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1.
Linda Zaoralkova Ales Hrdlicka Vitezslav Otruba Petr Sulovsky Nicole Gilon Detlef Günther Viktor Kanicky 《Chemical Papers》2011,65(6):769-781
The applicability of laser ablation (LA) inductively coupled plasma (ICP) spectrometry for assessing elemental distributions
in layered ceramics was investigated and compared with electron probe microanalysis (EPMA). Ordinary glazed wall tiles were
employed as model specimens due to their defined structure and composition. They were used for calibration in the analysis
of ancient pottery. A qualitative depth profile was acquired by single-spot laser drilling perpendicular to coatings with
a Nd:YAG (1064 nm) laser coupled with an ICP optical emission spectrometer (OES). The lower lateral resolution associated
with the laser spot diameter of 1.0 mm led to smoothing of the depth profile due to the averaging of local irregularities.
In addition, transverse line scans by ablation across the tile section using an ArF* (193 nm) laser coupled with an ICP mass
spectrometer (MS) were performed. LA-ICP-OES depth profiles and LA-ICP-MS transverse scans were validated by EPMA section
scans and 2D back-scattered electrons images. The LA-ICP-OES acquisition was less dependent on sample surface and layer irregularities,
whereas the transverse line scan over the tile section with the small-spot beam offered insight into the micromorphology of
the individual layer. The combined approach revealed the occurrence of individual mineral grains, micro-heterogeneities and
the character of interfaces between layers. 相似文献
2.
H. Scholze H. Stephanowitz E. Hoffmann J. Skole 《Fresenius' Journal of Analytical Chemistry》1994,350(4-5):247-252
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been used for the determination of selected elements in heterogeneous powdered soils. The precision of the method essentially depends on the homogeneity of the samples. Therefore the influence of sample inhomogeneity on the precision of analytical results has been checked. The statistical evaluation was carried out using a correlation function. In the context of the described experiments, it is necessary to analyze a volume of about 20 mm3 in order to obtain reliable information on the bulk composition of the heterogeneous samples. This corresponds to about 50 craters, each with a depth of 1 mm. The results can be used to calculate certain analytical parameters, particularly the sample homogeneity, depending on the necessary analytical volume and the representative mass for the quantitative analysis under previously defined conditions. In addition to these calculations, analytical experiments have been carried out which confirm the applicability of this approach. 相似文献
3.
Both the techniques mentioned provide molecular weight and structural information, but laser microprobe mass spectrometry (LMMS) also provides greater control over the degree of fragmentation and enhanced sensitivity. In addition, LMMS allows microprobe analysis (i.e., spatial resolution of a few μm2) as well as providing quantitative measurements. The less energetic nature of fast-atom-bombardment mass spectrometry (FAB-MS) makes it more suitable for the analysis of highly labile polar compounds and high-mass biopolymers. 相似文献
4.
The ability to focus the laser accurately onto the sample with a small beam diameter (2.0–3.0 μm) enables laser mass spectrometry to be used as a microprobe. Results from a fully automated ion-mapping system for laser mass spectrometry are described. These results show that the spatial resolution of the laser microprobe is primarily limited by the diameter of the laser beam. Factors such as laser power density, laser focus, sample preparation, and chemical environment influence the reproducibility of laser mass spectra significantly. Calibration curves obtained in the analysis of mixtures of phenanthrolines demonstrate that laser mass spectrometry can be used to quantify organic components. Preliminary results on the detection of neutral molecules resulting from metastable decomposition in the flight tube are also presented. 相似文献
5.
《Spectrochimica Acta Part B: Atomic Spectroscopy》1998,53(2):367-378
This paper presents a set of data which compares the potential and limitations of laser microprobe mass spectrometry (TOF-LMMS and FT-LMMS) and static secondary ion mass spectrometry (S-SIMS) for inorganic speciation at a microscopical level. In general LMMS yields prominent signals of adduct ions consisting of the intact molecule combined with a stable ion, which allows a direct identification of the analyte. S-SIMS also yields abundant diagnostic signals to specify the molecular composition. However, adduct ions are not always present, which means that the identification often relies on fingerprinting. Results further indicate that the potential and the application area of S-SIMS and FT-LMMS are complementary to one another. 相似文献
6.
