985 resultados para ESPECTROSCOPIA C-13 NMR
Resumo:
Raman spectroscopy has been used by fluid inclusionists to: 1) identify and quantitatively determine the relative abundances of gaseous species within fluid inclusions; 2) identify solid phases precipitating from, or accidentally trapped, within fluid inclusions; and 3) determine the detection limits of the C-13/C-12 ratio in the CO2 bearing phase of fluid inclusions.
Resumo:
Mississippi Tialley-type zinc-lead deposits and ore occurrences in the San Vicente belt are hosted in dolostones of the eastern Upper Triassic to Lower Jurassic Pucara basin, central Peru. Combined inorganic and organic geochemical data from 22 sites, including the main San Vicente deposit, minor ore occurrences, and barren localities, provide better understanding of fluid pathways and composition, ore precipitation mechanisms, Eh-pH changes during mineralization, and relationships between organic matter and ore formation. Ore-stage dark replacement dolomite and white sparry dolomite are Fe and rare earth element (REE) depleted, and Mn enriched, compared to the host dolomite. In the main deposit, they display significant negative Ce and probably Eu anomalies. Mixing of an incoming hot, slightly oxidizing, acidic brine (H2CO3 being the dominant dissolved carbon species), probably poor in REE and Fe, with local intraformational, alkaline, reducing waters explains the overall carbon and oxygen isotope variation and the distributions of REE and other trace elements in the different hydrothermal carbonate generations. The incoming ore fluid flowed through major aquifers, probably basal basin detrital units, with limited interaction with the carbonate host rocks. The hydrothermal carbonates show a strong regional chemical homogeneity, indicating access of the ore fluids by interconnected channelways near the ore occurrences. Negative Ce anomalies in the main deposit, that are absent at the district scale, indicate local ore-fluid chemical differences. Oxidation of both migrated and indigenous hydrocarbons by the incoming fluid provided the local reducing conditions necessary for sulfate reduction to H2S, pyrobitumen precipitation, and reduction of Eu3+ to Eu2+. Fe-Mn covariations, combined with the REE contents of the hydrothermal carbonates, are consistent with the mineralizing system shifting from reducing/rock-dominated to oxidizing/fluid-dominated conditions following ore deposition. Sulfate and sulfide sulfur isotopes support sulfide origin from evaporite-derived sulfate by thermochemical organic reduction; further evidence includes the presence of C-13-depleted calcite cements (similar to-12 parts per thousand delta(13)C) as sulfate pseudomorphs, elemental sulfur, altered organic matter in the host dolomite, and isotopically heavier, late, solid bitumen. Significant alteration of the indigenous and extrinsic hydrocarbons, with absent bacterial membrane biomarkers (hopanes) is observed. The light delta(34)S of sulfides from small mines and occurrences compared to the main deposit reflect a local contribution of isotopically light sulfur, evidence of local differences in the ore-fluid chemistry.
Resumo:
The authenticity of vegetable oils consumed in Slovenia and Croatia was investigated by carbon isotope analysis of the individual fatty acids by the use of gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS), and through carbon isotope analysis of the bulk oil. The fatty acids from samples of olive, pumpkin, sunflower, maize, rape, soybean, and sesame oils were separated by alkaline hydrolysis and derivatized to methyl esters for chemical characterization by capillary gas chromatography/mass spectrometry (GC/MS) prior to isotopic analysis. Enrichment in heavy carbon isotope (C-13) of th, bulk oil and of the individual fatty acids are related to (1) a thermally induced degradation during processing (deodorization, steam washing, or bleaching), (2) hydrolytic rancidity (lipolysis) and oxidative rancidity of the vegetable oils during storage, and (3) the potential blend with refined oil or other vegetable oils. The impurity or admixture of different oils may be assessed from the delta C-13(16:0) VS. delta C-13(18:1) covariations. The fatty acid compositions of Slovenian and Croatian olive oils are compared with those from the most important Mediterranean producer countries (Spain, Italy, Greece, and France).
Resumo:
Although hydrocarbon-bearing fluids have been known from the alkaline igneous rocks of the Khibiny intrusion for many years, their origin remains enigmatic. A recently proposed model of post-magmatic hydrocarbon (HC) generation through Fischer-Tropsch (FT) type reactions suggests the hydration of Fe-bearing phases and release of H-2 which reacts with magmatically derived CO2 to form CH4 and higher HCs. However, new petrographic, microthermometric, laser Raman, bulk gas and isotope data are presented and discussed in the context of previously published work in order to reassess models of HC generation. The gas phase is dominated by CH4 with only minor proportions of higher hydrocarbons. No remnants of the proposed primary CO2-rich fluid are found in the complex. The majority of the fluid inclusions are of secondary nature and trapped in healed microfractures. This indicates a high fluid flux after magma crystallisation. Entrapment conditions for fluid inclusions are 450-550 degrees C at 2.8-4.5 kbar. These temperatures are too high for hydrocarbon gas generation through the FT reaction. Chemical analyses of rims of Fe-rich phases suggest that they are not the result of alteration but instead represent changes in magma composition during crystallisation. Furthermore, there is no clear relationship between the presence of Fe-rich minerals and the abundance of fluid inclusion planes (FIPs) as reported elsewhere. delta C-13 values for methane range from -22.4% to -5.4%, confirming a largely abiogenic origin for the gas. The presence of primary CH4-dominated fluid inclusions and melt inclusions, which contain a methane-rich gas phase, indicates a magmatic origin of the HCs. An increase in methane content, together with a decrease in delta C-13 isotope values towards the intrusion margin suggests that magmatically derived abiogenic hydrocarbons may have mixed with biogenic hydrocarbons derived from the surrounding country rocks. (C) 2006 Elsevier BV. All rights reserved.
