Bacterial contamination of karst aquifers is a concern as water quality across the globe deteriorates in the face of decreasing water security. This study examined the transport and attenuation of two non-virulent isolates of Escherichia coli in relation to traditional groundwater tracers such as rhodamine WT dye and latex microspheres in two karst regions in Kentucky. Differential movement between the four tracers was observed in both epikarst and karst aquifer traces, with differences in behavior dependent on flow conditions. Attenuation was greater for the bacterial isolate containing the iha gene, compared to the isolate containing the kps gene. Microspheres of comparable size (1 µm diameter) were more easily remobilized during increases in discharge during the observed periods for both study sites. Bacteria were remobilized during storm events over 1 month after injection. Recoveries of tracers that were < 100% combined with observed remobilization during storm events illustrate the storage capacity of epikarst and karst aquifers with regard to potential contaminants.

Three studies were completed to investigate the influence of mineral assemblage on soil organic carbon (SOC) cycling and pedogenesis in forest soils. Two studies utilized a lithosequence of four parent materials (rhyolite, granite, basalt, limestone/volcanic cinders) under Pinus ponderosa, to explicitly quantify the contribution of parent material mineral assemblage to the character of the resulting soil. The first study explored variation in pedogenesis and elemental mass loss as a product of parent material through a combination of quantitative X-ray diffraction and elemental mass balance. Results indicated significant differences in degree of soil development, profile characteristics, and mass flux according to parent material.The second study utilized the same lithosequence of soils, but focused on organic C cycling. This study explored variation in SOC content among soils of differing mineralogy and correlations among soil physiochemical variables, SOC content, soil microbial community composition and respiration rates. Metal-humus complex and Fe-oxyhydroxide content emerged as important predictors of SOC dynamics across all parent materials, showing significant correlation with both SOC content and bacterial community composition. Results indicated that within a specific ecosystem, SOC dynamics and microbial community vary predictably with soil physicochemical variables directly related to mineralogical differences among soil parent materials.The third study focused specifically on the influence of goethite and gibbsite on dissolved organic matter characteristics and microbial communities which utilize DOM as a growth substrate. Iron and aluminum oxides were selected for this study due to their wide spread occurrence in soils and their abundance of reactive surface area, qualities which enable them to have a significant effect on SOC transported through forest soils. Results indicated that exposure to goethite and gibbsite surfaces induces significant differences in DOM quality, including changes in thermal properties, molecular structure, and concentrations of P and N. Investigation of the decomposer communities indicated that exposure to goethite and gibbsite surfaces caused significant differences in microbial community structure.These investigations emphasize the important role of mineral assemblage in shaping soil characteristics and regulating the cycling of C in soils, from the molecular scale to the pedon scale.

Upland environments are important sources of mercury (Hg) to downstream wetlands and water bodies. Hydrology is instrumental in facilitating Hg transport within, and export from watersheds. Two complementary studies were conducted to assess the role hydrological processes play in controlling Hg mobility and transport in forested uplands. A field study compared runoff and Hg fluxes from three, replicate hillslope plots during two contrasting spring snowmelt periods, in terms of snowpack depth and timing. Hillslope Hg fluxes were predominately flow-driven. The melting of soil frost significantly delayed a large portion of the Hg flux later into the spring following a winter with minimal snow accumulation. A microcosm laboratory study using a stable Hg isotope tracer applied to intact soil cores investigated the relative controls of soil moisture and precipitation on Hg mobility. Both hydrologic factors control the mobility of contemporary Hg; with greatest Hg flushing from dry soils under high-flow conditions.

Previous pulse-chase experiments have revealed a wide diversity of benthic response patterns to organic matter (OM) input depending on environmental setting, benthic community structure and experimental conditions i.e. quantity and quality of the added OM.  However, the mechanisms and interaction of environmental and biological factors that produce an observed response pattern are poorly understood. The present thesis set out to improve our current understanding on the set of parameters that determine benthic response patterns.  The core of this study was based on two pulse-chase experiments in two bathyal settings: the Faroe-Shetland Channel (FSC) and the SW Cretan slope in the E. Mediterranean (E. Med).  The sub-zero temperatures in the FSC enabled the observation of the benthic response in “slow-motion” and showed that the response is not static but instead might go through various “phases”.  In the warm E. Med, C processing rates were considerably lower compared to previous measurements in adjacent regions.  The discrepancy was attributed to the particularly refractory sedimentary OM at the sampling station with apparent consequences for the physiological state of the bacterial community.  Both experiments showed that bacterial metabolism and its regulation is a key factor determining the reaction of the benthic community to OM inputs.  This thesis provided further understanding on the short-term fate of organic C in deep-sea sediments but also raised certain issues that could be addressed in future studies.

