<p> Detailed Neodymium isotopic mapping was performed on grey gneisses from the Algonquin Park area of Ontario, in the Central Gneiss Belt of the southwestern Grenville Province. The Neodymium model ages determined were based upon the Depleted Mantle Model of DePaolo ( 1981c ) . The use of this model is supported by Lead-Lead dating of zircons obtained from an orthogneissic sample. </p> <p> The wide range of model ages found ( 1.5 - 1.86 Ga ) is attributed to the presence of a northwestward dipping, Andean style, ensialic continental margin arc that was active in the Mid-Proterozoic between 1.50 Ga and 1.65 Ga. The diapiric rise of plutons produced by the subduction zone intruded continental margin at least as old as 1.86 Ga as indicated by the oldest pluton in the field area. Variable amounts of mixing occurred between these orogenic rocks and the existing crustal rocks as illustrated by the variable Neodymium model ages determined for grey gneisses collected between 10 Km and 60 Km north of the Central Metasedimentary Belt Boundary Zone. Major element analysis and subsequent tectonic and petrographic discrimination diagrams such as the AFM plot and the granitoid discrimination diagram of LeFort and Debon ( 1983 ) also indicate that the rocks in the Algonquin Park area are calc-alkaline, and are similar to the Peruvian Coastal Batholith. </p> <p> For grey gneisses analyzed within 10 Km of the Central Metasedimentary Belt Boundary Zone, the range of ages is far more restricted, suggesting that an island arc approximately 1.45 Ga was transported by the subducting slab and later sutured onto the existing continental margin. </p> / Thesis / Bachelor of Science (BSc)

No description available.

No description available.

A área de estudo localiza-se na borda sul do Cráton São Francisco, no Cinturão Mineiro, este é porção integrante da Província Sul Mineira. Neste contexto ocorre um mosaico de terrenos arqueanos e paleoproterozóicos de alto a médio grau metamórfico e associações granitogreenstone. Os corpos plutônicos, estudados neste trabalho, fazem parte do abundante plutonismo paleoproterozóico intrusivo nos greenstone belts Nazareno (Arqueano) e Rio das Mortes (Proterozóico). Dentro deste contexto ocorre a zona de Cisalhamento do Lenheiro (ZCL), que delimita estes greenstones belts: Nazareno (ao sul da falha) e Rio das Mortes (ao norte da falha); assim como plutons paleoproterozóicos. Os plutons escolhidos para este trabalho foram: Gnaisse Granítico Fé, Granito Mama Rosa, Tonalito/Trondhjemito Cassiterita, Granito Ritápolis, Diorito Brumado e Quartzo Monzodiorito Glória, localizados ao norte da ZCL; e: Granitóide do Lajedo, Granitóide Gentio, Quartzo Diorito Dores do Campo, Quartzo Diorito do Brito, Granodiorito Brumado de Baixo e Granodiorito Brumado de Cima, localizados ao sul da ZCL. Os estudos petrográficos indicam as seguintes características para os corpos: Gnaisse Granítico Fé (monzogranito a sienogranito), Granito Mama Rosa (monzogranito), Tonalito/Trondhjemito Cassiterita (tonalito a granodiorito), Granito Ritápolis (tonalito, granodiorito, monzogranito e sienogranito), Diorito Brumado (Diorito, quartzo diorito e tonalito), Quartzo Monzodiorito Glória (quartzo diorito, quartzo monzodiorito e tonalito), Granitóide do Lajedo (granodiorito), Granitóide Gentio (k-feldspato granito), Quartzo Diorito Dores do Campo (quartzo-diorito), Quartzo Diorito do Brito (quartzo-diorito), Granodiorito Brumado de Baixo (granodiorito a monzogranito) e Granodiorito Brumado de Cima (granodiorito a monzogranito). Os plutons Fé, Mama Rosa e Lajedo possuem composição peraluminosa/metaluminosa, o Quartzo Diorito Dores do Campo é metaluminoso e o Granitóide Gentio é peraluminoso. O