Cette thèse démontre qu'une approche expérimentale systématique de complexité croissante permet de réévaluer le sens du potentiel redox (EH), et fournit une mise à jour sur l'interprétation de sa valeur dans les assemblages complexes de matrices minérales, des consortiums microbiens, des nutriments et des contaminants sous dynamique, oxydoréduction oscillant conditions. Pour étudier l'utilité des mesures EH dans les systèmes environnementaux saturés d'eau une cascade complète redox 500 à -350 mV (pH ~7.4) a été reproduit dans le laboratoire. Les expériences ont révélé que l'électrode de Pt classique redox répond à des processus microbiens dans une mesure différente en fonction de l'oxygénation et de la présence d'un tampon d'oxydo-réduction physique, chimique et. Les mesures du EH dans des matrices argileuses appauvris dans le tampon redox, tels que le couple électroactif Fe3 + / Fe2 +, par conséquent, se révèlent avoir une utilité limitée. Dans de tels environnements, les couples redox sensible abondantes, cependant, non électroactif, tels que O2 / H2O, CrO42- / Cr (OH) 3, NO3- / NO2- / NH 4 +, Sb (OH) 6- / Sb2O3, et HAsO42 - / H3AsO3 ne pas d'impact mesuré EH. Pour quantifier l'effet de l'oxydation des perturbations sur la mobilité des oxyanions dans la matrice argileuse, j'ai effectué des expériences de traitement par lots sous oscillations redox contrôlées. cycles successifs de conditions oxiques et anoxiques ont été imposées sur les suspensions argileuses modifiées avec un mélange d'oxyde As (V), Sb (V), Cr (VI) et N (V). la mobilité des oxyanions a été étudiée dans des conditions stériles, avec l'addition de carbone organique labile (éthanol), et avec l'addition de microbienne du sol inoculum. Spéciation analyses ont révélé des réactions irréversibles de réduction avec ou sans ajouts d'éthanol. Fraîchement réduite As (III), Sb (III), Cr (III) et N (III) ne sont pas ré-oxydée pendant les périodes subséquentes oxiques démontrant un comportement non-oscillant. Microbiologiquement induit des transformations de réduction a diminué les concentrations aqueuses de Sb et Cr par précipitation, enlevés N par volatilisation, alors préservé Comme dans la solution. En fonction de la diversité microbienne, altérées par l'addition d'inoculum dans le sol, deux types de contaminants imbrications sont caractérisés comme inhibiteurs de réduction et de non-inhibiteurs. Ces données, le représentant de l'environnement souterrain saturé (sous-sol> 20 m), est en outre par rapport à oxyanion mobilité dans l'environnement proche de la surface (la couche arable <0,15 m). Les principales différences entre les systèmes de la couche arable et du sous-sol sont dans la fraction d'oxyhydroxyde Fe-, Mn- et minéraux Al-, la diversité microbienne, pCO2, et la gamme des valeurs EH développées au cours des cycles d'oxydo-réduction. Par exemple, la gamme EH de plus de 900 mV (500 à -300 mV) dans la suspension de la couche arable est opposée à la gamme EH de 100 mV (350-250 mV) dans la suspension du sous-sol. En outre, dans la suspension de la couche arable, fort cycle redox de Fe et Mn coïncide avec la mobilité d'oscillation de As et Sb. Cette corrélation suggère le rôle crucial des minéraux oxyhydroxyde agissant non seulement comme principaux sorbants, mais aussi comme catalyseurs pour des réactions d'oxydation éventuellement contrôlant la réversibilité de la séquestration des contaminants. Par conséquent, appauvri en minéraux oxyhydroxyde, matrice argileuse est révélée environnement propice à la rétention des contaminants, car il peut supporter des oscillations périodiques redox sans libérer les contaminants de retour à la phase aqueuse sur l'échelle de temps expérimental. / This thesis demonstrates that a systematic experimental approach of increasing complexity allows reassessing the meaning of the redox potential (EH), and provides an update on the interpretation of its value in complex assemblages of mineral matrices, microbial consortiums, nutrients, and contaminants under dynamic, redox-oscillating conditions. To study the usefulness of EH measurements in water-saturated environmental systems a full redox cascade from +500 to -350 mV (pH ∼7.4) was reproduced in the laboratory. The experiments revealed that conventional Pt redox electrode responds to physical, chemical, and microbial processes to a different extent depending on