共查询到20条相似文献,搜索用时 12 毫秒
1.
B. Bousquet J.-B. Sirven L. Canioni 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1582-1589
A quantitative analysis of chromium in soil samples is presented. Different emission lines related to chromium are studied in order to select the best one for quantitative features. Important matrix effects are demonstrated from one soil to the other, preventing any prediction of concentration in different soils on the basis of a univariate calibration curve. Finally, a classification of the LIBS data based on a series of Principal Component Analyses (PCA) is applied to a reduced dataset of selected spectral lines related to the major chemical elements in the soils. LIBS data of heterogeneous soils appear to be widely dispersed, which leads to a reconsideration of the sampling step in the analysis process. 相似文献
2.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2001,56(6):865-875
We report on the application of laser-induced breakdown spectroscopy (LIBS) to the analysis of important minerals and the accumulation of potentially toxic elements in calcified tissue, to trace e.g. the influence of environmental exposure, and other medical or biological factors. This theme was exemplified for quantitative detection and mapping of Al, Pb and Sr in representative samples, including teeth (first teeth of infants, second teeth of children and teeth of adults) and bones (tibia and femur). In addition to identifying and quantifying major and trace elements in the tissues, one- and two-dimensional profiles and maps were generated. Such maps (a) provide time/concentration relations, (b) allow to follow mineralisation of the hydroxyapatite matrix and the migration of the elements within it and (c) enable to identify disease states, such as caries in teeth. In order to obtain quantitative calibration, reference samples in the form of pressed pellets with calcified tissue-equivalent material (majority compound of pellets is CaCO3) were used whose physical properties closely resembled hydroxyapatite. Compounds of Al, Sr and Pb were added to the pellets, containing atomic concentrations in the range 100–10 000 ppm relative to the Ca content of the matrix. Analytical results based on this calibration against artificial samples for the trace elements under investigation agree with literature values, and with our atomic absorption spectroscopy (AAS) cross-validation measurements. 相似文献
3.
We have added time resolution to laser-induced breakdown spectroscopy in two forms, by gating an optical multichannel analyzer (OMA) and by time-resolving the output of a photomultiplier with a boxcar amplifier. Spectra were obtained for temporal segments of 25 to 100 ns, from 25 ns to 50 µs after initiation of the breakdown. OMA spectra of oxygen illustrate the power of this technique for survey purposes. The photomultiplier-boxcar arrangement was used to detect phosphorus atoms from diisopropylmethyl phosphonate in air, and also to detect chlorine in air, both in real time. In the former experiments we detected 690 ppm (w/w) of phosphorus and project a limit of detection with our current apparatus of 15 ppm (w/w). For chlorine, we observed signal from 120 ppm (w/w) and project a limit of detection of 60 ppm (w/w). 相似文献
4.
A method for the quantitative elemental analysis of surface soil samples using laser-induced breakdown spectroscopy (LIBS)
was developed and applied to the analysis of bulk soil samples for discrimination between specimens. The use of a 266 nm laser
for LIBS analysis is reported for the first time in forensic soil analysis. Optimization of the LIBS method is discussed,
and the results compared favorably to a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method previously
developed. Precision for both methods was <10% for most elements. LIBS limits of detection were <33 ppm and bias <40% for
most elements. In a proof of principle study, the LIBS method successfully discriminated samples from two different sites
in Dade County, FL. Analysis of variance, Tukey’s post hoc test and Student’s t test resulted in 100% discrimination with no type I or type II errors. Principal components analysis (PCA) resulted in clear
groupings of the two sites. A correct classification rate of 99.4% was obtained with linear discriminant analysis using leave-one-out
validation. Similar results were obtained when the same samples were analyzed by LA-ICP-MS, showing that LIBS can provide
similar information to LA-ICP-MS. In a forensic sampling/spatial heterogeneity study, the variation between sites, between
sub-plots, between samples and within samples was examined on three similar Dade sites. The closer the sampling locations,
the closer the grouping on a PCA plot and the higher the misclassification rate. These results underscore the importance of
careful sampling for geographic site characterization. 相似文献
5.
