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31.
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   
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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   
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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   
36.
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   
37.
Radiogenic heat production (RHP) represents a significant fraction of surface heat flow, both on cratons and in sedimentary basins. RHP within continental crust—especially the upper crust—is high. RHP at any depth within the crust can be estimated as a function of crustal age. Mantle RHP, in contrast, is always low, contributing at most 1 to 2 mW/m2 to total heat flow. Radiogenic heat from any noncrystalline basement that may be present also contributes to total heat flow. RHP from metamorphic rocks is similar to or slightly lower than that from their precursor sedimentary rocks. When extension of the lithosphere occurs—as for example during rifting—the radiogenic contribution of each layer of the lithosphere and noncrystalline basement diminishes in direct proportion to the degree of extension of that layer. Lithospheric RHP today is somewhat less than in the distant past, as a result of radioactive decay. In modeling, RHP can be varied through time by considering the half lives of uranium, thorium, and potassium, and the proportional contribution of each of those elements to total RHP from basement. RHP from sedimentary rocks ranges from low for most evaporites to high for some shales, especially those rich in organic matter. The contribution to total heat flow of radiogenic heat from sediments depends strongly on total sediment thickness, and thus differs through time as subsidence and basin filling occur. RHP can be high for thick clastic sections. RHP in sediments can be calculated using ordinary or spectral gamma-ray logs, or it can be estimated from the lithology.  相似文献   
38.
Meretta Lake (Resolute Bay, Cornwallis Island, Nunavut, Canada) is a high arctic lake that received raw sewage for almost 50 years from the Canadian Department of Transport Base. The lake was sampled from 1968–72 during the International Biological Programme, as part of the Char Lake Project. As the number of users at the Transport Base declined throughout the 1990s, so too did the lake's nutrient levels, and Meretta Lake is now classified as oligotrophic. A previous diatom-based paleolimnological study revealed marked species assemblage shifts coincident with sewage inputs beginning in the late 1940s; however, because the core was taken at a time when nutrient levels were still relatively high (i.e., 1993), the diatom record did not yet track any signs of recovery. In this present study, we examined fossil diatom assemblages from a sediment core taken in 2001. Our results indicate a shift to the pre-impact diatom assemblages in the most recent sediments, indicating that the paleolimnological record is tracking the decreased nutrient inputs to this high arctic lake, and confirms that no significant lags exist in these largely ice-covered lakes.  相似文献   
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Environmental degradation and other socio-economic problems are too often discerned in contemporary pastoral systems in the wake of global economic change. This paper identifies cases where pastoral people respond to external pressures and opportunities in positive ways and adapt to changes. We hope that by doing this a framework of pastoral adaptations can be developed. The first part of this paper focuses on impacts of global economic change, which are mostly negative in nature. Through an extensive literature search in geography, anthropology, range management, and development field, the second part introduces cases that we categorize as positive adaptations.  相似文献   
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