排序方式: 共有47条查询结果,搜索用时 15 毫秒
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Michael Krachler Hendrik EmonsCarlo Barbante Giulio CozziPaolo Cescon William Shotyk 《Analytica chimica acta》2002,458(2):387-396
Four analytical approaches, based on different physical principles, for the determination of antimony (Sb) and arsenic (As) in ancient peat samples were critically evaluated: (a) open vessel digestion/hydride generation-atomic absorption spectrometry (HG-AAS), (b) closed-pressurized digestion in a microwave oven followed by sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS), (c) digestion in a microwave autoclave and subsequent quadrupole-inductively coupled plasma-mass spectrometry (Q-ICP-MS) measurements and (d) instrumental neutron activation analysis (INAA). The quality control scheme applied, always included the use of adequate plant reference materials to ensure the accuracy and precision of the analytical procedures. Additionally, two internal peat reference materials were analyzed using all four analytical approaches, generally showing good agreement for both elements. Method detection limits for As and Sb provided by all procedures were approximately 5 and 2 ng g−1 which is sufficiently low for the reliable quantification of both elements in ancient, pre-anthropogenic peat samples. A comparison of As and Sb concentrations in a set of peat samples determined by INAA, HG-AAS and SF-ICP-MS revealed that INAA underestimated the values in a systematic manner, whereas HG-AAS and SF-ICP-MS data agreed very well. Best precision of the results was obtained by analytical procedures involving HG-AAS or Q-ICP-MS and varied from 3.6 to 4.3% and 7.1 to 7.5% for As (at about 0.5 μg g−1) and Sb (at about 0.1 μg g−1), respectively. The highest sample throughput (40 samples per run accomplished in 2 h) combined with low risk of sample contamination could be realized in the high-pressure microwave autoclave. The amount of sample required by all approaches was 200 mg, except for INAA which needed at least 25 times more sample mass to achieve comparable detection limits. For the quantification of As and Sb, inductively coupled plasma-mass spectrometry (ICP-MS) was preferred over INAA and HG-AAS, mainly because (a) less sample is needed and (b) As and Sb can be determined simultaneously. In addition, ICP-MS offers the possibility to measure concurrently a wide range of other elements which also are of environmental interest. 相似文献
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Capodaglio G Toscano G Barbante C Gambaro A Scarponi G Cescon P 《Annali di chimica》2002,92(3):163-176
The methodology for using DPASV to study cadmium complexation in seawater is evaluated using EDTA as a model ligand and by analysing natural samples. The results show that the methodology gives an accurate evaluation of metal complexation when inert complexes are studied, both as regards the ligand concentration and the conditional stability constant; the error for both the parameters is lower than 10% at a ligand concentration of about 10(-8) M and a conditional stability constant of 10(9) M-1. Cadmium complexes with ligands present in natural seawater show an evident kinetic lability that may lead to underestimation of the conditional stability constant when a working electrode characterised by a very thick diffusion layer is used. The conditional stability constant in one water sample of the Adriatic coast ranged between 0.14 and 1.4 l/nmol using a rotating disk electrode at rotation rates of 300 and 6000 rpm. The results of cadmium complexation obtained for samples collected in coastal seawater show that the ligands present low specificity for the metal. 相似文献
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C. Barbante C. Turetta G. Capodaglio G. Scarponi 《International journal of environmental analytical chemistry》2013,93(4):457-477
Abstract Differential Pulse Anodic Stripping Voltammetry (DPASV) was applied to determine the lead concentration in recent snow at two sites in the Victoria Land region, East Antarctica. Snow samples were collected during the 6th Italian Scientific Expedition to Antarctica (austral Summer 1990–91) along the wall of 2.5 m-deep hand-dug pits and by coring to a depth of about 11 m. The measurements revealed that lead content in Antarctic snow increased continuously from 1965 (about 3 pg/g) to the early 1980s (maximum about 8 pg/g), after which a marked, rapid decrease took place during the second half of 1980s, down to 2–4 pg/g in 1991. Estimates of the lead contributions from rocks and soils, volcanoes and the marine environment, together with analysis of statistical data on non-ferrous metal production and gasoline consumption, and the corresponding lead emissions into the atmosphere of the Southern Hemisphere, show that a net anthropogenic component is present and support the hypothesis that the trend observed in Antarctic snow may be related to lead consumption in gasoline, which firstly was on the rise, then declined owing to the increased use of unleaded gasoline. 相似文献
