910 resultados para Heavier trivalent lanthanides
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Lithium isotopic compositions of hydrothermally altered sediments of Deep Sea Drilling Project (DSDP) site 477/477A, as well as high temperature vent fluids of the Guaymas Basin, have been determined to gain an understanding of lithium exchange during fluid-sediment interaction at this sediment-covered spreading center. Unaltered turbidite of the basin has a d6Li value of -10%, 5-7% heavier than fresh oceanic basalts. Contact metamorphism induced by a shallow sill intrusion results in a decrease of the lithium content of the adjacent sediments and a lighter isotopic value (-8%). Below the sill, sediments altered by a deep-seated hydrothermal system show strong depletions in lithium, while lithium isotopic compositions vary greatly, ranging from -11 to +1%. The shift to lighter composition is the result of preferential retention of the lighter isotope in recrystallized phases after destruction of the primary minerals. The complexity of the isotope profile is attributed to inhomogeneity in mineral composition, the tortuous pathway of fluids and the temperature effect on isotopic fractionation. The range of lithium concentration and d6Li values for the vent fluids sampled in 1982 and 1985 overlaps with that of the sediment-free mid-ocean ridge systems. The lack of a distinct expression of sediment input is explained in terms of a flow-through system with continuous water recharge. The observations on the natural system agree well with the results of laboratory hydrothermal experiments. The experimental study demonstrates the importance of temperature, pressure, water/rock ratio, substrate composition and reaction time on the lithium isotopic composition of the reacted fluid. High temperature authigenic phases do not seem to constitute an important sink for lithium and sediments of a hydrothermal system such as Guaymas are a source of lithium to the ocean. The ready mobility of lithium in the sediment under elevated temperature and pressure conditions also has important implications for lithium cycling in subduction zones.
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Stable isotopic and minor element compositions were measured on the fine fraction of pelagic carbonate sediments from Ocean Drilling Program Site 709 in the central Indian Ocean. This section ranges in age from 47 Ma to the present. The observed compositional variations are the result of either paleoceanographic changes (past oceanic chemical or temperature variations) or diagenetic changes. The CaCO3 record is little affected by diagenesis. From previous work, carbonate content is known to be determined by the interplay of biological productivity, water column dissolution, and dilution. The carbon isotopic record is generally similar to previously published curves. A good correlation was observed between sea-level high stands and high 13C/12C ratios. This supports Shackleton's hypothesis that as the proportion of organic carbon buried in marine sediments becomes larger, oceanic-dissolved inorganic carbon becomes isotopically heavier. This proportion appears to be higher when sea level is higher and organic carbon is buried in more extensive shallow-shelf sediments. The strontium content and oxygen isotopic composition of carbonate sediments are much more affected by burial diagenesis. Low strontium concentrations are invariably associated with high values of d18O, probably indicating zones of greater carbonate recrystallization. Nevertheless, there is an inverse correlation between strontium concentration and sea level that is thought to be a result of high-strontium aragonitic sedimentation on shallow banks and shelves during high stands. Iron and manganese concentrations and, to a lesser extent, magnesium and strontium concentrations and carbon isotopic ratios are affected by early diagenetic reactions. These reactions are best observed in a slumped interval of sediments that occurs between 13.0 and 17.5 Ma. As a result of microbial reduction of manganese and iron oxides and dissolved sulfate, it is hypothesized that small amounts of mixed-metal carbonate cements are precipitated. These have low carbon isotopic ratios and high concentrations of metals.
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In the years 2000 and 2001 we measured methane concentrations exceeding up to two orders of magnitude the equilibrium with the atmosphere in the water column on the SW-Spitsbergen continental shelf. This methane anomaly extended from its centre on the shelf westwards over the upper slope and eastwards well into the inner basins of the two southernmost Spitsbergen fjords, the Hornsundfjord and the van Mijenfjord. Methane concentrations and stable carbon isotopic ratios varied between 2 and 240 nM, and between -53 per mill and -20 per mill VPDB, respectively. Methane in high concentrations was depleted in 13C whereas in low concentrations d13CCH4 values were highly variable. On the continental shelf we found that methane discharged from seeps on top of sandy and gravelly banks is isotopically heavier than methane escaping from troughs filled with silty and clayey sediments. These distinct isotopic signatures suggest that methane is gently released from several inter-granular seepages or micro-seepages widely spread over the shelf. A potential migration path for thermogenic or hydrate methane may be the Hornsund Fracture Zone, a south-north running reactivated fault system created by stretching of the continental crust. After discharge into the water column, local water currents fed by Atlantic water, coastal water, and freshwater outflows from the fjords further determine pathways and fate of the methane. We used d18Owater and 222Rn data to trace origin and advection of the local water masses and water mixing processes. Methane spreads predominantly along pycnoclines and by vertical mixing. During transport methane is influenced simultaneously by oxidation and dilution, as well as loss into the atmosphere. Together these processes cause the spatial variability of the anomaly and heterogeneity in d13CCH4 in this polar shelf environment.