oxygenation and on the presence of a redox buffer. The measurements of EH in argillaceous matrices depleted in the redox buffer, such as the electroactive Fe3+/Fe2+ couple, thus, are shown to have limited usefulness. In such environments, the abundant redox-sensitive couples, yet non-electroactive, such as O2/H2O, CrO42-/Cr(OH)3, NO3-/NO2-/NH4+, Sb(OH)6-/Sb2O3, and HAsO42-/H3AsO3 do not impact measured EH. To quantify the effect of oxidizing perturbations on the mobility of oxyanions in the argillaceous matrix, I performed batch experiments under controlled redox oscillations. Successive cycles of oxic and anoxic conditions were imposed on the argillaceous suspensions amended with a mixture of oxidized As(V), Sb(V), Cr(VI), and N(V). Oxyanion mobility was investigated under sterile conditions, with the addition of labile organic carbon (ethanol), and with the addition of soil microbial inoculum. Speciation analyses revealed irreversible reduction reactions with and without ethanol additions. Freshly reduced As(III), Sb(III), Cr(III), and N(III) were not re-oxidized during subsequent oxic periods demonstrating non-oscillating behavior. Microbially induced reduction transformations decreased aqueous concentrations of Sb and Cr via precipitation, removed N via volatilization, while preserved As in the solution. Depending on microbial diversity, altered by the addition of soil inoculum, two types of contaminant interplays are characterized as inhibitory and non-inhibitory reductions. These data, the representative of saturated subsurface environment (subsoil > 20 m), is further compared to oxyanion mobility in the near-surface environment (topsoil < 0.15 m). The key differences between the topsoil and subsoil systems are in the fraction of oxyhydroxide Fe-, Mn-, and Al- minerals, microbial diversity, pCO2, and the range of EH values developed during redox cycles. For example, the EH range over 900 mV (from +500 to -300 mV) in the topsoil suspension is contrasted to the EH range of 100 mV (from +350 to +250 mV) in the subsoil suspension. Furthermore, in the topsoil suspension, strong redox cycling of Fe and Mn is coincident with the oscillating mobility of As and Sb. This correlation suggests the crucial role of oxyhydroxide minerals acting not only as major sorbents, but also as catalysts for oxidation reactions eventually controlling the reversibility of contaminant sequestration. Therefore, depleted in oxyhydroxide minerals, argillaceous matrix is shown to be suitable environment for contaminant retention, as it can stand periodical redox oscillations without releasing contaminants back to the aqueous phase on the experimental time scale.

O conhecimento da paleoceanografia do Oceano Atlântico Sul tem aumentado nas últimas décadas, porém ainda são raros os trabalhos sobre o Atlântico Sudoeste que utilizam dados de proxies de condições redox de massas d\'água, relacionados às mudanças climáticas entre os períodos Pleistoceno superior e Holoceno. Diante disso, esta Dissertação de Mestrado avaliou as condições redox das águas intermediárias do Atlântico Sudoeste nos últimos 40 mil anos. Este trabalho fez estudos de proxies geoquímicos - de condições redox (V/Sc, V/Cr, V/Al, Mn/Al e Ni/Co), de aporte de sedimentos terTMTMrígenos (Fe/Ca e Ti/Ca), de produtividade (COT, CaCO3) e origem da matéria orgânica (&#948;13C e C/N) - em um registro sedimentar marinho coletado na região do talude continental da margem sudeste brasileira, e os relacionou com as mudanças da Célula de Revolvimento Meridional do Atlântico (sigla em inglês AMOC - Atlantic Medirional Overturning Circulation) e com os principais eventos climáticos em escala orbital, como o Último Máximo Glacial, e de escala milenar, como os eventos tipo Heinrich Stadials, Younger Dryas e 8.2. Os resultados demonstram que, nos últimos 40 mil anos, as águas intermediárias que banham a costa sudeste brasileira apresentam níveis óxicos, o que classifica o ambiente como oxidante, porém foi possível observar variações na quantidade de oxigênio dissolvido nessas águas durante determinados eventos climáticos, bem como variações no aporte de sedimentos terrígenos e na produtividade. Em escala orbital a insolação de verão do Hemisfério Sul e a variação do nível do mar, governadas pelo ciclo de precessão, apresentam-se como os principais mecanismos que influenciam essas