Carbon and oxygen isotope geochemistry of Ediacaran outer platform carbonates, Paraguay Belt, central Brazil

Após a glaciação do final do Criogeniano, a região central do Brasil foi palco de extensa deposição de carbonatos plataformais do Grupo Araras. Este grupo inclui na sua base uma seqüência de capa carbonática sucedida por depósitos transgressivos de calcilutitos betuminosos e folhelhos de plataforma profunda. Dados de fácies e estratigráficos combinados com análises isotópicas de carbono e oxigênio da seção mais completa desses depósitos transgressivos, expostos no sinclinal da Guia, foram empregados para avaliar o paleambiente deposicional e para testar a correlação desses depósitos ao longo da faixa e também com outras unidades de outros continentes. A sucessão estudada consiste de 150 m de espessura de camadas tabulares de calcilutitos e folhelhos cinza a pretos com valores de d13CPDB negativos, entre -2,5 e -1 . O perfil de d13CPDB do sinclinal da Guia mostra clara correlação com a porção superior da Formação Guia da região de Cáceres, 200 km a sudoeste. O perfil de d13CPDB do Grupo Araras é comparável aos perfis de d13CPDB de outras unidades ediacaranas da parte sul da Faixa Paraguai, oeste do Canadá, e crátons do Congo e do Kalahari. Além disso, a distribuição de fácies, estratigrafia e o perfil isotópico do Grupo Araras são equiparáveis à porção média do Subgrupo Tsumeb na Namíbia, o que reforça a atribuição de idade Ediacarana para o Grupo Araras.

Petrogenesis of syntectonic granites emplaced at the transition from thrusting to transcurrent tectonics in post-collisional setting: Whole-rock and Sr-Nd-Pb isotope geochemistry in the Neoproterozoic Quatro Ilhas and Mariscal Granites, Southern Brazil

The Neoproterozoic post-collisional period in southern Brazil (650-580 Ma) is characterized by substantial volumes of magma emplaced along the active shear zones that compose the Southern Brazilian Shear Belt. The early-phase syntectonic magmatism (630-610 Ma) is represented by the porphyritic, high-K, metaluminous to peraluminous Quatro Ilhas Granitoids and the younger heterogranular, slightly peraluminous Mariscal Granite. Quatro II has Granitoids include three main petrographic varieties (muscovite-biotite granodiorite mbg; biotite monzogranite - bmz: and leucogranite - lcg) that, although sharing some significant geochemical characteristics, are not strictly comagmatic, as shown by chemical and Sr-Nd-Pb isotope data. The most primitive muscovite-biotite granodiorite was produced by contamination of more mafic melts (possibly with some mantle component) with peraluminous crustal melts; the biotite monzogranite, although more felsic, has higher Ca, MgO,TiO2 and Ba, and lower K2O, FeOt, Sr and Rb contents, possibly reflecting some mixing with coeval mafic magmas of tholeiitic affinity; the leucogranite may be derived from pure crustal melts. The Mariscal Granite is formed by two main granite types which occur intimately associated in the same pluton, one with higher K (5-6.5 wt.% K2O) high Rb and lower CaO, Na2O, Ba and Zr as compared to the other (3-5 wt.% of K2O). The two Mariscal Granite varieties have compositional correspondence with fine-grained granites (fgg) that occur as tabular bodies which intruded the Quatro Ilhas Granoitoids before they were fully crystallized, and are inferred to correspond to the Mariscal Granite feeders, an interpretation that is reinforced by similar U-Pb zircon crystallization ages. The initial evolution of the post-collisional magmatism, marked by the emplacement of the Quatro Ilhas Granitoids varieties, activated sources that produced mantle and crustal magmas whose emplacement was controlled both by flat-lying and transcurrent structures. The transition from thrust to transcurrent-related tectonics coincides with the increase in the proportion of crustal-derived melts. The transcurrent tectonics seems to have played an essential role in the generation of mantle-derived magmas and may have facilitated their interaction with crustal melts which seem to be to a large extent the products of reworking of orthogneiss protoliths. (C) 2012 Elsevier B.V. All rights reserved.

A rapid and efficient ion-exchange chromatography for Lu–Hf, Sm–Nd, and Rb–Sr geochronology and the routine isotope analysis of sub-ng amounts of Hf by MC-ICP-MS

