Oxidation of methane at the CH4/H2O-(CO2) transition zone in the external part of the Central Alps, Switzerland: Evidence from stable isotope investigations

With the aim of understanding the mechanisms that control the metamorphic transition from the CH4- to the H2O-(CO2)-dominated fluid zone in the Helvetic domain of the Central Alps of Switzerland, fluid inclusions in quartz, illite ``crystallinity'' index, vitrinite reflectance, and the stable isotope compositions of vein and whole rock minerals and fluids trapped in quartz were investigated along four cross-sections. Increasing temperature during prograde metamorphism led to the formation of dry gas by hydrocarbon cracking in the CH4-zone. Fluid immiscibility in the H2O-CH4-(CO2)-NaCl system resulted in cogenetic, CH4- and H2O-dominated fluid inclusions. In the CH4-zone, fluids were trapped at temperatures <= 270 +/- 5 degrees C. The end of the CH4-zone is markedby a sudden increase of CO2 content in the gas phase of fluid inclusions. At temperatures > 270 +/- 5 degrees C, in the H2O-zone, the total amount of volatiles within the fluid decreased below 1 mol% with no immiscibility. This resulted m total homogenization temperatures of H2O-(CO2-CH4)-NaCl inclusions below 180 degrees C. Hydrogen isotope compositions of methane in fluid inclusion have delta D values of less than -100 parts per thousand in the CH4-zone, typical for an origin through cracking of higher hydrocarbons, but where the methane has not equilibrated with the pore water. delta D values of fluid inclusion water are around -40 parts per thousand., in isotopic equilibrium with phyllosilicates of the whole rocks. Within the CH4 to H2O(CO2) transition zone, delta D(H2O) values in fluid inclusions decrease to -130 parts per thousand interpreted to reflect the contribution of deuterium depleted water from methane oxidation. In the H2O-zone, delta D(H2O) values increase again towards an average of -30 parts per thousand which is again consistent with isotopic equilibrium with host-rock phyllosilicates. delta C-13 values of methane in fluid inclusions from the CH4-zone are around -27 parts per thousand in isotopic equilibrium with calcite in veins and whole rocks. The delta C-13(CH4) values decrease to less than -35 parts per thousand at the transition to the H2O-zone and are no longer in equilibrium with the carbonates in the whole rocks. delta C-13 values of CO, are variable but too low to be in equilibrium with the wall rock fluids, compatible with a contribution of CO2 from closed system oxidation of methane. Differences in isotopic composition between host-rock and Alpine fissure carbonate are generally small, suggesting that the amount of CO2 produced by oxidation of methane was small compared to the C-budget in the rocks and local pore fluids were buffered by the wall rocks during precipitation of calcite within the fissures. (c) 2006 Elsevier B.V. All rights reserved.

Carbon-isotope stratigraphy and ammonite faunal turnover for the Middle Jurassic in the Southern Iberian palaeomargin

Variations in the stable carbon-isotope ratio of marine and continental sediments can reflect changes in sink and flux modifications of the palaeocarbon cycle. Here we report carbon-isotope compositions of Middle Jurassic marine carbonates from the Betic Cordillera (southern Spain), which represents an ideal region to link the stable carbon-isotope curves directly to ammonite zones and subzones, and thereby for the first time achieve an accurate chronostratigraphic calibration. The five sections studied represent basin and high swell deposits of the Southern Iberian palaeomargin. We find a similar delta C-13 of carbonates between different oceanic areas, suggesting a homogeneous carbon-isotope oceanic reservoir through the Middle Jurassic. The Aalenian-Bajocian transition is a critical period in ammonite evolution; hence the Early Jurassic fauna are replaced by new ammonite families which become dominant throughout the Middle and Late Jurassic. For this reason, we compared the delta C-13 values of carbonates with ammonite diversity and extinction rates at different taxonomical levels in order to explore the possible relationship between the carbon cycle and ammonite evolution. The carbon-isotope values of carbonates are not exactly linearly correlated with the extinction rate and ammonite diversity, but the main faunal turnovers follow minimum delta C-13 values, where extinct taxa are replaced by new ones. Likewise, radiation episodes are associated with increasing delta C-13 values and with transgressive sea-level rise. All these data support the idea that perturbations in the global carbon cycle reflect rapid palaeoenvironmental changes. We made detailed analyses of these faunal turnovers, using them as a proxy to identify major palaeoenvironmental crises in their ecosystems forced by modification in the carbon cycle. (c) 2006 Elsevier B.V All rights reserved.

