Boron isotope composition of tourmalinite and vein tourmalines associated with gold mineralization, Serra do Itaberaba Group, central Ribeira Belt, SE Brazil

Important concentrations of tourmaline occur as gold-bearing stratiform tourmalinites and in mineralized quartz-tourmaline veins at the Tapera Grande and Quartzito gold prospects in the Mesoproterozoic Serra do Itaberaba Group, central Ribeira Belt (Sao Paulo State, SE Brazil). The main rock types in both prospects constitute the volcanic-sedimentary Morro da Pedra Preta Formation, which formed in a submarine back-arc setting. At Tapera Grande, the volcanic-sedimentary sequence is composed of metabasic and metavolcaniclastic rocks, graphitic and sulfur-rich metapelites, banded iron formation, metandesite, metarhyolite, calcsilicates, tourmalinites and metahydrothermalites derived from mafic and felsic rocks. The Mesoproterozoic rocks at Quartzito prospect are lithologically similar but they have been affected by Neoproterozoic faulting and shearing and by the emplacement of granitic rocks, resulting in the formation of tourmaline-rich quartz-carbonate veins with gold and base metal mineralization. We conducted a chemical and B-isotope study of tourmalines in order to better understand the origin of the stratiform tourmalinites in the Morro da Pedra Preta Formation and their relationship with gold mineralization. The overall range of delta(11)B values obtained for the tourmalinite and vein tourmalines is between - 15%. and -5 parts per thousand, with the tourmalinites failing at the low end of this range (-15 to -8 parts per thousand). Such values are typical for continental crust and inconsistent with a primary marine boron signature as expected from the submarine-exhalative model for the gold prospects. We conclude from this that tourmaline formed or recrystallized from crustal fluids related to the amphibolite-grade metamorphism which affected the Serra do Itaberaba Group and that gold deposition occurred syn- to post-peak metamorphism by phase immiscibility, as attested by fluid inclusions in Tapera Grande tourmalinite tourmaline and quartz. The vein-hosted tourmalines at Quartzito have isotopically variable boron signatures, with heavier delta(11)B values of -5 parts per thousand to -8 parts per thousand for acicular green tourmalines and lighter values (-15 parts per thousand to -7 parts per thousand for light blue, Ti-firee tourmaline from quartz-carbonate veins). We attribute the heavier boron to fluids derived from the volcano-sedimentary rocks of marine affinity whereas the lighter boron was contributed by crustal fluids related to the granitoids or metasediments in the continental crust. (c) 2009 Elsevier B.V. All rights reserved.

Trace element geochemistry and Sr-Nd characteristics of Mesoproterozoic mafic intrusive rocks from Rondonia, Brazil, SW Amazonian Craton: Petrogenetic and tectonic inferences

The Amazonian Craton comprises an Archean domain surrounded by four successively younger Proterozoic tectonic provinces. Within the Rio-Negro-Juruena province the Serra da Providencia Intrusive Suite (1.60 and 1.53 Ga) consists of A-type rapakivi granites, charnockites and mangerites genetically associated with diabase dikes, gabbros and amphibolites lites. The original mafic melts were derived from a depleted mantle source (epsilon(Nd(T)) + 2.5 to +2.8; epsilon(Sr(T)) - 12.1). Underplated mafic magma induced melting of a short-lived fielsic crust, thus originating coeval felsic-inafic magmatism in a continental intraplate setting. The Colorado Complex, assigned to the Rondonian-San Ignacio province, comprises 1.35-1.36 Ga intrusive bimodal magmatism represented by monzonite gneisses associated with amphibolite, gabbro and metadiabase dikes intercalated with metasediments with detrital zircon that yield U-Pb ages of 1.35 to 1.42 Ga. Mafic samples display juvenile signatures (epsilon(Nd(T)) 0.0 to +5.2; epsilon(Sr(T)) -5.0 to -30.7) and are less contaminated than the Serra da Previdencia and Nova Brasiladndia ones. The generation of the basaltic magma is related to the subduction of an oceanic slab below the peridotite wedge (intraoceanic arc setting). Fluids and/or small melts from the slab impregnated the mantle. The Nova Brasilandia Sequence (Sunsas-Aguapei province) comprises a metasedimentary sequence intruded by 1.10-1.02 Ga metadiabases, gabbros, meta-gabbros, and amphibolites associated with granitic plutons (bimodal magmatism). The original tholeiitic magmas, derived from a depleted source (epsilon(Nd(T)) = +3.1 to +5.0), in a proto-oceanic setting, underwent subsequent contamination by the host rocks, as indicated by the isotopic and trace element data.