<p>Microorganisms mediate many biogeochemical processes critical to the functioning of ecosystems, which places them as an intermediate between environmental change and the resulting ecosystem response. Yet, we have an incomplete understanding of these relationships, how to predict them, and when they are influential. Understanding these dynamics will inform ecological principles developed for macroorganisms and aid expectations for microbial responses to new gradients. To address this research goal, I used two studies of environmental gradients and a literature synthesis.</p><p>With the gradient studies, I assessed microbial community composition in stream biofilms across a gradient of alkaline mine drainage. I used multivariate approaches to examine changes in the non-eukaryote microbial community composition of taxa (chapter 2) and functional genes (chapter 3). I found that stream biofilms at sites receiving alkaline mine drainage had distinct community composition and also differed in the composition of functional gene groups compared with unmined reference sites. Compositional shifts were not dominated by groups that could benefit from mining associated increases of terminal electron acceptors; two-thirds of responsive taxa and functional gene groups were negatively associated with mining. The majority of subsidies and stressors (nitrate, sulfate, conductivity) had no consistent relationships with taxa or gene abundances. However, methane metabolism genes were less abundant at mined sites and there was a strong, positive correlation between selenate reductase gene abundance and mining-associated selenium. These results highlighted the potential for indirect factors to also play an important role in explaining compositional shifts.</p><p>In the fourth chapter, I synthesized studies that use environmental perturbations to explore microbial community structure and microbial process connections. I examined nine journals (2009–13) and found that many qualifying papers (112 of 148) documented structure and process responses, but few (38 of 112 papers) reported statistically testing for a link. Of these tested links, 75% were significant. No particular approach for characterizing structure or processes was more likely to produce significant links. Process responses were detected earlier on average than responses in structure. Together, the findings suggested that few publications report statistically testing structure-process links; but when tested, links often occurred yet shared few commonalities in linked processes or structures and the techniques used for measuring them. </p><p>Although the research community has made progress, much work remains to ensure that the vast and growing wealth of microbial informatics data is translated into useful ecological information. In part, this challenge can be approached through using hypotheses to guide analyses, but also by being open to opportunities for hypothesis generation. The results from my dissertation work advise that it is important to carefully interpret shifts in community composition in relation to abiotic characteristics and recommend considering ecological, thermodynamic, and kinetic principles to understand the properties governing community responses to environmental perturbation.</p> / Dissertation

L’étude biogéochimique des sédiments sableux perméables est un domaine nouveau : le rôle de ces environnements dans les cycles biogéochimiques a longtemps été négligé en raison de leur pauvreté en matière organique et de la complexité des processus transitoires s’y déroulant. Les plages sableuses sont en effet soumises à de nombreux forçages physiques, dont la marée, la houle et la connexion avec l’aquifère continental. Le processus d’advection y est le mode de transport dominant. De grands volumes d’eau de mer chargée en matière organique sont plus ou moins filtrés par les sédiments perméables intertidaux. Le principal objectif de cette thèse était de caractériser les processus biogéochimiques induits par la recirculation de l’eau de mer et les apports d’eau douce dans la zone intertidale dans le cas d’une plage soumise à de fortes conditions hydrodynamiques : la plage du Truc Vert. Un suivi saisonnier des propriétés physico-chimiques des eaux porales a montré que les processus de respiration aérobie interviennent en zone intertidale, dans la lentille de recirculation de l’eau de mer. A l’échelle du littoral aquitain, ces processus représentent un apport annuel de 610 tonnes de nitrate et de 4400 tonnes de carbone inorganique dissous pour l’océan côtier, soit l’équivalent des apports de la Leyre, un petit fleuve drainant un bassin versant de 2000 km2 au sud-est du Bassin d’Arcachon. La macrofaune benthique est dominée par les Crustacés. Ces individus sont caractéristiques de ces milieux complexes, qu’ils subissent mais ne contrôlent pas : la macrofaune benthique contribue faiblement aux processus de respiration aérobie. Seuls 2% du déficit en oxygène des eaux porales du bas de plage leur est attribué en moyenne : les flux biogéochimiques observés en zone intertidale sont donc majoritairement induits par les processus