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The nature of OH species in natural clear quartz was investigated by means of in-situ IR measurements over the temperature
range –185 to 1000 °C. Reversible thermal behavior of OH species was examined for a sample pre-heated to 1000 °C for 1 hour.
At room temperature, the IR spectrum of the quartz sample examined includes an intense absorption peak at 3379 cm–1 which has been assigned to an OH stretching vibration associated with Al substituting for Si (OH(Al)). The major spectral
changes of the OH(Al) bond involve a systematic shift of its peak position and a decrease in its integral absorbance with
temperature. A quasi-linear increase of the peak position from –185 to 400 °C is interpreted to be due to the change in the
vibrational frequency of OH(Al) with hydrogen bond (H bond) distance. At higher temperatures, the IR frequency shows only
a slight change, indicating a small influence of the H bond. On the other hand, the gradual decrease of the integral absorbance
of OH(Al) with temperature indicates a decrease of this defect’s molar absorptivity without any reduction in defect concentration.
This is interpreted to result from a decrease in dipole moment of OH(Al) with temperature. A sudden shift of the vibrational
frequency from 3396 to 3386 cm–1 between 550 and 560 °C and a constant value of the integral absorbance from 535 to 570 °C were considered to be related to
the change in H bond distance during the structural transformation of α-quartz to its β-form. The local environment of OH(Al)
begins to change at temperatures below 570 °C, where the crystallographic α–β transition occurs.
Received: 18 February 1998/ Accepted: 10 July 1998 相似文献
305.
The composition of organic matter in a 34,000 yr sediment profile from Lago di Mezzano, central Italy, was investigated by bulk organic geochemical methods and analyses of lipid distributions. High relative amounts of long-chain fatty acids, n-alkanols and n-alkanes from the cuticular waxes of terrestrial plants in the Late Pleistocene sediments indicate a high relative proportion of allochthonous organic matter. In the Holocene sediments higher relative amounts of algal and bacterial lipids are detected which indicate a higher relative contribution of autochthonous organic matter. These results are corroborated by Hydrogen Index (HI) and Oxygen Index (OI) values from Rock-Eval pyrolysis which show a good general correlation with the TOC content indicating significant variations of the organic matter composition. Variations of HI and OI observed for different lithozones of the sediment profile can be related to environmental and climatic changes throughout the lake history. Both bulk organic geochemical and molecular data point to a good overall preservation of the organic matter. 相似文献
306.
Observations of the Nitrate Radical in the Marine Boundary Layer 总被引:3,自引:0,他引:3
B. J. Allan N. Carslaw H. Coe R. A. Burgess J. M. C. Plane 《Journal of Atmospheric Chemistry》1999,33(2):129-154
A study of the nitrate radical (NO3) has been conducted through a series of campaigns held at the Weybourne Atmospheric Observatory, located on the coast of north Norfolk, England. The NO3 concentration was measured in the lower boundary layer by the technique of differential optical absorption spectroscopy (DOAS). Although the set of observations is limited, seasonal patterns are apparent. In winter, the NO3 concentration in semi-polluted continental air masses was found to be of the order of 10 ppt, with an average turnover lifetime of 2.4 minutes. During summer in clean northerly air flows, the concentration was about 6 ppt with a lifetime of 7.2 minutes. The major loss mechanisms for the radical were investigated in some detail by employing a chemical box model, constrained by a suite of ancillary measurements. The model indicates that during the semi-polluted conditions experienced in winter, the major loss of NO3 occurred indirectly through reactions of N2O5, either in the gas-phase with H2O, or through uptake on aerosols. The most important direct loss was via reactions of NO3 with a number of unsaturated nonmethane hydrocarbons. The cleaner air masses observed during the summer were of marine origin and contained elevated concentrations of dimethyl sulfide (DMS), which provided the major loss route for NO3. The box model was then used to investigate the conditions in the remote marine boundary layer under which DMS will be oxidised more rapidly at night (by NO3) than during the day (by OH). This should occur if the concentration of NO2 is more than about 60% that of DMS. 相似文献
307.