variações. Em escala milenar a variabilidade da AMOC apresenta-se como o principal mecanismo responsável por essas variações. Dentre os eventos climáticos de escala milenar, o evento 8.2 demonstrou complexa variabilidade nas condições redox das águas intermediárias do Atlântico Sudoeste, uma vez que, durante sua ocorrência, observamos aumento das concentrações de oxigênio dessas águas e baixos valores de produtividade. / The interest in the paleoceanographic history of the South Atlantic Ocean has increased in the last decades, however there are still few studies regarding the redox conditions of the intermediate water masses of the Southwest Atlantic and their relationship to the climatic changes during the upper Pleistocene and Holocene. Within this context, this work aims to evaluate the redox conditions of the intermediate waters of the Southwest Atlantic in the last 40 ka. For this, geochemical proxies - of redox conditions (V/ Sc, V/ Cr, V/ Al, Mn/ Al and Ni/ Co), of terrigenous sediments supply (Fe/ Ca and Ti/ Ca), of productive (COT, CaCO3), and organic matter source (&#948;13C and C / N) - were applied to marine sediments from a core collected on the continental slope of the Brazilian Southeastern margin and then related it to changes in the Atlantic Meridional Overturning Circulation (AMOC) and with the main cold climatic events of North Atlantic, such as the Last Glacial Maximum and millennial scale, such as events type the Heinrich Stadials, Younger Dryas and 8.2. Our results show that, over the last 40,000 years, the redox conditions of the intermediate waters of the Brazilian Southeast margin present oxic levels, which classifies the environment as oxidant, however, variations was noticed in the amount of oxygen dissolved in these waters influenced by certain climatic events, as well as changes in the input of terrigenous sediments and in the productivity. In orbital scale, the summer insolation of the Southern Hemisphere and the variation of sea level, leaded by the cycle of precession, are presented as the main mechanisms that influence these variations. On the other hand, at millennia scale, the AMOC variability is the main mechanism responsible of these variations. Among the climate events at millennia scale, the event 8.2 demonstrated a complex variability of the redox conditions of the intermediate waters of the Southwest Atlantic, once during its occurrence we observed increase concentrations of oxygen in these waters and a decrease of productivity.

O conhecimento da paleoceanografia do Oceano Atlântico Sul tem aumentado nas últimas décadas, porém ainda são raros os trabalhos sobre o Atlântico Sudoeste que utilizam dados de proxies de condições redox de massas d\'água, relacionados às mudanças climáticas entre os períodos Pleistoceno superior e Holoceno. Diante disso, esta Dissertação de Mestrado avaliou as condições redox das águas intermediárias do Atlântico Sudoeste nos últimos 40 mil anos. Este trabalho fez estudos de proxies geoquímicos - de condições redox (V/Sc, V/Cr, V/Al, Mn/Al e Ni/Co), de aporte de sedimentos terTMTMrígenos (Fe/Ca e Ti/Ca), de produtividade (COT, CaCO3) e origem da matéria orgânica (&#948;13C e C/N) - em um registro sedimentar marinho coletado na região do talude continental da margem sudeste brasileira, e os relacionou com as mudanças da Célula de Revolvimento Meridional do Atlântico (sigla em inglês AMOC - Atlantic Medirional Overturning Circulation) e com os principais eventos climáticos em escala orbital, como o Último Máximo Glacial, e de escala milenar, como os eventos tipo Heinrich Stadials, Younger Dryas e 8.2. Os resultados demonstram que, nos últimos 40 mil anos, as águas intermediárias que banham a costa sudeste brasileira apresentam níveis óxicos, o que classifica o ambiente como oxidante, porém foi possível observar variações na quantidade de oxigênio dissolvido nessas águas durante determinados eventos climáticos, bem como variações no aporte de sedimentos terrígenos e na produtividade. Em escala orbital a insolação de verão do Hemisfério Sul e a variação do nível do mar, governadas pelo ciclo de precessão, apresentam-se como os principais mecanismos que influenciam essas variações. Em escala milenar a variabilidade da AMOC apresenta-se como o principal mecanismo responsável por essas variações. Dentre os eventos climáticos de escala milenar, o