Juraj Jasik Johannes Heitz Johannes D. Pedarnig Pavel Veis 《Spectrochimica Acta Part B: Atomic Spectroscopy》2009,64(10):1128
Laser-induced breakdown spectroscopy (LIBS) in the vacuum ultraviolet range (VUV, λ < 200 nm) is employed for the detection of trace elements in polyethylene (PE) that are difficult to detect in the UV/VIS range. For effective laser ablation of PE, we use a F2 laser (wavelength λ = 157 nm) with a laser pulse length of 20 ns, a pulse energy up to 50 mJ, and pulse repetition rate of 10 Hz. The optical radiation of the laser-induced plasma is measured by a VUV spectrometer with detection range down to λ = 115 nm. A gated photon-counting system is used to acquire time-resolved spectra. From LIBS measurements of certified polymer reference materials, we obtained a limit of detection (LOD) of 50 µg/g for sulphur and 215 µg/g for zinc, respectively.The VUV LIBS spectra of PE are dominated by strong emission lines of neutral and ionized carbon atoms. From time-resolved measurements of the carbon line intensities, we determine the temporal evolution of the electronic plasma temperature, Te. For this, we use Saha–Boltzmann plots with the electron density in the plasma, Ne, derived from the broadening of the hydrogen H-α line. With the parameters Te and Ne, we calculate the intensity ratio of the atomic sulphur and carbon lines at 180.7 nm and at 175.2 nm, respectively. The calculated intensity ratios are in good agreement with the experimentally measured results. 相似文献
6.
Candice M. Bridge Joseph Powell Katie L. Steele Michael E. Sigman 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1419-1425
Glass samples of four types commonly encountered in forensic examinations have been analyzed by laser-induced breakdown spectroscopy (LIBS) for the purpose of discriminating between samples originating from different sources. Some of the glass sets were also examined by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Refractive index (RI) measurements were also made on all glass samples and the refractive index data was combined with the LIBS and with the LA-ICP-MS data to enhance discrimination. The glass types examined included float glass taken from front and side automobile windows (examined on the non-float side), automobile headlamp glass, automobile side-mirror glass and brown beverage container glass. The largest overall discrimination was obtained by employing RI data in combination with LA-ICP-MS (98.8% discrimination of 666 pairwise comparisons at 95% confidence), while LIBS in combination with RI provided a somewhat lower discrimination (87.2% discrimination of 1122 pairwise comparisons at 95% confidence). Samples of side-mirror glass were less discriminated by LIBS due to a larger variance in emission intensities, while discrimination of side-mirror glass by LA-ICP-MS remained high. 相似文献
7.
A mobile double-pulse laser-induced breakdown spectroscopy system for industrial environments is presented. Its capabilities
as a process analytical technique for the recovery of metals from molten inorganic wastes are investigated. Using low-melting
glass doped with different amounts of additives as a model system for recycling slags, the optimum number of shots, laser
inter-pulse and acquisition delay times are optimized for solid and liquid (1200 °C) glass. Limits of detection from 7 ppm
(Mn) to 194 ppm (Zn) are achieved working at a distance of 75 cm from the sample. To simplify the quantification of molten
samples in an industrial furnace, the possibility is examined of using solid standards for analysis of molten material. 相似文献
8.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(7):1131-1140
In this paper, the capabilities of laser-induced breakdown spectroscopy (LIBS) for rapid analysis of multi-component pharmaceutical tablets are illustrated using several examples. The atomic line emission from an element present only in a particular component of the tablet (for instance, emission of phosphorus from the drug, or of magnesium from the lubricant) enables the quantitative analysis of that component. It is also demonstrated that simple schemes can significantly improve the analytical performance of LIBS in this context. In particular, internal standardization with a carbon line was found to enable the correction of a matrix effect, apart from improving the precision of measurement. Furthermore, an improvement in the linearity of calibration was observed when the plasma continuum emission was used as internal standard. Finally, in the case of drugs containing halogen species (e.g. F or Cl), producing the plasma in a helium atmosphere caused a seven to eight-fold increase of the signal-to-background ratio, thus improving sensitivity. These data illustrate the strengths of LIBS for fast at-line assessment of the reliability of pharmaceutical manufacturing processes. 相似文献
9.