de respiration aérobie des micro-organismes présents dans le sédiment. Soutenus par l’apport régulier d’oxygène dissous dans le milieu poral à chaque marée, ces processus sont également contrôlés par la température et la variabilité des apports de matière organique.Le déploiement de sondes autonomes dans le sédiment de la zone intertidale a également permis de préciser la variabilité à court terme des propriétés des eaux porales. L’extension de la lentille intertidale de recirculation de l’eau de mer est ainsi variable en fonction du marnage et les teneurs en oxygène mesurées en un point fixe de la plage varient légèrement en fonction de ce cycle. Ce travail a donc permis de démontrer que les processus de respiration aérobie varient principalement à l’échelle saisonnière. L’impact ponctuel et local des conditions météorologiques et de la houle a également été mis en évidence. Nous avons démontré l’existence d’un estuaire souterrain sous la plage du Truc Vert. La dynamique de ce système a été explorée grâce à l’installation de piézomètres en haut de plage. L’apport d’eaux douces continentales représente une source supplémentaire de nitrate et de carbone inorganique dissous pour l’océan côtier. L’étude biogéochimique de la nappe phréatique en arrière dune indique l’existence d’un découplage entre le front salin et le front redox au sein de l’estuaire souterrain, ainsi que l’existence d’un intense dégazage de CO2 au niveau de la dune.Les travaux réalisés durant cette thèse permettent de mieux comprendre les processus à l’œuvre dans les sédiments sableux des plages exposées et permettront ainsi le développement de modèles numériques complexes liant hydrologie et biogéochimie. Ils entraînent également de nombreuses perspectives à propos du rôle des plages sableuses à l’échelle locale (en cas de pollution par exemple) mais aussi sur les cycles biogéochimiques globaux, notamment en lien avec le réchauffement climatique et l’élévation du niveau marin (rejets de CO2, salinisation des aquifères côtiers). / Biogeochemical studies in permeable sandy sediments are recent: the role of these environments in biogeochemical cycles was neglected because of their poverty in organic matter and the complexity of transient processes affecting them. Sandy beaches are subject to various physical forcings like tide, waves and connexion with continental groundwaters. Advection is the leading mode of transport. Huge volumes of organic matter-bearing seawater are potentially filtered by permeable intertidal sediments. The main objective of this study was to characterize biogeochemical processes induced by seawater recirculation and groundwater discharge in the intertidal zone of an exposed beach: the Truc Vert beach.Seasonal monitoring of pore water properties showed that aerobic respiration processes occurred in the seawater recirculation plume. Extrapolated to the 240 km-long Aquitanian coast, these processes represent each year an annual release of 610 tons of nitrate and 4400 tons of dissolved inorganic carbon, i.e. the equivalent of the Leyre input, a small river draining a catchment area of 2000 km2 at the southeast part of the Arcachon lagoon.The benthic macrofauna is dominated by Crustaceans. These organisms have a low impact on biogeochemical cycles: the contribution of benthic macrofauna on oxygen deficits observed in the lower beach pore waters is insignificant (< 2%). Biogeochemical fluxes observed in the intertidal zone are mainly induced by the aerobic respiration of microorganisms living in the sediment. Supported by regular tidal inputs of dissolved oxygen on the pore space, these processes varied seasonnally with temperature and organic matter availability.The deployment of autonomous probes into the sediment of the intertidal zone allowed us to clarify the short-term variability of pore water properties. Extension of the intertidal saline plume evolved with the tidal amplitude. Oxygen levels measured at a given point of the beach varied slightly with the lunar cycle. This work showed that aerobic respiration processes varied mainly at the seasonal scale. The local impact of weather and swell was also evidenced.We showed the presence of a subterranean estuary in the Truc Vert beach and its dynamics was explored through the deployment of wells in the upper beach. The input of continental freshwater represents an additional source of nitrate and dissolved inorganic carbon in the coastal ocean. Chemical properties of the fresh groundwater located upstream the beach indicated a decoupling between the salinity gradient and the redox bareer within the subterranean estuary, as well as an intense CO2 degassing at the dune.This study allows to better understand the processes occuring in sandy sediments of exposed beaches and will allow to develop complex numerical models linking hydrological and biogeochemical processes. This work also provides many perspectives on the role of sandy beaches, both locally (in case of pollution, for example) and on global biogeochemical cycles, especially in relation to global warming and sea-level rise (CO2 emissions and seawater intrusion in coastal aquifers).

