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71.
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
72.
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
73.
Alan B. Binder 《Earth, Moon, and Planets》1975,13(4):431-473
In a previous paper, it was shown that the basic properties and the developmental history of a gravitationally differentiated Moon of fission origin match those known for the Moon. In the first part of this report, the models of a differentiated Moon are critically reviewed based on second order considerations of some of the chemical systems used to develope the earlier models and based on new lunar data. As a result, slightly updated models are developed and the results indicate that a Moon of fission origin has a feldspar rich crust (≈70% Or0.8Ab5.3An93.9 with ≈30% pyroxene and olivine) reaching an average depth of ≈65 km. A KREEP rich layer is located at the interface of the crust and the upper mantle. The upper mantle consists of peridotite (≈80% Wo10En70Fs20 and ≈20% Fo75–80 with ≈3% Al2O3 and ≈ 2% TiO2) and reaches a depth of 300–400 km. Below 300–400 km lies a dunite (≈Fo95) lower mantle. A simple model for the distribution of K, U and Th (and by inference, KREEP) in the differentiated Moon model is developed using a distribution coefficient of 0.1 for the three elements. This coefficient is derived from published data on the distribution of U in Apollo 11 basalts. The simple model successfully accounts for the observed K, U and Th contents of the various mare basalts and upland rocks and yields a heat flow of 21 erg cm?2s?1 for the Moon. A model for the fine structure of the peridotite upper mantle of the model Moon is developed based on the TiO2 and trace element variations observed in the various mare basalts. It is proposed that the upper mantle is rhythmically banded on the scale of 10's of km and that this banding leads to local variations of a factor of ±3 in the K, U and Th content, -10 +5 in the TiO2 content and -∞ +2 in the olivine content of the peridotite. It is also proposed that this banding leads to large scale horizontal inhomogenuities in the composition of the upper mantle. It is also shown that the formation of the primitive suite of upland rocks is easily explained by the cumulation of plagioclase, which carried varying amounts of pyroxene, olivine and melt with it, during the peritectic crystallization of the last 20% of the differentiating Moon. It is found that the 100 Mg/(Mg+Fe) ratios of the mafics and the An contents of the plagioclases of the rocks are controlled by several factors, the most important of which is the ratio of melt to crystals which together formed the various upland rocks. The inverse relationship between the An contents and the Mg contents of the upland rocks is a direct consequence of the differentiation sequence proposed. The results and models presented in this paper further support the hypothesis that the Moon formed as a result of fission from the proto-Earth. 相似文献
74.
Graham Ryder Douglas B. Stoeser Ursula B. Marvin Janice F. Bower John A. Wood 《Earth, Moon, and Planets》1975,14(3-4):327-357
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
75.
76.
A multimetric fish index, the Estuarine Fish Community Index (EFCI) of Harrison and Whitfield (2004), was applied to data
collected for 190 South African estuaries. Estuaries spanned three biogeographic regions and included three distinct estuarine
typologies. The EFCI is based on 14 metrics or measures that represent four broad fish community attributes: species diversity
and composition, species abundance, nursery function, and trophic integrity. Metric reference conditions and scoring criteria
were developed separately for each estuary type within each zoogeographic region. The final EFCI was applied to each estuary
by comparing its fish community with the appropriate reference. Index values ranged between 18 (very poor) and 66 (very good).
A comparison of the EFCI with independent measures of estuarine condition revealed that the index was able to effectively
differentiate between poor and good quality sites. Applying the EFCI to estuaries in which multiple samples were taken also
showed that the index is reproducible. The EFCI is both a robust and sensitive method for assessing the ecological condition
of estuarine systems; it is also an effective communication tool for converting ecological information into an easily understood
format for managers, policy makers, and the general public. 相似文献
77.
Comparison of histories of great earthquakes and accompanying tsunamis at eight coastal sites suggests plate-boundary ruptures of varying length, implying great earthquakes of variable magnitude at the Cascadia subduction zone. Inference of rupture length relies on degree of overlap on radiocarbon age ranges for earthquakes and tsunamis, and relative amounts of coseismic subsidence and heights of tsunamis. Written records of a tsunami in Japan provide the most conclusive evidence for rupture of much of the plate boundary during the earthquake of 26 January 1700. Cascadia stratigraphic evidence dating from about 1600 cal yr B.P., similar to that for the 1700 earthquake, implies a similarly long rupture with substantial subsidence and a high tsunami. Correlations are consistent with other long ruptures about 1350 cal yr B.P., 2500 cal yr B.P., 3400 cal yr B.P., 3800 cal yr B.P., 4400 cal yr B.P., and 4900 cal yr B.P. A rupture about 700-1100 cal yr B.P. was limited to the northern and central parts of the subduction zone, and a northern rupture about 2900 cal yr B.P. may have been similarly limited. Times of probable short ruptures in southern Cascadia include about 1100 cal yr B.P., 1700 cal yr B.P., 3200 cal yr B.P., 4200 cal yr B.P., 4600 cal yr B.P., and 4700 cal yr B.P. Rupture patterns suggest that the plate boundary in northern Cascadia usually breaks in long ruptures during the greatest earthquakes. Ruptures in southernmost Cascadia vary in length and recurrence intervals more than ruptures in northern Cascadia. 相似文献
78.
79.
80.
Douglas B. Kent James A. DavisLinda C.D. Anderson Brigid A. ReaJennifer A. Coston 《Geochimica et cosmochimica acta》2002,66(17):3017-3036
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