evento 8.2 demonstrou complexa variabilidade nas condições redox das águas intermediárias do Atlântico Sudoeste, uma vez que, durante sua ocorrência, observamos aumento das concentrações de oxigênio dessas águas e baixos valores de produtividade. / The interest in the paleoceanographic history of the South Atlantic Ocean has increased in the last decades, however there are still few studies regarding the redox conditions of the intermediate water masses of the Southwest Atlantic and their relationship to the climatic changes during the upper Pleistocene and Holocene. Within this context, this work aims to evaluate the redox conditions of the intermediate waters of the Southwest Atlantic in the last 40 ka. For this, geochemical proxies - of redox conditions (V/ Sc, V/ Cr, V/ Al, Mn/ Al and Ni/ Co), of terrigenous sediments supply (Fe/ Ca and Ti/ Ca), of productive (COT, CaCO3), and organic matter source (&#948;13C and C / N) - were applied to marine sediments from a core collected on the continental slope of the Brazilian Southeastern margin and then related it to changes in the Atlantic Meridional Overturning Circulation (AMOC) and with the main cold climatic events of North Atlantic, such as the Last Glacial Maximum and millennial scale, such as events type the Heinrich Stadials, Younger Dryas and 8.2. Our results show that, over the last 40,000 years, the redox conditions of the intermediate waters of the Brazilian Southeast margin present oxic levels, which classifies the environment as oxidant, however, variations was noticed in the amount of oxygen dissolved in these waters influenced by certain climatic events, as well as changes in the input of terrigenous sediments and in the productivity. In orbital scale, the summer insolation of the Southern Hemisphere and the variation of sea level, leaded by the cycle of precession, are presented as the main mechanisms that influence these variations. On the other hand, at millennia scale, the AMOC variability is the main mechanism responsible of these variations. Among the climate events at millennia scale, the event 8.2 demonstrated a complex variability of the redox conditions of the intermediate waters of the Southwest Atlantic, once during its occurrence we observed increase concentrations of oxygen in these waters and a decrease of productivity.

This study is a multi-proxy analysis of a 30-m section of a Barremian-Aptian succession of interbedded, grayish black (N2) and black (N1) limestones from a quarry of the Sierra de Prada. Index taxa include planktic foraminifera Globigerinelloides blowi and Hedbergella sigali, which combined with δ13C data from Cresmina and Gorgo a Cerbara sections indicate a late Barremian to early Aptian age. The rocks are organic-rich with 0.67 - 3.10 wt% total organic carbon (TOC). A marlstone interval (~1m) at 2.24 m has a low bioturbation index (1), TOC ~6.66 wt%, framboidal pyrite, and enrichment spikes of major, biolimiting, and redox-sensitive trace elements (Al, Si, Ti, P, Fe, and Mo, Cr, Cu, V, Th), indicating an anoxic episode. Biomarker analyses show a predominance of n-alkanes (≤nC20) at this level, suggesting an in situ origin of organic matter from phytoplankton. Pr/Phy ratios below 2 imply that organic matter did not reach overmaturity.

A mechanistic understanding of transport and degradation processes of modern agricultural pesticides, including chiral pesticides, is critical for predicting their fate in the environment. In agricultural landscapes, wetlands can intercept pesticide-contaminated runoff or groundwater and improve water quality through various retention and degradation processes, which remain unknown. In a downscaling approach, three different wetlands receiving agricultural runoff were used as 'natural laboratories' to investigate the fate of widely used pesticides. Overall, our results showed that dynamics of hydrological and redox conditions largely influenced pesticide sorption mechanisms and their distribution over time within wetland compartments, thereby controlling degradation processes. While large-scale studies provide integrative information on pesticide dissipation and distribution patterns with respect to wetland functioning, small-scale investigations using novel methods such as isotope and enantiomer analyses characterize underlying molecular processes governing pesticide degradation.