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Thesis (Master's)--University of Washington, 2016-06
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Polycrystalline cerium hydroxysulfate powders have been prepared by soft solution processing using various basic solvents. The crystals prepared have varying morphologies, spherical and flaky, depending on the solvent used. The crystals obtained from distilled water-pyridine and aqueous ammonia solvent mixtures are spherical, whereas those obtained from mixtures of distilled water and ethylenediamine or hydrazine hydrate are flaky. All the crystalline cerium hydroxysulfate samples display luminescence properties. It was found that the flaky crystals generally show a much stronger luminescence than their spherical counterparts.
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We present high spatial resolution ion-microprobe rare earth element (REE) data for discrete growth phases of complex polyphase zircons from early Archaean Amitsoq gneisses, outer Godthabsfjord, SW Greenland. In Matsuda diagrams, the two major growth phases, >3.8 Ga cores and ca. 3.65 Ga rims, have steep positive slopes from La to Lu, prominent positive Ce anomalies and negative Eu anomalies that are consistent with growth in a melt. Exceptions to this are non-cathodolurnmescent zircon developed between the cores and rims, sometimes truncating zoning in the cores, and late Archaean prismatic tip overgrowths, both of which exhibit flatter light REE (LREE) patterns and have small or no Eu anomaly, which we interpret as the result of metamorphism and/or small-degree, isolated partial melting. Our data support previous interpretations that the ca. 3.65 Ga zircon phase was generated in a melt, with the >3.8 Ga phase representing either original protolith zircons in a large degree partial melt or inherited zircons in an introduced magma. Regardless which of these two interpretations is correct for these, and similar, rocks in the outer GodthAbsfjord, the 3.65 Ga event will have profoundly affected isotopic systems and obscured beyond recognition any earlier igneous features such as cross-cutting relationships, which may only be assigned a minimum 3.65 Ga age. (C) 2003 Elsevier Science B.V. All rights reserved.
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Mycorthizae play a critical role in nutrient capture from soils. Arbuscular mycorrhizae (AM) and ectomycorrhizae (EM) are the most important mycorrhizae in agricultural and natural ecosystems. AM and EM fungi use inorganic NH4+ and NO3-, and most EM fungi are capable of using organic nitrogen. The heavier stable isotope N-15 is discriminated against during biogeochemical and biochemical processes. Differences in N-15 (atom%) or delta(15)N (parts per thousand) provide nitrogen movement information in an experimental system. A range of 20 to 50% of one-way N-transfer has been observed from legumes to nonlegumes. Mycorrhizal fungal mycelia can extend from one plant's roots to another plant's roots to form common mycorrhizal networks (CMNs). Individual species, genera, even families of plants can be interconnected by CMNs. They are capable of facilitating nutrient uptake and flux. Nutrients such as carbon, nitrogen and phosphorus and other elements may then move via either AM or EM networks from plant to plant. Both N-15 labeling and N-15 natural abundance techniques have been employed to trace N movement between plants interconnected by AM or EM networks. Fine mesh (25similar to45 mum) has been used to separate root systems and allow only hyphal penetration and linkages but no root contact between plants. In many studies, nitrogen from N-2-fixing mycorrhizal plants transferred to non-N-2-fixing mycorrhizal plants (one-way N-transfer). In a few studies, N is also transferred from non-N-2-fixing mycorrhizal plants to N-2-fixing mycorrhizal plants (two-way N-transfer). There is controversy about whether N-transfer is direct through CMNs, or indirect through the soil. The lack of convincing data underlines the need for creative, careful experimental manipulations. Nitrogen is crucial to productivity in most terrestrial ecosystems, and there are potential benefits of management in soil-plant systems to enhance N-transfer. Thus, two-way N-transfer warrants further investigation with many species and under field conditions.
