Journal: Spectrochimica Acta Part B: Atomic Spectroscopy

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66 articles found

Application of self-organizing maps to the study of U-Zr-Ti-Nb distribution in sandstone-hosted uranium ores

Author: Klus, J. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Chemometrics

DOI: 10.1016/j.sab.2017.03.008

Authors
Kaiser, J. ; Mikysek, P. ; Novotný, J. ; Novotný, K. ; Pořízka, P. ; Prochazka, D. ; Slobodník, M.

Keywords

Laser-Induced Breakdown Spectroscopy; Uranium ore; Elements distribution; Self-organizing maps;

Abstract

This paper presents a novel approach for processing the spectral information obtained from high-resolution elemental mapping performed by means of Laser-Induced Breakdown Spectroscopy. The proposed methodology is aimed at the description of possible elemental associations within a heterogeneous sample. High-resolution elemental mapping provides a large number of measurements. Moreover, typical laser-induced plasma spectrum consists of several thousands of spectral variables. Analysis of heterogeneous samples, where valuable information is hidden in a limited fraction of sample mass, requires special treatment. The sample under study is a sandstone-hosted uranium ore that shows irregular distribution of ore elements such as zirconium, titanium, uranium and niobium. Presented processing methodology shows the way to reduce the dimensionality of data and retain the spectral information by utilizing self-organizing maps (SOM). The spectral information from SOM is processed further to detect either simultaneous or isolated presence of elements. Conclusions suggested by SOM are in good agreement with geological studies of mineralization phases performed at the deposit. Even deeper investigation of the SOM results enables discrimination of interesting measurements and reveals new possibilities in the visualization of chemical mapping information. Suggested approach improves the description of elemental associations in mineral phases, which is crucial for the mining industry.

Area:

Geology ; Industry ; Mapping

Material:

Sandstone

Elements:

Lines [nm]:

Si I 251.43 nm Si I 288.16 nm

Lines [nm]:

Ti II 325.42 nm

Lines [nm]:

Fe I 358.12 nm

Lines [nm]:

Zr II 349.62 nm

Lines [nm]:

Nb II 255.14 nm

...

Emmision lines:
Si I 251.43 nm
Nb II 255.14 nm
Si I 288.16 nm
Ti II 325.42 nm
Zr II 349.62 nm
Fe I 358.12 nm
U II 409.01 nm

Combination of laser-induced breakdown spectroscopy and Raman spectroscopy for multivariate classification of bacteria

Author: Prochazka, D. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals Applications Chemometrics

DOI: 10.1016/j.sab.2017.11.004

Authors
Kaiser, J. ; Klus, J. ; Mazura, M. ; Novotný, J. ; Novotný, K. ; Pořízka, P. ; Prochazková, P. ; Rebrošová, K. ; Samek, O.

Keywords

Laser-induced breakdown spectroscopy; Raman spectroscopy; Chemometrics; Bacteria;

Abstract

In this work, we investigate the impact of data provided by complementary laser-based spectroscopic methods on multivariate classification accuracy. Discrimination and classification of five Staphylococcus bacterial strains and one strain of Escherichia coli is presented. The technique that we used for measurements is a combination of Raman spectroscopy and Laser-Induced Breakdown Spectroscopy (LIBS). Obtained spectroscopic data were then processed using Multivariate Data Analysis algorithms. Principal Components Analysis (PCA) was selected as the most suitable technique for visualization of bacterial strains data. To classify the bacterial strains, we used Neural Networks, namely a supervised version of Kohonen's self-organizing maps (SOM). We were processing results in three different ways - separately from LIBS measurements, from Raman measurements, and we also merged data from both mentioned methods. The three types of results were then compared. By applying the PCA to Raman spectroscopy data, we observed that two bacterial strains were fully distinguished from the rest of the data set. In the case of LIBS data, three bacterial strains were fully discriminated. Using a combination of data from both methods, we achieved the complete discrimination of all bacterial strains. All the data were classified with a high success rate using SOM algorithm. The most accurate classification was obtained using a combination of data from both techniques. The classification accuracy varied, depending on specific samples and techniques. As for LIBS, the classification accuracy ranged from 45% to 100%, as for Raman Spectroscopy from 50% to 100% and in case of merged data, all samples were classified correctly. Based on the results of the experiments presented in this work, we can assume that the combination of Raman spectroscopy and LIBS significantly enhances discrimination and classification accuracy of bacterial species and strains. The reason is the complementarity in obtained chemical information while using these two methods.

