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21.
Jan Kaiser 《Geochimica et cosmochimica acta》2008,72(5):1312-1334
Mass-spectrometric stable isotope measurements of CO2 use molecular ion currents at mass-to-charge ratios m/z 44, 45 and 46 to derive the elemental isotope ratios n(13C)/n(12C) and n(18O)/n(16O), abbreviated 13C/12C and 18O/16O, relative to a reference. The ion currents have to be corrected for the contribution of 17O-bearing isotopologues, the so-called ‘17O correction’. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing 13C/12C (13R), 17O/16O (17R) and 18O/16O (18R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO2 generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H3PO4 at 25 °C (VPDB-CO2). I find , 18RVSMOW/10−6 = 2005.20 ± 0.45, 13RVPDB-CO2/10-6= 11124 ± 45, and 18RVPDB-CO2/10-6=2088.37±0.90. I also rephrase the calculation scheme for the 17O correction completely in terms of relative isotope ratio differences (δ values). This reveals that only ratios of isotope ratios (namely, 17R/13R and 13R17R/18R) are required for the 17O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative 13C/12C difference, but not for18O/16O. Even though inter-laboratory differences can be corrected for by a common ‘ratio assumption set’ and/or normalisation, the ultimate accuracy of the 17O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between 17O/16O and 18O/16O isotope ratios. For highest accuracy in the 13C/12C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that allows direct measurement of 13R17R/18R. 相似文献
22.
Kathleen A. Radloff Anya R. Manning Brian Mailloux Yan Zheng M. Moshiur Rahman M. Rezaul Huq Kazi M. Ahmed Alexander van Geen 《Applied Geochemistry》2008
Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment. 相似文献
23.
A.M.D. van Rotterdam-Los S.P. Vriend M.J. van Bergen P.F.M. van Gaans 《Journal of Geochemical Exploration》2008,96(1):53-68
Acid water from the Banyuputih river (pH 3.5) is used for the irrigation of agricultural land in the Asembagus coastal area (East Java, Indonesia), with harmful consequences for rice yields. The river water has an unusual composition which is caused by seepage from the acidic Kawah Ijen crater lake into the river. This unique irrigation setting allows the study of soil acidification in situ. This paper assesses the effects of volcanogenically contaminated irrigation water on the chemical properties of the agricultural soils.The changes in soil properties were evaluated by comparing samples taken from the topsoil and sub-soil (1–3 m depth) from areas irrigated with acid water and areas irrigated with neutral water. The field survey thus resulted in four soil categories. Bulk soil composition, organic matter content, moisture content and particle size distribution were determined. Reactive phases were quantified with the selective extractions 1 M KCl, 0.1 M Na-pyrophosphate and 0.2 M acid ammonium oxalate (AAO).By comparing the four soil categories it is shown that the use of the naturally polluted irrigation water has had a large influence on the chemical composition of the topsoil. The composition of the soil solution has changed over the entire investigated soil profile. Furthermore the acid irrigation water has strongly modified the composition of the reactive phases, extracted as KCl, pyrophosphate, and AAO extractable elements, and also the bulk soil composition has been significantly modified. Overall this has resulted in the net dissolution of some elements and the net precipitation of others. The changes in the reactive phases and bulk soil composition are only apparent in the topsoil (0–20 cm) but not in the deeper soil. 相似文献
24.
H. W. van der Marel 《Contributions to Mineralogy and Petrology》1964,9(5):462-480
A scheme is presented for the identification and classification of chlorite and related minerals in sediments which is mainly based on X-ray characteristics of the orginal sample and the sample heated at 350°C and treated with K+ and with glycerol. Examples are given. It is emphasized that additional data about clay mineral genesis, electron microscopy, infrared spectroscopy and chemical analyses are needed for the ordening of a certain mineral in the proposed scheme. Many names of minerals so far found to occur in the clay separate of sediments proved to be synonymous (52 of a total of 88) and thus should be abandoned. They only give confusion and needlessly increase the many difficulties which already exist in the identification, classification and quantitative determination of this complicated group of minerals of about 36 well defined specimens which may be found in sediments. 相似文献
25.