Doctor of Philosophy / Department of Agronomy / Charles W. Rice / Increasing atmospheric CO2 concentrations and other greenhouse gases have been linked to global climate change. Soil organic C (SOC) sequestration in both agricultural and native ecosystems is a plausible option to mitigate increasing atmospheric CO2 in the short term. Laboratory and field studies were conducted to (1) understand the influence of soil water content on the temperature response of SOC mineralization (2) investigate burn and nutrient amendment effects on biogeochemical properties of tallgrass prairie and (3) assess perennial and annual plant management practices on biophysical controls on SOC dynamics. The laboratory study was conducted using soils collected from an agricultural field, currently planted to corn (C4 crop), but previously planted to small grain (C3) crops. The changes in cultivated crops resulted in a δ¹³C isotopic signature that was useful in distinguishing older from younger soil derived CO2-C during SOC mineralization. Soils were incubated at 15, 25 and 35 oC, under soil water potentials of -1, -0.03 and -0.01 MPa. Soil water content influenced the effect of temperature on SOC mineralization. The impact of soil water on temperature effect on SOC mineralization was greater under wetter soil conditions. Both young and older SOC were temperature sensitive, but SOC loss depended on the magnitude of temperature change, soil water content and experiment duration. Microbial biomass was reduced with increasing soil water content. The first field experiment investigated burn and nutrient amendment effects on soil OC in a tallgrass prairie ecosystem. The main plots were burned (B) and unburned (UB) tallgrass prairie and split plots were nutrient amendments (N, P or N+P including controls). Vegetation was significantly altered by burning and nutrient amendment. Treatment effects on either TN or SOC were depth-specific with no impact at the cumulative 0-30 cm depth. The P amendment increased microbial biomass at 0-5 cm which was higher in unburned than burned. However, at 5-15 cm depth N amendment increased microbial biomass which was higher in burned than unburned. In conclusion, soil OC in both burned and unburned tallgrass prairie may have a similar trajectory however; the belowground dynamics of the burned and unburned tallgrass prairie are apparently different. Another field experiment assessed SOC dynamics under perennial and annual plant management practices. The main plots were grain sorghum (Sorghum bicolor) planted in no-tillage (NT) or continuous tillage (CT), and replanted native prairie grass, (Andropogon gerardii) (RP). The spit plots were phosphorus (+P) and control without P (-P). The P amendment was used to repress arbuscular mycorrhizal fungi (AMF), known to influence soil aggregation. The macroaggregate >250 µm, SOC and TN were higher in RP and NT than CT. The relative abundances of AMF and saprophytic fungi were greater with less soil disturbance in RP and NT than in CT. Therefore, less soil disturbance in RP and NT increased AMF and fungal biomasses. The higher relative abundances of AMF and fungi with less soil disturbance increased macroaggregate formation in RP and NT, which resulted in higher SOC sequestration in RP and NT than CT.