Gnaisse Granítico Fé, Granito Mama Rosa e Granitóide Gentio variam desde o campo cálcioalcalino até shoshonítico em decorrência dos conteúdos de K2O, já o Granitóide do Lajedo é cálcio-alcalino e o Quartzo Diorito Dores do Campo varia de toleítico e cálcio-alcalino. Foram obtidas idades de cristalização U/Pb (TIMS) em zircão do: Gnaisse Granítico Fé (2191 ± 9 Ma), Granitóide do Lajedo (2208 ± 26 Ma), Granitóide Gentio (2066± 10 Ma - idade mínima) e Quartzo Diorito Dores do Campo (2198 ± 6 Ma). Os resultados dos isótopos de Nd/Sr dos corpos são: Gnaisse Granítico Fé (eNd(2190Ma) = - 3,1; TDM = 2,7 Ga; 87Sr/85Sri = 0,70497); Granito Mama Rosa (eNd(2121Ma) = - 5,3; TDM = 3,0 Ga; 87Sr/85Sri = 0,70497), Tonalito/Trondhjemito Cassiterita (eNd(2162Ma) = - 0,1; TDM = 2,5 Ga; 87Sr/85Sri = 0,73427), Granito Ritápolis (eNd(2121Ma) = - 2,4; TDM = 2,5 Ga; 87Sr/85Sri = 0,73427), Diorito Brumado (eNd(2131Ma) = - 2,6; TDM = 2,71 Ga; 87Sr/85Sri = 0,71362), Quartzo Monzodiorito Glória (eNd(2189Ma) = - 3,4; TDM = 2,7 Ga; 87Sr/85Sri = 0,70510), Granitóide do Lajedo (eNd(2208) = - 1,7; TDM = 2,6 Ga; 87Sr/85Sri = 0,70322), Granitóide Gentio (eNd(2066Ma) = - 10,8; TDM = 3,0 Ga; 87Sr/85Sri = 0,70021), Quartzo Diorito Dores do Campo (eNd(2198Ma) = - 0,1; TDM = 2,6 Ga; 87Sr/85Sri = 0,70445), Quartzo Diorito do Brito (eNd(2221Ma) = - 0,45; TDM = 2,6 Ga; 87Sr/85Sri = 0,70500), Granodiorito Brumado de Baixo (eNd(2218Ma) = - 0,68; TDM = 2,6 Ga; 87Sr/85Sri = 0,72726) e Granodiorito Brumado de Cima (eNd(2187Ma) = - 0,66; TDM = 2,5 Ga; 87Sr/85Sri = 0,73075). A integração dos dados geoquímicos, geocronológicos e isotópicos permitiu diferenciar a existência de dois conjuntos distintos, a norte e ao sul da ZCL. Os plutons: Brito, Brumado de Cima, Nazareno, Itutinga, Brumado de Baixo, Lajedo e Quartzo Diorito Dores do Campo, situados ao sul da zona de cisalhamento do Lenheiro, possuem uma contribuição de magmas paleoproterozóicos com baixa contaminação por materiais de curta vivência crustal. Esses plutons se enquadram na primeira etapa evolutiva do Cinturão, entre 2220 Ma e 2198 Ma. Os plutons Cassiterita, Brumado, Fé e Glória distribuídos ao norte desta ZCL, considerados da \"Fase Arco\" sugerem maior interação de magmas proterozóicos com componentes arqueanos relativamente ao outro conjunto isotópico; e uma cristalização tardia com relação ao grupo anterior. Já os plutons Ritápolis (2121 ± 7 Ma) e Mama Rosa situados neste mesmo bloco tectônico a norte da falha do Lenheiro, indicam uma maior interação de componentes arqueanos com magmas proterozóicos, com relação aos dois grupos anteriores, e no contexto evolutivo do Cinturão esses plutons se enquadram na fase sin- a tardi-colisional. E finalmente, o Granitóide Gentio, situado na porção sul da Zona de Cisalhamento do Lenheiro, possui uma maior interação dos magmas proterozóicos com componentes de crosta arqueana, e um posicionamento na fase final da evolução do Cinturão Mineiro, junto com as intrusões graníticas pós-tectônicas. Isto reforça a hipótese de haver pulsos magmáticos de caráter tectônico distinto, no âmbito da Província Sul Mineira. Adicionalmente, dados comparativos de idade U-Pb e TDM, do Cinturão Mineiro com a porção paleoproterozóica ao norte do Cráton São Francisco, indicam que a Orogênese Transamazônica foi um pouco mais precoce no Cinturão. Os protólitos das rochas plutônicas de ambas as porções tiveram uma gênese a partir de uma mistura de magma paleoproterozóico juvenil com componentes crustais arqueanos em maior ou menor quantidade. / The study area is located in the southern border of the São Francisco Craton, Mineiro Belt. This portion comprises part of the Sul Mineira Province. In this context occurs medium to