U-Pb geochronology of the southern Brasília belt (SE-Brazil): Sedimentary provenance, Neoproterozoic orogeny and assembly of West Gondwana

The Brasília belt borders the western margin of the São Francisco Craton and records the history of ocean opening and closing related to the formation of West Gondwana. This study reports new U-Pb data from the southern sector of the belt in order to provide temporal limits for the deposition and ages of provenance of sediments accumulated in passive margin successions around the south and southwestern margins of the São Francisco Craton, and date the orogenic events leading to the amalgamation of West Gondwana. Ages of detrital zircons (by ID-TIMS and LA-MC-ICPMS) were obtained from metasedimentary units of the passive margin of the São Francisco Craton from the main tectonic domains of the belt: the internal allochthons (Araxá Group in the Áraxá and Passos Nappes), the external allochthons (Canastra Group, Serra da Boa Esperança Metasedimentary Sequence and Andrelândia Group) and the autochthonous or Cratonic Domain (Andrelândia Group). The patterns of provenance ages for these units are uniform and are characterised as follows: Archean- Paleoproterozoic ages (3.4-3.3, 3.1-2.7, and 2.5-2.4Ga); Paleoproterozoic ages attributed to the Transamazonian event (2.3-1.9Ga, with a peak at ca. 2.15Ga) and to the ca. 1.75Ga Espinhaço rifting of the São Francisco Craton; ages between 1.6 and 1.2Ga, with a peak at 1.3Ga, revealing an unexpected variety of Mesoproterozoic sources, still undetected in the São Francisco Craton; and ages between 0.9 and 1.0Ga related to the rifting event that led to the individualisation of the São Francisco paleo-continent and formation of its passive margins. An amphibolite intercalation in the Araxá Group yields a rutile age of ca. 0.9Ga and documents the occurrence of mafic magmatism coeval with sedimentation in the marginal basin. Detrital zircons from the autochthonous and parautochthonous Andrelândia Group, deposited on the southern margin of the São Francisco Craton, yielded a provenance pattern similar to that of the allochthonous units. This result implies that 1.6-1.2Ga source rocks must be present in the São Francisco Craton. They could be located either in the cratonic area, which is mostly covered by the Neoproterozoic epicontinental deposits of the Bambuí Group, or in the outer paleo-continental margin, buried under the allochthonous units of the Brasília belt. Crustal melting and generation of syntectonic crustal granites and migmatisation at ca. 630Ma mark the orogenic event that started with westward subduction of the São Francisco plate and ended with continental collision against the Paraná block (and Goiás terrane). Continuing collision led to the exhumation and cooling of the Araxá and Passos metamorphic nappes, as indicated by monazite ages of ca. 605Ma and mark the final stages of tectonometamorphic activity in the southern Brasília belt. Whilst continent-continent collision was proceeding on the western margin of the São Francisco Craton along the southern Brasília belt, eastward subduction in the East was generating the 634-599Ma Rio Negro magmatic arc which collided with the eastern São Francisco margin at 595-560Ma, much later than in the Brasília belt. Thus, the tectonic effects of the Ribeira belt reached the southernmost sector of the Brasília belt creating a zone of superposition. The thermal front of this event affected the proximal Andrelândia Group at ca. 588Ma, as indicated by monazite age. The participation of the Amazonian craton in the assembly of western Gondwana occurred at 545-500Ma in the Paraguay belt and ca. 500Ma in the Araguaia belt. This, together with the results presented in this work lead to the conclusion that the collision between the Paraná block and Goiás terrane with the São Francisco Craton along the Brasília belt preceded the accretion of the Amazonian craton by 50-100 million years. © 2003 Elsevier B.V. All rights reserved.