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Piper DJ Barbante GJ Brack N Pigram PJ Hogan CF 《Langmuir : the ACS journal of surfaces and colloids》2011,27(1):474-480
The electrodeposition of the electrochemiluminescent (ECL) ruthenium complex, bis(2,2'-bipyridyl)(4'-(4-aminophenyl)-2,2'-bipyridyl)ruthenium(II), [Ru(bpy)(2)(apb)](2+), via the in situ formation of a diazonium species from aqueous media is reported. Surface characterization undertaken using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) determined that the layer is bound to the substrate via azo bonding. The layer displays good ECL activity and is stable over a long period of time. The excellent potential of this system for ECL sensing applications is demonstrated using the well-known ECL coreactant 2-(dibutylamino)ethanol (DBAE) as a model analyte, which can be detected to a level of 10 nM with a linear range between 10(-8) and 10(-4) M. 相似文献
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Barbante GJ Hogan CF Wilson DJ Lewcenko NA Pfeffer FM Barnett NW Francis PS 《The Analyst》2011,136(7):1329-1338
Using a combination of electrochemical, spectroscopic and computational techniques, we have explored the fundamental properties of a series of ruthenium diimine complexes designed for coupling with other molecules or surfaces for electrochemiluminescence (ECL) sensing applications. With appropriate choice of ligand functionality, it is possible to manipulate emission wavelengths while keeping the redox ability of the complex relatively constant. DFT calculations show that in the case of electron withdrawing substituents such as ester or amide, the excited state is located on the substituted bipyridine ligand whereas in the case of alkyl functionality it is localised on a bipyridine. The factors that dictate annihilation ECL efficiency are interrelated. For example, the same factors that determine ΔG for the annihilation reaction (i.e. the relative energies of the HOMO and LUMO) have a corresponding effect on the energy of the excited state product. As a result, most of the complexes populate the excited state with an efficiency (Φ(ex)) of close to 80% despite the relatively wide range of emission maxima. The quantum yield of emission (Φ(p)) and the possibility of competing side reactions are found to be the main determinants of ECL intensity. 相似文献
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Inductively coupled plasma mass spectrometry (ICP-MS) is a suitable tool for multi-element analysis at low concentration levels. Rare earth element (REE) determinations in standard reference materials and small volumes of molten ice core samples from Antarctica have been performed with an ICP-time of flight-MS (ICP-TOF-MS) system. Recovery rates for REE in e.g. SPS-SW1 amounted to ∼103%, and the relative standard deviations were 3.4% for replicate analysis at REE concentrations in the lower ng L−1 range. Analyses of REE concentrations in Antarctic ice core samples showed that the ICP-TOF-MS technique meets the demands of restricted sample mass. The data obtained are in good agreement with ICP-Quadrupole-MS (ICP-Q-MS) and ICP-Sector Field-MS (ICP-SF-MS) results. The ICP-TOF-MS system determines accurately and precisely REE concentrations exceeding 5 ng L−1 while between 0.5 and 5 ng L−1 accuracy and precision are element dependent. 相似文献
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Emily Kerr Egan H. Doeven Gregory J. Barbante Conor F. Hogan David J. Bower Paul S. Donnelly Timothy U. Connell Paul S. Francis 《Chemical science》2015,6(1):472-479
We demonstrate the mixed annihilation electrogenerated chemiluminescence of tris(2,2′-bipyridine)ruthenium(ii) with various cyclometalated iridium(iii) chelates. Compared to mixed ECL systems comprising organic luminophores, the absence of T-route pathways enables effective predictions of the observed ECL based on simple estimations of the exergonicity of the reactions leading to excited state production. Moreover, the multiple, closely spaced reductions and oxidations of the metal chelates provide the ability to finely tune the energetics and therefore the observed emission colour. Distinct emissions from multiple luminophores in the same solution are observed in numerous systems. The relative intensity of these emissions and the overall emission colour are dependent on the particular oxidized and reduced species selected by the applied electrochemical potentials. Finally, these studies offer insights into the importance of electronic factors in the question of whether the reduced or oxidized partner becomes excited in annihilation ECL. 相似文献