M. A. Lovell W. D. Ehmann W. R. Markesbery J. D. Robertson 《Journal of Radioanalytical and Nuclear Chemistry》1992,160(1):191-202
Laser microprobe mass spectrometry (LMMS) detection limits for mercury have been determined using mercury-doped Spurr's tissue embedding medium. Actual mercury concentrations were confirmed via INAA. Procedures have also been developed to measure lithium and indium concentrations in thin films of polymerized Spurr's samples via PIGE and PIXE. These elements are currently being investigated as laser power density internal standards in the analysis of human tissue for studies of trace element involvement in neurological diseases. 相似文献
7.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(5):975-985
The element ratios in aerosol particles produced by laser ablation (λ=266 nm, pulse length: 5 ns) of brass and steel in Ar and He and deposited in different segments of the transport tube to an ICP have been measured by ICP-MS. The data are compared with the ratios obtained by a corresponding bulk analysis. For brass, the element compositions of the aerosol particles deposited in different parts of the tube deviated from the bulk and varied along the tube. For steel, moderate agreement of the element ratios in the aerosols and the bulk was found. It is also shown that elemental ratios measured on-line by laser ablation ICP-MS with the laser-produced aerosol should not be calibrated by elemental ratios obtained with wet aerosols from aqueous solutions of the bulk. 相似文献
8.
Barbara Wagner Anna Nowak Ewa Bulska Jerzy Kunicki-Goldfinger Olivier Schalm Koen Janssens 《Mikrochimica acta》2008,162(3-4):415-424
9.
Strashnov Ilya Fernando Ruchika Izosimov Igor 《Journal of Radioanalytical and Nuclear Chemistry》2019,322(3):1437-1445
Trace analysis (at fg-level) of radioisotopes requires a considerable push in analytical technology. Among most sensitive are a Time-Resolved Laser-Induced Fluorescence (TRLIF) and Chemiluminescence (TRLIC) methods for detection of elemental compositions and valence states and a Resonance Ionisation Spectroscopy (RIS) in combination with mass spectrometry for isotope composition determination. The radioisotopes of interest in environmental radiochemistry and planetary science and their analysis using TRLIF/TRLIC/RIS are discussed. The aspects of the development of the new technology implementing these methods are also described.
相似文献10.
The spark erosion process in the ion source of the spark-source mass spectrometer is investigated by examining particles generated from aluminium and zinc alloys in an automated electron probe microanalyzer. For the element with the lowest melting point, selective evaporation was observed. Cross-sections of the sparked surface were examined. The thickness of the molten layer was found to be of the order of a few micrometers; the layer is locally homogeneous in chemical composition. 相似文献
11.
Tatiana Trejos Alejandra Flores José R. Almirall 《Spectrochimica Acta Part B: Atomic Spectroscopy》2010
Current methods used in document examinations are not suitable to associate or discriminate between sources of paper and gel inks with a high degree of certainty. Nearly non-destructive, laser-based methods using laser induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) were used to improve the forensic comparisons of gel inks, ballpoint inks and document papers based on similarities in elemental composition. Some of the advantages of these laser-based methods include minimum sample consumption/destruction, high sensitivity, high selectivity and excellent discrimination between samples from different origins. Figures of merit are reported including limits of detection, precision, homogeneity at a micro-scale and linear dynamic range. The variation of the elemental composition in paper was studied within a single sheet, between pages from the same ream, between papers produced by the same plant at different time intervals and between seventeen paper sources produced by ten different plants. The results show that elemental analysis of paper by LIBS and LA-ICP-MS provides excellent discrimination (> 98%) between different sources. Batches manufactured at weekly and monthly intervals in the same mill were also differentiated. The ink of more than 200 black pens was analyzed to determine the variation of the chemical composition of the ink within a single pen, between pens from the same package and between brands of gel inks and ballpoint inks. Homogeneity studies show smaller variation of elemental compositions within a single source than between different sources (i.e. brands and types). It was possible to discriminate between pen markings from different brands and between pen markings from the same brand but different model. Discrimination of ~ 96–99% was achieved for sets that otherwise would remain inseparable by conventional methods. The results show that elemental analysis, using either LA-ICP-MS or LIBS, provides an effective, practical and robust technique for the discrimination of document paper and gel inks with minimum mass removal (9–15 μg) and minimum damage to the document's substrate. 相似文献
12.