Es wurden die mikrobiellen Abbauprozesse an einem Standort mit gaswerkstypischer Schadstoffkontamination, v. a. BTEX und PAK, untersucht. Ziel war es, die relevanten mikrobiologischen Abbauprozesse mit gängigen Analysemethoden zu identifizieren und das Natural Attenuation-Potential zu bewerten. Neben einer Betrachtung der Schadstoffe im Feld wurde ein ausführliches hydrogeochemisches und mikrobiologisches Analyseprogramm durchgeführt. Der Schadstoffabbau wurde in Labor-Mikrokosmen unter für den Standort charakteristischen, überwiegend anaeroben Bedingungen untersucht. Methodik und Umfang der Untersuchungsmethoden wurden im Hinblick auf eine Anwendung an weiteren Standorten bewertet. Die Schadstoffausbreitung in der Fahne, die Keimzahluntersuchungen und eine deutliche Redoxzonierung mit einer Sukzession von Methanogenese, Sulfatreduktion und Fe(III)-Reduktion spiegelten mikrobielle Abbauprozesse wider. Dabei beeinflussten und überlagerten die Prozesse im Schadensherd die Prozesse in der Fahne stark. Die Felddaten gaben Hinweise auf abiotische Sekundärreaktionen zwischen den Redoxpaaren Fe(III)/Fe(II), Sulfat/Sulfid und O2/H2O. Die Berechnung der Assimilativen Kapazität (AC) zeigte ein gutes Angebot an CO2 und Sulfat, während die übrigen TEA Sauerstoff, Nitrat und auch Fe(III) am Standort stark limitiert waren. Dem stand eine von den Redoxbedingungen abhängige, unterschiedlich gute Abbaubarkeit der Modellschadstoffe Benzen, Toluen, Ethylbenzen, Naphthalin, Acenaphthen, Phenanthren und Pyren im Laborversuch gegenüber. Methanogenese wurde in keinem der Versuchsansätze beobachtet. Unter sulfatreduzierenden Bedingungen fand ein Abbau weniger Modellschadstoffe (Toluen, z.T. auch Ethylbenzen und Naphthalin) statt. Mit den TEA Nitrat und insb. Fe(III) erweiterte sich das Abbauspektrum gegenüber sulfatreduzierenden Bedingungen. Mit Sauerstoff fand ein Abbau aller im Grundwasser enthaltenen BTEX und PAK statt. Vor dem Hintergrund der AC und den Ergebnissen der Mikrokosmen bedarf es für einen vollständigen Schadstoffabbau im Feld einer Kombination verschiedener TEA-Prozesse, insb. eines Zusammenwirkens von Fe(III)- und Sulfatreduktion und eines Einflusses von Sauerstoff an den Fahnenrändern. Die unterschiedlichen Abbaumuster bzw. Abbaugeschwindigkeiten in Abhängigkeit der TEA machen das Einbeziehen der Redoxzonierung in eine Modellierung des Standortes erforderlich. Neben den TEA hatte die Verfügbarkeit der Makroelemente Phosphor und Stickstoff sowie von Mikroelementen einen Einfluss auf den Abbau. In den Respirometeruntersuchungen mit hohen Substratkonzentrationen war Phosphat in allen und Ammonium in einem Teil der Grundwässer, in Abhängigkeit von der Entnahmestelle im Feld, limitierend. Bei niedrigen Substratkonzentrationen in den Mikrokosmen trat kein Mangel an N und P auf. In allen Fällen hatte aber eine Zugabe von Mikroelementen einen förderlichen Effekt auf den Abbau. Die Methodik der Standortuntersuchungen folgte dem Prinzip der multiple lines of evidence. Die hydrochemischen Parameter O2, NO3-, Fe2+, Mn2+, SO42-, S2-, CH4, NH4+, PO43 waren geeignet, einen mikrobiellen Abbau und potentielle Limitationen durch Nährstoffe zu zeigen. Ein Vergleich der Ergebnisse der tiefenhorizontierten Beprobung mit einem stärker räumlich integrierenden Ansatz zeigte, dass ohne eine entsprechende räumliche Auflösung die AC überschätzt würde. Die Summenparameter, insb. die Toxizität, lieferten wertvolle Zusatzinformationen über die Gesamtkontamination. Der Abbau der (Modell-)Schadstoffe in den Mikrokosmen ermöglichte eine Einschätzung der generellen Abbaubarkeit der Schadstoffe am Standort, der Einflussparameter auf den Schadstoffabbau sowie möglicher Stimulationsmaßnahmen.