K. N. Bower T. W. Choularton M. W. Gallagher R. N. Colvile K. M. Beswick D. W. F. Inglis C. Bradbury B. G. Martinsson E. Swietlicki O. H. Berg S. -I. Cederfelt G. Frank J. Zhou J. N. Cape M. A. Sutton G. G. McFadyen C. Milford W. Birmili B. A. Yuskiewicz A. Wiedensohler F. Stratmann M. Wendisch A. Berner P. Ctyroky Z. Galambos S. H. Mesfin U. Dusek C. J. Dore D. S. Lee S. A. Pepler M. Bizjak B. Divjak 《Atmospheric Research》1999,50(3-4)
During March and April of 1995 a major international field project was conducted at the UMIST field station site on Great Dun Fell in Cumbria, Northern England. The hill cap cloud which frequently envelopes this site was used as a natural flow through reactor to examine the sensitivity of the cloud microphysics to the aerosol entering the cloud and also to investigate the effects of the cloud in changing the aerosol size distribution, chemical composition and associated optical properties. To investigate these processes, detailed measurements of the cloud water chemistry (including the chemistry of sulphur compounds, organic and inorganic oxidised nitrogen and ammonia), cloud microphysics and properties of the aerosol and trace gas concentrations upwind and downwind of the cap cloud were undertaken. It was found that the cloud droplet number was generally strongly correlated to aerosol number concentration, with up to 2000 activated droplets cm−3 being observed in the most polluted conditions. In such conditions it was inferred that hygroscopic organic compounds were important in the activation process. Often, the size distribution of the aerosol was substantially modified by the cloud processing, largely due to the aqueous phase oxidation of S(IV) to sulphate by hydrogen peroxide, but also through the uptake and fixing of gas phase nitric acid as nitrate, increasing the calculated optical scattering of the aerosol substantially (by up to 24%). New particle formation was also observed in the ultrafine aerosol mode (at about 5 nm) downwind of the cap cloud, particularly in conditions of low total aerosol surface area and in the presence of ammonia and HCl gases. This was seen to occur at night as well as during the day via a mechanism which is not yet understood. The implications of these results for parameterising aerosol growth in Global Climate Models are explored. 相似文献
308.
在地震地下流体观测研究中,基于氢氧同位素示踪技术研究地下水补给源及循环过程是常用的技术方法之一。本文给出了九江地震台2号观测井水、大气降水、周边水库水及高山泉水等样品的氢氧同位素测定结果,表明地下水δ~(18)O测值介于-7.59‰~-6.09‰,平均值-6.99‰,δD测值介于-45.22‰~-39.69‰,平均值-42.32‰,变异异数分别为0.09、0.16;大气降水δ~(18)O测值介于-13.00‰~-1.27‰,平均值-4.74‰,δD测值介于-96.13‰~-4.74‰,平均值-46.87‰,变异异数分别为0.40、0.56,与降水相比,地下水氢氧同位素变化更为稳定。大气降水氢氧同位素2017年5~10月表现为明显的降水效应,2018年11~4月表现为明显的温度效应,而地下水氢氧同位素并未表现出明显的降水效应和温度效应。氢氧同位素及过量氘揭示地下水在下渗补给前经历了明显的蒸发分馏作用,并与围岩进行~(18)O交换,δ~(18)O与δD计算得出的补给高程分别约为647、440m。九江台观测井的观测层地下水为大气降水成因的构造裂隙水,属于大气成因型且循环过程为较稳定的裂隙水补给并形成承压自流井。 相似文献
309.
松原5.7级地震震中区土壤氢气变化特征 总被引:2,自引:0,他引:2
2018年5月28日吉林松原发生5.7级地震,为了探究地震对断层气的影响以及震后断层气变化特征,震后在震中区进行了多期土壤氢气浓度观测工作,得到了震中区氢气浓度的最大值、背景值等多项指标。结合地震前后氢气浓度数据,分析震中区震前、震后氢气浓度趋势性变化情况,结果显示:在此次地震活动中,氢气浓度变化有"震前缓慢升高—临震下降—震后迅速升高—强余震前再次骤升"的现象;氢气浓度变化与地震活动间有很好的映震关系,主震对氢气浓度的上升起主要作用,而余震则起诱发作用,余震的活动会使赋存在地下岩石裂隙的氢气释放量增大,表明氢气对余震活动的响应较灵敏;另外,震后某一时刻空气中的氢气浓度也会升高,这可能与区域断层中的氢气逸散到大气中有一定关系。 相似文献
310.
以WFSD-2钻孔为研究对象,分析了随钻泥浆氢(H2)和汞(Hg)浓度特征,在垂向上存在显著不均匀性,出现多段浓度异常高值.研究表明:(1) H2和Hg浓度异常与次级断裂和岩石构造性质有较大关系,以断裂带或破碎带为通道运移而产生高值异常;(2)随钻泥浆H2和Hg浓度特征暗示了汶川地震WFSD-2孔中主滑移带位置,表明随钻流体特征是识别地下裂隙带、破碎带或断裂带的途径之一;(3) H2和Hg浓度异常还可能与构造块体边界强震活动和断裂带近场中等地震活动有关.本文研究结果为分析大震过程中深部流体活动行为提供了H2和Hg地球化学特征依据,对地震前兆机理研究也具有重要的参考价值. 相似文献