全文获取类型
收费全文 | 441篇 |
免费 | 25篇 |
国内免费 | 17篇 |
专业分类
化学 | 205篇 |
晶体学 | 1篇 |
力学 | 67篇 |
综合类 | 25篇 |
数学 | 92篇 |
物理学 | 93篇 |
出版年
2023年 | 5篇 |
2022年 | 10篇 |
2021年 | 10篇 |
2020年 | 10篇 |
2019年 | 7篇 |
2018年 | 11篇 |
2017年 | 8篇 |
2016年 | 12篇 |
2015年 | 13篇 |
2014年 | 24篇 |
2013年 | 60篇 |
2012年 | 19篇 |
2011年 | 16篇 |
2010年 | 18篇 |
2009年 | 22篇 |
2008年 | 18篇 |
2007年 | 25篇 |
2006年 | 20篇 |
2005年 | 21篇 |
2004年 | 22篇 |
2003年 | 11篇 |
2002年 | 15篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 6篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 10篇 |
1992年 | 10篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
排序方式: 共有483条查询结果,搜索用时 15 毫秒
11.
Extraction of Nonylphenol and Nonylphenol Ethoxylates from River Sediments: Comparison of Different Extraction Techniques 总被引:6,自引:0,他引:6
Summary Five different extraction techniques (Soxhlet, automated Randall, accelerated solvent extraction, microwave-assisted solvent extraction and extraction with a surfactant solution) have been evaluated for the determination of nonylphenol (NP) and nonylphenol ethoxylates (NPEO) in river sediments. All the techniques were applied to the same three samples collected from northern Italian rivers. The analyses were performed with two RP columns, with different stationary reversed phases—a classical C18 phase and a hexyl–phenyl phase. The recoveries and reproducibility of the different extraction techniques were comparable and all the methods gave reliable results. The variance of the results was dominated by the variance in sample homogeneity, sample preparation, and chromatographic analysis. A choice between the methods can be made on the basis of the cost and safety of each technique. Preliminary results obtained from use of a water-based extraction method with a surfactant solution (Tween-80), and its application to analysis of sediment and of worm tissue, are also presented.Presented at: Chemical Analysis and Risk Assessment of Emerging Contaminants, Barcelona, Spain, November 28–30, 2002 相似文献
12.
Ftima R. Moreira Cristina B. Maia Akie K. vila 《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(12):2141-2149
The determination of cobalt in marine sediments by electrothermal atomic absorption spectrometry was studied using no modifier and magnesium and titanium as modifiers. Titanium is one of the major sediment constituents, which widely affects the cobalt determination and it was studied as a chemical modifier since it was the only concomitant that increased the cobalt signal in the concentration range usually found in sediments. The performance of Mg and Ti as chemical modifiers was compared relative to maximum pyrolysis and atomization temperatures, linear calibration range, sensitivity and matrix effects. The pyrolysis curves showed that the analyte could be stabilized up to 1400 °C when either Ti or Mg(NO3)2 was present, while only 1000 °C could be used in the absence of a modifier. The optimum atomization temperature was 2500 °C in all cases. Analytical curves were compared using no modifier, 5 μg Ti and 100 μg Mg(NO3)2 as modifiers, and the linear range found was up to approximately 4 ng Co whether a modifier was used or not. With Ti as a chemical modifier, analytical curves for cobalt in aqueous solution and in a synthetic matrix resulted in the same sensitivity (m0=55 pg), whereas the use of Mg led to characteristic mass values of 59 and 72 pg in aqueous solution and in a synthetic matrix, respectively, showing some matrix effect. The detection limits (3σ, n=10) were 0.4 μg g−1 using no modifier and 0.3 μg g−1 with Ti as a modifier in the original matrix. A reference estuarine sediment NIST 1646 with a non-certified content of 10.5 μg g−1 Co was analyzed and the found value of 10.9±2.4 μg g−1, (n=3), using Ti as chemical modifier and calibration against aqueous standards, was in good agreement with the recommended value. 相似文献
13.