Geology and geochronology of the Betara region in south-southeastern Brazil: Evidence for possible Statherian (1.80-1.75 Ga) and Calymmian (1.50-1.45 Ga) extension events

The results of geological mapping, chemical analysis and radiometric dating of metabasic rocks of Betara Formation, and mapping and dating of those present in the Betara basement nucleus together with mylonitic granodiorite and syenogranite are reported here. U-Pb analysis of bulk zircon fractions from the metabasic rocks of the basement nucleus yielded a Statherian age of 1790 +/- 22 Ma, while the metabasic rocks from the upper part of the Betara Formation yielded a Calymmian age between 1500 and 1450 Ma. This age is a minimum for the deposition of the Betara Formation. The older metabasic rocks are associated with post-tectonic, possibly anorogenic syenogranite, while the younger ones are gabbro or very porphyritic ankaramite whose REE patterns are consistent with crystallization from an N-MORB parent magma. The observations and data point to the probable events associated with extensional processes of the end of Paleoproterozoic and early Mesoproterozoic. Similar registers of Statherian (1.80-1.75 Ga) and Calymmian (1.50-1.45 Ga) extensional events are recorded in other parts of the South American and African continents. The Neoproterozoic witnessed the formation and junction of the tectonic slices which formed the Apiai domain during the assemblage of western Gondwana. (C) 2010 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Nd and Pb isotope signatures on the Southeastern South American upper margin: Implications for sediment transport and source rocks

Neodymium and lead isotope values in sediment samples were used to interpret sediment transport and source rocks on the Southeastern South American upper margin. The sediments of the Argentinian margin exhibit an average epsilon(Nd) value of -1.9, indicating the influence of the Andean rocks as sediment sources. Sediments from the Rio de La Plata estuary show an average epsilon(Nd) value of -9.6 which is similar to that of the Southern Brazilian Upper Margin. Finally, sediments of Southeastern Brazil, which are associated with the transport of the Brazil Current exhibit an average epsilon(Nd) of -13.0. The Pb isotope signatures also confirm the differentiation of source rocks in the sedimentation of the study area. In addition, Pb isotopes helped to establish the extent of the influence of the Rio de La Plata on the sedimentation of the Southern Brazilian margin. In terms of Pb isotopes the sediments from the Rio de La Plata estuary and Southern Brazil are more radiogenic than those of Southeastem Brazil and the Argentinian margin. (c) 2007 Elsevier B.V. All rights reserved.

Isotopic characterization of the metabasites and amphibolites of the Acungui and Setuva Groups of the Ribeira Belt

Pb, Rb, Sr, Sm and Nd isotope analyses were carried out on amphibolitic rocks from Campo Largo (PR), Rio Branco do Sul (PR) and Adrianópolis (PR) and for the metabasite from Adrianópolis and Apiai (SP), all belonging to the Açungui and Setuva Groups, southern portion of the Ribeira Belt. These occurrences were chosen because each exhibits geochemical data indicative of a mantle source, having different signatures. Geochronologic determinations are available only for the Apiai metagabbro with Neoproterozoic ages of 617 ± 4 Ma (U/Pb in zircon) and 839 ± 85 Ma (Rb/Sr, whole rock). Age determinations by Sm/Nd mineral isochron using whole rock, plagioclase and pyroxene yield values of 885 ± 53 Ma for the Apiai metagabbro and 820 ± 84 Ma for the Adrianópolis metabasite. These results agree within error with the Rb/Sr isochron of 839 ± 85 Ma may possibly be interpreted as the time of extraction of the magma from the mantle, as suggested by positive εNd(850) values (+2,76) from an Adrianópolis sample. An εNd values versus 87Sr/86Sr diagram shows that each studied occurrence plots in a different position, following approximately the mantle array trend, the most primitive being the metabasite of Adrian-acopolis, near the MORB field, and the most enriched being the amphibolite from the same region, near the enriched mantle and or crustal contamination field. The distinct difference in isotopic signatures between the amphibolite and metabasite suggests derivation from different mantle sources, as supported by available geochemical data. Nevertheless, some of the samples show isotopic evidence of the action of metamorphism, crustal contamination and weathering.