Determinação de 'SB' e 'PB' em embalagens de poli(tereftalato) de etileno (PET) por espectrometria de absorção atômica com fonte contínua e de alta resolução em forno de grafite empregando amostragem direta de sólidos

Pós-graduação em Química - IQ

A simple method based on ICP-MS for estimation of background levels of arsenic, cadmium, copper, manganese, nickel, lead, and selenium in blood of the Brazillian population

Throughout the world, biomonitoring has become the standard for assessing exposure of individuals to toxic elements as well as for responding to serious environmental public health problems. However, extensive biomonitoring surveys require rapid and simple analytical methods. Thus, a simple and high-throughput method is proposed for the determination of arsenic (As), cadmium (Cd), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se) in blood samples by using inductively coupled plasma–mass spectrometry (ICPMS). Prior to analysis, 200 ml of blood samples was mixed with 500 ml of 10% v/v tetramethylammonium hydroxide (TMAH) solution, incubated for 10 min, and subsequently diluted to 10 ml with a solution containing 0.05% w/v ethylenediamine tetraacetic acid (EDTA) + 0.005% v/v Triton X-100. After that, samples were directly analyzed by ICP-MS (ELAN DRC II). Rhodium was selected as an internal standard with matrix-matching calibration. Method detection limits were 0.08, 0.04, 0.5, 0.09, 0.12, 0.04, and 0.1 mg//L for As, Cd, Cu, Mn, Ni, Pb, and Se, respectively. Validation data are provided based on the analysis of blood samples from the trace elements inter-\comparison program operated by the Institut National de Santé Publique du Quebec, Canada. Additional validation was provided by the analysis of human blood samples by the proposed method and by using electrothermal atomic absorption spectrometry (ETAAS). The method was subsequently applied for the estimation of background metal blood values in the Brazilian population. In general, the mean concentrations of As, Cd, Cu, Mn, Ni, Pb, and Se in blood were 1.1, 0.4, 890, 9.6, 2.1, 65.4, and 89.3 mg/L, respectively, and are in agreement with other global populations. Influences of age, gender, smoking habits, alcohol consumption, and geographical variation on the values were also considered. Smoking habits influenced the levels of Cd in blood. The levels of Cu, Mn, and Pb were significantly correlated with gender, whereas Cu and Pb were significantly correlated with age. There were also interesting differences in Mn and Se levels in the population living in the north of Brazil compared to the south.

Correlations among antiangiogenic factors and trace elements in hypertensive disorders of pregnancy

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Caracterização mineralógica e química das fontes de poeira e sua influência na atmosfera da região do polo cerâmico de Santa Gertrudes (SP)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Contrasted crustal sources as defined by whole-rock and Sr-Nd-Pb isotope geochemistry of neoproterozoic early post-collisional granitic magmatism within the Southern Brazilian Shear Belt, Camboriu, Brazil

The early phase of post-collisional granitic magmatism in the Camboriu region, south Brazil, is represented by the porphyritic biotite +/- hornblende Rio Pequeno Granite (RPG; 630-620 Ma) and the younger (similar to 610 Ma), equigranular, biotite +/- muscovite Serra dos Macacos Granite (SMG). The two granite types share some geochemical characteristics, but the more felsic SMG constitutes a distinctive group not related to RPG by simple fractionation processes, as indicated by its lower FeOt, TiO2, K2O/Na2O and higher Zr Al2O3, Na2O, Ba and Sr when compared to RPG of similar SiO2 range. Sr-Nd-Pb isotopes require different sources. The SMG derives from old crustal sources, possibly related to the Paleoproterozoic protoliths of the Camboriu Complex, as indicated by strongly negative epsilon Nd-t (-23 to -24) and unradiogenic Pb (e.g., Pb-206/Pb-204 = 16.0-16.3; Pb-207/Pb-204 = 15.3-15.4) and confirmed by previous LA-MC-ICPMS data showing dominant zircon inheritance of Archean to Paleoproterozoic age. In contrast, the RPG shows less negative epsilon Nd-t (-12 to -15) and a distinctive zircon inheritance pattern with no traces of post-1.6 Ga sources. This is indicative of younger sources whose significance in the regional context is still unclear; some contribution of mantle-derived magmas is indicated by coeval mafic dykes and may account for some of the geochemical and isotopic characteristics of the least differentiated varieties of the RPG. The transcurrent tectonics seems to have played an essential role in the generation of mantle-derived magmas despite their emplacement within a low-strain zone. It may have facilitated their interaction with crustal melts which seem to be to a large extent the products of reworking of Paleoproterozoic orthogneisses from the Camboriu Complex. (C) 2012 Elsevier Ltd. All rights reserved.

