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91.
92.
Drilling of the new Gotthard rail base tunnel (central Alps) opened a large number of water-conducting fractures in granite and gneiss of the crystalline basement. The overburden reaches locally more than 2000 m and water and rock temperature is up to 45 °C. The tunnel crosses a series of steeply dipping fractured rock units that also crop out at the surface above the tunnel. Recharge water enters the fractured rocks in the high mountainous area, migrates gravity driven to the sampling locality in the tunnel. Along its flow path it reacts with rocks exposed on the fractures where it dissolves the principal granite minerals, resulting in high-pH Na2CO3 waters.The tunnel waters contain unusually high concentrations of fluoride ranging from 5 to 29 mg/L. Alteration of F-bearing biotite to F-free chlorite is one of the sources of fluorine. The highest F-concentrations result from the equilibration of low-Ca waters with fluorite. Fluoride concentration is strongly lithology-dependent and sharp discontinuities in both, concentration and saturation state with respect to fluorite occur at the contacts of the different gneiss and granite slabs.Chloride concentrations vary between 1 and 1300 mg/L. In contrast, the Cl/Br mass ratio exhibits small variations and centers around 110 suggesting a common source for the Cl and Br, which is independent of the lithology. In the northern part of the tunnel, Cl and Br are chiefly derived from saline pore fluids of one lithology which is then mixed with low-salinity water along flow paths. Cl/Br ratios of the waters in the southern part of the tunnel section are similar to those measured in experimental leachates from different tunnel rocks, suggesting that leaching of metamorphic fluids in the pore space is the main source of both Cl and Br.  相似文献   
93.
The recent sediments of two lakes in the NE German lowland became seasonally laminated at different times. Anoxic bottom conditions resulted from a surplus of organic matter (OM), in the early stage indicated by irregularly laminated sediments comprising abundant iron-sulfide framboids. Their diagenetic formation predates the preservation of biochemical calcite varves. In the larger, deeper Lake Tiefer See near Klocksin, anoxia developed stepwise. A first anoxic pulse was contemporary with inflow narrowing by railway-dam construction and accumulation of OM. It was favored by a decrease of the intensity of lake circulation (turnover). Nutrients introduced from artificial fertilizer then increased the primary production (diatoms) to the point of OM surplus and seasonal laminae formation started 40 years later in 1924. In the smaller, shallower Lake Tiefer See in the Uckermark, a massive pulse of iron sulfide was centered around 1960, seven years after installation of piped field drainage into the lake. Anoxia developed rapidly with the nutrients drained from a fertilized groundwater catchment that is 10 times larger than the surface catchment, while surface erosion was reduced. Reducing bottom conditions became regular and the seasonal lamination was preserved after 1967. Morphological criteria to screen lakes for varved sediments should include reductions of natural lake inflow and catchment increase, such as by inflow of field drainage. Similar developments of increased nutrient input or intensity decrease of lake circulation may result from historical human activities but also from natural processes.  相似文献   
94.
A small scale and temporally limited CO2 injection test was performed in a shallow aquifer to investigate the geochemical impact of CO2 upon such aquifers and to apply and verify different monitoring methods. Detailed site investigation coupled with multiphase simulations were necessary to design the injection experiment and to set up the monitoring network, before CO2 was injected over a ten-day period at three injection wells, at a depth of 18?m below surface level into a quaternary sand aquifer located close to the town of Wittstock in Northeast Germany. Monitoring methods comprised groundwater sampling and standard analyses, as well as trace element analyses and isotope analyses; geoelectrical borehole monitoring; passive samplers to analyse temporally integrated for cations and multi-parameter probes that can measure continuously for dissolved CO2, pH and electrical conductivity. Due to CO2 injection, total inorganic carbon concentrations increased and pH decreased down to a level of 5.1. Associated reactions comprised the release of major cations and trace elements. Geoelectrical monitoring, as well as isotope analyses and multi-parameter probes proved to be suitable methods for monitoring injected CO2 and/or the alteration of groundwater.  相似文献   
95.