high metamorfic grade Archean and Paleoproterozoic terrains mosaic and granite-greenstone associations. The plutonic bodies, studied in this work, make part of volumous paleoproterozoic plutonism intrusive in to Nazareno greenstone belt (Archean) and Rio das Mortes greenstone belt (Proterozoic). The Lenheiro shear zone (LSZ delimits these greenstone belts: Nazareno (in the south) and Rio das Mortes (in the north); as well as the Paleoproterozoic plutons. The plutons chose for this work are: Fé Granitic Gneiss, Mama Rosa Granite, Cassiterita Tonalite/Trondhjemite, Ritápolis Granite, Brumado Diorite e Glória Quartz-Monzodiorite, located in the north LSZ; and: Lajedo Granitoid, Gentio Granitoid, Dores do Campo Quartz-Diorite, Brito Quartz-Diorite, Brumado de Baixo Granodiorite and Brumado de Cima Granodiorite, located in the south LSZ. Their petrographic characteristics are was follow: Fé Granitic Gneiss (monzogranite to sienogranite), Mama Rosa Granite (monzogranite), Cassiterita Tonalite/Trondhjemite (tonalite to granodiorite), Ritápolis Granite (tonalite, granodiorite, monzogranite and syenogranite), Brumado Diorite (diorite, quartz-diorite and tonalite), Glória Quartz-Monzodiorite (quartzdiorite, quartz-monzodiorite and tonalite), Lajedo Granitoid (granodiorite), Gentio Granitoid (kfeldspar granite), Dores do Campo Quartz-Diorite (quartz-diorite), Brito Quartz-Diorite (quartzdiorite), Brumado de Baixo Granodiorite (granodiorite to monzogranite) and Brumado de Cima Granodiorite (granodiorite to monzogranite). The Fé, Mama Rosa and Lajedo plutons have peraluminous/metaluminous composition, the Dores do Campo Quartz-Diorite is metaluminous and the Gentio Granitoid is peraluminous. The Fé Granitic Gneiss, Mama Rosa Granite and Gentio Granitoid alternate calc-alcaline trend to shoshonitic trends, in terms of K2O contents. The Lajedo Granitoid is calcic-alkaline and Dores do Campo Quartz-Diorite alternate toleiitic and calcic-alkaline caracteristics. We have obtained U-Pb ages (zircon) for the following rocks: Fé Granitic Gneiss (2191 ± 9 Ma), Lajedo Granitoid (2208 ± 26 Ma), Gentio Granitoid (2066± 10 Ma - minimum age) and Dores do Campo Quartz-Diorite (2198 ± 6 Ma). The geochemistry, geocronology and isotope information consent define the existence of two groups of plutons, in the north and south of LSZ. The plutons: Brito, Brumado de Cima, Nazareno, Itutinga, Brumado de Baixo, Lajedo and Quartzo Diorito Dores do Campo, located in south of LSZ, have Paleoproterozoic magma contribution with reducted contamination of short crustal life materials. These plutons belong to the first evolutive stage of the Mineiro Belt, between 2220 Ma and 2198 Ma. The plutons Cassiterita, Brumado, Fé and Glória located in north of LSZ, considered of the \"Arc Stage\" have significant Paleoproterozoic magma interation with Archean components compared to the other isotopic group; and a late cristalization time, between the north and the south group. The Ritápolis (2121 ± 7 Ma) and Mama Rosa plutons (north of the Lenheiros fault) display strong intersection with Archean components, and are tecnically related to the syn- to late- collision stage of the Mineiro belt evolution. The Gentio pluton shows similar isotopic characteristics, but it belongs to the pos-tectonic stage. Finaly, the U-Pb and ; TDM ages of the Mineiro belt plutons, compared with the Paleoproterozoic plutons that occursin the northen São Francisco craton, reveal that significant time differences took place during the Transamazonian orogeny. In addition, the auxilable isotopic characteristics of these plutons suggest the important role of mixing of Paleoproterozoic magmas and Archean protholits during magma genesis.