USING THE FRESHWATER BIVALVE Anodontites tenebricosus (LEA, 1834) AS A BIOMONITOR OF METALS IN THE RIBEIRA DE IGUAPE RIVER

USING THE FRESHWATER BIVALVE Anodontites tenebricosus (LEA, 1834) AS A BIOMONITOR OF METALS IN THE RIBEIRA DE IGUAPE RIVER. This study investigated the contamination of the Ribeira de Iguape River - RIR by Cd, Zn, Cr and Pb, using the bivalve Anodontites tenebrieosus as a biomonitor. Metal concentrations in tissue samples were measured by HR-ICPMS. Bivalve tissues exhibited mean levels of 1.00 mu g/g Cd: 152.89 mu g/g Zn; 14.79 mu g/g Cr and 4.40 mu g/g Pb. Lead concentrations were comparable to those reported for moderately contaminated sites. The results showed that Pb is bioavailable to the bivalves, exhibiting high concentrations and exceeding both natural and reference values for human consumption. The freshwater bivalve Anodontites tenebricosus is a suitable biomonitor of contamination by metals.

G'day Gondwana - the final accretion of a supercontinent: U-Pb ages from the post-orogenic Sao Vicente Granite, northern Paraguay Belt, Brazil

The Paraguay Belt in central South America is part of a larger chain of orogenic belts, including the Araguaia Belt to the northeast and potentially the Pampean Belt to the south, which are believed to mark the suture zone of the Clymene Ocean - interpreted amongst the youngest of the Gondwana amalgamation orogens. The post-orogenic Sao Vicente Granite crops out in the northern Paraguay Belt and cuts the basal unit of the deformed and metamorphosed Cuiaba Group. The age of this granite therefore provides a long sort after minimum age for orogenesis within the belt. Dating crystallisation of this important intrusion is challenging due to the presence of considerable common-Pb. However, based on LA-ICPMS dating of more than 100 zircons from three separate samples we interpret a robust crystallisation age for the Sao Vicente batholith at 518 +/- 4 Ma. This age constrains the termination of deformation within the Paraguay Belt and the final accretion of the supercontinent Gondwana. (C) 2011 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

U-Pb dating by zircon dissolution method using chemical abrasion

Chemical abrasion was carried out on zircons grains of the Temora II standard for U-Pb dating prior to analyses using in situ Laser Ablation-MultiCollector Ion Coupled Plasma Mass Spectrometer (LA-ICPMS) followed by the Isotope Dissolution Thermal Ionization Mass Spectrometer (ID-TIMS) method. The proposed methodology was herein applied in order to reduce primarily the effects of secondary Pb loss, the presence of common lead and/or silicate impurities. Nine Temora II zircon grains were analyzed by the laser ablation method yielding an age of 418.3±4.3 Ma. Zircon grains of a same population were separated for chemical abrasion before dissolution and mass spectrometry analyses. Six fractions of them were separated for isotope dissolution using 235U-205Pb mixed spike after we have checked and assured the laboratory conditions of low blank values for total Pb of less than 2 pg/g. The obtained U-Pb zircon age by the ID-TIMS method was 415.7±1.8 Ma (error 0.43 %) based on four successful determinations. The results are consistent with the published ages for the Temora diorite (Temora I â 416.75±1.3 Ma; Temora II â 416.78±0.33 Ma) and established as 416±0.33 Ma. The technique is thus recommended for high precision U-Pb zircon analyses (error < 1 %), mainly for high resolution stratigraphic studies of Phanerozoic sequences.