La zone côtière marseillaise présente de forts contrastes. Elle est soumise à de nombreux apports en nutriments et matière organique par le Rhône, les rejets urbains (Marseille) et l'atmosphère. L'objectif de ce travail était de développer, valider et utiliser un modèle tridimensionnel couplé physique-biogéochimique afin d'étudier la réponse de l'écosystème aux différents forçages hydrodynamiques (upwelling, tourbillon anticyclonique marseillais, intrusion du Courant Nord...) et notamment la modulation des apports naturels et anthropiques associés. Le développement du modèle a permis de mettre en évidence la nécessité de bien représenter l'hydrodynamique et les rejets terrestres plutôt que d'augmenter la complexité du modèle biogéochimique dans cette zone côtière. L'étude des simulations réalistes, d'images satellites et de mesures issues de campagnes en mer a fourni des informations sur les caractéristiques spatiales et temporelles de la zone côtière. Cette zone présente des variations saisonnières très marquées, ainsi qu'une forte variabilité journalière due à une succession de forçages hydrodynamiques et terrestres très intenses et de courte durée. Les informations acquises au cours de cette thèse, notamment grâce au calcul de bilans de matière, ont permis de proposer une hiérarchisation de l'impact des évènements étudiés sur la biogéochimie à l'échelle de la baie de Marseille et de la zone côtière. Finalement, les forçages hydrodynamiques ont comme principal effet d'exporter les perturbations anthropiques et terrigènes au large ce qui permet de maintenir l'état oligotrophique dans une majeure partie de la zone côtière, hormis à proximité de l'embouchure du Rhône. / Marseille coastal zone is a contrasted area which is submitted to many inputs of nutrients and organic matter by the Rhone, by discharges from the Marseille city and the atmosphere. The objective of this study was to develop, validate and use a 3D coupled physical/biogeochemical model to study the impact of different hydrodynamic forcings (upwelling, anticyclonic eddy (ME), intrusion of the Northern Current ...) on the ecosystem, in particular the modulation of natural and anthropogenic inputs by these forcings. In this coastal zone, model development highlighted that improving the accuracy of hydrodynamics and terrestrial input was more benefit rather than complicating the biogeochemical model. Comparison with field measurements showed that even if the model have some defaults, it reproduces well enough chlorophyll-a and nutrients. The study of realistic simulations, satellite images and sea campaigns measurements provided information on the spatial and temporal characteristics of this coastal zone. This area is characterized by seasonal variations, but also by a strong daily variability due to very intense and short-lived hydrodynamic and terrestrial forcings. The information acquired during this thesis, including through the use of mass budgets, allowed to propose a hierarchy of the impacts on the biogeochemistry of the studied events occurring across the Bay of Marseilles and the coastal zone. Finally, hydrodynamic forcings appeared to mainly export the anthropogenic and terrigenous inputs offshore which maintained the oligotrophic state in most of the coastal zone, except near the mouth of the Rhone River.

Afin de mieux appréhender l’ouverture actuelle de la forêt boréale au nord du Québec et d’identifier les facteurs qui en sont responsables, cette thèse a étudié la dynamique, la stabilité et la résilience des deux types d’écosystèmes forestiers en jeu dans la zone de transition, au cours du temps. Ces écosystèmes, les pessières à mousses, denses, et les pessières à lichens, beaucoup moins denses (dites « ouvertes »), partagent la même espèce ligneuse dominante (Picea mariana). La thèse s’est concentrée sur le développement d’outils géochimiques innovants en paléoécologie permettant de retracer la structure et la composition présentes et passées des écosystèmes terrestres, puis sur la reconstruction du régime des feux par analyses de charbons. Elle démontre dans un premier temps que les deux écosystèmes ont des sols aux propriétés physico-chimiques distinctes, et sont entretenus par les interactions sol-végétation-climat. Le deuxième volet montre que les enregistrements chimiques sont également différents dans les sédiments récents de lacs d’étude, selon s’ils sont entourés de pessières à mousses ou à lichens. Grâce aux proxys géochimiques calibrés, le troisième chapitre reconstruit l’histoire de la végétation et des feux au cours de l’Holocène. Il met en évidence une rupture majeure dans la structure des écosystèmes, observée vers 4500-4000 ans calibrés avant présent, et permet de conclure à une ouverture de la forêt boréale à cette période en raison d’une augmentation de la fréquence de feux. La stabilité précaire des états actuels est mise en perspective avec le contexte présent d’augmentation des feux dans la région et les mesures d’aménagement à adapter en conséquence. / In order to better figure out the ongoing transition of the boreal forest in northern Quebec and to identify the responsible factors, this thesis studied the dynamics, stability and resilience of the two forest ecosystems at stake, over time. These ecosystems, the closed-canopy dense moss forest and the open lichen woodland, share the same dominant tree species (black spruce, Picea mariana). The thesis focused on the development of innovative geochemical tools in palaeoecological studies that could track present and past terrestrial ecosystem structure and composition, and then focused on the reconstruction of past fire regimes through lacustrine charcoal analyses. A first step demonstrated that the soils of both ecosystems displayed distinct physical and chemical properties and are maintained by the feedback interactions in the soil-vegetation-climate system. The second step showed that modern sediments of study lakes recorded variations in their chemical composition depending on whether they were surrounded by moss forest or lichen woodland. Using the so calibrated geochemical proxies, the third chapter reconstructed the vegetation and fire histories during the Holocene. A major disruption in ecosystem structure was evidenced 4500-4000 years calibrated before present and led to the conclusion of a boreal forest opening at that time due to an increase in fire frequency. The precariousness of the present states stability is discussed in light with the current context of fire increase in the study region and suggests that forest management should be adapted consequently.