The method of in situ high pressure neutron diffraction was employed to measure reliable diffraction patterns to help illuminate the density-driven structural transformations in GeO2, SiO2, B2O3 and GeSe2 glass. The majority of this neutron diffraction work employed the diffractometer D4c at the ILL with a Paris-Edinburgh press which enabled the pressure range from ambient to 8 GPa to be accessed. In the cases of GeO2 and GeSe2 glass, the neutron diffraction with isotopic substitution (NDIS) protocol was developed to provide benchmark experimental results to test the results obtained from various molecular dynamics simulations using different theoretical schemes. For GeO2 glass, from a combination of neutron diffraction and molecular dynamics results, it was found that the increase in density of the glass initially occurs through a reorganisation of corner-shared GeO4 tetrahedra on an intermediate length scale as the pressure is increased from ambient to 5 GPa. At higher pressures, there is a progression from a tetrahedral to an octahedral glass, via the formation of 5-fold coordinated Ge atoms which have a predominantly square pyramidal geometry. In the work on SiO2 and B2O3 glass the pressure range for the in situ high pressure neutron diffraction results was extended to 14.5 GPa and 17.5 GPa, respectively, by using the PEARL diffractometer at ISIS. For both materials the neutron diffraction results provide complementary information to pressure x-ray diffraction studies helping to elucidate the mechanism of network collapse. In the case of SiO2 glass, densification over the measured pressure range occurs predominantly by a reorganisation of corner shared SiO4 tetrahedra on an intermediate length scale. In the case of B2O3 glass, the B-O coordination number changes from 3 to ∼ 3.9 at the pressure is increased from ∼ 8 to 17.5 GPa. For GeSe2 glass, from a combination of neutron diffraction and molecular dynamics results, it was found that the density increase from ambient pressure up ∼ 8 GPa occurs by a reorganisation of both corner and edge-sharing GeSe4 tetrahedra on an intermediate length scale. Above this pressure, 5- and 6-fold coordinated Ge atoms start to form at a similar density and homopolar bonds play an intimate role in the formation of these higher coordinated polyhedra.

Não existe um consenso do efeito da suplementação de glutamina sobre a síntese protéica. No entanto, sugere-se que em animais desnutridos submetidos a trauma orgânico ou não, a glutamina além de seu papel no metabolismo energético, poderia ter efeito sobre a taxa de reciclagem protéica, tornando-se um aminoácido, condicionalmente, essencial. O objetivo deste trabalho foi determinar a incorporação protéica do aminoácido marcado 13C leucina em proteínas do plasma e da mucosa intestinal em ratos portadores de desnutrição protéico-calórica, suplementados ou não com glutamina via oral. Os animais foram pareados pelo peso/idade e subdivididos em 5 grupos: grupo controle nutrido (grupo 1), grupo controle desnutrido (grupo 2), grupo realimentado (grupo 2 A), grupo realimentado e suplementado com proteína e glutamina (grupo 2B) e grupo realimentado e suplementado com glutamina, a suplementação de glutamina por via oral durante 14 dias (0,42g/kg/dia). O estudo não teve por objetivo avaliar a fisiopatologia da desnutrição, mas sim o efeito terapêutico da oferta de glutamina no tratamento de animais desnutridos e em analogia, ao que ocorreria com pacientes desnutridos e internados. O estudo cinético efetuou-se por meio de infusão contínua &#61504; 620&#61549;mol/h L-[1-13C]-leucina durante 4 horas. O grupo de animais desnutridos (grupo 2), que recebeu 50% da alimentação recomendada, perdeu peso continuamente durante o experimento. Os grupos que receberam tratamentos dietoterápicos recuperaram o peso corporal, independente do tipo de realimentação e/ou suplementação de glutamina. O nitrogênio urinário teve comportamento similar ao do peso, ratificando o efeito de um tratamento dietético, independente da fonte de suplementação glutâmica. Os resultados de concentração plasmática de aminoácidos não foram uniformes tanto para os aminoácidos essenciais quanto para os aminoácidos considerados não essenciais. Reforçando tanto o ganho de peso, como a excreção de nitrogênio, tiveram comportamento semelhante independente da suplementação de glutamina. Na concentração plasmática de glutamina a diferença foi 649&#61617;12 vs 171&#61617;14&#61549;mol/l, no grupo controle nutrido (grupo 1) e grupo controle desnutrido (grupo 2), respectivamente. Houve diferença significativa de enriquecimento plasmático isotópico de 13C leucina 1,27&#61617;0,5 vs 3,2&#61617;1,2, e enriquecimento de 13C KIC 1,93&#61617;0,6 vs 4,04&#61617;0,9 MPE%, respectivamente nos grupos 1 e 2. O enriquecimento isotópico de 13C leucina na proteína da mucosa intestinal, mostrou-se