The application of resonance-enhanced multiphoton ionization (REMPI) spectroscopy for the ultrasensitive detection of molecules originating from laser desorption experiments performed on a variety of substrates is reviewed. Laser-induced desorption from surfaces is capable of producing intact gas-phase molecules, even from polar, non-volatile, high-molecular-weight and thermally labile substances. REMPI is a highly efficient and optically selective ionization method, which, coupled with laser desorption allows the direct chemical analysis of complex mixtures, without the need for previous sample purification and separation steps. The use of REMPI spectroscopy is discussed in two contexts: (1) for the direct chemical analysis of complex mixtures, e.g., environmental samples, by laser desorption/laser postionization mass spectrometry and (2) for measurements of internal state distribution of molecules laser-desorbed from sub-monolayers surface films to gain insight into the laser desorption mechanism.Presented at the 13th International Symposium on Microchemical Techniques (ISM), held in Montreux, Switzerland, May 16–20,1994 相似文献
13.
Wim Van Roy Herbert Struyf Paul Kennis Luc Van Vaeck René Van Grieken Claudia Andrle 《Mikrochimica acta》1995,120(1-4):121-137
Laser microprobe mass spectrometry (LMMS) is a technique for local analysis of inorganic and organic constituents in the m range. This paper will focus on selected applications. First of all, element detection is illustrated by data from a 50-nm TiW layer on silicon and by the detection of residual Cr on HPLC column packing material. Speciation capabilities of LMMS are demonstrated on pure substances and on a coated neo-ceramic. Finally, the feasibility of organic analysis is shown in the case of a biologically active compound and dyed cloth fibres. 相似文献
14.
François-Xavier d'Abzac Anne-Magali Seydoux-Guillaume Jérôme Chmeleff Lucien Datas Franck Poitrasson 《Spectrochimica Acta Part B: Atomic Spectroscopy》2011,66(9-10):671-680
The characteristics of infra red femtosecond laser-induced aerosols are studied for monazite (LREE, Th(PO4)) ablation and correlations are established with inductively coupled plasma-mass spectrometry (ICP-MS) signals. Critical parameters are tested within wide ranges of values in order to cover the usual laser ablation -ICP-MS analysis conditions: pulse energy (0.15 < E0 < 1 mJ/pulse), pulse width (60 < τ < 3000 fs), ablation time (t ≤ 10 min) and transport length (l ≤ 6.3 m). Transmission electron microscopy reveals that aerosols are made of agglomerates of ~ 10 nm particles and 20–300 nm phosphorus depleted condensed spherical particles. These structures are not affected by any laser ablation parameter. Particle counting is performed using electronic low pressure impaction. Small changes on particle size distribution are noticed. They may be induced either by a peak of ablation rate in the first 15 s at high fluence (larger particles) or the loss of small particles during transport. We found a positive correlation between I (ICP-MS mean signal intensity in cps) and N (particle density in cm? 3) when varying E0 and t, suggesting that N is controlled by the irradiance (P0 in W·cm? 2). Elemental ratio measurements show a steady state signal after the initial high ablation rate (mass load effect in the plasma torch) and before a late chemical fractionation, induced by poor extraction of bigger, early condensed spherical particles from the deepening crater. Such chemical fractionation effects remain within uncertainties, however. These effects can be limited by monitoring E0 to shorten the initial transient state and delay the attainment of an unfavorable crater aspect ratio. Most adopted settings are for the first time deduced from aerosol characteristics, for infra red femtosecond laser ablation. A short transport (l < 4.0 m) limits the agglomeration of particles by collision process along the tube. Short τ is preferred because of higher P0, yet no benefit is found on ICP-MS signal intensity under 200 fs. Under such pulse widths the increased particle production induces more agglomeration during transport, thereby resulting in higher mass load effects that reduce the ionization efficiency of the plasma torch. Thus, pulse energy must be set to get an optimal balance between the need for a high signal/background ratio and limitation of mass load effects in the plasma torch. 相似文献
15.
Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ30Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ30Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the μg g−1-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous stable isotope measurement and chemical composition analysis LASS-ICP-MS in combination with MC-ICP-MS is the method of choice. 相似文献
16.