Environmental changes in the western Amazônia: morphological framewor, geochemistry, palynology and radiocarbon dating data

Os sedimentos do lago Coari, de ambiente de terra firme esculpido nos depósitos do Plio-Pleistocenos, e o Acará, típico lago de várzea e ambos formados nos sedimentos quaternários da planície de inundação do médio Solimões, no oeste da Amazônia, Brasil, foram estudados para investigar as condições ambientais durante sua formação. Este estudo inclui dados da composição mineralógica, química, isótopos de Pb, palinologia, datações de radiocarbono e a configuração morfológica dos lagos obtida por imagens SRTM. As condições geológica e ambiental dos lagos variam e sugerem que suas evoluções refletem processos autogenéticos em condições de floresta úmida e chuvosa. Embora caulinita, quartz, muscovita, illita e esmectita sejam os principais minerais em ambos os lagos, a geoquímica indica fonte distinta, os sedimentos do lago Acará têm maior concentração de Al2O3, Fe2O3, FeO, CaO, K2O, MgO, Na2O, P2O5, Ba, V, Cu, Ni, Zn, Pb, Sr, Li, Y e La e têm mais Pb radiogênico que os sedimentos do lago Coari. As idades de radiocarbono sugerem que há aproximadamente 10160 anos AP o lago Coari iniciou o desenvolvimento devido a avulsão do rio Solimões, enquanto o lago Acará foi formado devido ao abandono de meandro do rio Solimões e retendo o domínio das gramíneas nas suas praias há aproximadamente 3710 anos AP.

Geochemistry and Pb-207/Pb-206 zircon ages of granitoids from the southern portion of the Tamboril-Santa Quiteria granitic-migmatitic complex, Ceara Central Domain, Borborema Province (NE Brazil)

The Tamboril-Santa Quiteria Complex is an important Neoproterozoic granitic-migmatitic unit from the Ceara Central Domain that developed from ca. 650 to 610 Ma. In general the granitoids range in composition from diorite to granite with predominance (up to 85%) of granitic to monzogranitic composition with biotite as the main mafic AFM phase. Geochemical and Pb-207/Pb-206 evaporation zircon geochronology studies were applied in a group of these abundant monzogranitic rocks from the region of Novo Oriente in the southern portion of the Ceara Central Domain. In this area the granitoids are weakly peraluminous biotite granitoids and deformed biotite granitoids of high-K calc-alkaline and ferroan composition, which we interpreted as primary magmas (segregated diatexites) derived from the partial melting of crustal material. The close temporal relation of this magmatism with local eclogitic and regional high temperature metamorphism in Ceara Central Domain point out to an orogenic setting, arguably emplaced during the collisional stage. Subordinate coeval juvenile mantle incursions are also present. This crustally derived magmatism is the primary product of the continental thickening that resulted from the collision between the rocks represented by the Amazonian-West African craton (Sao Luiz cratonic fragment) to the northwest and the Paleoproterozoic-Archean basement of the Borborema Province to the southeast along the Transbrasiliano tectonic corridor. (C) 2011 Elsevier Ltd. All rights reserved.

Petrology and geochemistry of Lipari Island (Aeolian archipelago): constraints on magma genesis and evolution

