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41.
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A mathematical model has been developed in which carbon isotope fractionation during thermal cracking of n-paraffins can be simulated. The model has been calibrated based on data from laboratory cracking experiments carried out on n-octadecane. Relative rate constants for cleavage of C12-C12, C12-C13 and C13-C13 bonds agree with the experimental values obtained by other workers.Application of this model to the process of petroleum formation gives good agreement with some existing experimental data, but suggests that a review of our understanding of isotope fractionation during thermal cracking may be necessary. The relative importance of the degree to which the organic material has been cracked and of the type of the organic material in influencing δC13 values is discussed.The present model predicts that cracking of n-paraffin distributions having initial odd or even carbon number predominances can induce isotopic inhomogeneity among the homologs of the resulting distribution. The model exhibits some deficiencies in explaining or predicting the δC13 values of ethane and propane in relation to methane in gases and of oils and associated methane. Explanations for these discrepancies may lie in the simplicity of our mathematical model, in our assumption of initial isotopic homogeneity within molecules and in our use of only n-paraffins as the source molecules for the cracking reactions.  相似文献   
43.
Mathematical models have been developed which simulate both random and nonrandom thermal cracking of branched and straight-chain hydrocarbons. Application of these models to n-paraffins suggests that thermal cracking alone cannot be the dominant mechanism in formation of the n-paraffin distributions present in crude oils. Application to isoprenoid hydrocarbons indicates that nonrandom cracking could be important in producing the isoprenoid distributions found in oils.Results of the mathematical modeling show that methane formation should, as predicted from energy considerations, be kinetically disfavored. It therefore is likely that substantial quantities of methane are produced from saturated hydrocarbons only under thermal conditions more severe than those under which oil is produced.The mathematical models employed are adaptable for other geochemical applications, such as isotope fractionation.  相似文献   
44.
Boulder 1, Station 2, Apollo 17 is a stratified boulder containing dark clasts and dark-rimmed light clasts set in a light-gray friable matrix. The gray to black clasts (GCBx and BCBx) are multigenerational, competent, high-grade metamorphic, and partially melted breccias. They contain a diverse suite of lithic clasts which are mainly ANT varieties, but include granites, basaltic-textured olivine basalts, troctolitic and spinel troctolitic basalts, and unusual lithologies such as KREEP norite, ilmenite (KREEP) microgabbro, and the Civet Cat norite, which is believed to be a plutonic differentiate. The GCBxs and BCBxs are variable in composition, averaging a moderately KREEPy olivine norite. The matrix consists of mineral fragments derived from the observed lithologies plus variable amounts of a component, unobserved as a clast-type, that approximates a KREEP basalt in composition, as well as mineral fragments of unknown derivation. The high-temperature GCBxs cooled substantially before their incorporation into the friable matrix of Boulder 1. The light friable matrix (LFBx) is texturally distinct from the competent breccia clasts and, apart from the abundant ANT clasts, contains clasts of a KREEPy basalt that is not observed in the competent breccias. The LFBx lacks such lithologies as the granites and the Civet Cat norite observed in the competent breccias and in detail is a distinct chemical as well as textural entity. We interpret the LFBx matrix as Serenitatis ejecta deposited in the South Massif, and the GCBx clasts as remnants of an ejecta blanket produced by an earlier impact. The source terrain for the Serenitatis impact consisted of the competent breccias, crustal ANT lithologies, and the KREEPy basalts, attesting to substantial lunar activity prior to the impact. The age of the older breccias suggests that the Serenitatis event is younger than 4.01±0.03 b.y.  相似文献   
45.
46.
Integrated, in situ textural, chemical and electron microprobe age analysis of monazite grains in a migmatitic metapelitic gneiss from the western Musgrave Block, central Australia has identified evidence for multiple events of growth and recrystallisation during poly-metamorphism in the Mesoproterozoic. Garnet + sillimanite-bearing metapelite underwent partial melting and segregation to palaeosome and leucosome during metamorphism between 1330 and 1296 Ma, with monazite grains in leucosome recording crystallisation at 1300 Ma. Monazite breakdown during melting is inferred to have occurred in the palaeosome. During a subsequent granulite facies event at 1200 Ma, deformation and metamorphism of leucosome and palaeosome resulted in partial disturbance of ages and potential minor growth on 1300 Ma monazite in leucosome. Growth of new, high-Y (+HREE) monazite in palaeosome domains occurred during garnet breakdown in the presence of sillimanite to cordierite and spinel, as a result of post-peak isothermal decompression. Diffusive enrichment of resorbed garnet rims in Y + HREE suggests garnet breakdown occurred slower than volume diffusion of REE. Monazite in both palaeosome and leucosome were subsequently partially to penetratively recrystallised during a retrogression event that is suggested to have occurred at 1150–1130 Ma. The intensity of recrystallisation and disturbance of ages appears linked to proximity to retrogressed garnet porphyroblasts and their occurrence in the relatively reactive or ‘fertile’ local environments provided by the palaeosome/mesosome volumes, which caused localised changes in retrogressive fluids towards compositions more aggressive to monazite. Like reaction textures, it is apparent that domainal equilibrium and reaction may control or at least strongly influence monazite REE and U–Th–Pb chemistry and hence ages.  相似文献   
47.
48.