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Factors influencing the rate of cannibalism in juvenile blue-swimmer crabs Portunus pelagicus were investigated under controlled conditions using time-lapse video recordings. This study was undertaken to improve blue-swimmer crab culture and experimentally addressed (1) prey vulnerability (2) cannibal-victim interactions, and (3) activity patterns of juveniles in varying degrees of refuge. Crabs used in the study were aged 15 weeks and sorted into two size classes; small (less than or equal to 60 mm carapace width (CW)) and large (greater than or equal to65 mm CW) of a similar sex ratio. Vulnerability and thus survival was influenced by body size variation, moult stage and refuge availability. Crabs with carapace width less than or equal to 60 mm were more vulnerable than larger individuals, as indicated by significant differences in survival rates. As predicted, juveniles in transition stages associated with ecdysis were especially vulnerable. Premoult (redliner) crabs appeared to be in a high state of agitation as evidenced by the frequency of agonistic encounters and this may be a contributing factor to the high mortality observed at this critical premoult stag. increases in refuge density increased survival of juveniles proportionally, indicating that the quantity of shelter is important for reducing cannibalism in this species. Cannibal-victim interactions were frequently asymmetrical in terms of size and moult stage. Cannibals were significantly heavier than victims, and were predominantly at intermoult stage. Sexual biases among cannibals and victims were not found in this study. Activity patterns of juveniles were influenced by the experimental conditions. Crabs provided with high refuge showed reduced aggressive activity and increased time spent resting, but unchanged locomotion or feeding activity. Regular grading as well as the presence of suitable shelter for newly moulted crabs is recommended for improving culture of P. pelagicus. Research into inducing synchronous moulting may also yield promising results. (C) 2004 Elsevier B.V. All rights reserved.
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Arsenic has been classified as a human carcinogen based on epidemiological data however the mechanism of its carcinogenicity is still unclear. Urinary biomarkers for chronic arsenic exposure would be valuable as an early warning indicator for timely interventions. In this study, young female C57BI/6J mice were given drinking water containing 0, 100, 250 and 500 mug As-v/L as sodium arsenate ad libitum for 12 months. Urine was collected bimonthly for urinary arsenic methylation assay and porphyrin analysis. All detectable arsenic species showed strong linear correlation with administered dosage and the arsenic methylation patterns were similar in all three treatment groups. No significant changes of methylation patterns were observed over time for either the control or test groups. Urinary coproporphyrin III was significantly increased in the 8th month in 250 and 500 mug/L groups and remained significantly dose-related after 10 and 12 months. Coproporphyrin I also showed a significant dose-response relationship after 12 months. Our results confirm that urinary arsenic is a useful biomarker for internal dose. The alteration of porphyrin profile suggests that arsenic can affect the heme metabolism and this may occur prior to the onset of arsenic induced carcinogenesis. (C) 2004 Elsevier Ireland Ltd. All rights reserved.
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The diagrammatic strong-coupling perturbation theory (SCPT) for correlated electron systems is developed for intersite Coulomb interaction and for a nonorthogonal basis set. The construction is based on iterations of exact closed equations for many - electron Green functions (GFs) for Hubbard operators in terms of functional derivatives with respect to external sources. The graphs, which do not contain the contributions from the fluctuations of the local population numbers of the ion states, play a special role: a one-to-one correspondence is found between the subset of such graphs for the many - electron GFs and the complete set of Feynman graphs of weak-coupling perturbation theory (WCPT) for single-electron GFs. This fact is used for formulation of the approximation of renormalized Fermions (ARF) in which the many-electron quasi-particles behave analogously to normal Fermions. Then, by analyzing: (a) Sham's equation, which connects the self-energy and the exchange- correlation potential in density functional theory (DFT); and (b) the Galitskii and Migdal expressions for the total energy, written within WCPT and within ARF SCPT, a way we suggest a method to improve the description of the systems with correlated electrons within the local density approximation (LDA) to DFT. The formulation, in terms of renormalized Fermions LIDA (RF LDA), is obtained by introducing the spectral weights of the many electron GFs into the definitions of the charge density, the overlap matrices, effective mixing and hopping matrix elements, into existing electronic structure codes, whereas the weights themselves have to be found from an additional set of equations. Compared with LDA+U and self-interaction correction (SIC) methods, RF LDA has the advantage of taking into account the transfer of spectral weights, and, when formulated in terms of GFs, also allows for consideration of excitations and nonzero temperature. Going beyond the ARF SCPT, as well as RF LIDA, and taking into account the fluctuations of ion population numbers would require writing completely new codes for ab initio calculations. The application of RF LDA for ab initio band structure calculations for rare earth metals is presented in part 11 of this study (this issue). (c) 2005 Wiley Periodicals, Inc.