Banks CE Kruusma J Moore RR Tomcík P Peters J Davis J Komorsky-Lovrić S Compton RG 《Talanta》2005,65(2):423-429
Three different electroanalytical techniques for the detection of manganese in marine sediments are evaluated. The anodic stripping voltammetry of manganese at an in situ bismuth-film-modified boron-doped diamond electrode and cathodic stripping voltammetry at a carbon paste electrode are shown to lack the required sensitivity and reproducibility whereas cathodic stripping voltammetry at a bare boron-doped diamond electrode is shown to be reliable and selective with a limit of detection, from applying a 60 s accumulation period of 7.4 × 10−7 M and a sensitivity of 0.24 A M−1. The method was used to evaluate the manganese content of marine sediments taken from Šibenik, Croatia. 相似文献
14.
Cadmium concentration in lake sediments is determined by suspending the solid samples in a solution containing 5% (v/v) concentrated nitric acid and 0.1% (v/v) Triton X-100. Three modifiers were tested for the direct determination. The furnace temperature programmes and appropriate amount for each modifier were optimised to get the highest signal and the best separation between the atomic and background signals. The drying stage is performed by programming a 400 °C temperature, a ramp time of 25 s and hold time of 10 s on the power supply of the atomiser. No ashing step is used and platform atomisation is carried out at 2200 °C. W–Rh permanent modifier combined with conventional modifier by delivering 10 μl of 0.50% (w/v) NH4H2PO4 solution was the best chemical modifier for cadmium determination. This modifier also acts as a liquid medium for the slurry, thus simplifying the procedure. Calibration is performed using aqueous standards in the 1–5 μg l−1 range. The optimised method gave a limit of detection of 0.56 ng ml−1, characteristic mass of 10.1±0.8 pg for aqueous standard, 9.6±0.7 pg for slurry samples containing different Cd concentrations and good precision (7.6–5.2%). The method was validated by analysing four certified reference lake sediment materials: LKSD-1, LKSD-2, LKSD-3 and LKSD-4; satisfactory recoveries were obtained (90.0–96.3%) and no statistical differences were observed between the experimental and the certified cadmium concentration. The developed methodology was used to determine cadmium in three ‘real’ sediment samples from lakes in the area of Wielkopolski National Park, Poland. 相似文献
15.
A new chelating polymeric sorbent has been developed using Merrifield chloromethylated resin anchored with quinoline-8-ol (HQ). The modified polymeric resin was characterized by FT-IR spectroscopy and elemental analysis. The HQ anchored resin showed superior binding affinity for U(VI) over Th(IV) and La(III). The influence of various physicochemical parameters on the recovery of U(VI) were optimized by both static and dynamic methods. The phase exchange kinetic studies performed for U(VI) revealed that <5 min was sufficient for reaching equilibrium metal ion sorption. The maximum sorption capacity of HQ anchored resin for U(VI) was found to be 120.30 mg g−1 of resin which is higher than other solid phase extraction sorbents reported so far excepting N,N-dibutyl, N′-benzoyl thiourea sorbed Amberlite XAD-16. The developed HQ anchored polymeric resin is highly selective as none of the extraneous species were found to have any deleterious effect. Solid phase extraction (SPE) studies performed using HQ anchored polymeric resin offered enrichment factor of 100 and the lowest concentration below which recoveries become non-quantitative is 5 μg l−1. The accuracy of the developed SPE method in conjunction with Arsenazo III procedure was tested by analyzing marine sediment (MESS-3) and soil (IAEA–Soil 7) reference materials. Furthermore, the above procedure has been successfully employed for the analysis of real soil and sediment samples. 相似文献
16.
P. Garrigues C. Raoux P. Lemaire A. Mathieu D. Ribera J. F. Narbonne 《International journal of environmental analytical chemistry》2013,93(3):379-387
Abstract Biochemical indices based on enzymatic activities have been determined in fish and mussels sampled in various different coastal locations in the Mediterranean Sea. Preliminary results show a good agreement between biochemical measurements in marine organisms and chemical analyses of polycyclic aromatic hydrocarbons present in sediments. The results obtained suggest the use of biochemical indices for application in chemical contaminant biomonitoring. 相似文献
17.