Benjamin E. Naes Sayuri Umpierrez Scott Ryland Cleon Barnett Jose R. Almirall 《Spectrochimica Acta Part B: Atomic Spectroscopy》2008
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), micro X-ray fluorescence spectroscopy (μXRF), and laser induced breakdown spectroscopy (LIBS) are compared in terms of discrimination power for a glass sample set consisting of 41 fragments. Excellent discrimination results (> 99% discrimination) were obtained for each of the methods. In addition, all three analytical methods produced very similar discrimination results in terms of the number of pairs found to be indistinguishable. The small number of indistinguishable pairs that were identified all originated from the same vehicle. The results also show a strong correlation between the data generated from the use of µXRF and LA-ICP-MS, when comparing µXRF strontium intensities to LA-ICP-MS strontium concentrations. A 266 nm laser was utilized for all LIBS analyses, which provided excellent precision (< 10% RSD for all elements and < 10% RSD for all ratios, N = 5). The paper also presents a thorough data analysis review for forensic glass examinations by LIBS and suggests several element ratios that provide accurate discrimination results related to the LIBS system used for this study. Different combinations of 10 ratios were used for discrimination, all of which assisted with eliminating Type I errors (false exclusions) and reducing Type II errors (false inclusions). The results demonstrate that the LIBS experimental setup described, when combined with a comprehensive data analysis protocol, provides comparable discrimination when compared to LA-ICP-MS and μXRF for the application of forensic glass examinations. Given the many advantages that LIBS offers, most notably reduced complexity and reduced cost of the instrumentation, LIBS is a viable alternative to LA-ICP-MS and μXRF for use in the forensic laboratory. 相似文献
17.
Jan Claereboudt Magda Claeys Herman Geise Renaat Gijbels Akos Vertes 《Journal of the American Society for Mass Spectrometry》1993,4(10):798-812
The use of laser microprobe mass spectrometry (LMMS) for the structural characterization of thermolabile quaternary phosphonium salts has been evaluated. A comparison has been made between LM mass spectra obtained by direct analysis of “neat” organic salts and the corresponding “matrix-assisted” LM mass spectra. Main limitations of LMMS for the direct analysis of neat organic salts (i.e., no matrix) result from (1) formation of artifact ions that originate from thermal degradation and surface recombination reactions and (2) poor shot-to-shot reproducibility of the spectra. Dilution of the organic salts in a suitable, UV-absorbing matrix (e.g., nicotinic acid) significantly enhances the quality of the LM mass spectra. Improvements are: (1) an increase of the ion yield of preformed cations, (2) reduction or elimination of thermal decomposition and other deleterious surface reactions, and (3) a much better shot-to-shot spectral reproducibility. An interesting analytical feature is that these LM mass spectra, which contain only a few matrix peaks, can be obtained for subnanogram amounts of sample. The results also show that triphenylphosphonium salts with polycyclic aromatic substituents can be used as “molecular thermometers” to probe both the temperatures experienced by the sample molecules during the laser-induced desorption ionization process and the internal energies of the desorbed ion species. In this way, quaternary phosphonium salts can be used for evaluating whether improvements have been achieved by applying different sample treatments. Comparison of four different matrices (i.e., nicotinic acid, ammonium chloride, glycerol, and 3-nitrobenzylalcohol) indicates that the effectiveness of a matrix to reduce thermal degradation and to decrease the internal energies of the ions depends on the UV-absorption characteristics and the volatilization/sublimation temperature of the matrix material. 相似文献
18.
Applications of the laser microprobe mass analyzer for characterizing the surface of chemically modified minerals (crown ether/montmorillonite and organosilane/sepiolite) and for detecting micro-crystallites at the surface of an inorganic matrix (brucite surface layer of chrysotile fibers) were investigated using laser desorption conditions. The laser microprobe is shown to be a versatile tool for these applications. 相似文献
19.