O complexo estuarino-lagunar de Cananéia-Iguape, localizado na porção sul do litoral do Estado de São Paulo, integra uma importante reserva ambiental e um ecossistema costeiro extremamente produtivo. A região abriga o canal do Valo Grande, construído há mais de 160 anos, o qual favorece a introdução água doce do rio Ribeira de Iguape diretamente no sistema estuarino contribuindo à importantes alterações biogeoquímicas como o aporte de nutrientes, metais e outros elementos pouco solúveis, que acabam tendo como destino os sedimentos. No presente trabalho foi realizada a coleta de amostras da coluna de água e de sedimentos de superfície ao longo do complexo estuarino-lagunar de Cananéia-Iguape e ambientes contíguos. Também houve a realização de perfis de sedimento na região sul do estuário, considerada mais preservada. O objetivo principal foi avaliar os processos que regem a distribuição dos Elementos Terras Raras (ETR) nos sedimentos do sistema, conhecendo as propriedades hidroquímicas do sistema, associando e comparando os ETR a outros elementos presentes em baixas concentrações, de modo natural ou resultantes de alterações de origem antrópica, utilizando padrões de fracionamento, anomalias e assinatura geoquímica de minerais que atuam na distribuição dos ETR verificando seu potencial para evidenciar a origem e interpretar níveis naturais e efeitos antrópicos aos quais o Complexo está submetido. Os resultados mostraram que as características hidroquímicas na região norte do Complexo encontram-se fortemente influenciadas pelo aporte de águas fluviais via Valo Grande e pelos processos biogeoquímicos associados a ele, enquanto a região sul apresentou-se mais conservada, mostrando equilíbrio biogeoquímico natural de sistemas estuarinos, oferecendo maior suporte à produção primária. Nos sedimentos de superfície, as concentrações elementares de Al, As, Ba, Ca, Cd, Co, Cr, Cs, Fe, Hg, Hf, P, Pb, Rb, Sb, Sc, Th, U, Zn, Zr e ETR* apresentaram distribuição bastante relacionada às características deposicionais/texturais, de forma que a maioria destes elementos tiveram maiores concentrações em regiões de baixa energia hidrodinâmica, no interior do rio Ribeira de Iguape e no mar Pequeno. Considerando como referência os valores guias de qualidade dos sedimentos canadenses (TEL e PEL), os elementos As, Cd, Pb, Cr, Hg e Zn apresentaram concentração abaixo dos valores que indicam frequente ocorrência de efeitos adversos nos organismos aquáticos (PEL), mas foi observado que em alguns locais, As, Cr, Pb e Zn superaram os valores de concentração que indicam uma baixa probabilidade de ocorrência de efeitos adversos à biota (TEL). Fatores de enriquecimento calculados com relação à crosta continental superior (FEUCC) e ao background geoquímico regional (FEBG) apontaram regiões onde ocorrem concentrações de Pb, P e Sb acima dos níveis considerados naturais, entretanto evidenciaram que os altos valores de As e Cr estariam relacionados a um enriquecimento natural dos sedimentos na região. No caso dos ETR, o FEUCC e FEBG indicaram enriquecimento na região do mar adjacente ao estuário e em estações no rio Ribeira e no Valo Grande. A aplicação de modelagem através da regressão múltipla linear mostrou que os valores, que seriam normalmente considerados anômalos, são naturais e refletem a presença de minerais pesados nestes locais. Outros elementos que parecem naturalmente enriquecidos onde há ocorrência minerais pesados são: As, Ca, Cr, Th, U, além dos elementos ditos sinalizadores, como Hf e Zr. Anomalias de Ce mostraram a possível relação com processos de oxidação de Ce+3 a Ce+4 mediada biológicamente nas zonas mais produtivas do estuário. Dos quatro perfis de sedimento obtidos na região sul do estuário, três mostraram seções com valores de FEUCC e FEBG para Pb que sugerem contribuição antrópica. Tais padrões decrescem em direção ao sul do sistema, porém praticamente não mostram variação temporal. Nenhuma concentração de Pb superou o valor de TEL nos testemunhos estudados. Zn e Hg mostraram enriquecimentos pontuais em diferentes seções do testemunho T3. Com relação aos ETR, houve novamente a observação de enriquecimento causado por minerais pesados, e os teores modelados parecem refletir níveis naturais para estes elementos nos quatro testemunhos. Tais informações podem ser utilizadas na ampliação do uso de ferramentas biogeoquímicas de avaliação e prevenção de riscos aos quais o sistema estudado está sujeito, e na tomada de decisão pelo poder