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We have previously shown that a division of the f-shell into two subsystems gives a better understanding of the cohesive properties as well the general behavior of lanthanide systems. In this article, we present numerical computations, using the suggested method. We show that the picture is consistent with most experimental data, e.g., the equilibrium volume and electronic structure in general. Compared with standard energy band calculations and calculations based on the self-interaction correction and LIDA + U, the f-(non-f)-mixing interaction is decreased by spectral weights of the many-body states of the f-ion. (c) 2005 Wiley Periodicals, Inc.
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Clark 1 (diphenylarsine chloride) and Clark 2 ( diphenylarsine cyanide) were used as chemical weapon agents (CWA), and the soil contamination by these CWA and their degraded products, diphenyl and phenyl arsenicals, has been one of the most serious environmental issues. In a series of comparisons in toxicity between trivalent and pentavalent arsenicals we investigated differences in the accumulation and toxicity of phenylarsine oxide (PAO(3+)) and phenylarsonic acid (PAA(5+)) in rat heart microvascular endothelial cells. Both the cellular association and toxicity of PAO(3+) were much higher than those of PAA(5+), and LC50 values of PAO(3+) and PAA(5+) were calculated to be 0.295 muM and 1.93 mM, respectively. Buthionine sulfoximine, a glutathione depleter, enhanced the cytotoxicity of both PAO(3+) and PAA(5+). N-Acetyl-L-cysteine (NAC) reduced the cytotoxicity and induction of heme oxygenase-1 (HO-1) mRNA in PAO(3+)-exposed cells, while NAC affected neither the cytotoxicity nor the HO-1 mRNA level in PAA(5+)-exposed cells. The effect of NAC may be due to a strong affinity of PAO(3+) to thiol groups because both NAC and GSH inhibited the cellular accumulation of PAO(3+), but PAA(3+) increased tyrosine phosphorylation levels of cellular proteins. These results indicate that the inhibition of protein phosphatases as well as the high affinity to cellular components may confer PAO(3+) the high toxicity.
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We report kinetic molecular sieving of hydrogen and deuterium in zeolite rho at low temperatures, using atomistic molecular dynamics simulations incorporating quantum effects via the Feynman-Hibbs approach. We find that diffusivities of confined molecules decrease when quantum effects are considered, in contrast with bulk fluids which show an increase. Indeed, at low temperatures, a reverse kinetic sieving effect is demonstrated in which the heavier isotope, deuterium, diffuses faster than hydrogen. At 65 K, the flux selectivity is as high as 46, indicating a good potential for isotope separation.
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The effect of soil puddling on growth of lowland rice (Oryza sativa) and post-rice mungbean (Vigna radiata) was investigated using mini rice beds under controlled glasshouse conditions. Each mini rice bed was approximately 1 m(3) in size. Three different soil types were used: a well-drained, permeable loam; a hardsetting, structurally unstable silty loam; and a medium clay. Rice yields were reduced by low puddling compared with high puddling intensity on the loam but not affected on the heavier textured soils (silty loam and clay). Yield of mungbean was reduced on highly puddle, structurally unstable soil, indicating that puddling should be reduced on structurally unstable soils. Under glasshouse condition where crop establishment was not a limiting factor and plant available water in 0.65 m of soil was 100 mm, mungbean yields of >1 t/ha were achieved. However, under conditions where subsoil water reserves were depleted for the production of vegetative biomass during initial optimal growing condition, grain yield remained well below 1 t/ha.
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Study objective: Low birth weight predicts cardiovascular disease in adulthood, and one possible explanation is that children with lower birth weight consume more fat than those born heavier. Therefore, the objective of this study was to investigate associations between birth weight and childhood diet, and in particular, to test the hypothesis that birth weight is inversely related to total and saturated fat intake. Design: Prospective cohort study. Setting: South west England. Participants: A subgroup of children enrolled in the Avon longitudinal study of parents and children, with data on birth weight and also diet at ages 8, 18, 43 months, and 7 years ( 1152, 998, 848, and 771 children respectively). Main results: Associations between birth weight and diet increased in strength from age 8 to 43 months, but had diminished by age 7 years. Fat, saturated fat, and protein intakes were inversely, and carbohydrate intake was positively associated with birth weight at 43 months of age, after adjusting for age, sex, and energy intake. After adjustment for other confounders, all associations were weakened, although there was still a suggestion of a relation with saturated fat ( -0.48 (95% CI -0.97, 0.02) g/day per 500 g increase in birth weight. Similar patterns were seen in boys and girls separately, and when the sample was restricted to those with complete data at all ages. Conclusions: A small inverse association was found between birth weight and saturated fat intake in children at 43 months of age but this was not present at 7 years of age. This study therefore provides little evidence that birth weight modifies subsequent childhood diet.