B. Sansoni W. Brunner G. Wolff H. Ruppert R. Dittrich 《Fresenius' Journal of Analytical Chemistry》1988,331(2):154-169
Summary Multi-element analysis by ICP source mass spectrometry for practically matrix-free natural waters, coming from a granitic area and, therefore, rich in trace elements, has been compared with ICP-atomic emission, ICP atomic fluorescence and atomic absorption spectrometry. The following elements have been investigated and their concentrations are in the decreasing order: Ca, Si, Na, Mg, K, Al; Sr, Mn, Ba, Fe, Rb, Zn, B, U, Y, Li, La, Be, Cs, Co, Cr, V, Sb, Bi, Th, Cu, Cd, Ni, Se, Pb, As, Hg, Mo, Tl, Sn. The concentration ranges were between 10 ppm and <0.01 ppb.As a measure of agreement between the different methods under investigation, two criteria have been used (a) the relative variation coefficient VK (%) of the mean element concentration of an element, determined by different methods in all the 98 water samples and (b) the linear, logarithmic and Spearman rank correlation coefficients between ICP-MS and each of the other methods. Detection limits are given from literature for about 32 elements using different methods.The elements Ca, Na, Mg, K, Mn, Sr, Zn, Fe, Li, Cu have been determined with ICP-MS, ICP-AES and AAS; Al, Ba with ICP-MS and ICP-AES; Si only with ICP-AES, whereas B, Be, Bi, Co, Cr, Cs, Hg, La, Mo, Ni, Pb, Rb, Sb, Sn, Th, Tl, U, V, Y only with ICP-MS. In all 34 of the investigated 36 elements could be analysed by ICP-MS, 14 (from about 20 possible) by AAS, 13 by ICP-AES and 12 by ICP-AFS.The agreement between ICP-MS and ICP-AES as well as between ICP-MS and AAS in most cases is remarkably good according to (a). VK (%) for each element in 98 water samples is in the range from ±2.6 to 10% for Na, Mg, Ca, K, Fe, Sr, Ba, Cu, Li (increasing order). Cd and Zn have unexpectedly higher values (±17.3 and ±20.5%); Cd concentrations are, however, near the detection limit.Comparing the different methods on the basis of correlation coefficients according to (b), gives for the Spearman rank correlation coefficient over the whole range of concentrations, respectively for ICP-MS/ICP-AES, AAS, ICP-AFS in case of Ca: 0.998; 0.984; 0.899; Na: 0.993; 0.991; 0.978; Mg: 0.997; 0.993; 0.959; K: 0.986; 0.942; 0.677; Al: 0.987; -; -; Fe: 0.864; 0.974; 0.701; Mn: 0.989; 0.990; 0.198; Sr: 0.988; 0.992; -; Zn: 0.894; 0.819; 0.300; Cu: -; 0.977; 0.202; Li: -; 0.907; 0.586.It is evident from these trace element concentrations as well as the electrical conductivities, that only about three fourths of the investigated samples are typical granitic waters and the remaining ones are associated with different geological background. The samples have been mainly radon waters with more than 18 nCi/l of Rn-222.
6th Contribution to the principles of trace analysis of elements and radionuclides
Dedicated to Professor Dr. H. Kelker, Frankfurt, on the occasion of his 65th birthday 相似文献
Vergleichende Instrumentelle Multielementanalyse I: Vergleich von ICP-Massenspektrometrie mit ICP-Atomemissionsspektrometrie, ICP-Atomfluorescenzspektrometrie und Atomabsorptionsspektrometrie zur Analyse natürlicher Wässer aus einem Granitgebiet
6th Contribution to the principles of trace analysis of elements and radionuclides
Dedicated to Professor Dr. H. Kelker, Frankfurt, on the occasion of his 65th birthday 相似文献
20.
Management of domestic wastes often relies on incineration, a process that eliminates large amount of wastes but also produces toxic residues that concentrate heavy metals. Those hazardous secondary wastes require specific treatment. Vitrification is seen as a powerful way to stabilise them. However, concern exists about the long term behaviour of these glass wastes and the potential release of toxic species into the environment. The answers will come with further investigation into the physico-chemical evolution of the vitrified wastes and the mobility of hazardous elements within the matrix with appropriate analytical methods. Laser ablation coupled with inductively coupled mass spectrometry (LA-ICP-MS) is a challenging technique for the chemical analysis of trace elements in solid materials. This paper presents an evaluation of the potential of LA- ICP-MS for macro and microanalysis of trace metals in domestic vitrified wastes with regards to other physical analytical techniques of solids such as scanning electronprobe X-ray energy dispersive spectroscopy (SEM-EDXS). Two typical samples, vitreous and crystallised, are used to compare the analytical performances of the two techniques. SEM-EDXS was used for mineralogical characterisation and chemical analysis of the mineralogical phases. Relative micro-analysis and bulk quantitative analysis of 30 major, minor and trace elements was performed by LA-ICP-MS: precision was between 10 and 20% for most elements and quantitative analysis proved possible with an accuracy of 20% and relative detection limits of 0.1 mg kg(-1). 相似文献