Area:

Health ; Instrumentation

Material:

Bacteria

Elements:

Lines [nm]:

N I 742.36 nm N I 744.23 nm N I 746.83 nm

Lines [nm]:

Na I 589.00 nm Na I 589.59 nm

Lines [nm]:

Mg II 279.55 nm Mg II 280.27 nm

Lines [nm]:

K I 766.49 nm K I 769.90 nm

Lines [nm]:

Ca II 393.37 nm Ca II 396.85 nm

...

Emmision lines:
Mg II 279.55 nm
Mg II 280.27 nm
Ca II 393.37 nm
Ca II 396.85 nm
Na I 589.00 nm
Na I 589.59 nm
H I 656.28 nm
N I 742.36 nm
N I 744.23 nm
N I 746.83 nm
K I 766.49 nm
K I 769.90 nm
O I 777.19 nm

2d distribution mapping of quantum dots injected onto filtration paper by laser-induced breakdown spectroscopy

Author: Škarková, P. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.03.016

Authors
Farka, Z. ; Hrdlička, A. ; Jebavá, A. ; Kaiser, J. ; Klus, J. ; Lubal, P. ; Novotný, K. ; Pořízka, P.

Keywords

Quantum dots; Laser-induced breakdown spectroscopy; Chemical mapping; Filtration paper; Fluorescence microscopy;

Abstract

In this study, the feasibility of Quantum dots (QDs) 2D distribution mapping on the substrate by Laser-Induced Breakdown Spectroscopy (LIBS) was examined. The major objective of this study was to describe phenomena occurring after applying aqueous solutions of QDs onto filtration paper. Especially, the influence of pH and presence of Cu2 + cations in QDs solutions on LIBS signal was investigated. Cadmium Telluride QDs (CdTe QDs) were prepared by formation of nanosized semiconductor particles in so called “one-pot” synthesis. CdTe QDs were capped by glutathione or by 3-mercaptopropionic acid. The technique described in this work allows detection of QDs injected on the selected substrate – filtration paper. Results obtained from LIBS experiments were collated with a comparative method, fluorescence microscopy, which showed variations in the distribution of QDs on the substrate surface and possibilities for quenching. Due to the immediate signal response, relatively simple instrumentation and automatization possibility, LIBS offers promising and fast alternative to other techniques, as it is able to detect also nanoparticles with no visible luminescence.

Area:

Biology ; Nanoparticles

Material:

Quantum dot

Elements:

Lines [nm]:

Cd I 508.58 nm

Emmision lines:
Cd I 508.58 nm

Improvement of the Laser-Induced Breakdown Spectroscopy method sensitivity by the usage of combination of Ag-nanoparticles and vacuum conditions

Author: Sládková, L. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2016.11.005

Authors
Čelko, L. ; Hrdlička, A. ; Kaiser, J. ; Novotný, K. ; Pořízka, P. ; Prochazka, D. ; Remešová, M. ; Škarková, P.