Resumo:
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.
Resumo:
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.
Resumo:
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.
Resumo:
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.
Resumo:
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.
Resumo:
Hypolactasia associated with severe iron-deficiency anemia has been reported in several studies. The objective of the present study was to determine whether hypolactasia is associated with the degree and duration of iron-deficiency anemia. Newly weaned male Wistar rats were divided into a control group receiving a diet supplemented with iron (C) and an experimental group (E) receiving a diet not supplemented with iron (iron-deficiency diet). The animals were studied on the 3rd, 5th, 7th, 14th, 21st, 28th and 35th days of the experiment, when overall and iron nutritional status and disaccharidase activity in the small intestine were determined by the Dahlqvist method. A reduction in weight occurred in the anemic animals starting on the 5th day of the study. Anemia was present in the experimental animals, with a progressive worsening up to the 14th day (hemoglobin: C = 13.27 and E = 5.37) and stabilizing thereafter. Saccharase and maltase activities did not differ significantly between groups, whereas lactase showed a significant reduction in total (TA) and specific activity (SA) in the anemic animals starting on the 21st day of the study. Median lactase TA for the C and E groups was 2.27 and 1.25 U on the 21st day, 2.87 and 1.88 U on the 28th day, and 4.20 and 1.59 U on the 35th day, respectively. Median lactase SA was 0.31 and 0.20 U/g wet weight on the 21st day, 0.39 and 0.24 U/g wet weight on the 28th day, and 0.42 and 0.23 U/g wet weight on the 35th day, respectively. These findings suggest a relationship between the enzymatic alterations observed and both the degree and duration of the anemic process. Analysis of other studies on intestinal disaccharidases in anemia suggests that the mechanism of these changes may be functional, i.e., that the enterocytes may suffer a reduction in their ability to synthesize these enzymes.
Resumo:
Contient : 1 "Antes a filha que o vinho. Farça." ; 2 "A apotheose de Hercules. Drama em trez actos. Lisboa, 1806." ; 3 "Drama em hum só acto, que se intitula : A appariçaõ a Affonso Henriques no campo de Ourique, representado no theatro nacional do Salitre, no mes de março (na quaresma) de 1813." ; 4 "A quanto obriga amor ou Os doidos da data moderna. Entremez." ; 5 "Drama intitulado : Argonauta escravo." ; 6 "Comedia emtitulada : Armida e Reinaldo, em dous actos." ; 7 "Opera. Os asombros da constancia : Volugeso e Berenice. Copiada aos 20 de novembro de 1788." ; 8 et 9 "A assembleia rafada ou A velha taful. Farça composta por hum anonimo, ampliada por Alexandre José Victor da Costa Sequeira, copiada aos 29 de novembro de 1817." Deux exemplaires, dont un non daté et sans le nom de l'arrangeur ; 10 "As astucias de Zanguizarra ou Os velhos logrados. Farça que se repprezentou no theatro nacional da rua dos Condes, com geral aceitaçaõ, composta pelo ponto Ricardo Jozé Fortuna, copiada aos 20 de abril de 1818." ; 11 "A audiencia ou A eschola dos principes, drama sentimental de trez actos, que se repprezentou no theatro nacional da rua dos Condes, com geral aceitaçaõ, composto pelo actor Antonio Jozé de Paula, copiado aos 20 de setembro de 1817." ; 12 "O aventureiro nocturno. Drama em 3 actos. Anno de 1814. Por A. R. C." ; 13 "O aviso á gazeta. Farça."