Advances in the chemical and isotopic characterisation of geological and environmental materials can often be ascribed to technological improvements in analytical hardware. Equally, the creation of novel methods of data acquisition and interpretation, including access to better reference materials, can also be crucial components enabling important breakthroughs. This biennial review highlights key advances in either instrumentation or data acquisition and treatment, which have appeared since January 2010. This review is based on the assessments by scientists prominent in each of the given analytical fields; it is not intended as an exhaustive summary, but rather provides insight from experts of the most significant advances and trends in their given field of expertise. In contrast to earlier reviews, this presentation has been formulated into a unified work, providing a single source covering a broad spectrum of geoanalytical techniques. Additionally, some themes that were not previously emphasised, in particular thermal ionisation mass spectrometry, accelerator‐based methods and vibrational spectroscopy, are also presented in detail.  相似文献   
96.
97.
In order to contribute to a reliable, easy-to-handle and economically viable erosion risk assessment of contaminated riverine sites, the present study aims to implement master-variables best characterising the sediment stability. Thus, a wide range of sediment properties was related to the critical shear stress for mass erosion, determined in the SETEG (Stroemungskanal zur Ermittlung der tiefenabhaengigen Erosionsstabilitaet von Gewaessersedimenten) pressurised channel, with special emphasis on vertical and temporal gradients in the Lauffen reservoir on the River Neckar. Over the course of 1 year, positive impacts of some macrofauna species and benthic diatoms on the sediment stability were detected for the sediment surface (0.5 cm). However, a high seasonal variability of biological parameters caused varying relations with erosion resistance in the upper sediment layers as shown for the colloidal carbohydrates. Considering only deeper sediment layers (5–35 cm), a more general pattern could be revealed with correlations between the critical shear stress and single sediment properties such as depth, grain size, total organic carbon (TOC), cation exchange coefficient (CEC), carbohydrates and proteins. Firstly, the influence of physico-chemical and biological properties on erosion resistance became evident, even over depths at 0–35 cm. Secondly, inter-particle forces are most important for erosion resistance. These are enhanced in fine-grained sediment layers, offering high binding capacities but also strengthened by polymeric substances permeating the void space and coating particles. These covariance patterns of sedimentological and biological parameters are addressed by multivariate statistical tests (principal component analysis), resulting in a higher magnitude of the correlation coefficient between critical shear stress and the master-variables in main component II (polymeric substances, grain size, TOC, CEC; R=0.77) compared to single correlations.  相似文献   
98.
Calorimetric and experimental data on AlF-bearing titanite are presented that yield thermodynamic properties of CaAlFSiO4, as well as activity-composition relations of binary titanite CaTiOSiO4-CaAlFSiO4. The heat capacity of synthetic CaAlFSiO4 was measured with differential scanning calorimetry between 170 and 850 K: CP=689.96-0.38647T+2911300T-2-8356.1T-0.5+0.00016179T2 Based on low-temperature heat capacity calculations with lattice vibrational theory (Debye model), the calorimetric entropy of CaAlFSiO4 can be expected to lie between 104.7 and 118.1 J mol-1 K-1. The temperature of the P21/a to A2/a phase change was determined calorimetrically for a titanite with XAl=0.09 (Ttransition=390 K). The decrease of the transition temperature at a rate of about 11 K per mol% CaAlFSiO4 is in good agreement with previous TEM investigations. The