Keywords

Laser-Induced Breakdown Spectroscopy; Silver nanoparticles; Low pressure conditions; Sensitivity improvement;

Abstract

In this work we studied the effect of vacuum (low pressure) conditions on the behavior of laser-induced plasma (LIP) created on a sample surface covered with silver nanoparticles (Ag-NPs), i.e. Nanoparticles-Enhanced Laser-Induced Breakdown Spectroscopy (NELIBS) experiment in a vacuum. The focus was put on the step by step optimization of the measurement parameters, such as energy of the laser pulse, temporally resolved detection, ambient pressure, and different content of Ag-NPs applied on the sample surface. The measurement parameters were optimized in order to achieve the greatest enhancement represented as the signal-to-noise ratio (SNR) of NELIBS signal to the SNR of LIBS signal. The presence of NPs involved in the ablation process enhances LIP intensity; hence the improvement in the analytical sensitivity was yielded. A leaded brass standard was analyzed with the emphasis on the signal enhancement of Pb traces. We gained enhancement by a factor of four. Although the low pressure had no significant influence on the LIP signal enhancement compared to that under ambient conditions, the SNR values were noticeably improved with the implementation of the NPs.

Area:

Industry ; Nanoparticles

Material:

Leaded brass

Elements:

Lines [nm]:

Pb I 368.35 nm Pb I 405.78 nm

Emmision lines:
Pb I 368.35 nm
Pb I 405.78 nm

Analysis of carbon and nitrogen signatures with laser-induced breakdown spectroscopy; the quest for organics under Mars-like conditions

Author: Dequaire, T. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.02.015

Authors
Beck, P. ; Buch, A. ; Coll. P. ; Cousin, A. ; Gasnault, O. ; Jaber, M. ; Lasne, J. ; Maurice, S. ; Meslin, P. Y. ; Rapin, W. ; Szopa, C. P. P.

Keywords

INDUCED PLASMA SPECTROSCOPY; CHEMCAM INSTRUMENT SUITE; VACUUM-ULTRAVIOLET; QUANTITATIVE-ANALYSIS; GALE CRATER; RADIATION CONDITIONS; STEEL ANALYSIS; SURFACE; MOLECULES; ROVER

Abstract

Organic matter has been continuously delivered by meteorites and comets to Mars since its formation, and possibly formed in situ by abiogenic and/or biogenic processes, This organic matter may be preserved from the harsh oxidizing environment of Mars in specific locations. Together with water, organic molecules are necessary to the emergence of life as we know it. Since the first martian landers, scientists have been searching for organics and until today, only one positive detection has been made by a Gas Chromatography Mass Spectrometer (GCMS) instrument onboard the Curiosity rover. In this article we investigate a complementary approach to guide the search for organic matter using ChemCam, the first Laser-Induced Breakdown Spectroscopy (LIBS) instrument on Mars. This experimental study focuses on the analysis of carbon and nitrogen LIBS signatures in organoclay samples and allows the determination of the critical level (L-c) and limit of detection (LoD) of these elements with LIBS under Mars-like conditions, giving new insights into the search of organic matter on Mars. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry ; Mars

Material:

Clay ; Mineral

Elements:

Lines [nm]:

O I 777.42 nm O I 777.54 nm

Lines [nm]:

C II 723.64 nm

Lines [nm]:

N II 500.52 nm

Emmision lines:
N II 500.52 nm
C II 723.64 nm
O I 777.42 nm
O I 777.54 nm

Accuracy improvement of quantitative analysis of unburned carbon content in fly ash using laser induced breakdown spectroscopy

Author: Pan, G. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.03.001

Authors
Dong, M. R. ; Lu, J. D. ; Yu, J. H.

Keywords

Laser-induced breakdown spectroscopy; Carbon emission; Plasma temperature; Fly ash; Unburned carbon;ONLINE ANALYSIS; INDUCED PLASMAS; COAL; LIBS; SPECTROMETRY; NITROGEN; BOILER; STEEL; AIR