The peraluminous tonalite–monzogranite Port Mouton Pluton is a petrological, geochemical, structural, and geochronological anomaly among the many Late Devonian granitoid intrusions of the Meguma Lithotectonic Zone of southern Nova Scotia. The most remarkable structural feature of this pluton is a 4-km-wide zone of strongly foliated (040/subvertical) monzogranites culminating in a narrow (10–30 m), straight, zone of compositionally banded rocks that extends for at least 3 km along strike. The banded monzogranites consist of alternating melanocratic and leucocratic compositions that are complementary to the overall composition of that part of the pluton, suggesting an origin by mineral–melt and mineral–mineral sorting. Biotite and feldspar are strongly foliated in the plane of the compositional bands. These compositional variations and foliations originated by a process of segregation flow during shearing of the main magma with a crystallinity of 55–75%. Subsequent minor brittle fracturing of feldspars, twinning of microcline, development of blocky sub-grains in quartz, and kinking of micas demonstrate overprinting by a high-temperature deformation straddling the monzogranite solidus. Small folds and late sigmoidal dykes indicate dextral movement on the shear zone. This Port Mouton Shear Zone (PMSZ) is approximately co-linear with the only outcrops of Late Devonian mafic intrusions in the area, two of which are syn-plutonic with well-developed mingling textures in the marginal tonalite of the Port Mouton Pluton. Also closely co-linear with the mafic intrusions are a granitoid dyke that extends well beyond the outer contact of the Port Mouton Pluton, a swarm of large aligned angular xenolithic slabs, a zone of thin wispy schlieren banding, a large Be-bearing pegmatite, and a breccia pipe with abundant garnetiferous metapelitic xenoliths. In various ways, the shear zone may control all of these features. The Port Mouton Shear Zone is parallel to many other NE-trending faults and shear zones in the northern Appalachians, probably related to the docking of the Meguma Zone along the Cobequid–Chedabucto Fault system.  相似文献   
49.
Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales.  相似文献   
50.
Uranium co-precipitation with iron oxide minerals   总被引:2,自引:0,他引:2  
In oxidizing environments, the toxic and radioactive element uranium (U) is most soluble and mobile in the hexavalent oxidation state. Sorption of U(VI) on Fe-oxides minerals (such as hematite [α-Fe2O3] and goethite [α-FeOOH]) and occlusion of U(VI) by Fe-oxide coatings are processes that can retard U transport in environments. In aged U-contaminated geologic materials, the transport and the biological availability of U toward reduction may be limited by coprecipitation with Fe-oxide minerals. These processes also affect the biological availability of U(VI) species toward reduction and precipitation as the less soluble U(IV) species by metal-reducing bacteria.To examine the dynamics of interactions between U(VI) and Fe oxides during crystallization, Fe-oxide phases (containing 0.5 to 5.4 mol% U/(U + Fe)) were synthesized by means of solutions of U(VI) and Fe(III). Wet chemical (digestions and chemical extractions) and spectroscopic techniques were used to characterize the synthesized Fe oxide coprecipitates after rinsing in deionized water. Leaching the high mol% U solids with concentrated carbonate solution (for sorbed and solid-phase U(VI) species) typically removed most of the U, leaving, on average, about 0.6 mol% U. Oxalate leaching of solids with low mol% U contents (about 1 mol% U or less) indicated that almost all of the Fe in these solids was crystalline and that most of the U was associated with these crystalline Fe oxides. X-ray diffraction and Fourier-transform infrared (FT-IR) spectroscopic studies indicate that hematite formation is preferred over that of goethite when the amount of U in the Fe-oxides exceeds 1 mol% U (∼4 wt% U). FT-IR and room temperature continuous wave luminescence spectroscopic studies with unleached U/Fe solids indicate a relationship between the mol% U in the Fe oxide and the intensity or existence of the spectra features that can be assigned to UO22+ species (such as the IR asymmetric υ3 stretch for O = U = O for uranyl). These spectral features were undetectable in carbonate- or oxalate-leached solids, suggesting solid phase and sorbed U(VI)O22+ species are extracted by the leach solutions. Uranium L3-edge x-ray absorption spectroscopic (XAFS) analyses of the unleached U-Fe oxide solids with less than 1 mol% U reveal that U(VI) exists with four O atoms at radial distances of 2.19 and 2.36 Å and second shell Fe at a radial distance at 3.19 Å.Because of the large ionic radius of UO22+ (∼1.8 Å) relative to that of Fe3+ (0.65 Å), the UO22+ ion is unlikely to be incorporated in the place of Fe in Fe(III)-oxide structures. Solid-phase U(VI) can exist as the uranyl [U(VI)O22+] species with two axial U-O double bonds and four or more equatorial U-O bonds or as the uranate species (such as γ-UO3) without axial U-O bonds. Our findings indicate U6+ (with ionic radii of 0.72 to 0.8 Å, depending on the coordination environment) is incorporated in the Fe oxides as uranate (without axial O atoms) until a point of saturation is reached. Beyond this excess in U concentration, precipitating U(VI) forms discrete crystalline uranyl phases that resemble the uranyl oxide hydrate schoepite [UO2(OH)2·2H2O]. Molecular modeling studies reveal that U6+ species could bond with O atoms from distorted Fe octahedra in the hematite structure with an environment that is consistent with the results of the XAFS. The results provide compelling evidence of U incorporation within the hematite structure.  相似文献   
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