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The sulfur isotopic composition of carbonate associated sulfate (CAS) has been used to investigate the geochemistry of ancient seawater sulfate. However, few studies have quantified the reliability of δ34S of CAS as a seawater sulfate proxy, especially with respect to later diagenetic overprinting. Pyrite, which typically has depleted δ34S values due to authigenic fractionation associated with bacterial sulfate reduction, is a common constituent of marine sedimentary rocks. The oxidation of pyrite, whether during diagenesis or sample preparation, could thus adversely influence the sulfur isotopic composition of CAS. Here, we report the results of CAS extractions using HCl and acetic acid with samples spiked with varying amounts of pyrite. The results show a very strong linear relationship between the abundance of fine-grained pyrite added to the sample and the resultant abundance and δ34S value of CAS. This data represents the first unequivocal evidence that pyrite is oxidized during the CAS extraction process. Our mixing models indicate that in samples with much less than 1 wt.% pyrite and relatively high δ34Spyrite values, the isotopic offset imparted by oxidation of pyrite should be much less than ? 4‰. A wealth of literature exists on the oxidation of pyrite by Fe3+ and we believe this mechanism drives the oxidation of pyrite during CAS extraction, during which the oxygen used to form sulfate is taken from H2O, not O2. Consequently, extracting CAS under anaerobic conditions would only slow, but not halt, the oxidation of pyrite. Future studies of CAS should attempt to quantify pyrite abundance and isotopic composition.  相似文献   
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The whole-rock geochemistry of metamorphosed greywackes, arenites and arkoses within the Mesoproterozoic Namaqua-Natal-Maudheim Province is interpreted with the aim of establishing geochemical correlations and defining common sediment source terrains. Metasediments of the Mfongosi Group of the Natal Sector of the Namaqua-Natal Metamorphic Province were sampled from their type area in the Mfongosi Valley. Metagreywackes from the northern limits of the Mfongosi Valley, directly adjacent to the Kaapvaal Craton, show ocean island arc signatures while metagreywackes from the southern limits of the Mfongosi Valley, near the contact with the Madidima Thrust of the Natal nappe zone, show mainly active continental margin signatures. Interleaved, geochemically distinct low-Ca+Na, high-K metamorphosed arkoses to lithic arkoses indicate a minor passive margin sediment component. Geochemical classification of low-grade Ahlmannryggen Group greywackes, arenites and arkoses of the Grunehogna Province, Antarctica, indicates both active and passive continental margin sediment sources. An oceanic island arc signature is not evident in Ahlmannryggen Group data. The active continental margin signature in both Natal Sector and Grunehogna Province metasediments potentially provides for a common link between these terranes. Discriminant Function Analysis, using three pre-defined provenance sub-sets within the Mfongosi Group and two pre-defined provenance sub-sets within the Ahlmannryggen Group, indicate that metasediments with active continental margin signatures from both groups are geochemically identical, implying that the active continental margin of the Grunehogna Province shed immature sediments westwards (African azimuths) into the developing, narrow or restricted Mesoproterozoic ‘Mfongosi Basin.’ This was accompanied by minor sediment influx from a stable continental platform, potentially the Kaapvaal Craton. Oblique and diachronous collision, initiated in the southwestern portions of the combined Natal Sector/Grunehogna Province system produced a laterally variable Mfongosi Group, which formed in the ‘Mfongosi Basin’. Coarse-grained sediments dominated in its eastern portions while basalts with thin sapropelite units dominated in its western portions.  相似文献   
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A diver-operated piston corer suitable for collecting cores of >3 m length from fine-grained nearshore sediment has been developed. The corer uses a platform that rests on the sediment surface supporting both the operators and a derrick that maintains the piston at the sediment-water interface. The core is insected into and recovered from the sediment manually. The technique offers several advantages; low cost, minimal disruption of the sediment-water interface, little compaction of the sediment, the ability to collect longer length cores than is possible with gravity corers, and the ability to be deployed from relatively small boats. Dissolved ammonium and inorganic carbon data are presented from a 3.3-m core collected by this technique from Tomales Bay, California.  相似文献   