La compréhension des mécanismes de transport et de dégradation des pesticides émergents est primordiale pour prédire leur devenir dans l’environnement. Les zones humides peuvent intercepter des eaux de ruissellement ou des souterraines contaminées par les pesticides et les traiter par le biais de processus de rétention et de dégradation, encore peu connus. Dans une approche multi-échelles, trois zones humides recevant des eaux polluées par les pesticides ont été utilisées comme des « laboratoires naturels » pour étudier le devenir de pesticides couramment utilisés. Cette thèse souligne l’influence des conditions hydrologiques et redox sur la distribution des pesticides au sein des différents compartiments des zones humides ainsi que sur leur potentiel de dégradation. Alors que les études à grande échelle fournissent des informations intégratives sur la dissipation et la rétention des pesticides en lien avec le développement de la végétation, les études à petite échelle utilisant des techniques innovantes telles que les analyses isotopiques et énantiomériques permettent l’exploration des processus moléculaires de dégradation des pesticides. / A mechanistic understanding of transport and degradation processes of modern agricultural pesticides, including chiral pesticides, is critical for predicting their fate in the environment. In agricultural landscapes, wetlands can intercept pesticide-contaminated runoff or groundwater and improve water quality through various retention and degradation processes, which remain unknown. In a downscaling approach, three different wetlands receiving agricultural runoff were used as ‘natural laboratories’ to investigate the fate of widely used pesticides. Overall, our results showed that dynamics of hydrological and redox conditions largely influenced pesticide sorption mechanisms and their distribution over time within wetland compartments, thereby controlling degradation processes. While large-scale studies provide integrative information on pesticide dissipation and distribution patterns with respect to wetland functioning, small-scale investigations using novel methods such as isotope and enantiomer analyses characterize underlying molecular processes governing pesticide degradation.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-03-10T16:04:52Z No. of bitstreams: 1 Dissertação Rut Díaz.pdf: 5376355 bytes, checksum: 1871a7342c4a6ea883cf39428d4b8c22 (MD5) / Made available in DSpace on 2017-03-10T16:04:52Z (GMT). No. of bitstreams: 1 Dissertação Rut Díaz.pdf: 5376355 bytes, checksum: 1871a7342c4a6ea883cf39428d4b8c22 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica Ambiental. Niterói, RJ / A região de Cabo Frio (RJ) é uma área de ressurgência que favorece a produtividade primária e promove elevado acúmulo de matéria orgânica (MO) nos sedimentos, a qual afeta as condições redox do ambiente de sedimentação e na interface água-sedimento, promovendo efeitos sobre a especiação inorgânica do enxofre (S). O presente estudo utiliza a geoquímica inorgânica das espécies reduzidas do S, operacionalmente definidas como acid-volatile sulfufide (AVS) e chromium-reducible sulfur (CRS), a composição isotópica (δ34S) do sulfato da água intersticial e do CRS, e a razão COT/CRS (carbono orgânico total/CRS) para avaliar a diagênese recente do S e a condição redox nos sedimentos. Adicionalmente foi estudada a morfologia da pirita e a distribuição de tamanho dos frambóides através de microscopia eletrônica de varredura (MEV) para inferir o estado de oxidação do ambiente de formação. Foram coletados quatro box-cores na plataforma continental do Sistema de Ressurgência de Cabo Frio (SRCF) para este estudo. Os conteúdos de COT variam entre 0,8 e 2,3%, as maiores concentrações foram observadas nas estações