Organic geochemistry across the Permian-Triassic transition at the Idrijca Valley, Western Slovenia

Bulk and molecular stable C isotopic compositions and biomarker distributions provide evidence for a diverse community of algal and bacterial organisms in the sedimentary organic matter of a carbonate section throughout the Permian-Triassic (P/Tr) transition at the Idrijca Valley, Western Slovenia. The input of algae and bacteria in all the Upper Permian and Lower Scythian samples is represented by the predominance of C-15-C-22 n-alkanes, odd C-number alkylcyclohexanes, C-27 steranes and substantial contents Of C-21-C-30 acyclic isoprenoids. The occurrence of odd long-chain n-alkanes (C-22-C-30) and C29 steranes in all the samples indicate a contribution of continental material. The decrease of C-org and C-carb contents, increase of Rock-Eval oxygen indices, and C-13-enrichment of the kerogen suggest a decrease in anoxia of the uppermost Permian bottom water. The predominance of odd C-number alkylcycloalkanes, C-27 steranes, and C-17 n-alkanes with delta(13)C values similar to-30parts per thousand, and C-13-enrichment of the kerogens in the lowermost Scythian samples are evidence of greater algal productivity. This increased productivity was probably sustained by a high nutrient availability and changes of dissolved CO2 speciation associated to the earliest Triassic transgression. A decrease Of Corg content in the uppermost Scythian samples, associated to a C-13-depletetion in the carbonates (up to 4parts per thousand) and individual n-alkanes (up to 3.4parts per thousand) compared to the Upper Permian samples, indicate lowering of the primary productivity (algae, cyanobacteria) and/or higher degradation of the organic matter. (C) 2003 Elsevier Ltd. All rights reserved.

Basin-internal derivation of hydrocarbons in the Witwatersrand Basin, South Africa: evidence from bulk and molecular δ13C data

Gold in the quartz-pebble conglomerates of the late Archean Witwatersrand Basin, South Africa, is often intimately associated with carbonaceous matter of organic/biogenic origin which occurs in the form of stratiform carbon seams and paragenetically late bitumen nodules. Both carbon forms are believed to be formed by solidification of migrating hydrocarbons. This paper presents bulk and molecular chemical and stable carbon isotope data for the carbonaceous matter, all of which are used to provide a clue to the source of the hydrocarbons. These data are compared with those from intra-basinal shales and overlying dolostone of the Transvaal Supergroup. The delta C-13 values of the extracts from the Witwatersrand carbonaceous material show small differences (up to 2.4 parts per thousand) compared to the associated insoluble organic matter. This suggests that the auriferous rocks were stained by mobile hydrocarbons produced by thermal and oxidative alteration of indigenous bitumens, a contribution from hydrocarbons derived from intra-basinal Witwatersrand shales cannot be excluded. Individual aliphatic hydrocarbons of the various carbonaceous materials were subjected to compound specific isotope analysis using on-line gas chromatography/combustion/stable isotope ratio mass spectrometry (GC/C/IRMS). The limited variability of the molecular parameters and uniform delta C-13 values of individual n-alkanes (-31.1 +/- 1.7 parts per thousand) and isoprenoids (-30.7 +/- 1.1 parts per thousand) in the Witwatersrand samples exclude the mixing of oils from different sources. Carbonaceous matter in the dolostones shows distinctly different bulk and molecular isotope characteristics and thus cannot have been the source of the hydrocarbons in the Witwatersrand deposits. All the various forms of Witwatersrand carbon appear indigenous to the Witwatersrand Basin, and the differences between them are explained by variable, in general probably short (centimeter- to meter-scale) hydrocarbon migration during diagenesis and subsequent hydrothermal infiltration. (C) 2001 Elsevier Science B.V. All rights reserved.

Up-conversion effect of Er- and Yb-doped ZnO thin films

Visible up-conversion in ZnO:Er and ZnO:Er:Yb thin films deposited by RF magnetron sputtering under different O2-rich atmospheres has been studied. Conventional photoluminescence (325 nm laser source) and up-conversion (980 nm laser source) have been performed in the films before and after an annealing process at 800 °C. The resulting spectra demonstrate that the thermal treatment, either during or post-deposition, activates optically the Er3+ ions, being the latter process much more efficient. Moreover, the atmosphere during deposition was also found to be an important parameter, as the deposition under O2 flow increases the optical activity of Er+3 ions. In addition, the inclusion of Yb3+ ions into the films has shown an enhancement of the visible up-conversion emission at 660 nm by a factor of 4, which could be associated to either a better energy transfer from the 2F5/2 Yb level to the 4I11/2 Er one, or to the prevention of having Er2O3 clustering in the films.