The development and improvement of MC-ICP-MS instruments have fueled the growth of Lu–Hf geochronology over the last two decades, but some limitations remain. Here, we present improvements in chemical separation and mass spectrometry that allow accurate and precise measurements of 176Hf/177Hf and 176Lu/177Hf in high-Lu/Hf samples (e.g., garnet and apatite), as well as for samples containing sub-nanogram quantities of Hf. When such samples are spiked, correcting for the isobaric interference of 176Lu on 176Hf is not always possible if the separation of Lu and Hf is insufficient. To improve the purification of Hf, the high field strength elements (HFSE, including Hf) are first separated from the rare earth elements (REE, including Lu) on a first-stage cation column modified after Patchett and Tatsumoto (Contrib. Mineral. Petrol., 1980, 75, 263–267). Hafnium is further purified on an Ln-Spec column adapted from the procedures of Münker et al. (Geochem., Geophys., Geosyst., 2001, DOI: 10.1029/2001gc000183) and Wimpenny et al. (Anal. Chem., 2013, 85, 11258–11264) typically resulting in Lu/Hf < 0.0001, Zr/Hf < 1, and Ti/Hf < 0.1. In addition, Sm–Nd and Rb–Sr separations can easily be added to the described two-stage ion-exchange procedure for Lu–Hf. The isotopic compositions are measured on a Thermo Scientific Neptune Plus MC-ICP-MS equipped with three 1012 Ω resistors. Multiple 176Hf/177Hf measurements of international reference rocks yield a precision of 5–20 ppm for solutions containing 40 ppb of Hf, and 50–180 ppm for 1 ppb solutions (=0.5 ng sample Hf 0.5 in ml). The routine analysis of sub-ng amounts of Hf will facilitate Lu–Hf dating of low-concentration samples.

Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin

Interstitial water and sediment samples of the Integrated Ocean Drilling Program (IODP) expedition 313 "New Jersey Shallow Shelf" were analyzed for chemical composition and stable isotope ratios. A total of 222 water samples were collected from the cores by Rhizon samplers and squeezing of fresh core material. Water was analyzed for its stable oxygen and hydrogen isotope geochemistry (d2H and d18O) at sites M0027A and M0029A, and the carbon isotope composition of the dissolved inorganic carbon (d13CDIC) (all sites). In addition, organic material (Corg) and inorganic carbonates from sediments were analyzed for their carbon ratios (d13Corg and d13Ccarb), and in case of the carbonates also for oxygen (d18Ocarb). Carbon isotopes were also analyzed in samples containing enough methane gas (d13Cmeth). Pore fluids from site M0027A were analyzed for the sulfur isotope composition of dissolved sulfate (d34S). The combination of isotope analyses of all phases (interstitial water, sediment, and gas) with pore water chemistry is expected to enable a better understanding of processes in the sediment and will help to identify the origin of fluids under the New Jersey shelf.

SHRIMP zircon geochronology and geochemistry of Phanerozoic granitoids in southeastern Korea

Phanerozoic granitoids are widespread in the Korean Peninsula and form a part of the East Asian Cordilleran-type granitoid belt extending from southeastern China to Far East Russia. Here we present SHRIMP zircon U-Pb ages and geochemical and Nd isotopic compositions of Late Paleozoic to Early Jurassic granitoid plutons in the northern Gyeongsang basin, southeastern Korea; namely the Jangsari, Yeongdeok, Yeonghae, and Satkatbong plutons. The granite and associated gabbroic rocks from the Jangsari pluton were coeval and respectively dated at 257.3 ± 2.0 Ma and 255.7 ± 1.4 Ma. This result represents the first finding of a Late Paleozoic pluton in South Korea. Three granite samples from the Yeongdeok pluton yielded a slightly younger age span ranging from 252.9 ± 2.5 Ma to 246.7 ± 2.1 Ma. Two diorite samples from the Yeonghae pluton gave much younger ages of 195.1 ± 1.9 Ma and 196.3 ± 1.6 Ma. An Early Jurassic age of 192.4 ± 1.6 Ma was also obtained from a diorite sample from the Satkatbong pluton. The mineral assemblage and Al2O3/(Na2O + K2O) versus Al2O3/(CaO + Na2O + K2O) relationship indicate that all the analyzed plutons are subduction zone granitoids. Enrichments in large-ion-lithophile-elements and depletions in high-field-strength-elements of these plutons are also concordant with geochemical characteristics typical for the subduction zone magma. The presence of Late Permian to Early Triassic arc system is in contrast with the conventional idea that the arc magmatism along the continental margin of the Korean Peninsula has commenced from Early Jurassic after the termination of Triassic collisional orogenesis. The epsilon-Nd(t) values of the granitoid plutons are consistently positive (2.4-4.6), suggesting that crustal residence time of the basement beneath the Gyeongsang basin is relatively short. Moreover, the reevaluation of previously-published data reveals that geochemical compositions of the Yeongdeok pluton are compatible with those of high-silica adakites; La/Yb = 37.5-114.6, Sr/Y = 138.2-214.0, SiO2 = 62.9-72.0 wt. %, Al2O3 = 15.5-17.0 wt. %, Sr = 562-1173 ppm, MgO = 0.4-1.6 wt. %, Y = 3-6 ppm, Yb = 0.18-0.45 ppm, and Eu/Eu* = 0.92-1.31. The occurrence of adakites in southeastern Korea, and presumably in the Hida belt of central-western Japan, is indicative of a hot subduction regime developing at least partly along the East Asian continental margin during the Permian-Triassic transition period.