Uso do bivalve límnico Anodontites tenebricosus (LEA, 1834) no biomonitoramento de metais do Rio Ribeira de Iguape

This study investigated the contamination of the Ribeira de Iguape River - RIR by Cd, Zn, Cr and Pb, using the bivalve Anodontites tenebricosus as a biomonitor. Metal concentrations in tissue samples were measured by HR-ICPMS. Bivalve tissues exhibited mean levels of 1.00 µg/g Cd; 152.89 µg/g Zn; 14.79 µg/g Cr and 4.40 µg/g Pb. Lead concentrations were comparable to those reported for moderately contaminated sites. The results showed that Pb is bioavailable to the bivalves, exhibiting high concentrations and exceeding both natural and reference values for human consumption. The freshwater bivalve Anodontites tenebricosus is a suitable biomonitor of contamination by metals.

Dati geochimici ed ecologici di foraminiferi planctonici. Implicazioni paleoceanografiche in due aree chiave: Oceano Meridionale e Mare Mediterraneo.

La studio della distribuzione spaziale e temporale della associazioni a foraminiferi planctonici, campionati in zone con differente regime idrografico, ha permesso di comprendere che molte specie possono essere diagnostiche della presenza di diverse masse d’acqua superficiali e sottosuperficiali e di diversi regimi di nutrienti nelle acque oceaniche. Parte di questo lavoro di tesi si basa sullo studio delle associazioni a foraminiferi planctonici attualmente viventi nel Settore Pacifico dell’Oceano Meridionale (Mare di Ross e Zona del Fronte Polare) e nel Mare Mediterraneo (Mar Tirreno Meridionale). L’obiettivo di questo studio è quello di comprendere i fattori (temperatura, salinità, nutrienti etc.) che determinano la distribuzione attuale delle diverse specie al fine di valutarne il valore di “indicatori” (proxies) utili alla ricostruzione degli scenari paleoclimatici e paleoceanografici succedutisi in queste aree. I risultati documentano che la distribuzione delle diverse specie, il numero di individui e le variazioni nella morfologia di alcuni taxa sono correlate alle caratteristiche chimico-fisiche della colonna e alla disponibilità di nutrienti e di clorofilla. La seconda parte del lavoro di tesi ha previsto l’analisi degli isotopi stabili dell’ossigeno e del rapporto Mg/Ca in gusci di N. pachyderma (sin) prelevati da pescate di micro zooplancton (per tarare l’equazione di paleo temperatura) da un box core e da una carota provenienti dalla zona del Fronte Polare (Oceano Pacifico meridionale), al fine di ricostruire le variazioni di temperatura negli ultimi 13 ka e durante la Mid-Pleistocene Revolution. Le temperature, dedotte tramite i valori degli isotopi stabili dell’ossigeno, sono coerenti con le temperature attuali documentate in questa zona e il trend di temperatura è paragonabile a quelli riportati in letteratura anche per eventi climatici come lo Younger Dryas e il mid-Holocene Optimum. I valori del rapporto Mg/Ca misurato tramite due diverse tecniche di analisi (laser ablation e analisi in soluzione) sono risultati sempre molto più alti dei valori riportati in letteratura per la stessa specie. La laser ablation sembra carente dal punto di vista del cleaning del campione e da questo studio emerge che le due tecniche non sono comparabili e che non possono essere usate indifferentemente sullo stesso campione. Per quanto riguarda l’analisi dei campioni in soluzione è stato migliorato il protocollo di cleaning per il trattamento di campioni antartici, che ha permesso di ottenere valori veritieri e utili ai fini delle ricostruzioni di paleotemperatura. Tuttavia, rimane verosimile l’ipotesi che in ambienti particolari come questo, con salinità e temperature molto basse, l’incorporazione del Mg all’interno del guscio risenta delle condizioni particolari e che non segua quindi la relazione esponenziale con la temperatura ampiamente dimostrata ad altre latitudini.