Comportamento da laranjera 'Folha Murcha' em sete porta-enxertos no noroeste do Paraná

Este trabalho avaliou por um período de 14 anos, em Paranavaí-PR, o comportamento de plantas de laranjeira 'Folha Murcha' enxertadas nos porta-enxertos: limoeiros 'Cravo' (Citrus limonia), 'Rugoso da África' (Citrus jambhiri) e 'Volkameriano' (Citrus volkameriana), citrangeiro 'C-13' (Citrus sinensis x Poncirus trifoliata), trifoliata (Poncirus trifoliata), tangerineiras 'Sunki' (Citrus sunki) e 'Cleópatra' (Citrus reshni). O delineamento experimental utilizado foi o de blocos ao acaso, com sete tratamentos (porta-enxertos) e quatro repetições, com três plantas por parcela. Os volumes das copas de plantas em tangerineira 'Cleópatra' e limoeiro 'Rugoso da África' foram significativamente maiores. Plantas em limoeiro 'Cravo' apresentaram a menor diferença entre os diâmetros dos troncos do porta-enxerto e da copa. A produção acumulada foi superior nas plantas em limoeiro 'Rugoso da África' e tangerineira 'Cleópatra' e menor em plantas sobre o trifoliata. A alternância da produção não foi acentuada nas plantas sobre os porta-enxertos avaliados. O teor de sólidos solúveis totais foi significativamente superior nos frutos obtidos de plantas enxertadas em trifoliata e menor em limoeiro 'Rugoso da África'. A qualidade do suco apresentou-se dentro dos padrões aceitáveis para variedades-copa de laranjeiras. A tangerineira 'Cleópatra' e o limoeiro 'Rugoso da África' são porta-enxertos promissores para a laranjeira 'Folha Murcha' nas condições avaliadas.

Nova rota de preparação do 2-cloro-1,3,2-dioxofosfolana e 2-cloro-4,5-benzo-1,3,2-dioxofosfolana e caracterização por espectroscopia de RMN multinuclear

A new method for the preparation of 2-chloro-1,3,2-dioxaphospholane (1) and 2-chloro-4,5-benzo-1,3,2-dioxaphospholane (2), are reported. The modifications introduced in the synthetic route improved the yield and facilitated the control of reaction, but the synthesis require longer reaction time. The compounds were characterized by ¹H, 13C{¹H} and31P{¹H} NMR spectroscopy. Due to the complexity of the spin system AA'BB'X (A, A', B, B' = ¹H; X = 31P) of 2, a simulation of the ¹H NMR spectra was done and it's in agreement with the bibliography.

Aumento da resolução de espectros de RMN 13C de ácidos húmicos em solução através do tratamento prévio com KCl 0,03 mol L-1

High levels of Fe and Mn present in some soils and compost organic matter decrease the resolution of 13C NMR spectra of humic substances. Addition of KCl up to a concentration of 0,03 mol L-1 to humic substances extracts followed by centrifugation is an efficient method of eliminating clays and minerals containing high levels of paramagnetic metals such as Fe and Mn thus increasing the resolution of 13C NMR spectra.

Síntese, caracterização e propriedades espectroscópicas de criptatos de lantanídeo do tipo [LnÌ(bipy)2py(CO2Et) 2(3+)]

This work reports on the synthesis, characterization (infrared and hidrogen nmr spectra) and photophysical properties (luminescence spectra and emission quantum yield) of the lanthanide cryptates [LnÌ(bipy)2py(CO2Et) 2]3+ with Ln = Eu3+, Tb3+ or Gd3+, which can be applied as efficient Light-Conversion-Molecular-Devices. From emission spectra of [EuÌ(bipy)2py(CO2Et) 2]3+ it was possible to assign C3 symmetry to the metal ion. The spectroscopic studies show a higher emission quantum yield (q=25%) for [TbÌ(bipy)2py(CO2Et) 2]3+ in aqueous solution, whereas the europium cryptate presents q=14%. This is justified by a more efficient energy transfer between triplet and emission levels of terbium (T->5D4).