público no sentido da conservação ambiental da região. / The estuary-lagoon complex of Cananéia-Iguape, in the southern portion of the coast of São Paulo state, is part of an important environmental reserve and an extremely productive coastal ecosystem. The region encloses the Valo Grande channel, built more than 160 years ago, which favors the introduction of fresh water from Ribeira de Iguape river directly into the estuarine system contributing to important biogeochemical changes in the region. Through this channel, many nutrients arrive at the estuary, as well as, metals and other slightly soluble elements, that end up as sediments. In this research, samples of the water column and surface sediments were collected in the estuary-lagoon complex of Cananéia-Iguape and contiguous environments, as well as, sediment profiles in the south of the estuary, considered to be the most conserved region. The main objective of this study was to evaluate the processes that govern the distribution of rare earth elements (REE) in the sediments of the system, associating and comparing them to other elements, both essential and toxic, using fractionation patterns, anomalies and the geochemical signature of minerals that act in the distribution of REE to evaluate the origin and interpret natural levels and the amplitude of possible anthropic effects to which the Complex is submitted. The results show that the hydrochemical characteristics in the northern region of the complex are strongly influenced by the provision of fresh water through Valo Grande channel and its resulting biogeochemical processes, while the southern region is more conserved, showing the natural biogeochemical balance of estuarine systems, offering greater support to primary production. The elemental concentrations of Al, As, Ba, Ca, Cd, Co, Cr, Cs, Fe, Hg, Hf, P, Pb, Rb, Sb, Sc, Th, U, Zn, Zr and REE* in the surface sediments, show distribution related to depositional/textural characteristics, in such a way most of these elements presented their highest concentrations in regions of recognized low hydrodynamic energy, in the Ribeira de Iguape river and Mar Pequeno region. A comparison of the values obtained for As, Cd, Pb, Cr, Hg and Zn with the Canadian sediment quality guidelines (TEL and PEL) shows that none of the evaluated elements reached concentrations indicating a frequent occurrence of negative effects on aquatic organisms (PEL), however, As, Cr, Pb and Zn have sometimes exceeded concentration values indicating a low probability of occurrence of adverse effects on biota (TEL). Enrichment factors calculated in relation to the upper continental crust (FEUCC) and the regional geochemical background (FEBG) pointed out regions where Pb, P and Sb accumulated above the levels considered natural, however have shown that the high values of As and Cr are related to a natural enrichment of the sediments in the region. For the REE, FEUCC and FEBG indicated enrichment in the sea region adjacent to the estuary and at stations in Ribeira de Iguape river and Valo Grande. Data modeling through linear multiple regression showed that the values, which would normally be considered anomalous, are natural and reflect the presence of heavy minerals at these sites. Other elements that appear to be naturally enriched where there is the indication of occurrence of such minerals are As, Ca, Cr, Th, U, in addition to the signaling elements Hf and Zr. Ce anomalies showed a possible relationship with biologically mediated Ce+3 to Ce+4 oxidation processes in the most productive areas of the estuary. Out of the four sediment profiles obtained in the southern region of the estuary, three showed sections with FEUCC and FEBG values for Pb suggesting anthropogenic contribution. Such values decrease towards the south of the system, however showed a small time variation. None of the obtained Pb values overcame the values of TEL for such sediment profiles. Zn and Hg showed one-off enrichments in different sections of T3 sediment core. Regarding REE, there was again the observation of enrichment caused by heavy minerals in one of the sediment cores, and the modeled contents seem to reflect natural levels for these elements in the four cores. Such information can be used in the expansion of the biogeochemical tools for assessment and prevention of the risks to which the studied system is subject and in the decision making by the public sector towards the environmental preservation of the region.