Isotope geochemical and geochronologic studies of basement units in the Central Western Carpathians (Slovakia)

In dieser Arbeit werden geochronologische und isotopen-geochemische Daten zur Entwicklung der Zentralen Westlichen Karpathen präsentiert. Die Karpathen bilden die östliche Fortsetzung der Alpen und können in drei Alpine Grundgebirgsdecken unterteilt werden, von denen zwei, die Veporische und die Gemerische, bearbeitet wurden. In der Veporischen Einheit wurden polymetamorphe Grundgebirgseinheiten untersucht, um deren genaue Altersstellung zu definieren und sie isotopengeochemisch zu klassifizieren. Dagegen wurde in der der Gemerischen Einheit, welche die Veporische Einheit überlagert, ein spezialisierter S-Typ Granit im Detail untersucht, um die petrogenetischen Prozesse, die zur magmatischen Entwicklung dieses Granits geführt haben, zu identifizieren. U-Pb Datierungen an Zirkonen der Veporischen Grundgebirgseinheiten zeigen für die gesamte Veporische Einheit ordovizische Entsehungsalter an (440-470 Ma). Diese Datierungen revidieren publizierte kambrische Entstehungsalter dieses Grundgebirges. Die Isotopensignatur (epsilon Nd und 87Sr/86Sr) der ordovizischen Grundgebirgseinheiten, bestehend aus stark überprägten Amphiboliten und Gneissen, ist von der Signatur der sich im Norden anschliessenden Tatrischen Einheit gut unterscheidbar. Die Bleiisotopenzusammensetzung dieser Gesteine ist stark krustal geprägt und überschneidet sich mit der der Tatrischen Einheit. Zusammen mit den T-DM Altern sind diese Einheiten vergleichbar mit prävariskischen Einheiten der Alpen. Somit kann das ordovizische Grundgebirge zu den peri-Gondwana Terranen gezählt werden, die an einem aktiven Kontinentalrand im Norden von Gondwana gebildet wurden. In den Gesteinen der Veporischen Einheit wurde im Weiteren eine starke metamorphe überprägung und intensiver felsischer Magmatismus karbonischen Alters erkannt (320-350 Ma). Dieses Ereignis ist zeitgleich mit dem Magmatismus, welcher hauptsächlich in der sich im Norden anschliessenden Tatrischen Einheit beobachtet wird. Dieser gehört der variskischen Orogenese an. Intensive alpine Deformation und Metamorphose konnte in der südlichen Veporischen Einheit anhand der Einzelzirkondatierungen und der Isotopendaten der ordovizischen Einheiten nachgewiesen werden. Am Dlha Dolina Granit in der Gemerischen Einheit können starke Fraktionierungs- und Auto-Metasomatose-Effekte beobachtet werden. Durch die magmatische Fraktionierung wird eine Anreicherung der SEE erzeugt, wogegen die Metasomatose die SEE stark verarmt. Es kommt sogar zur Ausbildung eines Tetraden Effektes im SEE Muster, welche den starken Einfluss von Fluiden während der spät-magmatischen Phase belegt. Gesamtgesteins Pb-Pb Daten beschränken das minimale Intrusionsalter dieses Granites auf 240 Ma. Dieses Alter ist in guter übereinstimmung mit den Sr-Isotopendaten der magmatisch dominierten Gesteine, wohingegen die stark metasomatisch geprägten Gesteine ein zu radiogenes 87Sr/86Sri aufweisen. Während dieser Arbeit wurde intensiv mit der Blei-Isotopenzusammensetzung von Gesamtgesteinsproben gearbeitet. Um die Auswertung dieser Daten optimieren zu können wurde ein Computerscript für das GPL Programm Octave erstellt. Die Hauptaufgabe dieses Scripts besteht darin, Regressionen für geochronologische Anwendungen gemäss York (1969) zu berechnen. Ausserdem können mu und kappa-Werte für diese Regressionen berechnet und eine Hauptkomponentenanalyse, welche hilfreich für den Vergleich von zwei Datensätzen ist, durchgeführt werden. Am Ende der vorliegenden Arbeit wird die analytische Methode für einen Mikrowellen beschleunigten Säureaufschluss von granitoidem Material zur Bestimmung der Sr- und Nd-Isotopenzusammensetzung und der Elementkonzentrationen vorgestellt. Diese kombinierte Methode nutzt ein TIMS für die Sr und Nd Isotopenmessungen und eine Einzelkollektor-ICPMS zur Bestimmung der SEE, Rb und Sr Konzentrationen, welche mithilfe von relativen Sensitivitätsfaktoren gegenüber einem internen Standard quantifiziert werden. Diese Methode wird durch Messungen von internationalen Referenzmaterialien bewertet. Die Ergebnisse zeigen eine Reproduzierbarkeit von <10% für die Elementkonzentrationen und von <5% für Elementverhältnisse.