displacement of the reaction anorthite + fluorite = CaAlFSiO4 in the presence of CaTiOSiO4 was studied with high P-T experiments. Titanite behaves as a non-ideal, symmetrical solid-solution. The thermodynamic properties of CaAlFSiO4 consistent with a multi-site mixing model are: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBam % XvP5wqSXMqHnxAJn0BKvguHDwzZbqegm0B1jxALjhiov2Daebbnrfi % fHhDYfgasaacH8srps0lbbf9q8WrFfeuY-Hhbbf9v8qqaqFr0xc9pk % 0xbba9q8WqFfea0-yr0RYxir-Jbba9q8aq0-yq-He9q8qqQ8frFve9 % Fve9Ff0dmeaabaqaciaacaGaaeqabaWaaeaaeaaakeaafaqaaiWaca % aabaGaeeyrauKaeeOBa4MaeeiDaqNaeeiAaGMaeeyyaeMaeeiBaWMa % eeiCaaNaeeyEaKNaeeiiaaIaee4Ba8MaeeOzayMaeeiiaaIaeeOzay % Maee4Ba8MaeeOCaiNaeeyBa0MaeeyyaeMaeeiDaqNaeeyAaKMaee4B % a8MaeeOBa4MaeeiiaaIaeeikaGIaeeyzauMaeeiBaWMaeeyzauMaee % yBa0MaeeyzauMaeeOBa4MaeeiDaqNaee4CamNaeeykaKIaeeiiaaIa % emizaq2aaSbaaSqaaiabdAgaMbqabaGccqWGibasdaahaaWcbeqaai % abicdaWaaaaOqaaiabg2da9iabgkHiTiabikdaYiabiEda3iabisda % 0iabicdaWiabc6caUiabiIda4iabgglaXkabiodaZiabc6caUiabic % daWiabbccaGiabbUgaRjabbQeakjabb2gaTjabb+gaVjabbYgaSnaa % CaaaleqabaGaeyOeI0IaeGymaedaaaGcbaGaee4uamLaeeiDaqNaee % yyaeMaeeOBa4MaeeizaqMaeeyyaeMaeeOCaiNaeeizaqMaeeiiaaIa % ee4CamNaeeiDaqNaeeyyaeMaeeiDaqNaeeyzauMaeeiiaaIaeeyzau % MaeeOBa4MaeeiDaqNaeeOCaiNaee4Ba8MaeeiCaaNaeeyEaKNaeeii % aaIaee4uam1aaWbaaSqabeaacqqGWaamaaaakeaacqqG9aqpcqqGXa % qmcqqGWaamcqqG0aancqqGUaGlcqqG5aqocqGHXcqScqqGXaqmcqqG % UaGlcqqGXaqmcqqGGaaicqqGkbGscqqGTbqBcqqGVbWBcqqGSbaBda % ahaaWcbeqaaiabgkHiTiabigdaXaaakiabbUealnaaCaaaleqabaGa % eyOeI0IaeGymaedaaaGcbaGaeeyta0KaeeyyaeMaeeOCaiNaee4zaC % MaeeyDauNaeeiBaWMaeeyzauMaee4CamNaeeiiaaIaeeiCaaNaeeyy % aeMaeeOCaiNaeeyyaeMaeeyBa0MaeeyzauMaeeiDaqNaeeyzauMaee % OCaiNaeeiiaaYaamWaaeaacqWGxbWvdaWgaaWcbaGaemisaG0aaWba % aWqabeaacqGHsislaaaaleqaaOGaeeivaqLaem4vaC1aaSbaaSqaai % abdohaZbqabaaakiaawUfacaGLDbaaaeaacqGH9aqpcqaIXaqmcqaI % ZaWmcqGGUaGlcqaI2aGncqGHXcqScqaIWaamcqGGUaGlcqaI0aanca % aMe8UaeeOsaOKaeeyBa0Maee4Ba8MaeeiBaW2aaWbaaSqabeaacqGH % sislcqaIXaqmaaaaaaaa!E403!
Enthalpy of formation (elements) df H0
amp; = - 2740.8 ±3.0kJmol - 1
Standard state entropy S0
amp; = 104.9 ±1.1 Jmol - 1 K - 1
WV) was determined from the excess volume of mixing based on XRD measurements (214ᆦ J mol-1 kbar-1), as well as refined from the piston-cylinder experimental results (198뀺 J mol-1 kbar-1), demonstrating consistency between crystal structure data and thermodynamic properties. The stability of AlF-bearing titanite Ca(Ti,Al)(O,F)SiO4 was investigated by thermodynamic modelling in the system Ca-Al-Si-Ti-O-F-H-C and subsystems. The petrogenetic grids are in good agreement with natural mineral assemblages, in that very Al-rich titanite (XAl>0.65ǂ.15) is generally absent because it is either unstable with respect to other phases, or its stability field lies outside the P-T conditions realised on Earth. The grids explain both the predominant occurrence of natural Al-rich titanite at high metamorphic grade such as eclogite facies conditions, as well as its scarcity in blueschist facies rocks. Wide spacing of the Al-isopleths for titanite of many high-grade assemblages prevents their use as geobarometers or thermometers. The instability of end-member CaAlFSiO4 with respect to other phases in most assemblages modelled here is consistent with the hypothesis that the presence of structural stresses in the crystal lattice of CaAlFSiO4 influences its thermodynamic stability. The titanite structure is not well suited to accommodate Al and F instead of Ti and O, causing the relatively high Gibbs free energy of CaAlFSiO4, manifested in its standard state properties. Thus, the increasing amount of CaAlFSiO4 along the binary join is the reason why titanite with XAl>0.65ǂ.15 becomes unstable in most petrogenetic grids presented here. The compositional limit of natural titanite (XAlƸ.54) probably reflects the point beyond which the less stable end member begins to dominate the solid-solution, affecting both crystal structure and thermodynamic stability.  相似文献   
99.
