全文获取类型
收费全文 | 149篇 |
免费 | 14篇 |
国内免费 | 23篇 |
专业分类
测绘学 | 5篇 |
大气科学 | 72篇 |
地球物理 | 21篇 |
地质学 | 32篇 |
海洋学 | 29篇 |
天文学 | 4篇 |
综合类 | 15篇 |
自然地理 | 8篇 |
出版年
2024年 | 1篇 |
2022年 | 3篇 |
2021年 | 2篇 |
2019年 | 1篇 |
2018年 | 5篇 |
2017年 | 2篇 |
2016年 | 2篇 |
2015年 | 5篇 |
2014年 | 4篇 |
2013年 | 6篇 |
2012年 | 6篇 |
2011年 | 3篇 |
2010年 | 6篇 |
2009年 | 12篇 |
2008年 | 6篇 |
2007年 | 10篇 |
2006年 | 8篇 |
2005年 | 16篇 |
2004年 | 11篇 |
2003年 | 6篇 |
2002年 | 7篇 |
2001年 | 5篇 |
2000年 | 5篇 |
1999年 | 8篇 |
1998年 | 5篇 |
1997年 | 1篇 |
1996年 | 9篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 1篇 |
排序方式: 共有186条查询结果,搜索用时 15 毫秒
1.
1 INTRODUCTION Active oxygen free radicals can damage cell structure, even kill the cells, causing aging and cer- tain serious diseases (Bors et al., 1989). Usually, the production and scavenging of active oxygen free radicals are in balance in healthy hu… 相似文献
2.
To determine if Cu mediated reactions on atmospheric particles are important to HO2 chemistry in the ambient atmosphere, Cu molalities were calculated from measured Cu aerosol particle concentrations, mass and number size distribution data from a site in central Sweden. A comparison of characteristic times indicates that at low relative humidities the reaction is limited by the mass transport of gas phase HO2 to the particle surface and not by the chemical kinetics of the aqueous reaction. Comparison of half-lives for particle reactions and the gas phase destruction of HO2 to form H2O2 indicate that heterogeneous reactions on aerosol particles may have important consequences on the chemistry of HO2 and H2O2 in the troposphere. 相似文献
3.
Lars Olov Andersson 《Physics and Chemistry of Minerals》2008,35(9):505-520
The EPR spectra of Maxixe-type beryl contain a large number of overlapping signals. The angular dependence of the 1:3:3:1
signal typical for the CH3 radical shows that this radical is located at the center of the channel cavity with its symmetry axis parallel to the crystal
c-axis and is rotating around this axis. Its EPR spectrum is axially symmetric with g
// = 2.00263, g
⊥ = 2.00249 and A// = 2.288 mT, A⊥ = 2.256 mT. These anisotropies have the opposite signs of those found for surface-adsorbed methyl radicals. Hydrogen atoms
are located at position 2a at the center of the beryl cavity and the EPR parameters of the narrow doublet signal are A
0 = 1,407 MHz and g = 2.00230. Another doublet signal, which is broader and has axial symmetry with g
// = 2.00265, g
⊥ = 2.00625 and A// = 0.895 mT, A⊥ = 0.885 mT, could come from a HCO3 radical. One narrow and easily saturated signal with g
// = 2.00227 and g
⊥ = 2.00386 is interpreted to arise from a carbon monoxide radical in the beryl channel, oriented with its axis parallel to
the crystal c-axis. Additional weak doublet lines, which have similar g values as the carbon monoxide radical, are created by nearby hydrogens. A powder spectrum with g
// = 2.0017 and g
⊥ = 2.0004 appears upon UV irradiation of the single crystal and is easily saturated. This spectrum is interpreted to arise
from a carbon dioxide radical, which rotates around its symmetry axis. 相似文献
4.
