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1.
We present molecular orbital/density functional theory (MO/DFT) calculations that predict a greater isotopic fractionation in redox reactions than in reactions involving ligand exchange. The predicted fractionation factors, reported as 1000·ln(56-54α), associated with equilibrium between Fe-organic and Fe-H2O species were <1.6‰ in vacuo and <1.2‰ in solution when the oxidation state of the system was held constant. These fractionation factors were significantly smaller than those predicted for equilibrium between different oxidation states of Fe, for which 1000·ln(56-54α) was >2.7‰ in vacuo and >2.2‰ in solution when the bound ligands were unchanged. The predicted 56Fe/54Fe ratio was greater in complexes containing Fe3+ and in complexes with shorter Fe-O bond lengths; both of these trends follow previous theoretical results. Our predictions also agree with previous experimental measurements that suggest that the largest biological fractionations will be associated with processes that change the oxidation state of Fe, and that identification of biologically controlled Fe isotope fractionation may be difficult when abiotic redox fractionations are present in the system. The models studied here also have important implications for future theoretical isotope calculations, because we have discovered the necessity of using vibrational frequencies instead of reduced masses when predicting reduced partition functions in aqueous-phase species. 相似文献
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Ahna L. Van Gaest Craig M. Young John J. Young Alicia R. Helms & Shawn M. Arellano 《Marine Ecology》2007,28(1):199-207
Bathynerita naticoidea (Gastropoda: Neritidae) and Methanoaricia dendrobranchiata (Polychaeta: Orbiniidae) are two of the most abundant invertebrates associated with cold‐seep mussel beds in the Gulf of Mexico. At the methane seep known as Brine Pool NR‐1 (27 °43.415 N, 91 °16.756 W; 650 m depth), which is surrounded by a broad band of mussels (Bathymodiolus childressi), these species have distinctly different patterns of abundance, with the gastropod being found mostly at the outer edge of the mussel bed (average density in November 2003: 817 individuals·m−2 in outer zone, 20·m−2 in inner zone) and the polychaete being found almost exclusively near the inner edge (average density in November 2003: 3155 individuals·m−2 in inner zone, 0·m−2 in outer zone), adjacent to the brine pool itself. The salinity of the brine pool exceeds 120, so we hypothesized that M. dendrobranchiata should be more tolerant of high salinities than B. naticoidea. The opposite proved to be true. The gastropods were capable of withstanding salinities at least as high as 85, whereas the polychaetes died at salinities higher than 75. Both species were osmoconformers over the range of salinities (35–75) tested. Behavioral responses of B. naticoidea to salinities of 50, 60, and 70 were investigated in inverted vertical haloclines. Gastropods generally did not enter water of salinity greater than 60, but tolerated short periods at 60. Behavioral avoidance of brine should limit the vertical distribution of B. naticoidea in the inner zone to the top 2.5–5 cm of the mussel bed. Behavior is also a likely (though unproven) mechanism for controlling horizontal distribution of this species across the mussel bed. Methanoaricia dendrobranchiata can tolerate short excursions into the brine, but probably avoids hypersaline conditions by aggregating on the tops of the mussels. 相似文献
5.
The conditional acid dissociation constants (pKa′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pKa′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln−1):The estimated accuracy of pH measurements using these calculated pKa′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities. 相似文献
6.
Shane M. Ohline Malcolm R. Reid Shamus L.G. Husheer Kim I. Currie Keith A. Hunter 《Marine Chemistry》2007
Accurate measurement of seawater pH has long been sought by marine chemists (for example: [Dickson, A.G. 1993a. The measurement of sea water pH. Marine Chemistry, 44, 131–142, Dickson, A.G. 1993b. pH buffers for sea water media based on the total hydrogen ion concentration scale. Deep-Sea Research, 40, 107–118; Zhang, 1996; Tapp, M., Hunter, K.A., Currie, K. and Macaskill, B. 2000. Apparatus of continuous-flow underway spectrophotometric measurement of surface water pH. Marine Chemistry 72(2–4), 193–202; Friis, K., Koetzinger, A., Wallace, D.W.R. 2004. Spectrophotometric pH measurement in the ocean: Requirements, design and testing of an autonomous charge-coupled device detector system. Limnology and Oceanography: Methods 2, 126–136]. Recently, such attempts have taken on greater significance as anthropogenic carbon dioxide emissions may create rapidly changing oceanic pH. Spectrophotometric techniques have been accepted generally as the best for determination of seawater pH. Here we report a new technique using thymol blue as the indicator dye and fitting the entire spectrum from 400 to 900 nm rather than measuring the absorbance values at only two or three points in the spectrum. This full-spectrum modelling enables a reduction in signal to noise over other techniques. In the laboratory, we find with seawater samples a pH precision increase of five-fold “within” a sample and seven-fold “between” samples when comparing the full spectrum to the three-point method of analysis [Zhang, H., Byrne, R.H. 1996. Spectrophotometric pH measurements of surface seawater at in-situ conditions: absorbance and protonation behaviour of thymol blue. Marine Chemistry 52, 17–25]. 相似文献
7.