significativo entre os grupos 1 e 2, respectivamente, 0,0024&#61617;0,0006 vs 0,0020&#61617;0,0001 MPE% e o enriquecimento isotópico de 13C leucina livre apresentou-se semelhante com diferença entre os grupos 1 e 2, respectivamente 0,0019&#61617;0,00030 vs 0,0028&#61617;0,0007 MPE%. A taxa de síntese fracionada (FSR) foi menor no grupo controle desnutrido (grupo 2) 0,0037&#61617;0,0007/h em comparação ao grupo controle nutrido (grupo 1) 0,0044&#61617;0,0005/h e similar nos grupos experimentais. Conclui-se que a oferta de glutamina não estimulou ou alterou a incorporação protéica de aminoácido marcado, sendo que os resultados obtidos nos grupos suplementados com glutamina assemelharam-se aos encontrados no grupo de animais tratados com dieta. Desta maneira, sugere-se que o uso de suplemento de glutamina via oral não seja necessário no tratamento de animais desnutridos. / Nutritional status recovery is thought more effective when there are amino acids, especially, glutamine supplementation. The aim of the study was to verify the effect of glutamine on duodenal mucosa protein synthesis in the nourished or malnourished rats. The experimental groups animals received oral diet glutamine supplementation (0.42g/kg/day) for 14 days while the control group did not. Thereafter, kinetic study with L-[1-13C]-leucine to 4-h and biopsies of duodenal mucosa were done. The malnourished groups showed 25% weight loss with increase urinary nitrogen. Amino acid concentration in the plasma of control group was not significantly different with from that of the experimental groups. The result showed that 13C enrichment in the plasma and biopsy sample of the malnourished group is higher than that of the nourished group, but that of the fractional synthetic rate (FSR) is inverse; FSR of the nourished group is higher 0.0044&#61617;0.0005/h than that of the malnourished group 0.0037&#61617;0.0007/h.We conclude that oral supplementation glutamine does not acutely stimulate duodenal protein incorporation in malnourished rats, regardless the refilling protocol, with or without glutamine.

This thesis describes a study in petroleum geochemistry and specifically of the application of Land-plant derived hydrocarbons to elucidating source matter type, depositional environment and thermal maturity of crude oils. Large volumes of petroleum have been generated from land-plant organic matter in many parts of the world, but especially in the Tertiary deltaic provinces of the USA, Canada, Africa, Southeast Asia, Australia and New Zealand. Compared to oils from other regions, these oils have a relatively complex pattern of biomarkers or molecular fossils, a feature reflecting the diversity of deltaic depositional environments and the advanced state of plant evolution during late Mesozoic and Tertiary time. The molecular and carbon isotopic composition of these oils is useful in identifying the character of their source beds and also in understanding the conditions that give rise to oil-prone sediments generally.Despite their widespread occurrence in oils and sediments, land-plant biomarkers have been used less frequently than compounds of algal origin as markers for source, depositional environment and thermal maturity. The present work sets out to extend the range of land-plant biomarker and isotope tools available to the petroleum geochemist and to provide a firmer foundation for some of the existing tools. A systematic study of the biomarker and n-alkane carbon-isotope composition of a set of late Mesozoic/Tertiary-age oils was carried out as a preamble to more focussed investigations. A comparison of the biomarker and n-alkane isotope data showed that parameters such as the oleanane/hopane ratio overestimate the higher plant contribution to marine deltaic oils. The abundance of bicadinane isomers was found to be much more variable than that of the oleananes, probably because of their close association with the highly resinous, dipterocarp hardwoods of ++ / Southeast Asia. However, small amounts of bicadinanes were found in an oil from outside the paleogeographic range of the dipterocarp family, indicating a more general source. Retention indices based on the regular hopane series were calculated for the main bicadinane and methyl bicadinane isomers and for a group of oleanoid triterpanes.Source rock depositional setting proved to be the primary control on the shape of the n-alkane isotope profile, with negatively sloping curves being characteristic of fluvio-deltaic and marginal lacustrine oils and flat or positively sloping curves typical of marine oils. The difference is probably related to the bacterial reworking of higher plant matter in the fluvio-deltaic environment. A slight isotopic anomaly at n-C(subscript)17 correlates with the abundance of algal-derived steranes and may indicate a minor marine contribution to the source of an