Statistical uncertainty in the quantitative analysis of solid samples in motion by laser-induced breakdown spectroscopy (LIBS) has been assessed. For this purpose, a LIBS demonstrator was designed and constructed in our laboratory. The LIBS system consisted of a laboratory-scale conveyor belt, a compact optical module and a Nd:YAG laser operating at 532 nm. The speed of the conveyor belt was variable and could be adjusted up to a maximum speed of 2 m s− 1. Statistical uncertainty in the analytical measurements was estimated in terms of precision (reproducibility and repeatability) and accuracy. The results obtained by LIBS on shredded scrap samples under real conditions have demonstrated that the analytical precision and accuracy of LIBS is dependent on the sample geometry, position on the conveyor belt and surface cleanliness. Flat, relatively clean scrap samples exhibited acceptable reproducibility and repeatability; by contrast, samples with an irregular shape or a dirty surface exhibited a poor relative standard deviation. 相似文献
10.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(7):1167-1179
Single and double pulse laser-induced breakdown spectroscopy (LIBS) was carried out on aluminum samples in air. In the case of double pulse excitation, experiments were conducted by using the same laser source operated at the same wavelength (1064 nm in most cases here presented). A lowering of the second pulse plasma threshold was observed, together with an overall enhancement in line emission for the investigated time delay between the two pulses (40–60 μs). The laser-induced plasma originated by a single and double pulse was investigated near ignition threshold with the aim to study possible dynamical mechanisms in different regimes. Currently available spectroscopic diagnostics of plasma, such as the line broadening and shift due Stark effects, have been used in the characterization in order to retrieve electron densities, while standard temperature measurements were based on Boltzmann plot. Plasma relevant parameters, such as temperature and electron density, have been measured in the plasma decay on a long time scale, and compared with crater shape (diameter and inferred volume). The comparison of double with single pulse laser excitation was carried out while keeping constant the energy per pulse; the influence of laser energy was investigated as well. Results here obtained suggest that use of the double pulse technique could significantly improve the analytical capabilities of LIBS technique in routine laboratory experiments. 相似文献
11.
Ayyalasomayajula KK Dikshit V Yueh FY Singh JP Smith LT 《Analytical and bioanalytical chemistry》2011,400(10):3315-3322
Laser-induced breakdown spectroscopy (LIBS) has been employed for the analysis of slurry samples. Quantitative analysis of
slurry samples is crucial and challenging. The problems associated with slurry samples include splashing, surface turbulence,
and the difficulties of obtaining reproducible samples due to sedimentation. The LIBS analysis has achieved limited success
due to inherent disadvantages when applied to slurry samples. In order to achieve improved measurement precision and accuracy,
a spin-on-glass sampling method was evaluated. Five elements (Al, Ca, Fe, Ni, and Si) were examined in five slurry simulants
containing varying amounts of each ion. Three calibration models were developed by using univariate calibration, multiple
linear regression, and partial least square regression. LIBS analysis results obtained from the partial least square regression
model were determined to be the best fit to results obtained from inductively coupled plasma optical emission spectroscopy
analysis. 相似文献
12.