Petrogenetic evolution of Uralian-Alaskan-type mafic-ultramafic complexes in the southern and middle Urals, Russia

The PhD thesis at hand consists of three parts and describes the petrogenetic evolution of Uralian-Alaskan-type mafic ultramafic complexes in the Ural Mountains, Russia. Uralian-Alaskan-type mafic-ultramafic complexes are recognized as a distinct class of intrusions. Characteristic petrologic features are the concentric zonation of a central dunite body grading outward into wehrlite, clinopyroxenite and gabbro, the absence of orthopyroxene and frequently occurring platinum group element (PGE) mineralization. In addition, the presence of ferric iron-rich spinel discriminates Uralian-Alaskan-type complexes from most other mafic ultramafic rock assemblages. The studied Uralian-Alaskan-type complexes (Nizhnii Tagil, Kytlym and Svetley Bor) belong to the southern part of a 900 km long, N–S-trending chain of similar intrusions between the Main Uralian Fault to the west and the Serov-Mauk Fault to the east. The first chapter of this thesis studies the evolution of the ultramafic rocks tracing the compositional variations of rock forming and accessory minerals. The comparison of the chemical composition of olivine, clinopyroxene and chromian spinel from the Urals with data from other localities indicates that they are unique intrusions having a characteristic spinel and clinopyroxene chemistry. Laser ablation-ICPMS (LA-ICPMS ) analyses of trace element concentrations in clinopyroxene are used to calculate the composition of their parental melt which is characterized by enriched LREE (0.5-5.2 prim. mantle) and other highly incompatible elements (U, Th, Ba, Rb) relative to the HREE (0.25-2.0 prim. mantle). A subduction-related geotectonic setting is indicated by a positive anomaly for Sr and negative anomalies for Ti, Zr and Hf. The mineral compositions monitor the evolution of the parental magmas and decipher differences between the studied complexes. In addition, the observed variation in LREE/HREE (for example La/Lu = 2-24) can be best explained with the model of an episodically replenished and erupted open magma chamber system with the extensive fractionation of olivine, spinel and clinopyroxene. The data also show that ankaramites in a subduction-related geotectonic setting could represent parental magmas of Uralian-Alaskan-type complexes. The second chapter of the thesis discusses the chemical variation of major and trace elements in rock-forming minerals of the mafic rocks. Electron microprobe and LA-ICPMS analyses are used to quantitatively describe the petrogenetic relationship between the different gabbroic lithologies and their genetic link to the ultramafic rocks. The composition of clinopyroxene identifies the presence of melts with different trace element abundances on the scale of a thin section and suggests the presence of open system crustal magma chambers. Even on a regional scale the large variation of trace element concentrations and ratios in clinopyroxene (e.g. La/Lu = 3-55) is best explained by the interaction of at least two fundamentally different magma types at various stages of fractionation. This requires the existence of a complex magma chamber system fed with multiple pulses of magmas from at least two different coeval sources in a subduction-related environment. One source produces silica saturated Island arc tholeiitic melts. The second source produces silica undersaturated, ultra-calcic, alkaline melts. Taken these data collectively, the mixing of the two different parental magmas is the dominant petrogenetic process explaining the observed chemical variations. The results further imply that this is an intrinsic feature of Uralian-Alaskan-type complexes and probably of many similar mafic-ultramafic complexes world-wide. In the third chapter of this thesis the major element composition of homogeneous and exsolved spinel is used as a petrogenetic indicator. Homogeneous chromian spinel in dunites and wehrlites monitors the fractionation during the early stages of the magma chamber and the onset of clinopyroxene fractionation as well as the reaction of spinel with interstitial liquid. Exsolved spinel is present in mafic and ultramafic rocks from all three studied complexes. Its composition lies along a solvus curve which defines an equilibrium temperature of 600°C, given that spinel coexists with olivine. This temperature is considered to be close to the temperature of the host rocks into which the studied Uralian-Alaskan-type complexes intruded. The similarity of the exsolution temperatures in the different complexes over a distance of several hundred kilometres implies a regional tectonic event that terminated the exsolution process. This event is potentially associated with the final exhumation of the Uralian-Alaskan-type complexes along the Main Uralian Fault and the Serov-Mauk Fault in the Uralian fold belt.