Experiments were conducted in the field to determine the non-chemical loss rate of methyl iodide in seawater and to examine production rates of methyl halides. The loss rate of added C13 labelled methyl iodide, present at concentrations similar to those found in seawater, corrected for chemical loss due to reaction with Cl− varied from < 1 to 18% day− 1, with a mean value of 7%. This rate of loss is much lower than that which was proposed by Bell et al. [Bell, N., Hsu, L., Jacob, D. J., Schultz, M. G., Blake, D. R., Butler, J. H., King, D. B., Lobert, J. M., Maier-Reimer, E., 2002. Methyl iodide: Atmospheric budget and use as a tracer of marine convection in global models, Journal of Geophysical Research-Atmospheres 107(D17), 4340-4351.] to account for the large discrepancies between observed and predicted mid-latitude concentrations of CH3I based on their global photochemical source model. The suitability of several types of container for seawater incubations was studied and only quartz tubes appeared to be free of experimental artifact. Collapsible polyvinyl fluoride containers showed major production of methyl halides on irradiation with simulated sunlight. Polyethylene containers caused spurious production of methyl iodide at lower rates. 相似文献
5.
The kinetics of the aqueous phase reactions of NO3 radicals with HCOOH/HCOO– and CH3COOH/CH3COO– have been investigated using a laser photolysis/long-path laser absorption technique. NO3 was produced via excimer laser photolysis of peroxodisulfate anions (S2O
8
2–
) at 351 nm followed by the reactions of sulfate radicals (SO
4
–
) with excess nitrate. The time-resolved detection of NO3 was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO3 with formic acid (1) and formate (2) rate coefficients ofk
1=(3.3±1.0)×105 l mol–1 s–1 andk
2=(5.0±0.4)×107 l mol–1 s–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k
1(T)=(3.4±0.3)×1010 exp[–(3400±600)/T] l mol–1 s–1 andk
2(T)=(8.2±0.8)×1010 exp[–(2200±700)/T] l mol–1 s–1. The rate coefficients for the reactions of NO3 with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k
3=(1.3±0.3)×104 l mol–1 s–1 andk
4=(2.3±0.4)×106 l mol–1 s–1. The temperature dependences for these reactions are described by:k
3(T)=(4.9±0.5)×109 exp[–(3800±700)/T] l mol–1 s–1 andk
4(T)=(1.0±0.2)×1012 exp[–(3800±1200)/T] l mol–1 s–1. The differences in reactivity of the anions HCOO– and CH3COO– compared to their corresponding acids HCOOH and CH3COOH are explained by the higher reactivity of NO3 in charge transfer processes compared to H atom abstraction. From a comparison of NO3 reactions with various droplets constituents it is concluded that the reaction of NO3 with HCOO– may present a dominant loss reaction of NO3 in atmospheric droplets. 相似文献
6.
不同涂层的二氧化铅电极催化性能的比较 总被引:2,自引:0,他引:2
研究了热分解法和电沉积法制备二氧化铅电极的工艺,通过对苯酚的电解和生成羟基自由基的量,比较了两种方法制得的电极的催化性能,并比较了采用电沉积法制备电极时掺杂铋或镧对电极的催化性能的影响。实验结果表明,这4种电极都具有良好的电催化性能,并且明显降低了槽电压,且对苯酚的降解均符合一级反应动力学,电沉积法制得的电极的催化性能优于热分解法制得的电极,掺镧的电极优于无掺杂和掺铋的电极。 相似文献
7.
The formation of superoxide and hydroxyl radicals at the surface of smectite clays due to oxygen reduction is demonstrated
by electron paramagnetic resonance spectroscopy. The yield of hydroxyl radicals is mainly a function of particle size of the
clays and depends, to a lesser extent, on the clay lattice iron. Synthetic laponite clay with small platelet size (∼20 nm)
and without lattice iron is leading in the formation of hydroxyl radicals followed by montmorillonite (∼200 nm). Fluorohectorite
(∼2000 nm) was inactive to hydroxyl radical formation by oxygen reduction.
Received: 20 January 2001 / Accepted: 7 August 2001 相似文献
8.
