer la contribution des rejets urbains dans les flux du milieu récepteur. La contamination en mercure a fait l'objet d'un suivi particulier du fait de la présence d'une source significative de mercure dans la région. Enfin, une réflexion sur l'amélioration des calculs de flux par l'utilisation de relations entre les ETM/carbone organique particulaire (COP) et un paramètre mesurable en continu (MES, Q) a été menée en parallèle de l'exploitation de ces résultats. Mots-clés : Matières en suspension ; Dynamique des flux ; Nutriments ; Eléments traces métalliques ; Mercure ; Rejets urbains (par temps de pluie et temps sec), sondes de turbidité et spectrométrique. / The growing awareness of the contamination of rivers has led to the establishment of more rigorous regulations related to urban waste, and to the setting of water quality objectives to be achieved for aquatic environment. However, grab sampling remains an important limitation for the estimation of contaminant flux, and the need for constant monitoring is present in both natural environment and urban sanitation. This study focuses on the quantification of the proportion of urban waste in the Grenoble area to the total flux of 1) suspended solids (TSS), 2) nutrients (nitrogen and phosphorus), 3) organic carbon and 4) metals trace element (MTE) of the receiving environment; the Isère (an alpine river). This work was supported by a network of continuous discharge measurements (Q) and TSS (turbidimetry), both upstream and downstream of Grenoble associated with regular sampling campaigns, with a higher measurement frequency during flood events. A spectrometric probe upstream was also placed upstream. Detailed measurement campaigns on major sub-basins of the sewerage network were performed during the study period as part of the sanitation master plan of Grenoble. The combination of these two approaches allowes to relate the spatio-temporal variations of TSS, nutrients, organic carbon and MTE in the urban water network of Grenoble and in the receiving environment (the Isère) for the years 2011 and 2012. Flows of the traced parameters have been established to determine the contribution of urban waste flows in the receiving environment, over these two years. Finally, a study on how to improve the flow calculations by the use of relations between MTE / particulate organic carbon (POC ) and a continuous measurable parameter (MES, Q ) was conducted in parallel with these results. Key words: suspended solids, Nutrients, metals trace element; Mercury; urban waste; turbidimetry and spectrometric probe

O Reservatório do Rio Grande faz parte do Complexo Billings, apesar de ser separado do Corpo Central pela barragem Anchieta. Esse reservatório está localizado na Região Metropolitana de São Paulo e é aproveitado para usos múltiplos, incluindo abastecimento público, recreação, lazer e corpo receptor de dejetos industriais e domésticos. No presente trabalho, foi estudada a coluna d’água de 6 pontos de coleta ao longo desse reservatório, em duas excursões a campo, uma em março e outra em outubro de 2004. Foram feitas medições de pH, temperatura, condutividade elétrica, oxigênio dissolvido (OD), transparência da coluna d’água, material em suspensão, sólidos totais, clorofila a, feoftina e compostos nitrogenados. Os dados foram tratados estatisticamente por meio de análise multivariada não paramétrica tipo PCA. Durante o mês de março, houve estratificação térmica, de pH e de condutividade elétrica. No mês de outubro houve maiores concentrações de clorofila a e menor transparência do disco de Secchi. O Índice de Estado Trófico, calculado a partir da clorofila a e a partir da profundidade do disco de Secchi, revelaram um ambiente meso a eutrófico. Foram registrados teores de NH4+, OD e clorofila a referentes a classes de uso menos nobres, de acordo com a Resolução CONAMA n° 357 de 17/03/2005. A análise estatística mostrou que os dois primeiros eixos explicam 55% da variância dos dados. O nitrogênio total e o pH são as variáveis que mais contribuem para compor os eixos 1 e 2, respectivamente, refletindo a importância do estado trófico para a caracterização do reservatório e a carga de esgoto que o corpo d’água recebe. Os pontos de amostragem se segregaram de acordo com a data de coleta, sem demonstrar padrão no sentido montante-jusante. O Reservatório do Rio Grande, Complexo Billings, está localizado na Região Metropolitana de São Paulo, e é um importante local de recreação e de onde é extraída água para o abastecimento de cidades da Grande São Paulo. Os sedimentos lacustres são um reservatório concentrado de contaminantes, dentre os quais se destacam os metais-traço. Esses metais podem ser incorporados à biota, acumulados e transferidos ao longo da rede trófica (bioacumulação e biomagnificação) ou permanecer biologicamente indisponíveis na forma de complexos insolúveis ou muito estáveis e refratários. Em ambiente anóxido, o sulfeto pode controlar a disponibilidade de íons metálicos livre, pois reage com os metais para formar um sal insolúvel potencialmente não biodisponível. Neste trabalho, foi utilizado método de extração ácida fraca a frio para a determinação dos Sulfetos Volatilizáveis por Acidificação (SVA) e dos íons metálicos extraídos simultaneamente (MES). SVA foi quantificado por espectrofotometria visível, enquanto Cd, Cu, Ni, Pb, Cr e Zn por ICP-AES. Matéria orgânica (MO) e a porcentagem de silte e argila, fases