da porção média da plataforma. Baixos valores de enxofre total (ST) (< 0,2%) e CRS (< 0,05%) foram encontrados nas camadas superficiais, ocorrendo incremento com a profundidade, indicando o aumento da sulfato redução (SR). As estações com o maior conteúdo de ST foram as localizadas na porção média da plataforma, sendo este padrão de acumulação favorecido pela presença dos vórtices sob a plataforma. A razão COT/CRS indica que o fator limitante para a formação da pirita é o enxofre. Até 50% do S pode estar associado a MO, caracterizando o processo de sulfidização da MO. A composição isotópica do sulfato ao longo dos perfis é mantida constante entre +18,7 e +23‰ e sem fracionamento com respeito ao sulfato da água do mar (+ 21‰), indicando baixas taxas de SR. No entanto, a composição isotópica do CRS apresentou sinais altamente empobrecidos em 34S (-25,6 até -40,8 ‰), indicando reações de oxidação no ciclo do S, promovidas pela intensa bioturbaçao na área e/ou pelo regime hidrodinâmico regional. As diferentes características morfológicas, como as superfícies de oxidação nos microcristais, os processos de crescimento secundário e os poliframboides encontrados nas análises morfológicas da pirita, assim como também a variabilidade na distribuição dos diâmetros dos frambóides evidenciaram uma formação sob condição redox altamente dinâmica. Estes resultados confirmam a complexidade hidrodinâmica do SRCF, o qual afeta inúmeros processos sobre a plataforma, dentre os quais a diagênese no ciclo do enxofre / The Cabo Frio region (RJ) is an upwelling area, which favors the high primary productivity and promotes accumulation of organic matter (OM) in sediments, affecting the redox conditions of the sedimentation environment, the sediment-water interface and mainly the speciation of inorganic sulfur (S). Therefore, this study uses the inorganic geochemistry of reduced S species operationally defined as acid-volatile sulfufide (AVS) and chromium-reducible sulfur (CRS), the isotopic composition (δ34S) of pore water sulfate and CRS, and the COT / CRS ratio (total organic carbon / CRS), to evaluate the recent S diagenesis and redox conditions in sediments. Additionally, was study the pyrite morphology and size distribution of framboids by scanning electron microscopy (SEM) to infer the oxidation state of the environment. In this sense, were collected four box-cores on the continental shelf of the upwelling system of Cabo Frio (SRCF). The TOC contents range from 0.8 to 2.3%, the highest concentrations were observed at stations in the middle shelf. Low values of total sulfur (TS) (<0.2%) and CRS (<0.05%) were found in the superficial layers occurring an increase with depth, indicating an increase in sulfate reduction. The stations with the highest content of ST were located in the middle shelf, this pattern of accumulation is favored by the presence of cyclonic eddy under the platform. The COT/CRS ratio indicates that the limiting factor for the pyrite formation is the sulfur. The isotopic composition of sulfate did not vary much with the sediment depths and is kept constant between +18.7 and +23 ‰ and without fractionation of sulfate with respect to sea water (21 + ‰) indicating low net sulfate reductions, but the isotopic composition of the CRS is highly depleted (-25.6 to -40.8 ‰), indicating oxidation reactions in the cycle of S, promoted by the intense bioturbation in the area and the regional hydrodynamic regime. The different morphological characteristics observed, such as surface oxidation in the microcrystals, the processes of secondary growth and poliframboides found, as well as the variability in the framboids diameters distribution, show the formation under highly dynamic redox condition. These results confirm the complexity of SRCF due to the occurrence of different hydrodynamic conditions over the shelf