UHP metamorphic rocks of the Eastern Rhodope Massif, NE Greece: new constraints from petrology, geochemistry and zircon ages

In this PhD thesis, a multidisciplinary study has been carried out on metagranitoids and paragneisses from the Eastern Rhodope Massif, northern Greece, to decipher the pre-Alpine magmatic and geodynamic evolution of the Rhodope Massif and to correlate the eastern part with the western/central parts of the orogen. The Rhodope Massif, which occupies the major part of NE Greece and S Bulgaria, represents the easternmost part of the Internal Hellenides. It is regarded as a nappe stack of high-grade units, which is classically subdivided into an upper unit and a lower unit, separated by a SSE-NNW trending thrust plane, the Nestos thrust. Recent research in the central Greek Rhodope Massif revealed that the two units correspond to two distinct terranes of different age, the Permo-Carboniferous Thracia Terrane, which was overthrusted by the Late Jurassic/Early Cretaceous Rhodope Terrane. These terranes are separated by the Nestos suture, a composite zone comprising metapelites, metabasites, metagranitoids and marbles, which record high-pressure and even ultrahigh-pressure metamorphism in places. Similar characteristic rock associations were investigated during this study along several well-constrained cross sections in vincity to the Ada, Sidiro and Kimi villages in the Greek Eastern Rhodope Massif. Field evidence revealed that the contact zone of the two terranes in the Eastern Rhodope Massif is characterized by a mélange of metapelites, migmatitic amphibolites/eclogites, strongly sheared orthogneisses and marbles. The systematical occurrence of this characteristic rock association between the terranes implies that the Nestos suture is a continuous belt throughout the Greek Rhodope Massif. In this study, a new UHP locality could be established and for the first time in the Greek Rhodope, metamorphic microdiamonds were identified in situ in their host zircons using Laser-Raman spectroscopy. The presence of the diamonds as well as element distribution patterns of the zircons, obtained by TOF-SIMS, indicate metamorphic conditions of T > 1000 °C and P > 4 GPa. The high-pressure and ultrahigh-pressure rocks of the mélange zone are considered to have formed during the subduction of the Nestos Ocean in Jurassic times at ~150 Ma. Melting of metapelitic rocks at UHP conditions facilitated the exhumation to lower crustal levels. To identify major crust forming events, basement granitoids were dated by LA-SF-ICPMS and SHRIMP-II U-Pb analyses of zircons. The geochronological results revealed that the Eastern Rhodope Massif consists of two crustal units, a structurally lower Permo-Carboniferous unit corresponding to the Thracia Terrane and a structurally upper Late Jurassic/Early Cretaceous unit corresponding to the Rhodope Terrane, like it was documented for the Central Rhodope Massif. Inherited zircons in the orthogneisses from the Thracia Terrane of the Eastern Rhodope Massif indicate the presence of a pre-existing Neoproterozoic and Ordovician-Silurian basement in this region. Triassic magmatism is witnessed by the zircons of few orthogneisses from the easternmost Rhodope Massif and is interpreted to be related to rifting processes. Whole-rock major and trace element analyses indicate that the metagranitoids from both terranes originated in a subduction-related magmatic-arc environment. The Sr-Nd isotope data for both terranes of the Eastern and Central Rhodope Massif suggest a mixed crust-mantle source with variable contributions of older crustal material as already indicated by the presence of inherited zircons. Geochemical and isotopic similarity of the basement of the Thracia Terrane and the Pelagonian Zone implies that the Thracia Terrane is a fragment of a formerly unique Permo-Carboniferous basement, separated by rifting and opening of the Meliata-Maliac ocean system in Triassic times. A branch of the Meliata-Maliac ocean system, the Nestos Ocean, subducted northwards in Late Jurassic times leading to the formation of the Late Jurassic/Early Cretaceous Rhodope magmatic arc on remnants of the Thracia Terrane as suggested by inherited Permo-Carboniferous zircons. The ~150 Ma zircon ages of the orthogneisses from the Rhodope Terrane indicate that subduction-related magmatism and HP/UHP metamorphism occurred during the same subduction phase. Subduction ceased due to the closure of the Nestos Ocean in the Late Jurassic/Early Cretaceous. The post-Jurassic evolution of the Rhodope Massif is characterized by the exhumation of the Rhodope core complex in the course of extensional tectonics associated with late granite intrusions in Eocene to Miocene times.