fluvio-deltaic oil. A study of sediments from the South Sumatra Basin and New Zealand showed that the n-alkane isotope profile is determined mainly by source matter type and is little influenced by thermal maturity or depositional environment.Based on the results of the work described above, three aspects were chosen for further examination. These were: a) the factors controlling the carbon isotopic composition of n-alkanes and of resin-derived compounds in terrigenous oils; b) the influence of source, maturity and biodegradation on the abundance of bicadinanes, especially the effect of maturity on the isomer distribution, and c) the factors controlling the abundance of oleananes and rearranged oleananes in oils and Ancient sediments, especially the role of depositional environment.A preliminary study using sediments, from the Visayan Basin (Philippines) showed the bicadinane isomeric distribution to be sensitive to maturity. This suggested new maturity parameters which would be ++ / resistant to even severe biodegradation and largely immune to interference from diagenetic effects. A more detailed study of a marine-fluvio-deltaic depositional sequence from the South Sumatra Basin confirmed that the maturity indices based on bicadinanes and aromatic analogs were less subject to non-maturity influences than those based on the steranes and aromatic hydrocarbons. The values obtained for the bicadinane indices were compared with the maturity required for oil generation as estimated by kinetic modelling and with conventional maturity indicators such as sterane epimerisation and the methyl phenanthrene index. Values for several of the indices were also measured for 17 Tertiary-age oils from Southeast Asia, Papua New Guinea, New Zealand and Australia. The main bicadinane maturity indicator (BMI-1) continues to change into the oil window and hence is useful in ranking the relative maturity of oils as well as sediments. Values of BMI-1 for two oils having unusually low sterane maturities were found to be normal and, in the light of this observation, the conventional explanation for low sterane epimerisation of many Tertiary-age oils was critically evaluated.The oleananes, as markers for the angiosperms, provide valuable source and age information when present in an oil. Nevertheless, their abundance is not quantitatively related to the land plant input and indeed their presence results from a small "leak" in diagenetic processes leading primarily to aromatic oleanoids. Evidence is presented that contact of plant matter with seawater during early diagenesis enhances the expression of oleananes in a mature sediment or oil. Oleananes are absent or present at very low concentrations in samples from the base of an Eocene coal seam affected by post-depositional seawater intrusion. However, their abundance increases toward the top of the seam in correlation with ++ / % organic sulphur, dibenzothiophene/phenanthrene and the homohopane index. Similarly, in deltaic sediments from the South Sumatra Basin, oleanane/hopane is strongly correlated with indicators of marine influence such as C[subscript 27]/C[subscript 29] steranes and of oxic/anoxic conditions such as the homohopane index. In each case, increasing oleanane abundance is accompanied by a reduction in the extent of aromatisation and, for the South Sumatra Basin, the proportion of A-ring contracted oleananes. An angiosperm-derived Miocene coal from the Philippines, deposited under freshwater conditions, shows abundant aromatic oleanoids but no oleananes. These results show that oleananes need to be used with caution as age and source markers in fluvio- deltaic and lacustrine petroleum systems. On the other hand, their sensitivity to early diagenetic conditions may make them useful in locating effective source rocks in such systems.Compounds derived from plant resins are major components of some terrigenous oils. Although recent studies have elucidated the molecular structure of resinites, very little information was available on the carbon isotope composition of resinites prior to the present study. No carbon isotope studies of resin-derived compounds in oils had been performed. Hence, carbon stable isotope analyses were carried out on a set of modern and fossil resins of diverse origins and compound specific isotope analysis was used to characterise individual hydrocarbons in resin pyrolysates and oils derived from resinitic source matter. The results showed that "Class V' resinites derived from gymnosperms are enriched in the heavy carbon isotope compared with the angiosperm-derived "Class W' resinites. Furthermore, both the fossil resinites themselves and individual hydrocarbons derived from them are isotopically heavy compared with modern plant resins. The reasons for ++ / these differences and their implications for petroleum geochemical studies are discussed.