A full set of geochemical and Sr, Nd and Pb isotope data both on bulk-rock and mineral samples is provided for volcanic rocks representative of the whole stratigraphic succession of Lipari Island in the Aeolian archipelago. These data, together with petrographic observations and melt/fluid inclusion investigations from the literature, give outlines on the petrogenesis and evolution of magmas through the magmatic and eruptive history of Lipari. This is the result of nine successive Eruptive Epochs developing between 271 ka and historical times, as derived from recentmost volcanological and stratigraphic studies, combined with available radiometric ages and correlation of tephra layers and marine terrace deposits. These Eruptive Epochs are characterized by distinctive vents partly overlapping in space and time, mostly under control of the main regional tectonic trends (NNW-SSE, N-S and minor E-W). A large variety of lava flows, scoriaceous deposits, lava domes, coulees and pyroclastics are emplaced, ranging in composition through time from calcalkaline (CA) and high-K (HKCA) basaltic andesites to rhyolites. CA and HKCA basaltic andesitic to dacitic magmas were erupted between 271 and 81 ka (Eruptive Epochs 1-6) from volcanic edifices located along the western coast of the island (and subordinately the eastern Monterosa) and the M.Chirica and M.S.Angelo stratocones. These mafic to intermediate magmas mainly evolved through AFC and RAFC processes, involving fractionation of mafic phases, assimilation of wall rocks and mixing with newly injected mafic magmas. Following a 40 ka-long period of volcanic quiescence, the rhyolitic magmas were lately erupted from eruptive vents located in the southern and north-eastern sectors of Lipari between 40 ka and historical times (Eruptive Epochs 7-9). They are suggested to derive from the previous mafic to intermediate melts through AFC processes. During the early phases of rhyolitic magmatism (Eruptive Epochs 7-8), enclaves-rich rocks and banded pumices, ranging in composition from HKCA dacites to low-SiO2 rhyolites were erupted, representing the products of magma mixing between fresh mafic magmas and the fractionated rhyolitic melts. The interaction of mantle-derived magmas with the crust represents an essential process during the whole magmatic hystory of Lipari, and is responsible for the wide range of observed geochemical and isotopic variations. The crustal contribution was particularly important during the intermediate phases of activity of Lipari when the cordierite-bearing lavas were erupted from the M. S.Angelo volcano (Eruptive Epoch 5, 105 ka). These lavas are interpreted as the result of mixing and subsequent hybridization of mantle-derived magmas, akin to the ones characterizing the older phases of activity of Lipari (Eruptive Epochs 1-4), and crustal anatectic melts derived from dehydration-melting reactions of metapelites in the lower crust. A comparison between the adjacent islands of Lipari and Vulcano outlines that their mafic to intermediate magmas seem to be genetically connected and derive from a similar mantle source affected by different degrees of partial melting (and variable extent of crustal assimilation) producing either the CA magmas of Lipari (higher degrees) or the HKCA to SHO magmas of Vulcano (lower degrees). On a regional scale, the most primitive rocks (SiO2<56%, MgO>3.5%) of Lipari, Vulcano, Salina and Filicudi are suggested to derive from a similar MORB-like source, variably metasomatized by aqueous fluids coming from the slab and subordinately by the additions of sediments.

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.

Variation of stable silicon isotopes: Analytical developments and applications in Precambrian geochemistry

Die vorliegende Dissertation behandelt die Gesamtgesteinsanalyse stabiler Siliziumisotope mit Hilfe einer „Multi Collector-ICP-MS“. Die Analysen fanden in Kooperation mit dem „Royal Museum for Central Africa“ in Belgien statt. Einer der Schwerpunkte des ersten Kapitels ist die erstmalige Analyse des δ30Si –Wertes an einem konventionellen Nu PlasmaTM „Multi-Collector ICP-MS“ Instrument, durch die Eliminierung der den 30Si “peak” überlagernden 14N16O Interferenz. Die Analyse von δ30Si wurde durch technische Modifikationen der Anlage erreicht, welche eine höherer Massenauflösung ermöglichten. Die sorgsame Charakterisierung eines adäquaten Referenzmaterials ist unabdingbar für die Abschätzung der Genauigkeit einer Messung. Die Bestimmung der „U.S. Geological Survey“ Referenzmaterialien bildet den zweiten Schwerpunkt dieses Kapitales. Die Analyse zweier hawaiianischer Standards (BHVO-1 and BHVO-2), belegt die präzise und genaue δ30Si Bestimmung und bietet Vergleichsdaten als Qualitätskontrolle für andere Labore. Das zweite Kapitel befasst sich mit kombinierter Silizium-/Sauerstoffisotope zur Untersuchung der Entstehung der Silizifizierung vulkanischer Gesteine des „Barberton Greenstone Belt“, Südafrika. Im Gegensatz zu heute, war die Silizifizierung der Oberflächennahen Schichten, einschließlich der „Chert“ Bildung, weitverbreitete Prozesse am präkambrischen Ozeanboden. Diese Horizonte sind Zeugen einer extremen Siliziummobilisierung in der Frühzeit der Erde. Dieses Kapitel behandelt die Analyse von Silizium- und Sauerstoffisotopen an drei unterschiedlichen Gesteinsprofilen mit unterschiedlich stark silizifizierten Basalten und überlagernden geschichteten „Cherts“ der 3.54, 3.45 und 3.33 Mill. Jr. alten Theespruit, Kromberg und Hooggenoeg Formationen. Siliziumisotope, Sauerstoffisotope und die SiO2-Gehalte demonstrieren in allen drei Gesteinsprofilen eine positive Korrelation mit dem Silizifizierungsgrad, jedoch mit unterschiedlichen Steigungen der δ30Si-δ18O-Verhältnisse. Meerwasser wird als Quelle des Siliziums für den Silizifizierungsprozess betrachtet. Berechnungen haben gezeigt, dass eine klassische Wasser-Gestein Wechselwirkung die Siliziumisotopenvariation nicht beeinflussen kann, da die Konzentration von Si im Meerwasser zu gering ist (49 ppm). Die Daten stimmen mit einer Zwei-Endglieder-Komponentenmischung überein, mit Basalt und „Chert“ als jeweilige Endglieder. Unsere gegenwärtigen Daten an den „Cherts“ bestätigen einen Anstieg der Isotopenzusammensetzung über der Zeit. Mögliche Faktoren, die für unterschiedliche Steigungen der δ30Si-δ18O Verhältnisse verantwortlich sein könnten sind Veränderungen in der Meerwasserisotopie, der Wassertemperatur oder sekundäre Alterationseffekte. Das letzte Kapitel beinhaltet potentielle Variationen in der Quellregion archaischer Granitoide: die Si-Isotopen Perspektive. Natriumhaltige Tonalit-Trondhjemit-Granodiorit (TTG) Intrusiva repräsentieren große Anteile der archaischen Kruste. Im Gegensatz dazu ist die heutige Kruste kaliumhaltiger (GMS-Gruppe: Granit-Monzonite-Syenite). Prozesse, die zu dem Wechsel von natriumhaltiger zu kaliumhaltiger Kruste führten sind die Thematik diesen Kapitels. Siliziumisotopenmessungen wurden hier kombiniert mit Haupt- und Spurenelementanalysen an unterschiedlichen Generationen der 3.55 bis 3.10 Mill. Yr. alten TTG und GMS Intrusiva aus dem Arbeitsgebiet. Die δ30Si-Werte in den unterschiedlichen Plutonit Generationen zeigen einen leichten Anstieg der Isotopie mit der Zeit, wobei natriumhaltige Intrusiva die niedrigste Si-Isotopenzusammensetzung aufweisen. Der leichte Anstieg in der Siliziumisotopenzusammensetzung über die Zeit könnte auf unterschiedliche Temperaturbedingungen in der Quellregion der Granitoide hinweisen. Die Entstehung von Na-reichen, leichten d30Si Granitoiden würde demnach bei höheren Temperaturen erfolgen. Die Ähnlichkeit der δ30Si-Werte in archaischen K-reichen Plutoniten und phanerozoischen K-reichen Plutoniten wird ebenfalls deutlich.