Barreda FA Trichard F Barbier S Gilon N Saint-Jalmes L 《Analytical and bioanalytical chemistry》2012,403(9):2601-2610
The potential of laser-induced breakdown spectroscopy (LIBS) for the rapid determination of platinum in liquid silicone oils has been evaluated in the framework of on-line process control. A comparison of LIBS sensitivity between three setups designed for liquid analysis (static, liquid jet and flowing liquid) was performed using a 266 nm Nd/YAG laser irradiation. Best results were obtained using the flowing liquid setup and a similar limit of detection was obtained using the liquid jet. The effect of different buffer gases (Ar, He, N(2), etc.) on the signal sensitivity was studied in liquid jet analysis and best values were obtained with a nitrogen sheath gas. Detection limits were in the 100 mg/kg range for both setups. Quantitative determination of platinum in real liquid samples was also investigated using both liquid jet and flowing liquid setups. Calibration curves were plotted for Pt with the liquid jet and the flowing liquid setups under optimised temporal acquisition parameters (delay time and gate width). A normalisation using a silicon line was applied and recovery ranged from 3 to 15% for Pt in catalyst samples with both setups showing that LIBS is a sensitive and accurate method for on-line applications. 相似文献
13.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(1):121-135
We have studied the combination of fourth-harmonic (266 nm) and fundamental (1064 nm) Nd:YAG laser pulses of the same irradiance. On a metallic target (Al), a sequence of ultraviolet (UV) and near-infrared (NIR) pulses produces deeper craters and can lead under certain conditions to analyte signal enhancements larger than those obtained with a NIR–NIR sequence. Compared to a single NIR pulse, signal enhancements by factors of approximately 30 for the Si I 288.16-nm line and 100 for the Al II 281.62-nm line were observed with double pulses of the same total energy. This effect correlates with a substantial increase in plasma temperature, with ionic lines and lines having a higher excitation energy experiencing a larger enhancement. Moreover, the optimal pulse separation is found to be larger for ionic than for neutral lines (∼3 compared to ∼0.1 μs). Another finding of this study concerns the combination of two different wavelengths (266 and 1064 nm) in a single ‘mixed-wavelength’ pulse, a scheme that also leads to an enhanced laser-induced breakdown spectroscopy (LIBS) sensitivity. It is proposed that the double-pulse and mixed-wavelength approaches are both capable of temperature and signal enhancement for the same reason: a larger portion of laser energy is absorbed in the plasma region containing the analyte atoms, instead of being absorbed at the sample surface or in the atmosphere. 相似文献
14.
Jose Manuel Andrade Gabriele Cristoforetti Stefano Legnaioli Giulia Lorenzetti Vincenzo Palleschi Abdallah A. Shaltout 《Spectrochimica Acta Part B: Atomic Spectroscopy》2010
In this work we compare the analytical results obtained by traditional calibration curves (CC) and multivariate Partial Least Squares (PLS) algorithm when applied to the LIBS spectra obtained from ten brass samples (nine standards of known composition and one ‘unknown’). Both major (Cu and Zn) and trace (Sn, Pb, Fe) elements in the sample matrix were analyzed. After the analysis, the composition of the ‘unknown’ sample, measured by X-ray Fluorescence (XRF) technique, was revealed. The predicted concentrations of major elements obtained by rapid PLS algorithms are in very good agreement with the nominal concentrations, as well as with those obtained by the more time-consuming CC approach. A discussion about the possible effects leading to discrepancies of the results is reported. The results of this study open encouraging perspectives towards the development of cheap LIBS instrumentation which would be capable, despite the limitations of the experimental apparatus, to perform fast and precise quantitative analysis on complex samples. 相似文献
15.
We present a new method for improving the reliability of quantitative analysis by laser-induced breakdown spectroscopy (LIBS). The method can be considered as a variation of the calibration-free LIBS approach; although not completely standard-less, only one standard of known composition and similar matrix to the one to be analyzed is needed. On the other hand, the one-point calibration approach allows the empirical determination of essential experimental and spectroscopic parameters, whose knowledge is often imprecise or lacking; the result is a definite improvement of the trueness of LIBS analysis with respect to the traditional calibration-free approach.The characteristics and advantages of the proposed one-point calibration LIBS approach will be demonstrated on a set of copper-based samples of known composition. 相似文献
16.