Óxido misto de ítrio-alumínio dopado com Eu(III)

In this work, we report the synthesis and the photoluminescence features of Eu(III)-doped yttrium-aluminium oxide obtained by non-hydrolytic sol-gel routes. After heating the powders above 600 ºC the XRD patterns show the presence of the Y4Al2O9 (YAM) and Y3Al5O12 (YAG) phases. At 800 and at 1500 ºC the PL spectra display the Eu(III) lines characteristic of the YAM monoclinic phase. The 5D0->7F2 transition is favored relatively to the 5D0->7F1 lines. However, at 1100 ºC the cubic YAG is the preferential phase and the 5D0->7F1 transition dominates the spectrum. The Eu(III) ions lie in a centrosymmetrical site. The different solvents used in the sol-gel synthesis also change the relative proportion between these two phases. This is monitored analyzing the modifications in the relative intensity between the 5D0->7F2 and the 5D0->7F1 transitions.

Simulação de desdobramentos complexos de espectros de RMN de ¹H

Complex ¹H NMR spectra multiplets that cannot be easily understood by simple inspection are rather frequent in the daily work of the organic chemistry analyst. The multiple and excellent new techniques available from modern instruments usually provide satisfactory solutions, but there are still many cases where a simulation is necessary, at least to obtain a final confirmation. It is extremely convincing to see that a graph, obtained by calculations with chemical-shift and coupling-constant values only, can be virtually identical to the experimental spectrum. This paper describes a computer program to make such calculations. The program is free and can be downloaded from http://artemis.ffclrp.usp.br/NMR.htm (click on SimEsp_NMR_Compil.zip). All routines are also available and may be used without any restrictions. The paper includes a fairly detailed discussion about how the calculations are made.

Cânfora: um bom modelo para ilustrar técnicas de RMN

The use of Nuclear Magnetic Resonance spectroscopy to establish the three-dimensional structures of molecules is an important component of modern Chemistry courses. The combination of techniques that can be used for this purpose is conveniently illustrated by their application to the camphor molecule. This paper presents applications of several techniques used in NMR spectral interpretation in an increasing order of complexity. The result of individual experiments is illustrated in order to familiarize the user with the way connectivity through bonds and through space is established from 1D/2D-NMR spectra and molecular stereochemistry is determined from different NMR experiments.

Caracterização da pureza de fosfatidilcolina da soja através de RMN de ¹H e de 31P

A strategy is proposed to evaluate the purity of phosphatidylcholine from soybean lecithin, obtained by extraction or column chromatography, using the integrals ratio of ¹H NMR spectra. Integrals of methylene signals, around 1.3 and 1.6 ppm, are added and divided by the integral of the choline methyl groups, around 3.3 ppm. Before purification, a ratio of 19.68±1.37 was determined. Using extraction, a ratio of 10.70±0.61 was found, while from column chromatography, a value of 2.99±0.25 was detected. 31P NMR of standard phosphatidylcholine showed signals at -0.2 and -0.9 ppm, whereas the purified one showed a single signal at -0.9 ppm.

Alcaloides iboga de Peschiera affinis (Apocynaceae) - Atribuição inequívoca dos deslocamentos químicos dos átomos de hidrogênio e carbono: atividade antioxidante

Six known alkaloids iboga type and the triterpen α- and β-amyrin acetate were isolated from the roots and stems of Peschiera affinis. Their structures were characterized on the basis of spectral data mainly NMR and mass spectra. 1D and 2D NMR spectra were also used to unequivocal ¹H and 13C chemical shift assignments of alkaloids. The ethanolic extract of roots, alkaloidic and no-alkaloidic fractions and iso-voacristine hydroxyindolenine and voacangine were evaluated for their antioxidative properties using an autographic assay based on β-carotene bleaching on TLC plates, and also spectrophotometric detection by reduction of the stable DPPH (2,2-diphenyl-1-picrylhydrazyl) free radical.

Flavonoides e outros compostos isolados de Mimosa artemisiana Heringer e Paula

This the first phytochemical investigation of Mimosa artemisiana (Leguminosae-Mimosoideae) describing the isolation and identification of quercitrin, myricitrin, 3,5,4´-trihydroxi-6,7-dimethoxyflavone (6,7-dimethylkaepferol), flavolignans, 3-O-β-D-glucopyranosil sitosterol, lupeol, sitostenone, stigmastenone, campestenone, sitosterol, stigmasterol, campesterol, methyl indole-3-carboxilate and indole-3-carboxaldehyde in the extracts from the leaves and wood of this plant. This is the first registry of 6,7-dimethoxy,4'-hydroxy-flavona and the flavonolignans in this genera. The isolation of all metabolites was made by chromatographic methods and the structures were established on the basis of IR, MS, ¹H and 13C NMR spectra analysis, comparison with literature data and GC-MS of mixtures analysis.