Resumo:
Palladium and platinum complexes of pyridoxamine, pyridoxine and pyridoxal have been prepared. The structures of the complexes PtCI2PM.H20, trans-PdC12 (PN)2 and [PLH+ ]2[PtC16] 2- ,H20 have been determined by use of single crystal x-ray studies. The compounds PdC12PH, trans-PdC12 (PN) 2 , cis-PdCI2 (PN)2 and cis PdC12 (PL)2 were also studied by use of carbon-13 nmr spectroscopy. All the complexes have also been characterised by use of infrared spectral studies. In the complexes, PtCI2PM.H20 and PdC12PM, the ligand pyridoxamine is chela ted to the metal through the aminomethyl nitrogen and the phenolate oxygen atoms whereas in the complexes, trans-PdCI2 (PN)2' cis-PdCI2 (PN)2 and cis-PdC12 (PL)2 the vitamin B6 ligands are coordinated to the metal through the pyridine ring nitrogen. The compounds [PLH+ ]2[PtCI6] 2- .H20 and [PMH2] 2+ [PdCI4] 2- .H20have no direct metal-ligand bonding, In all the complexes, the metal maintains a square planar coordination except in [PLH +] 2[PtCI6] 2- ,H20 where the metal is octahedrally coordinated. PH pyridoxamine [PMH ] 2+ = diprotonated pyridoxamine 2 PN = pyridoxine PL pyridoxal PLH+ protonated pyridoxal
Resumo:
This thesis describes the chemoenzymatic synthesis of three morphine alkaloids. The total synthesis of dihydrocodeine and hydrocodone was accomplished starting from bromobenzene in 16 and 17 steps, respectively. The key steps included a microbial oxidation of bromobenzene by E. coli JM109 (pDTG601A), a Kazmaier-Claisen rearrangement of glycinate ester to generate C-9 and C-14 stereo centers, a Johnson-Claisen rearrangement to set the C-13 quaternary center, and a C-10/C-11 ring closure via a Friedel-Crafts reaction. In addition, the total synthesis of ent-hydromorphone starting from β-bromoethylbenzene in 12 steps is also described. The key reactions included the enzymatic dihydroxylation of β-bromoethylbenzene to the corresponding cis-cyclohexadienediol, a Mitsunobu reaction, and an oxidative dearomatization followed by an intramolecular [4+2] cycloaddition.
Resumo:
El presente proyecto es una idea que trata de mirar principalmente que hace competitiva a un país, cuales son los pasos, que se requiere y que entes y personas deben estar relacionados con el proyecto para lograrlo. Es necesario mirar el caso de varios países y ciudades para saber cómo pasaron de ser entes territoriales comunes y corrientes para convertirse en naciones con buen desarrollo y buenas expectativas de vida. Para esto se tiene que relacionar un concepto clave que ayuda a entender la competitividad de lospaíses y es la productividad territorial. A parte resaltar una autora, SaskiaSassen, que habla de ciudades tan competitivas que llegaron a ser ciudades globales. La idea del trabajo es llegar a unas estrategias específicas que ayuden a un ente territorial a ser más competitivo y productivo tomando como base países y ciudades que ya lo han implementado. Al final lograr destacar estrategias y dar recomendaciones de cómo el estado colombiano, el sector privado y la sociedad pueden impulsar, intervenir, aumentar e innovar para obtener una competitividad y productividad importante para el país.
Resumo:
Ofrecer una pauta de pensamiento y acción que permita resolver operativamente algunos problemas planteados por la instrucción a padres y educadores dentro del marco de la Psicología de la modificación de conducta. Crear manuales que sirvan al psicólogo y/o pedagogo para poder llevar adelante cursos de modificación de conducta para educadores y padres. Para el curso de educadores y especialistas se utilizaron 4 muestras: a) 10 educadores de EGB especialistas en activo de Pedagogía terapéutica; b) 9 educadores de EGB con la misma titulación; c) 13 educadores de EGB (la mayoría directores); d) 8 educadores de EGB. La muestra del curso de padres la constituyen los oyentes del programa de radio. El informe final incluye una revisión histórica y bibliográfica de la (reciente) Psicología de la modificación de la conducta que fundamentalmente resalta su demostrada eficacia en la resolución de problemas educativos. Posteriormente describe los cursos realizados (para profesores de EGB y especialistas en Pedagogía terapéutica por un lado, y para padres a través de la radio, por otro) y los evalúa. La evaluación de los cursos se lleva a cabo a través de variados criterios incluyendo 2 estudios de casos: 1) Efectos de la observación de fichas en una clase de deficientes mentales, y cambio de precio en un sistema de Economía. 2) Modelamiento comportamental en un caso de oligofrenia profunda con base orgánica. Cuestionario de preguntas a cumplimentar por los asistentes al curso de educadores después de cada sesión. Cuestionario de evaluación del curso. Correspondencia de los oyentes. Porcentajes. Estudios de casos. Puesta a punto de unos esquemas sobre un texto básico en modificación de conducta en ambientes educativos para profesores de EGB y especializados en Pedagogía terapéutica. Realización de cursos -formulación de un primer texto-guía, las sesiones de los cursos deberán ser espaciadas, sería aconsejable 20 por curso -, realizada la experiencia utilizando los mass media (la radio) se hace patente la necesidad de depurar su duración y aligerar su contenido para el entorno social canario. La modificación de conducta ofrece grandes posibilidades de aplicación en los ámbitos educativos. Es factible la realización de cursos encaminados a ofrecer una información útil en modificación de conducta para padres y profesores. Resulta claro que se pueden utilizar los medios de comunicación social para establecer contacto con los padres, con el fin de poder perfilar programas de acción comunitaria.