Extractable hydrocarbon and carbon isotope geochemistry of Lower Cretaceous sediments of the Exmouth Plateau

The organic geochemical character of rocks selected from Aptian, Valanginian, and Berriasian clay stone and siltstone sequences encountered in Ocean Drilling Program (ODP) Holes 762C and 763C on the Exmouth Plateau was determined by means of a variety of analytical procedures. These sequences represent distal portions of the Mesozoic Barrow delta, in which petroleum source rocks and reservoirs exist on the Australian continent. The organic matter at the ODP sites is thermally immature type III material. Biomarker hydrocarbon compositions are dominated by long-chain, waxy n-alkanes and by C29 steranes, which reflect the land-plant origin of organic matter. Organic carbon d13C values ranged from -26 per mil to -28 per mil, consistent with a C3 land-plant source. Kerogen pyrolysate compositions and hopane isomerization ratios revealed progressively larger contributions of recycled organic matter as the depth of the deltaic sedimentary layers became greater.

Sr, Nd, and Pb isotope geochemistry of ODP Hole 104-642E

ODP Leg 104 recovered 914 m of volcanics at Site 642 on the Vøring Plateau in the Norwegian Sea. The upper series of these volcanics correlates with seaward-dipping seismic reflectors (DRS), and is tholeiitic in character. The lower series underlies the DRS and is broadly andesitic in character. Rb-Sr, Sm-Nd, and Pb isotopic analyses show that upper series samples have isotopic features characteristic of MORB, except for one dike sample that has a Pb isotopic composition that may indicate interaction of its parent magma with older continental crust. The five most silicic samples from the lower series, which occur high up in the sequence, define a 63 ± 19 Ma Rb-Sr whole-rock isochron age, and have an initial 87Sr/86Sr of 0.7116 ± 0.0004. Other lower series samples have lower initial 87Sr/86Sr, but all are greater than any upper series rock. The combined evidence of initial 87Sr/86Sr, initial epsilon-Nd values, Sm-Nd model ages, Pb isotopic compositions, and petrographic features clearly indicate that lower series rocks were derived, at least in part, from continental crustal source materials. That the DRS is underlain by rocks of continental character is an important observation, constraining models for the development of DRS-type passive continental margins.

Osmium-isotope geochemistry of ODP Site 159-959

Analyses of Re, Os, and Ir concentrations, as well as Os-isotopic compositions, are reported for a suite of sediments from Ocean Drilling Program Site 959. These samples vary in age from late Neogene to Late Cretaceous, and represent a range in depositional oxidation-reduction conditions from suboxic in the Neogene to anoxic in the Late Cretaceous. Age assignments based on shipboard biostratigraphic data are used to calculate initial 187Os/186Os ratios of Neogene nannofossil/foraminifer oozes and Eocene to upper Oligocene laminated diatomites. These calculated initial ratios are in general agreement with published data constraining the Os-isotopic evolution of seawater through time, indicating that the Os-isotopic composition of these sediments is controlled largely by the Os isotopic composition of contemporaneous seawater. Results from analyses of Upper Cretaceous to lower Paleocene claystones do not exhibit elevated Ir concentrations and exhibit Re-Os systematics that are highly consistent with closed-system production of 187Os by in situ 187Re decay. Scatter in both the Cretaceous and Cenozoic data sets is likely the result of the influence of nonhydrogenous Os, carried by clastics, on the bulk sediment Os-isotopic composition, or post-depositional mobility of Re and/or Os.

Assessing Fracture Connectivity using Stable and Clumped Isotope Geochemistry of Calcite Cements

Understanding flow path connectivity within a geothermal reservoir is a critical component for efficiently producing sustained flow rates of hot fluids from the subsurface. I present a new approach for characterizing subsurface fracture connectivity that combines petrographic and cold cathodoluminescence (CL) microscopy with stable isotope analysis (δ18O and δ13C) and clumped isotope (Δ47) thermometry of fracture-filling calcite cements from a geothermal reservoir in northern Nevada. Calcite cement samples were derived from both drill cuttings and core samples taken at various depths from wells within the geothermal field. CL microscopy of some fracture filling cements shows banding parallel to the fracture walls as well as brecciation, indicating that the cements are related to fracture opening and fault slip. Variations in trace element composition indicated by the luminescence patterns reflect variations in the composition and source of fluids moving through the fractures as they opened episodically. Calcite δ13C and δ18O results also show significant variation among the sampled cements, reflecting multiple generations of fluids and fracture connectivity. Clumped isotope analyses performed on a subset of the cements analyzed for conventional δ18O and δ13C mostly show calcite growth temperatures around 150°C—above the current ambient rock temperature, which indicates a common temperature trend for the geothermal reservoir. However, calcite cements sampled along faults located within the well field showed both cold (18.7°C) and hot (226.1°C) temperatures. The anomalously cool temperature found along the fault, using estimates from clumped isotope thermometry, suggests a possible connection to surface waters for the geothermal source fluids for this system. This information may indicate that some of the faults within the well field are transporting meteoric water from the surface to be heated at depth, which then is circulated through a complex network of fractures and other faults.