Methylierung von anorganischem Quecksilber im Intestinaltrakt des Kompostwurms Eisenia foetida

Im Rahmen dieser Arbeit wurde die Methylierung von Quecksilber in Intestinaltrakt des Kompostwurms Eisenia foetida untersucht. Des Weiteren wurden aerobe und anaerobe Mikroorganismen aus dem Darmtrakt von Eisenia fotida isoliert, identifiziert und auf ihr Potential zur Methylierung von Quecksilber getestet. Die Bestimmung von Methylquecksilber erfolgte mittels GC-ICPMS (Gaschromatographie mit induktiv gekoppelter Plasma-Massenspektrometrie) und GC-AFS (Gaschromatographie- Atomfluoreszenzspektrometrie). Für die GC-ICPMS erfolgte die Quantifizierung des Methylquecksilbers mittels der Isotopenverdünnungsmethode. Die Extraktion des Methylquecksilbers aus dem Wurmgewebe erfolgte durch einen alkalischen Aufschluss mit TMAH (Tetramethylammoniumhydroxid) und anschließender Derivatisierung des Methylquecksilbers durch Natriumtetrapropylborat. Für die Extraktion des gebildeten Methylquecksilbers aus Bakterienkulturen wurde eine Extraktion mit einer methanolischen Kaliumhydroxidlösung verwendet. Wie bei dem Wurmgewebe wurde das Methylqueckilsber ebenfalls mit Natriumtetrapropylborat derivatisiert.rnrnFür die Untersuchung einer in vivo Methylquecksilberbildung in bodenlebenden Invertebraten wurde der Kompostwurm Eisenia foetida als Modellorganismus verwendet. Die Tiere wurden aus einer Kultur in einen Boden überführt, der mit anorganischem Quecksilber versetzt wurde. Nach zehn Tagen Inkubationszeit wurden die Würmer entnommen und das Methylquecksilber extrahiert. Um eine mögliche Methylierung von Quecksilber durch Bodenorganismen auszuschließen wurde sowohl steriles als auch unsteriles Bodenmaterial verwendet. In den Wurmproben aus dem unsterilen Bodenmaterial konnte eine Konzentration an Methylquecksilber von 17,4 ng/g Trockengewicht (Boden ohne Zugabe von Quecksilber) und 62,4 ng/g Trockengewicht (Boden mit Quecksilberzugabe). Bei den Wurmproben aus sterilem Bodenmaterial lag die Konzentration an Methylquecksilber bei 17,2 ng/g Trockengewicht (Boden ohne Zugabe von Quecksilber) und 51,9 ng/g Trockengewicht (Boden mit Quecksilberzugabe).rnrnBei den Bakterienkulturen konnte in Reinkulturen keine Methylierung von Quecksilber nachgewiesen werden. In einer fakultativ anaeroben Mischkultur konnte eine Methylierung von Quecksilber beobachtet werden. Für die Identifizierung der Mikroorganismen wurde die 16s rDNA mittels PCR amplifiziert und anschließend über eine DGGE aufgetrennt. Die Banden wurden ausgeschnitten und sequenziert. Dabei konnten drei Enterobacteriaceen identifiziert werden.rn