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The concentrations of222Rn and226Ra in the water column and in the sediments of Santa Barbara and San Nicolas Basins have been measured semi-annually over the last four years. Approximately one-third of excess radon profiles obtained in the water column in these basins can be adequately fit with a one-dimensional eddy diffusion-decay model. Exponential profiles in the center of San Nicolas Basin yield a vertical eddy diffusivity of 26±16 cm2/s and 3.4±1.0 cm2/s for Santa Barbara Basin. The application of a two-dimensional eddy diffusion-decay model to profiles obtained in the center and on the margins of San Nicolas Basin produces a better fit than is found using a one-dimensional vertical eddy diffusivity. The two-dimensional model for San Nicolas Basin predicts a vertical eddy diffusivity of 17 cm2/s and a horizontal eddy diffusivity of 105 cm2/s. These values are in reasonable agreement with those predicted from the vertical buoyancy gradient and the horizontal length scale.The vertically integrated radon excess (standing crop) in the water column of Santa Barbara Basin averages 53±23 atoms/m2 s. This is in good agreement with the flux across the sediment-water interface of 60±15 atoms/m2 s, calculated by measuring radon emanation in the sediments as a function of depth and applying a molecular diffusion-reaction model. Hence, one-dimensional molecular diffusion accurately predicts the flux of radon from the laminated Santa Barbara Basin sediments. In San Nicolas Basin the integrated radon excess in the water column is 376±143 atoms/m2 s, but the diffusive randon flux from San Nicolas Basin sediments averages only 190±53 atoms/m2 s. This descrepancy indicates that a non-diffusive process, probably macrofaunal irrigation, supplies much of the flux of radon from San Nicolas Basin sediments.  相似文献   
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Compositions of coexisting ilmenite and titano-magnetite commonly have been used to establish the conditions of formation for igneous and metamorphic rocks (Buddington-Lindsley geothermometer/oxybarometer). Temperatures so determined for some rocks are lower than might be expected for magmatic crystallization. These low temperatures are the result of re-equilibration of the Fe-Ti oxides during slow cooling. This process is one in which titano-magnetites are oxidized and ilmenites are reduced upon cooling along a buffer curve or in the presence of a fluid of constant composition. Textural studies indicate that the reduction of the ilmenite-hematite phase may be the slower reaction consequently, the rate-controlling step of the re-equilibration.The kinetics of the reduction reactions in the two-phase region between the joins for the ilmenite-hematite and magnetite-ulvöspinel solid solution series were studied by thermogravimetric analysis at controlledfO2. With experiments conducted near the Ni/NiO and QFM buffers, annealed ilmenite(ss) synthetic charges were reduced isothermally. The temperature range for the experiments was 900–1250°C, with total gas-flow rates of 0.35 and 1.0 cm/s. Kinetic data were collected by measuring the weight change during each experiment as a function of time. Additionally, a cooling-rate (0.5°C/hr) experiment was conducted near the QFM buffer from 1150 to 985°C starting with an ilmenite-saturated spinel phase.At 1200°C and 0.35 cm/s flow rate, the reaction mechanism is an interfacial process where mass transport of the reacting gases is the rate-controlling step. In isothermal experiments at 1100°C and lower, diffusion of reactants through a solid product layer was the controlling mechanism. The activation energy for this diffusion process is 59±6 kcal/mole. Significant enhancement of diffusion occurs along grain boundaries.Although the individual phases may re-equilibrate internally upon cooling, the Fe-Ti contents must remain unchanged for proper use of this mineral indicator-i.e. no external re-equilibration. It is imperative that the kinetics of the situation be appreciated. These preliminary kinetic experiments indicate that extreme caution must be exercised when applying this ilmenite/titano-magnetite geothermometer/oxybarometer. These phases may only truly “quench” in the parameters of formation in the case of certain hypabyssal and extrusive occurrences  相似文献   
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This study used optical brighteners (OB) released from septic systems to show that groundwater flow direction is largely controlled by the structural framework in a faulted karst groundwater system. Effective protection of groundwater resources requires that groundwater systems are adequately characterized and source water protection areas (SWPA) are developed for drinking water wells. Karst aquifers are among the most sensitive to contamination due to high recharge rates, and among the most difficult aquifers to characterize due to heterogeneity, and anisotropy. Because septic systems may be used to treat wastewater within SWPAs for karst aquifers there is a need to characterize these groundwater systems using tracers. The objective of this study was to characterize groundwater flow in a faulted portion of the Edwards aquifer in Bexar County, Texas using OB that are released as incidental tracers from septic systems. This study included measurement of water levels, sampling of groundwater and surface water, analysis for OB, and spatial analysis in a GIS. Results show that OB intensities were highest to the southwest of the septic area, a direction that is sub-parallel to the fault and fracture orientation and nearly perpendicular to the hydraulic gradient. This indicates that movement of OB, solutes, or non-aqueous liquids/solids in a faulted karst system can be largely controlled by fault/fracture orientation and structural relay ramps.  相似文献   
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