Karen L. Hunter Dewayne A. Fox Lori M. Brown Kenneth W. Able 《Estuaries and Coasts》2006,29(3):487-498
Modification of brackish marshes by nonindigenousPhragmites australis has occurred across a broad geographical area in eastern North America. Among its effects on marsh processes,Phragmites may be increasingly unfavorable to marsh surface fishes as its invasion progresses within an estuary. We assessed the effect
of thePhragmites invasion on resident marsh surface fishes by examining the population response ofFundulus heteroclitus (mummichog, 5–48 mm TL) andF. luciae (spotfin killifish, 5–41 mm TL) to four distinct invasion stages in three estuaries of the U.S. mid Atlantic region (New
Jersey, Delaware, and Maryland). We documented precipitous declines in mean catch per unit effort ofF. heteroclitus in pit traps from natural marsh (51.6), through initial (33.8), early (12.3), and late invasion stages (2.4) across all sites.
A similar pattern was documented forF. luciae, with mean catch per unit effort in pit traps declining from natural marsh (48.9), through initial (39.1), early (9.3), and
late invasion stages (2.7). Population structure of both species also changed somewhat across invasion stages such that we
collected a narrower size range of individuals of both species from late invasion stages. Patterns suggest that as thePhragmites invasion progresses, there is a decline in habitat function for larval and juvenileF. heteroclitus and an increased risk of extirpation ofF. luciae from brackish marshes along the east coast of the U.S. 相似文献
8.
Reconstructing recent limnological history often relies on lead-210 dating to accurately ascribe a chronology to a sediment
profile. In Lake Okeechobee, Florida, a large, shallow subtropical lake that may experience severe mixing, multiple dating
methods are required to confirm that conformable sedimentation has been preserved and that the assumptions of the 210Pb method are satisfied. This study uses stratigraphic profiles of heavy metals, 137Cs, PCBs and pollen as independent dating markers to validate the sediment chronology as determined by 210Pb for three cores from the central mud zone of the lake. Unsupported 210Pb and most dating markers show distinct concentration/depth profiles, suggesting that the sediments have not been severely
mixed for at least the last 75 years. Onset and maximum activity of the radioisotope 137Cs in the cores coincides with the 210Pb-dated interval of 1945–1970. This agrees well with the known timing of atmospheric deposition of 137Cs that resulted from above-ground nuclear testing during late 1940s until 1963. Sediment core profiles of atmospherically
deposited metals such as Zn and Pb, which reflect regional increases during industrialization and decreases after regulation
in the 1970s, exhibit expected concentration increases and peaks coinciding within 5–15 years of the predicted 210Pb dates. Uranium, a contaminant in some phosphate fertilizers, shows large concentration increases at core depths dated to
be about 1950 by 210Pb, matching the intensification of agriculture after WWII. PCBs, which are expected to peak in the early 1970s, were measured
in one core, and the observed peak corresponds to a 210Pb date of about 1960. Pollen makers were unable to verify specific events, but increases in disturbance taxa and declines
in native types correspond generally with the expected dates assigned by 210Pb dating. Conformity between the 210Pb defined dates and independent markers of < ±15 years confirm that Lake Okeechobee sediments do preserve a sequential and
reliable stratigraphic history of the lake, useful for reconstructing past limnological conditions. 相似文献
9.
Uranium co-precipitation with iron oxide minerals 总被引:2,自引:0,他引:2
Martine C. DuffJessica Urbanik Coughlin Douglas B. Hunter 《Geochimica et cosmochimica acta》2002,66(20):3533-3547
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
10.
A Permeable Reactive Barrier for Treatment of Heavy Metals 总被引:8,自引:0,他引:8