M.A. van Leeuwe L.A. Villerius J. Roggeveld R.J.W. Visser J. Stefels 《Marine Chemistry》2006,102(3-4):267-275
A recent development in algal pigment analysis by high-performance liquid chromatography (HPLC) is the application of automation. An optimization of a complete sampling and analysis protocol applied specifically in automation has not yet been performed. In this paper we show that automation can only be successful if the various methodological aspects of the sampling and analysis protocol are considered in coherence. We introduce an optimized protocol that involves freeze-drying of the sample, subsequent extraction in 90% acetone and the application of water-packing during analysis. The method was evaluated on both natural plankton populations and a broad spectrum of microalgal cultures: Thalassiosira weisflogii (Bacillariophyceae), Emiliania huxleyi (Prymnesiophyceae), Phaeocystis globosa and Phaeocystis antarctica (Prymnesiophyceae) and Pyramimonas sp. (Prasinophyceae). Whereas pigment extracts were unstable in methanol, with recorded chlorophyll a losses from 10% to 60% per day, pigment degradation rates in acetone were generally less than 1% over 18 h storage in the autosampler (4 °C). In addition, it was found that the extraction efficiency of acetone significantly increased upon freeze-drying prior to extraction. Increases as high as 50–60% were measured in P. antarctica. The application of water-packing of the sample during injection resulted in improved peak shape and peak separation, without diluting the pigment concentrations. Automation is especially beneficial for application in the field, when mixed algal assemblages and low biomass put a high demand on the sensitivity as well as reproducibility of the method. 相似文献
26.
Mjelde Rolf Fjellanger Jan Petter Digranes Per Kodaira Shuichi Shimamura Hideki Shiobara Hajime 《Marine Geophysical Researches》1997,19(1):81-96
A 140 km long wide-angle seismic profile has been acquired by use of 6 Ocean Bottom Seismographs across the Jan Mayen Ridge, North Atlantic. The profile was acquired twice; once with a traditionally tuned standard source and secondly with a somewhat smaller source tuned on the first bubble pulse. Analysis of the frequency content of the data reveals that the single-bubble source within the 10-15 Hz frequency range generates a signal with a level about 5 db above that of the standard source. These differences can partly be related to differences in airgun depth. The higher output level for these frequencies enables the single-bubble source to resolve intra-crustal structures with a higher degree of certainty, when compared to the data acquired by use of the standard source array. The standard source seems to generate slightly more energy for frequencies around 6 Hz, probably due to the use of a large 1200 in/sup3 gun in this array. These low frequencies a re of importance for mapping of lower crustal and upper mantle structures, and it is recommended that this is taken into account when seismic sources for mapping of deep crustal and upper mantle structures are designed. 相似文献
27.
In order to prevent the generation of spurious free sub- and superharmonics of random waves in a laboratory channel, the control signal for the wave board has to be derived according to a higher-order wave theory. An expression for this control signal has been derived with the perturbation method of multiple scales. It is much less complex and requires less computation time than the expressions obtained from the full second-order theory. The new method for second-order subharmonics was verified experimentally for waves with bichromatic and continuous first-order spectra. The data were analysed with the complex-harmonic principal-component analysis to reduce the influence of noise. 相似文献
28.
Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (FeR) in the absence and presence of 2 μM Dp, FeR being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H2O2 and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for FeR. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for FeR, iron(III) and iron(II), respectively, using a 60 s deposition time.The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of FeR ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column. 相似文献
29.
M. B. de Groot H. den Adel T. P. Stoutjesdijk C. J. van Westenbrugge 《Coastal Engineering》1995,26(3-4)
Flow slides may affect the stability of dikes. A flow slide is an instability of a submerged slope caused by liquefaction of loose, (medium) fine sand. Whether a flow slide will occur depends on the properties of the sand, which are a function of its density, and the geometry of the slope, as determined by wave and current induced scour and sedimentation. The influence of sand properties and the geometry parameters on the risk of flow slides are discussed. The application of a flow slide prediction method to an example and a risk analysis is briefly discussed. 相似文献
30.
The uptake of a chemical species by an aquatic microorganism is modelled considering two kinds of sites where Langmuirian adsorption is followed by first order internalisation kinetics. Simpler models, such as only one internalisation route (while most of the adsorption takes place on non-internalising sites) or a linear isotherm for adsorption on one or both sites, become limiting cases of this double-Langmuirian model. The model considers the sites located on the spherical (or semi-spherical) surface of the organism, and takes diffusion from the medium into explicit account. The numerical solution for the internalisation flux shows a maximum. We provide an estimate for the time needed to reach a certain proximity to steady state. The transient solution confirms that the analytical expressions for the steady-state flux are usually valid and that the accumulated amounts reflect the impact of the short-time uptake. The Instantaneous Steady-State Approximation (ISSA), where an intercept of the linear regression of accumulated amount as a function of time is interpreted as an adsorbed amount, can be critically assessed with the transient numerical code for two cases: (i) when the total burden of metal on the cell is the input data and (ii) when an extraction procedure provides further information on the adsorbed and internalised amount. 相似文献