Matthieu Baudelet Myriam Boueri Jin Yu Samuel S. Mao Vincent Piscitelli Xianglei Mao Richard E. Russo 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1329-1334
Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample. 相似文献
17.
Christian Bohling Konrad Hohmann Dirk Scheel Christoph Bauer Wolfgang Schippers Jrg Burgmeier Ulrike Willer Gerhard Holl Wolfgang Schade 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1519-1527
An all-fiber-coupled laser-induced breakdown spectroscopy (LIBS) sensor device is developed. A passively Q-switched Cr4+Nd3+:YAG microchip laser is amplified within an Yb fiber amplifier, thus generating high power laser pulses (pulse energy Ep = 0.8 mJ, wavelength λ = 1064 nm, repetition rate frep. = 5 kHz, pulse duration tp = 1.2 ns). A passive (LMA) optical fiber is spliced to the active fiber of an Yb fiber amplifier for direct guiding of high power laser pulses to the sensor tip. In front of the sensor a plasma is generated on the surface to be analyzed. The plasma emission is collected by a set of optical fibers also integrated into the sensor tip. The spectrally resolved LIBS spectra are processed by application of principal component analysis (PCA) and analyzed together with the time-resolved spectra with neural networks. Such procedure allows accurate analysis of samples by LIBS even for materials with similar atomic composition. The system has been tested successfully during field measurements at the German Armed Forces test facility at Oberjettenberg.
The LIBS sensor is not restricted to anti-personnel mine detection but has also the potential to be suitable for analysis of bulk explosives and surface contaminations with explosives, e.g. for the detection of improvised explosive devices (IEDs). 相似文献
18.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2006,61(2):200-209
We report on recently developed analytical software to model laser-induced breakdown spectroscopy emission spectra and predict sample composition using a proposed calibration-free algorithm. The model uses a database of atomic emission lines to create a theoretical emission spectrum for selected elements using defined plasma parameters. The resulting theoretical spectrum is fitted to experimental data obtained from a laser-induced breakdown spectroscopy instrument comprising of four compact spectrometers that image the plasma emission. Elemental concentrations are obtained by comparing observed and predicted spectra while varying the plasma temperature and relative elemental concentrations. The use of the model for analysis of major elements in bauxites, brass and mineral samples as well as the analysis of laboratory air is demonstrated. For the majority of elements investigated agreement within 25% is achieved between estimated and certified values. 相似文献
19.
As applications for laser-induced breakdown spectroscopy (LIBS) become more varied with a greater number of field and industrial LIBS systems developed and as the technique evolves to be more quantitative that qualitative, there is a more significant need for LIBS systems capable of analysis with the use of a single laser shot. In single-shot LIBS, a single laser pulse is used to form a single plasma for spectral analysis. In typical LIBS measurements, multiple laser pulses are formed and collected and an ensemble-averaged method is applied to the spectra. For some applications there is a need for rapid chemical analysis and/or non-destructive measurements; therefore, LIBS is performed using a single laser shot. This article reviews in brief several applications that demonstrate the applicability and need for single-shot LIBS. 相似文献
20.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2005,60(7-8):926-934
A kinetic model of the laser-induced breakdown spectroscopy (LIBS) plume of lead in argon has been developed to gain an understanding of the physical and chemical factors controlling the LIBS signature. This model includes processes involving ion chemistry, excitation, ionization, and other processes affecting the concentrations of argon and lead atoms (in 9 different electronic states) and their ions. A total of 15 chemical species and 90 reactions are included in the model. Experimental measurements of the temporal dependence of a number of lead emission lines in the LIBS plume of metallic lead have been made in argon and air. The modeling results are compared with these observations and with previous modeling of LIBS of lead in air. 相似文献