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The complexation of dissolved Ni has been evaluated in a rapidly-flushed, rural estuary (Tweed, UK) by ligand exchange-adsorptive cathodic stripping voltammetry. Results suggest the presence of strongly binding ligands, L, throughout, with average stability constants of about 1019 and which are saturated by ambient Ni concentrations. Equilibrium speciation calculations incorporating these constants in WHAM, version 6, predict an increase in Ni complexation (as NiL) from about 50% of total dissolved Ni in fresh water to over 90% in sea water. Equivalent calculations using the default-mode fulvic and humic substances (FS and HS, respectively) encoded in the WHAM database predict a reduction in complexation (as NiFS + NiHS) from about 20% in fresh water to less than 1% in sea water. Discrepancies arising from the two approaches are largely attributed to the different analytical detection windows employed. Thus, a better representation of Ni complexation is derived from including both types of complexant in the speciation calculations, resulting in estimates of net complexation in excess of 60% of total dissolved Ni throughout the estuary. The uncertainties and assumptions inherent in all computations illustrate the difficulty in measuring or predicting metal complexation in estuaries.  相似文献   
13.
Using the diving submersible survey NAUTICA we investigated the central part of the Caribbean large igneous province (CLIP) to observe and sample internal portions of this proposed oceanic plateau. Most of the samples are gabbroic and doleritic rocks; basalts are scarce. Radiometric dating by 40Ar/39Ar incremental heating experiments indicate that the intrusive rocks are Campanian in age (81–75 Ma). In some places these intrusive rocks underlie older Santonian (85–83 Ma) extrusive basaltic rocks, suggesting that the Campanian rocks represent a sill injection and an underplating episode. Results of the diving program supplemented by information from ODP and DSDP drilling sites document a 20 m.y. period (94–75 Ma) of igneous activity in the submerged portion of the Caribbean large igneous province (CLIP). In the northern part of the Beata Ridge late Campanian and/or post Campanian uplift is documented by prominent Maastrichtian (71–65 Ma) erosion and the establishment of a Paleocene-middle Eocene (65–49 Ma) carbonate platform. During and after the uplift an extensional period is indicated by seismic images and the subsidence (3 km depth) of the carbonate platform. Paleocene ages (55–56 Ma) determined on some volcanic samples are attributed to localised decompression mantle melting that accompanied the extension. We document a prolonged period of magmatic and tectonic events that do not fit with the current models of short-lived plateau formation during mantle plume initiation but shares many similarities with the constructional histories of other oceanic large igneous provinces.  相似文献   
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The evaluation of ocean simulations against observed datasets is essential to assess their realism and to guide model development, but often remains qualitative, and ignores certain datasets. This paper presents a three-dimensional, quantitative comparison of a 1/6° Atlantic numerical simulation (CLIPPER) with the WOCE current meter dataset in terms of mean velocity and eddy kinetic energy. Our metrics reveal the good behaviour of CLIPPER open boundary conditions and forcing with respect to full-depth current records. Due to its still moderate resolution, however, the model globally underestimates the observed mean speeds and eddy activity. This discrepancy is barely noticeable at low latitudes but increases toward the poles, probably since the poleward decrease of the Rossby radius exceeds that of the horizontal grid step. At least in this eddy-admitting regime, it is suggested that the numerics of geopotential-coordinate models like ours dissipate mean and eddy momentum at depth and adversely affect current–topography interactions.  相似文献   
16.
Chromophoric dissolved organic matter (CDOM) was measured in the spring and summer in the northern Gulf of Mexico with the ECOShuttle, a towed, instrumented, undulating vehicle. A submersible pump mounted on the vehicle supplied continuously flowing, uncontaminated seawater to online instruments in the shipboard laboratory and allowed discrete samples to be taken for further analysis. CDOM in the northern Gulf of Mexico was dominated by freshwater inputs from the Mississippi River through the Birdfoot region and to the west by discharge from the Atchafalaya River. CDOM was more extensively dispersed in the high-flow period in the spring but in both time periods was limited by stratification to the upper 12 m or so. Thin, subsurface CDOM maxima were observed below the plume during the highly stratified summer period but were absent in the spring. However, there was evidence of significant in situ biological production of CDOM in both seasons.The Mississippi River freshwater end member was similar in spring and summer, while the Atchafalaya end member was significantly higher in the spring. In both time periods, the Atchafalaya was significantly higher in CDOM and dissolved organic carbon (DOC) than the Mississippi presumably due to local production and exchange within the coastal wetlands along the lower Atchafalaya which are absent along the lower Mississippi. Nearshore waters may also have higher CDOM due to outwelling from coastal wetlands. High-resolution measurements allow the differentiation of various water masses and are indicative of rapidly varying (days to weeks) source waters. Highly dynamic but conservative mixing between various freshwater and marine end members apparently dominates CDOM distributions in the area with significant in situ biological inputs (bacterial degradation of phytoplankton detritus), evidence of flocculation, and minor photobleaching effects also observed. It is clear that high-resolution measurements and adaptive sampling strategies allow a more detailed examination of the processes that control CDOM distributions in river-dominated systems.  相似文献   
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In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g−1), Cu (1330 μg g−1) and Cd (12 μg g−1) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (Kd) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.  相似文献   
19.
The determination of trace amounts of inorganic elements by electrothermal atomic absorption spectrophotometry (ETA-AAS) or inductively coupled plasma atomic emission spectrometry (ICP-AES) suffers from some kinds of interference due to the inorganic fraction of the matrix of many environmental samples. The ratio between a major matrix element and the analyzed trace element plays an important role in the spectrochemical behaviour of the latter. The resulting enhancing or depressing effect also gives rise to severe faults when the well known standard addition method (SAM) is used. The present work shows the interactions due to the presence of elements such as calcium, sodium, potassium, magnesium and iron during the spectrochemical determinations of trace amounts of cadmium in marine mussels. A possible liquid anion exchange extraction is suggested for the analysis of cadmium by ETA-AAS.  相似文献   
20.
The generation and propagation of surface waves resulting from suddenly created disturbances over water surfaces is investigated. The initial boundary conditions defining the disturbance are given either by a velocity of the free surface, an initial elevation of the free surface or a pressure impulsively applied on the free surface. It is shown that the corresponding three forms of solutions are related by a simple time derivative. Linear solutions are obtained in the cases where the wave motion is assumed to be nondispersive, mildly dispersive and fully dispersive, as well as in the case where the motion is given by the method of stationary phase. Criteria are established to indicate the limit of validity of each method.  相似文献   
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