K. Wallmann M. Kersten J. Gruber U. Förstner 《International journal of environmental analytical chemistry》2013,93(1-4):187-200
Abstract The binding forms of Co, Cd, Cu, Pb, and Zn in an anoxic, sulfide-bearing sediment were investigated by performing both thermodynamic equilibrium calculations and sequential extractions. Care was taken to maintain oxygen-free conditions during the whole experiment. The calculations suggested that trace metals were bound to sulfidic minerals. Sequential extraction results, however, showed increased importance of exchangeable and reducible fractions in the order Cu < Cd < Pb < Zn < Co. Thermodynamic equilibrium calculations of the chemical reactions during extraction showed that Cd, Co, Pb, and Zn sulfides are to a significant extent soluble in the acetate-exchangeable (step 1 + 2) and oxalate-reducible (step 3) fractions. Neglecting the dissolution of sulfide minerals would lead to a misinterpretation of the experimental results. 相似文献
18.
M. C. Villa-lojo E. Beceiro-GonzÁlez E. Alonso-Rodríguez D. Prada-Rodríguez 《International journal of environmental analytical chemistry》2013,93(3):377-389
Abstract The speciation of arsenic in the environment is among others controlled by reduction, methylation and oxidation processes and therefore influenced by the prevailing redox conditions. In this study we have analyzed sediments taken from La Coruña estuary in the north west of Spain. Inorganic (trivalent and pentavalent) and the organic (MMA and DMA) arsenic speciation is related to Eh, Fe and Mn load. The various of the arsenic species concentration and other parameters was analyzed at different depths in some of the sampling points. Low arsenic concentrations (1–10 μg·g–1) were found. In spite of oxidising conditions (Eh values between 31–96 mV), most of the samples showed a higher As(V) percentage than As (III). Principal component analysis was made to see a sample groups and the results showed that speciation depends on reducing conditions (Eh and Mn). 相似文献
19.
Maria G. Bettoli Lorenzo Cantelli Damiano Quarin Marzia Ravanelli Laura Tositti Ottavio Tubertini 《International journal of environmental analytical chemistry》2013,93(3-4):321-330
Abstract 210Pb is widely used to determine accumulation rates in order to obtain a time scale in environmental samples. The most accurate method uses the determination of 210Pb via its grand-daughter 210Po by alpha spectrometry. Unfortunately this method requires a complex wet-chemistry procedure to achieve the separation of 210Po from its matrix. In this work a simplified procedure for the chemical separation of 210Po is proposed and applied to three marine sediment cores and a 10 m snow core collected in Antarctica. The calculated sedimentation rates for marine sediments range from 0.053 to 0.071 cm y?1. The mean annual accumulation rate for the snow is 16.6 cm y?1 w.e. A comparison with literature data in the same region is given. 相似文献
20.
Joan Albaiges Joan Grimalt 《International journal of environmental analytical chemistry》2013,93(2-4):281-293
Abstract Two exercises (MEDCAL I and II) were conducted in our Department during November 1984 and October 1986, with participants from the Mediterranean region, for testing the IOC Manual for the determination of petroleum hydrocarbons in sediments (IOC, Manuals and Guides, No. 11). The gas chromatographic analysis of the saturated hydrocarbon fraction provided, at the best, a precision of 60% (relative standard deviation RSD) for n-alkanes (mean conc. 0.89 μg/g) and 56 % for the unresolved complex mixture (UCM) (mean conc. 16μg/g). The CPI and the pristane/phytane ratio provided better results (13% RSD). The aromatic fractions, analysed by UV-fluorescence, yielded in total a mean concentration of 10μg/g of chrysene equivalents with a 49% RSD. The extraction-partition step was confirmed to be the main source of error in the analysis because when the results were corrected for recoveries, the RSD were reduced to 17, 30 and 6% for n-alkanes, UCM and total aromatics, respectively. Our reference intra-laboratory precision was, respectively, 18, 14 and 14%. 相似文献