Geochemical and Strontium Isotope Characterization of Produced Waters from Marcellus Shale Natural Gas Extraction

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ∼375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (εSr SW = +13.8 to +41.6, where εSr SW is the deviation of the 87Sr/86Sr ratio from that of seawater in parts per 104); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

Investigation of young water inflow in karst aquifers using SF6–CFC–3H/He–85Kr–39Ar and stable isotope components

Karst aquifers are known for their wide distribution of water transfer velocities. From this observation, a multiple geochemical tracer approach seems to be particularly well suited to provide a significant assessment of groundwater flows, but the choice of adapted tracers is essential. In this study, several common tracers in karst aquifers such as physicochemical parameters, major ions, stable isotopes, and d13C to more specific tracers such as dating tracers – 14C, 3H, 3H–3He, CFC-12, SF6 and 85Kr, and 39Ar – were used, in a fractured karstic carbonated aquifer located in Burgundy (France). The information carried by each tracer and the best sampling strategy are compared on the basis of geochemical monitoring done during several recharge events and over longer time periods (months to years). This study’s results demonstrate that at the seasonal and recharge event time scale, the variability of concentrations is low for most tracers due to the broad spectrum of groundwater mixings. The tracers used traditionally for the study of karst aquifers, i.e., physicochemical parameters and major ions, efficiently describe hydrological processes such as the direct and differed recharge, but require being monitored at short time steps during recharge events to be maximized. From stable isotopes, tritium, and Cl� contents, the proportion of the fast direct recharge by the largest porosity was estimated using a binary mixing model. The use of tracers such as CFC-12, SF6, and 85Kr in karst aquifers provides additional information, notably an estimation of apparent age, but they require good preliminary knowledge of the karst system to interpret the results suitably. The CFC-12 and SF6 methods efficiently determine the apparent age of baseflow, but it is preferable to sample the groundwater during the recharge event. Furthermore, these methods are based on different assumptions such as regional enrichment in atmospheric SF6, excess air, and flow models among others. 85Kr and 39Ar concentrations can potentially provide a more direct estimation of groundwater residence time. Conversely, the 3H–3He method is inefficient in the karst aquifer for dating due to 3He degassing.

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.