Es wurden die mikrobiellen Abbauprozesse an einem Standort mit gaswerkstypischer Schadstoffkontamination, v. a. BTEX und PAK, untersucht. Ziel war es, die relevanten mikrobiologischen Abbauprozesse mit gängigen Analysemethoden zu identifizieren und das Natural Attenuation-Potential zu bewerten. Neben einer Betrachtung der Schadstoffe im Feld wurde ein ausführliches hydrogeochemisches und mikrobiologisches Analyseprogramm durchgeführt. Der Schadstoffabbau wurde in Labor-Mikrokosmen unter für den Standort charakteristischen, überwiegend anaeroben Bedingungen untersucht. Methodik und Umfang der Untersuchungsmethoden wurden im Hinblick auf eine Anwendung an weiteren Standorten bewertet. Die Schadstoffausbreitung in der Fahne, die Keimzahluntersuchungen und eine deutliche Redoxzonierung mit einer Sukzession von Methanogenese, Sulfatreduktion und Fe(III)-Reduktion spiegelten mikrobielle Abbauprozesse wider. Dabei beeinflussten und überlagerten die Prozesse im Schadensherd die Prozesse in der Fahne stark. Die Felddaten gaben Hinweise auf abiotische Sekundärreaktionen zwischen den Redoxpaaren Fe(III)/Fe(II), Sulfat/Sulfid und O2/H2O. Die Berechnung der Assimilativen Kapazität (AC) zeigte ein gutes Angebot an CO2 und Sulfat, während die übrigen TEA Sauerstoff, Nitrat und auch Fe(III) am Standort stark limitiert waren. Dem stand eine von den Redoxbedingungen abhängige, unterschiedlich gute Abbaubarkeit der Modellschadstoffe Benzen, Toluen, Ethylbenzen, Naphthalin, Acenaphthen, Phenanthren und Pyren im Laborversuch gegenüber. Methanogenese wurde in keinem der Versuchsansätze beobachtet. Unter sulfatreduzierenden Bedingungen fand ein Abbau weniger Modellschadstoffe (Toluen, z.T. auch Ethylbenzen und Naphthalin) statt. Mit den TEA Nitrat und insb. Fe(III) erweiterte sich das Abbauspektrum gegenüber sulfatreduzierenden Bedingungen. Mit Sauerstoff fand ein Abbau aller im Grundwasser enthaltenen BTEX und PAK statt. Vor dem Hintergrund der AC und den Ergebnissen der Mikrokosmen bedarf es für einen vollständigen Schadstoffabbau im Feld einer Kombination verschiedener TEA-Prozesse, insb. eines Zusammenwirkens von Fe(III)- und Sulfatreduktion und eines Einflusses von Sauerstoff an den Fahnenrändern. Die unterschiedlichen Abbaumuster bzw. Abbaugeschwindigkeiten in Abhängigkeit der TEA machen das Einbeziehen der Redoxzonierung in eine Modellierung des Standortes erforderlich. Neben den TEA hatte die Verfügbarkeit der Makroelemente Phosphor und Stickstoff sowie von Mikroelementen einen Einfluss auf den Abbau. In den Respirometeruntersuchungen mit hohen Substratkonzentrationen war Phosphat in allen und Ammonium in einem Teil der Grundwässer, in Abhängigkeit von der Entnahmestelle im Feld, limitierend. Bei niedrigen Substratkonzentrationen in den Mikrokosmen trat kein Mangel an N und P auf. In allen Fällen hatte aber eine Zugabe von Mikroelementen einen förderlichen Effekt auf den Abbau. Die Methodik der Standortuntersuchungen folgte dem Prinzip der multiple lines of evidence. Die hydrochemischen Parameter O2, NO3-, Fe2+, Mn2+, SO42-, S2-, CH4, NH4+, PO43 waren geeignet, einen mikrobiellen Abbau und potentielle Limitationen durch Nährstoffe zu zeigen. Ein Vergleich der Ergebnisse der tiefenhorizontierten Beprobung mit einem stärker räumlich integrierenden Ansatz zeigte, dass ohne eine entsprechende räumliche Auflösung die AC überschätzt würde. Die Summenparameter, insb. die Toxizität, lieferten wertvolle Zusatzinformationen über die Gesamtkontamination. Der Abbau der (Modell-)Schadstoffe in den Mikrokosmen ermöglichte eine Einschätzung der generellen Abbaubarkeit der Schadstoffe am Standort, der Einflussparameter auf den Schadstoffabbau sowie möglicher Stimulationsmaßnahmen.