A. Gelencsér A. Hoffer G. Kiss E. Tombácz R. Kurdi L. Bencze 《Journal of Atmospheric Chemistry》2003,45(1):25-33
Current climate models seem to underestimate the flux of solar energy absorbed by the global troposphere. All of these models are constrained with the assumption that cloud droplets consist of pure water. Here we demonstrate in a simple laboratory experiment that aromatic hydroxy-acids which are found in continental fine aerosol can react with hydroxyl radicals under typical conditions prevalent in cloud water influenced by biomass burning. The reactions yield colored organic species which do absorb solar radiation. We also suggest that the products of such reactions may be humic-like substances whose presence in continental aerosol has been confirmed but their source mechanisms are still much sought after. We also attempt to give a first order estimate of the enhancement of water absorption at a visible wavelength under atmospheric conditions. 相似文献
9.
Rate constants for the gas-phase reactions of OH radicals, NO3 radicals and O3 with the C7-carbonyl compounds 4-methylenehex-5-enal [CH2=CHC(=CH2)CH2CH2CHO], (3Z)- and (3E)-4-methylhexa-3,5-dienal [CH2=CHC(CH3)=CHCH2CHO] and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm3 molecule–1 s–1 units) were: for 4-methylenehex-5-enal, (1.55 ± 0.15) × 10–10, (4.75 ± 0.35) × 10–13 and (1.46 ± 0.12) × 10–17 for the OH radical, NO3 radical and O3 reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61 ± 0.35) × 10–10, (2.17 ± 0.30) × 10–12, and (4.13 ± 0.81) × 10–17 for the OH radical, NO3 radical and O3 reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52 ± 0.65) × 10–10, (1.75 ± 0.27) × 10–12, and (5.36 ± 0.28) × 10–17 for the OH radical, NO3 radical and O3 reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10 ± 0.19) × 10–10, (1.81 ± 0.35) × 10–12, and (6.98 ± 0.40) × 10–17 for the OH radical, NO3 radical and O3 reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO3 radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less. 相似文献
10.
Sulfide and iron control on mercury speciation in anoxic estuarine sediment slurries 总被引:2,自引:0,他引:2
Seunghee Han Anna Obraztsova Patrizia Pretto Dimitri D. Deheyn Joris Gieskes Bradley M. Tebo 《Marine Chemistry》2008,111(3-4):214-220
In order to understand the role of sulfate and Fe(III) reduction processes in the net production of monomethylmercury (MMHg), we amended anoxic sediment slurries collected from the Venice Lagoon, Italy, with inorganic Hg and either potential electron acceptors or metabolic byproducts of sulfate and Fe(III) reduction processes, gradually changing their concentrations. Addition of sulfide (final concentration: 0.2–6.3 mM) resulted in an exponential decrease in the sulfate reduction rate and MMHg concentration with increasing concentrations of sulfide. Based on this result, we argue that the concentration of dissolved sulfide is a critical factor controlling the sulfate reduction rate, and in turn, the net MMHg production at steady state. Addition of either Fe(II) (added concentration: 0–6.1 mM) or Fe(III) (added concentration: 0–3.5 mM) resulted in similar trends in the MMHg concentration, an increase with low levels of Fe additions and a subsequent decrease with high levels of Fe additions. The limited availability of dissolved Hg, associated with sulfide removal by precipitation of FeS, appears to inhibit the net MMHg production in high levels of Fe additions. There was a noticeable reduction in the net MMHg production in Fe(III)-amended slurries as compared to Fe(II)-amended ones, which could be caused by a decrease in the sulfate reduction rate. This agrees with the results of Hg methylation assays using the enrichment cultures of anaerobic bacteria: whereas the enrichment cultures of sulfate reducers showed significant production of MMHg (4.6% of amended Hg), those of Fe(III), Mn(IV), and nitrate reducers showed no production of MMHg. It appears that enhanced Fe(III)-reduction activities suppress the formation of MMHg in high sulfate estuarine sediments. 相似文献