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1.
The carbon isotopic fractionation between CO2 vapour and sodamelilite (NaCaAlSi2O7) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag2C2O4 was the source of CO2 and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the 13C of coexisting vapour was determined directly by capsule piercing. CO2 solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO2 dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO2 reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO2 solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO2 vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring13C enrichment in CO2 vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO2 vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.  相似文献   
2.
The study of carbon abundance and isotopic composition in extraterrestrial samples is fraught with problems related to contamination in the terrestrial environment and during sample handling. A stepped combustion method is described which demonstrates that progress can be made towards resolving the indigenous species from contamination which for the most part burns at low temperature (< 425 ± 25 ±C). The proposed method is not applicable to samples which have indigenous phases burning at low temperatures e.g. the C1 and C2 carbonaceous chondrites. A number of examples where its application is possible are given. Even meteorites collected immediately after their fall, such as Allende, contain a proportion of extraneous carbon which has deleterious effects on any bulk estimate of isotopic composition. “Falls” which have spent a considerable time in museum collections and “finds” (other than Antarctic samples) can be considered as grossly contaminated. Bulk isotope and carbon abundance measurements in the literature for most samples having less than 1 wt% C are thus of questionable value. Antarctic samples have much less contamination of an organic nature but all seem to contain a weathering component which can be easily recognised and hence disregarded in estimates of bulk composition. Stepped combustion, applied to an Apollo 11 lunar soil which has not been specially stored and which now contains, due to contamination, nearly twice as much carbon as when originally collected, can still afford data closely resembling those obtained from the sample when it was first returned to Earth.  相似文献   
3.
The petroporphyrins of a Cretaceous crude oil, La Paz, from western Venezuela are shown to be a mixture of etio and DPEP homologues (C27-C39) maximising at C30 and C31, respectively. Minor amounts of rhodoporphyrins (C30-C39) are also present. Thin-layer chromatography afforded fractions which have been shown by mass spectrometry to contain up to 80% of a single-molecular-weight species. Oxidative degradation of La Paz petroporphyrins to maleimides and mass-spectrometric study of t.l.c. fractions indicate that some of these porphyrins are to a great extent incompletely substituted. Dealkylation reactions have presumably played an important role in their geologic history. Furthermore, the relative simplicity of the alkyl substitution pattern of the La Paz petroporphyrins suggests that transalkylation reactions have not taken place to any significant extent.The fraction of petroporphyrins isolated from the asphaltenes contains a higher proportion of the DPEP homologues than do the total petroporphyrins isolated from the original crude oil.  相似文献   
4.
Abstract— The nature and isotopic composition of carbonaceous components in a variety of ordinary chondrites have been studied using stepped combustion. The samples were chosen to include falls, finds and Antarctic meteorites; specimens from all three chemical groups (H, L and LL) have been analysed. Effort was concentrated mostly on the low petrologic type meteorites (i.e., type 3); however, types 4–6 were also included in the study. Apart from terrestrial contaminants and weathering products, some of the unequilibrated ordinary chondrites appear to contain an indigenous organic component. In addition, most of the samples studied show evidence for an amorphous/graphitic component. This exists as C-rich aggregates or as carbon associated with “Huss” matrix. There does not appear to be any difference in δ13C for this carbon between Antarctic and non-Antarctic meteorites. In contrast, low temperature carbon in Antarctic samples is characterized by a 13C-enrichment. This is thought to be due to the influence of terrestrial weathering products introduced in the Antarctic. Curiously, the low temperature carbon in non-Antarctic finds appears to be intermediate in δ13C between Antarctic finds and non-Antarctic falls. This suggests that the weathering processes which are so obviously apparent from Antarctic samples may also extend, albeit in a more limited way, to non-Antarctic meteorites.  相似文献   
5.
Abstract— Isotopic analysis of nesquehonite recovered from the surface of the LEW 85320 H5 ordinary chondrite shows that the δ13C and δ18O values of the two generations of bicarbonate (Antarctic and Texas) are different: δ13C = +7.9‰ and +4.2‰; δ18O = +17.9‰ and + 12.1‰ respectively. Carbon isotopic compositions are consistent with equilibrium formation from atmospheric carbon dioxide at ?2 ± 4 °C (Antarctic) and +16 ± 4 °C (Texas). Oxygen isotopic data imply that the water required for nesquehonite precipitation was derived from atmospheric water vapour or glacial meltwater which had locally exchanged with silicates, either in the meteorite or in underlying bedrock. Although carbonates with similar δ13C values have been identified in the SNC meteorites EETA 79001 and Nakhla, petrographic and temperature constraints argue against their simply being terrestrial weathering products.  相似文献   
6.