importantes na complexação de metais, também foram quantificadas. Os resultados foram comparados com valores-guias de qualidade de sedimento sugeridos pela USEPA (relação molar &#8721; MES-SVA) e pelo Conselho Canadense do Ministério do Meio Ambiente (CCME) e também com Valores de Referência Regionais (VRR) estabelecidos para a Bacia do Alto-Tietê. Os resultados mostraram haver excesso de sulfeto em relação aos teores de metais, o que indica um baixo potencial tóxico. Houve um aumento do teor de SVA da ordem de 100 vezes do ponto 4 (montante) ao ponto 26 (jusante). No entanto, as concentrações de metais foram superiores ao VRR, especialmente Cu (102,7 vezes maior), Cd (46,2 vezes) e Pb (12,5 vezes). Também foram registradas concentrações maiores que as sugeridas pelo CCME (9,3; 8,3 e 2,9 vezes maior para Cu, Pb e Cd, respectivamente). À exceção do Zn, todos os metais analisados apresentaram incremento no sentido montante-jusante. A análise estatística tipo PCA demonstrou que a variação dos dados de metais possui correlação com a variação de MO, ao invés de SVA, o que sugere a importância da MO no controle da biodisponibilidade de metais. / The Rio Grande branch is a part of Billings Complex and is isolated from the central body by Anchieta Dam. This reservoir is located in São Paulo Metropolitan Region and has multiple uses, including water supply, recreation, leisure, receptor of domestic and industrial wastewater. At the present work, the water column was studied in 6 stations along the reservoir, in two different days (one in March and the other in October, 2004). We measured pH, temperature, electric conductivity, dissolved oxygen (DO), transparence of water column, suspended material, total solid, chlorophyll a, feoftin, nitrogenated substances. The data was treated by means of a PCA, a multivariate non-parametric analysis. During March, the water column was stratified because of temperature, pH and electric conductivity. During October, there were higher chlorophyll a concentrations and lower transparence. Trofic State Index was calculated from chlorophyll a and from Secchi disc data, and showed a meso to eutrofic environment. Some NH4+, DO and chlorophyll a concentrations are those of classes designated for less noble uses according to Brazilian law CONAMA n° 357 of 17/03/2005. The statistical analysis showed that the first two axis where responsible for 55% of the total data variance. Total nitrogen and pH were the variables that contributed most for the composition of axis 1 and 2. This reflects the importance of trofic state for the reservoir’s characteristics. The stations were segregated according to the sampling date, with no high-low direction pattern. Rio Grande reservoir, Billings Complex, is located in São Paulo Metropolitan Region. It is an important recreation place from where water is extracted in order to supply cities nearby. Lacustrine sediments are concentrated pool for chemicals, among which are trace metals. These metals may be taken up by organisms, accumulated by them and transferred along the food web (bioaccumulation and biomagnification) or may remain biologically unavailable as insoluble, stable and refractory complexes. In anoxic environments, sulfide may be responsible for metal free ion availability control, since it reacts with metal ions and forms an insoluble salt, potentially not bioavailable. At the present work, it was used a weak-acid extraction method for the acid volatile sulfide (AVS) and the simultaneously extracted metals (SEM) determination. Cd, Cu, Ni, Pb, Cr and Zn were quantified by means of an ICP-AES and AVS by means of visible spectrophotometer. Organic matter (OM) and clay-silt percentiles, important phases for metal complexation, were also measured. Results were compared to sediment quality guidelines suggested by USEPA (&#8721; MES-SVA molar relation) and by Canadian Council of Ministers of Environment (CCME) as well by Regional Reference Values (RRV) established for the Alto-Tietê basin. There was an increase of AVS concentration of 100 folds from station 4 (near the riverine region) to station 26 (near the dam). Results showed excess of sulfide compared with metals, what means a low toxic potential. On the other hand, metal concentrations were above RRV, specially Cu (102,7 times greater), Cd (46,2 times greater) and Pb (12,5 times greater). There were also concentrations greater than values suggested by CCME (9,3; 8,3 and 2,9 times greater for Cu, Pb and Cd, respectively). Excepted by Zn, all metals showed increasing patterns from upper to lower regions of the reservoir. PCA statistical analysis demonstrated that the metal data variation has a correlation with OM variation, instead with AVS, and suggests the importance of OM in controlling metal bioavailability in the studied system.