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Clinopyroxene, olivine, plagioclase and hydrous fluid lithium partition coefficients have been measured between 800-1100oC at 1 GPa. Clinopyroxene-fluid partitioning is a function of temperature (ln DLicpx/fluid = -7.3 (+0.5) + 7.0 (+0.7) * 1000/T) and appears to increase with increasing pyroxene Al2O3 content. Olivine-fluid partitioning of lithium is a function of temperature (ln DLiol/fluid = -6.0 (+2.0) + 6.5 (+2.0) * 1000/T) and appears to be sensitive to olivine Mg/Fe content. Anorthite-fluid lithium partitioning is a function of feldspar composition, similar to the partitioning of other cations in the feldspar-fluid system. Isotopic fractionation between clinopyroxene and fluid, Licpx-fluid, has been measured between 900-1100oC and ranges from -0.3 to -3.4 ‰ (±1.4 ‰). Lithium diffusion has been measured in clinopyroxene at 800-1000oC and in olivine at 1000oC. The lithium diffusion coefficient is independent of the diffusion gradient as values are the same if the flux of lithium is into or out of the crystal and ranges from -15.19 ± 2.86 m2/s at 800oC to -11.97 ± 0.86 m2/s at 1000oC. Lithium diffusion in olivine was found to be two orders of magnitude slower than for clinopyroxene at similar conditions. Closure temperatures calculated for lithium diffusion in clinopyroxene range from ~400 to ~600oC. These results demonstrate that lithium equilibration between fluids and minerals is instantaneous, on a geological timescales. The confirmation of instantaneous equilibration, combined with min-fluid partition coefficients and values for Licpx-fluid, permits quantitative modeling of the evolution of lithium concentration and isotopic composition in slab-derived fluids during transport to the arc melt source. Our results indicate that fluids migrating by porous flow will rapidly exchange lithium with the mantle, effectively buffering the fluid composition close to ambient mantle values, and rapidly attenuating the slab lithium signature. Fluid transport mechanisms involving fracture flow are required to maintain a slab-like lithium signature (both elemental and isotopic) from the slab to the melt source of island arc basalts. This study demonstrates that mineral-fluid equilibration is rapid, and as a result the lithium content of minerals can only reliably represent chemical exchange in the very latest stages of the sample’s history.

Clinopyroxene, olivine, plagioclase and hydrous fluid lithium partition coefficients have been measured between 800-1100oC at 1 GPa. Clinopyroxene-fluid partitioning is a function of temperature (ln DLicpx/fluid = -7.3 (+0.5) + 7.0 (+0.7) * 1000/T) and appears to increase with increasing pyroxene Al2O3 content. Olivine-fluid partitioning of lithium is a function of temperature (ln DLiol/fluid = -6.0 (+2.0) + 6.5 (+2.0) * 1000/T) and appears to be sensitive to olivine Mg/Fe content. Anorthite-fluid lithium partitioning is a function of feldspar composition, similar to the partitioning of other cations in the feldspar-fluid system. Isotopic fractionation between clinopyroxene and fluid, Licpx-fluid, has been measured between 900-1100oC and ranges from -0.3 to -3.4 ‰ (±1.4 ‰). Lithium diffusion has been measured in clinopyroxene at 800-1000oC and in olivine at 1000oC. The lithium diffusion coefficient is independent of the diffusion gradient as values are the same if the flux of lithium is into or out of the crystal and ranges from -15.19 ± 2.86 m2/s at 800oC to -11.97 ± 0.86 m2/s at 1000oC. Lithium diffusion in olivine was found to be two orders of magnitude slower than for clinopyroxene at similar conditions. Closure temperatures calculated for lithium diffusion in clinopyroxene range from ~400 to ~600oC. These results demonstrate that lithium equilibration between fluids and minerals is instantaneous, on a geological timescales. The confirmation of instantaneous equilibration, combined with min-fluid partition coefficients and values for Licpx-fluid, permits quantitative modeling of the evolution of lithium concentration and isotopic composition in slab-derived fluids during transport to the arc melt source. Our results indicate that fluids migrating by porous flow will rapidly exchange lithium with the mantle, effectively buffering the fluid composition close to ambient mantle values, and rapidly attenuating the slab lithium signature. Fluid transport mechanisms involving fracture flow are required to maintain a slab-like lithium signature (both elemental and isotopic) from the slab to the melt source of island arc basalts. This study demonstrates that mineral-fluid equilibration is rapid, and as a result the lithium content of minerals can only reliably represent chemical exchange in the very latest stages of the sample’s history.