7.
Abstract— The Saharan meteorite Acfer 094 is a unique type of carbonaceous chondrite. Mineralogical and petrological considerations and O isotopes are unable to distinguish unambiguously between a CO3 vs. CM2 classification. The other important light elements, C and N, have systematics that do not match any previously recognised meteorite group. Particularly important in this respect is the very low C/N ratio and δ13C of the macromolecular C. Acfer 094 has more diamond and SiC, especially X type grains, than any other specimen studied, suggesting minimal thermal or aqueous processing to decrease its very primitive status.  相似文献   
8.
Abstract— A set of cristobalite- and tridymite-rich igneous clasts (CB1 to CB8) have been found in Parnallee (LL3.6). They consist of clinoenstatite, minor feldspathic mesostasis and cristobalite veined by endiopsideaugite. The largest clast, CB8, is 1.6 cm in diameter and contains veined tridymite and cristobalite, clinoenstatite (zoned to ferroaugite and pyroxferroite Fs75.6Wo20.0) and plagioclase. Compared to bulk ordinary chondrites (OC), the bulk clasts are depleted in Al (0.02–0.8× OC), Na and K and enriched in Si (1.6–2.0× OC) and Ca (1.3–4.5× OC). Bulk CB8 has LREE > HREE (La/Lu = 1.6) with a positive Eu anomaly (Eu/Eu* = 2.4). Textural observations suggest that the clasts cooled rapidly (24–420 °C/h) above 1200 °C. Clasts CB1—CB8 contain the isotopically heaviest O yet found in ordinary chondrites (up to δ17O = +8.7%o, δ18O = +11.6%o). Enrichment in the heavy isotopes of O is dependent on the proportion of cristobalite (or tridymite) in the clasts. A regression line CRIL (Cristobalite Line), with slope 0.77, is defined by the isotopic compositions of CB1—CB8, the Farmington clast and ordinary chondrite chondrules. An 16O-poor gas reservoir, whose composition must lie at some point along the extension of CRIL, has undergone varying degrees of isotopic exchange with most ordinary chondrite material. Silica polymorphs have undergone the greatest degree of exchange because of their open, framework structures. Silicon in CB1—CB8 has normal isotopic ratios. A model is proposed that involves differentiation of H-group material through extraction of volatile elements in a vapour phase, loss of an Fe-Ni-S melt and metastable crystallisation (60–70%) of olivine. The calculated residual liquid is silica-oversaturated and its subsequent predicted crystallisation sequence resembles that preserved in CB1—CB8. This model may require two stages of heating, the second one prior to cristobalite crystallisation (if the silica polymorph crystallises within its predicted stability field of > 1500 °C). Isotopic exchange took place either when CB1—CB8 were ejected from their parent body due to impact or near the surface of the parent body, perhaps in an ejecta blanket setting. The latter option is preferred because it is more consistent with our igneous model.  相似文献   
9.
Abstract— A preliminary investigation into the carbon isotopic composition of deep-sea spherules has been undertaken. A variety of particles have been analysed including both melted and unmelted samples of type S (stony) and type I (iron) spherules, emphasis being placed on surveying the carbon in different sorts of particles rather than analysing large numbers of samples. Some general observations can be made: there appear to be four different sorts of carbonaceous materials in the spherules. Melted and unmelted spherules of either type I or S, apparently contain two forms of low temperature combustible carbon distinguished, not by combustion temperature, but by isotopic composition. The low temperature of combustion is commensurate with these forms of carbon being organic in nature. The most likely explanation for this carbon is terrestrial biogenic contamination although there exists the possibility that there are some indigenous organic materials. Unmelted type S spherules contain a high temperature carbon component, characterised by a very minor 13C-enrichment, which is considered to be indigenous to the sample. All melted samples contain only small amounts of high temperature carbon with an isotopic composition suggestive of handling blank.  相似文献   
10.
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