We present results of analyses on a sediment core from Lake Karakul, located in the eastern Pamir Mountains, Tajikistan. The core spans the last ~29 cal ka. We investigated and assessed processes internal and external to the lake to infer changes in past moisture availability. Among the variables used to infer lake-external processes, high values of grain-size end-member (EM) 3 (wide grain-size distribution that reflects fluvial input) and high Sr/Rb and Zr/Rb ratios (coinciding with coarse grain sizes), are indicative of moister conditions. High values in EM1, EM2 (peaks of small grain sizes that reflect long-distance dust transport or fine, glacially derived clastic input) and TiO2 (terrigenous input) are thought to reflect greater influence of dry air masses, most likely of Westerly origin. High input of dust from distant sources, beginning before the Last Glacial Maximum (LGM) and continuing to the late glacial, reflects the influence of dry Westerlies, whereas peaks in fluvial input suggest increased moisture availability. The early to early-middle Holocene is characterised by coarse mean grain sizes, indicating constant, high fluvial input and moister conditions in the region. A steady increase in terrigenous dust and a decrease in fluvial input from 6.6 cal ka BP onwards points to the Westerlies as the predominant atmospheric circulation through to present, and marks a return to drier and even arid conditions in the area. Proxies for productivity (TOC, TOC/TN, TOC Br ), redox potential (Fe/Mn) and changes in the endogenic carbonate precipitation (TIC, δ18O Carb ) indicate changes within the lake. Low productivity characterised the lake from the late Pleistocene until 6.6 cal ka BP, and increased rapidly afterwards. Lake level remained low until the LGM, but water depth increased to a maximum during the late glacial and remained high into the early Holocene. Subsequently, the water level decreased to its present stage. Today the lake system is mainly climatically controlled, but the depositional regime is also driven by internal limnogeological processes.  相似文献   
100.
Monitoring during three meteorologically different spring seasons in 2012, 2013, and 2014 revealed that temperature increase in spring, which influences spring lake mixing duration, markedly affected nutrient availability and diatom deposition in a sediment trap close to the bottom of deep Tiefer See, NE Germany. Deposition of Stephanodiscus taxa and small Cyclotella taxa was much higher after late ice out and a deep, short lake mixing period in spring 2013, compared to that after gradual warming and lengthy lake mixing periods in spring 2012 and 2014, when only brief or marginal ice cover occurred. Availability of dissolved Si and P was 33 and 20 % higher, respectively, in 2013 compared to 2014. The observed relation between high (low) diatom deposition and short (lengthy) mixing duration in spring was applied to varved sediments deposited between AD 1924 and 2008. Low detrital Si content in trapped material and a sediment core enabled use of µXRF-counts of Si as a proxy for diatom silica. The spring mixing duration for 1951–2008 was derived from FLake-model calculations. The spring warming duration related to lake mixing was approximated from air temperatures for 1924–2008 using the dates when daily mean air temperature exceeded 5 °C (start) and 10 °C (end). Diatom silica deposition showed a significant (p < 0.0001) inverse linear relationship with the modeled spring mixing duration (R2 = 0.36) and the spring warming duration (R2 = 0.28). In both cases, the relationship is strengthened when data from the period of low diatom production (1987–2005) is excluded (R2 = 0.59 and R2 = 0.35). Part of this low diatom production is related to external nutrient supply that favored growth of cyanobacteria at the expense of diatoms. This approach shows that diatom Si deposition was strongly influenced by the availability of light and nutrients, related to the duration of lake mixing and warming in spring, during most of the studied period. The remaining unexplained variability, however, indicates that additional factors influence Si deposition. Further tests in other deep, temperate lakes are necessary to verify if this relation is a common feature and consequently, if diatom Si can be used as a proxy for spring mixing duration in such lakes.  相似文献   
Margules parameter [ WH- TWs ]
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