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-05-29T17:53:20Z No. of bitstreams: 1 Dissertação Ester Ceschini.pdf: 1250748 bytes, checksum: 9594b56261da9429314abdc4fcd0d813 (MD5) / Made available in DSpace on 2017-05-29T17:53:20Z (GMT). No. of bitstreams: 1 Dissertação Ester Ceschini.pdf: 1250748 bytes, checksum: 9594b56261da9429314abdc4fcd0d813 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / O estudo da geoquímica de contaminantes (como os metais de origem antropogênica) no ecossistema de manguezal pode contribuir para uma melhor compreensão das funções e d os serviços ambientais prestados por este ecossistema. Este conhecimento dev e ser traduzido pa ra a sociedade, para fins de conservação e manutenção dos recursos naturais dos manguezais para as gerações futuras. Neste estudo, a distribuição de metais de interesse ambiental (Fe, Mn, Zn, Cu e Pb) entre o sedimento e os compartimentos vegetais (raízes, troncos, galhos e folhas de Rhizophora mangle ) foi avaliada numa área recuperada de manguezal no Aterro Sanitário de Gramacho, Baía de Guanabara, Duque de Caxias ( RJ). Além disto, foram realizadas atividades junto a alu nos do sistema de ensino formal em prol da conscientização para a preservação ambiental, baseada no conhecimento da importância dos manguezais para a dinâmica de contaminantes em áreas costeiras. No estudo da biogeoquímica de metais, foram realizadas análi ses do material vegetal, das placas - de - ferro (depósitos de óxidos sobre as raízes ) e do sedimento (extrações em HCl 1 mol/L). A distribuição das concentrações médias dos elementos nos sedimentos não esteve estatisticamente correlacionada com a variação da granulometria ou da matéria orgânica. O s resultados evidenciam que a matéria orgânica está fortemente associada à fração silte . O pH do sedimento está dentro da normalidade para florestas de manguezal , não sugerindo forte efeito de aportes de chorume do at erro sanitário. Os coeficientes de acumulação nos compartimentos da vegetação em relação ao sedimento mostraram que as raízes finas, sem placas - de - ferro, apresentaram o maior enriquecimento em Zn, Cu e Pb. As placas - de - ferro foram mecanismos eficientes de exclusão de Fe e Mn, mas não em relação aos outros metais. O Mn teve distribuição diferenciada, pois as folhas constituem o compartimento vegetal que apresentou as maiores concentrações. Foi evidenciada uma baixa incorporação e translocação dos contaminant es metálicos (Zn, Cu e Pb) na vegetação, favorecendo a manutenção destes elementos nos sedimentos e partes subterrâneas da vegetação, o que contribui para a capacidade de retenção de metais pelo ecossistema de manguezal. O desenvolvimento do estudo junto a os alunos do ensino básico mostrou que os alunos evoluíram de concepções prévias de senso comum, para respostas que demonstraram ganho de conhecimento a partir das atividades realizadas. Houve uma recomendação maior por parte dos alunos em relação à realiz ação de saída de campo, como forma de haver um maior aproveitamento. Neste cenário, a Educação Ambiental através do ensino da Geoquímica Ambiental no ensino básico pode ser um meio para favorecer a melhor percepção dos alunos em relação a um ecossistema fu ndamental para proporcionar uma melhor qualidade de vida ao homem. Desta forma, pode -se obter uma melhor construção do comportamento voltado para a valorização do ambiente / The study of contaminants geochemistry (such as anthropogenic metals) in mangrove ecosystems can contribute to a better comprehension on the functions and services of th ese ecosystems, which should be translated to the society. This knowledge should be applied for the mangrove resources conservation for future generations. In this study, the distribution of metals of environmental interest (Fe, Mn, Zn, Cu and Pb) between sediments and vegetation compartments (roots, stems, branches and leaves of Rhizophora mangle ) was evaluated in a restored mangrove area in the Gramacho Landfill, Guanabara Bay, Duque de Caxias (RJ). Moreover, activities with formal school education studen ts were carried out in order to improve their environmental preservation conscience, based on the knowledge on the mangrove importance for coastal areas. In the study of metal biogeochemistry, analysis of vegetation material, iron plaques (oxide deposits o n the roots) and sediment cores (extractions in 1 mol/L HCl) were carried out. Average metal concentrations in sediments cores were not correlated with sediment grain size and organic matter content. Zinc, Cu and Pb concentrations exceeded local background levels. Se diment pH was within the normal range for mangrove forests, suggesting no strong effect of landfill leachate input . Coefficients of accumulation in the vegetation compartments ( in relation to the sediment concentrations) showed that the fine roo ts, without iron plaques , showed the greatest enrichment in Zn, Cu and Pb . Iron plaques were efficient mechanisms of exclusion for Fe and Mn, but not in relation to other metals. The Mn showed a different distribution, because the leaves are the plant comp artment that had the highest concentrations. The results showed a low incorporation and translocation of metal contaminants (Zn, Cu and Pb) in the vegetation, favoring the maintenance of these elements in sediments and subterranean parts of the vegetation, which contributes to the metal retention capacity of mangrove ecosystem. The development of the study with school students showed an evolution from previous conceptions of common sense , show ing knowledge gain. There was a major recommendation from the stu dents regarding the field trip s as a way to improve this knowledge gain. In this scenario, environmental education through E nvironmental Geochemistry teaching in basic education can be a way to promote better understandi ng of students in relation to ecolog ically important ecosystems that provid es a better quality of life to human populations that use their resources . Th en , a better behavior toward environment valorization could be constructed