Abstract

Laser ablation chemical analysis of fly ash samples was studied by laser-induced breakdown spectroscopy (LIES). Ablation was performed using a 1064 nm Nd:YAG laser in air environment. The molecular emission CN was measured together with the atomic carbon (CI). The combination of atomic and molecular carbon emissions (CI and CN) was available to establish the calibration model for quantitative analysis of the unburned carbon content in fly ash. In order to further improve the measurement accuracy, the matrix effect of fly ash samples was presented and it is found that two lines of the same element in the same order could be used to characterize the plasma temperature. The influence of laser energy on plasmas temperature was studied to estimate the correction factor with the ratio of two Mg ionic lines (Mg II 279.5 nm and Mg II 280.2 nm). The results showed that the combination of carbon atomic and molecular emissions with plasmas temperature correction could improve the accuracy and precision for quantitative analysis of unburned carbon in fly ash samples. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Environment

Material:

Carbon ; Fly ash

Elements:

Lines [nm]:

Mg I 516.73 nm Mg II 279.55 nm Mg II 280.27 nm

Lines [nm]:

C I 247.86 nm C I 193.09 nm

Lines [nm]:

Fe I 388.70 nm

Emmision lines:
C I 193.09 nm
C I 247.86 nm
Mg II 279.55 nm
Mg II 280.27 nm
Fe I 388.70 nm
Mg I 516.73 nm

Quantitative analysis of metals in waste foundry sands by calibration free-laser inducedbreakdown spectroscopy

Author: Pace, D. M. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.03.007

Authors
Di Rocco, H. O. ; Garcia, F. A. ; Legnaioli, S. ; Lorenzetti, G. ; Miguel, R. E. ; Palleschi, V. ; Pardini, L.

Keywords

Laser-induced breakdown spectroscopy; LIBS; Waste sand; Plasma characterization;SELF-ABSORPTION COEFFICIENTS; INDUCED PLASMA; EMISSION-LINES; NEUTRAL ATOM; LIBS; EMPHASIS; PROFILE; ALLOYS; MATRIX

Abstract

Laser-induced breakdown spectroscopy (LIBS) was applied for quantitative analysis of the elemental composition of waste molding and core sands produced from industry as part of the casting process. To perform the analysis, waste foundry sands (WFS) were collected from metalcasting foundries and prepared in the form of solid pellets with the addition of polyvinyl alcohol as binder. The measurements were carried out using the Mobile double pulse instrument for LIBS analysis (Mod)). The spectral analysis was carried out with the calibration free approach (CF-LIBS). Metal elements commonly found in WFS including Al, Ba, Fe, Li, Mg, Mn, Pb, Ti, Zr, and Zn, were detected and quantified. The metal concentrations for WFS were compared with virgin sand to assess the influence of the casting material as well as the binders used in the foundries to reclaim the sands. The results demonstrated the feasibility of LIBS method as an alternative or complementary technique for the chemical characterization of WFS. (c) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Foundry sand

Elements:

Lines [nm]:

Ti I 334.19 nm Ti I 364.27 nm Ti I 365.35 nm Ti I 390.48 nm Ti I 398.18 nm Ti I 399.86 nm Ti I 453.48 nm Ti I 454.88 nm Ti I 498.17 nm Ti I 499.11 nm Ti I 499.95 nm Ti I 500.72 nm Ti I 501.42 nm Ti I 503.84 nm Ti II 323.90 nm Ti II 334.94 nm Ti II 336.12 nm Ti II 337.28 nm Ti II 338.38 nm Ti II 375.93 nm Ti II 376.13 nm

Lines [nm]:

Fe I 249.06 nm Fe I 302.06 nm Fe I 306.72 nm Fe I 357.01 nm Fe I 368.75 nm Fe I 374.56 nm Fe I 374.95 nm Fe I 376.38 nm Fe I 385.64 nm Fe I 385.99 nm Fe I 432.58 nm Fe I 438.35 nm Fe I 440.48 nm Fe II 235.45 nm Fe II 240.49 nm Fe II 258.59 nm Fe II 259.94 nm Fe II 261.19 nm Fe II 273.95 nm Fe II 274.93 nm

Lines [nm]:

Ca I 422.67 nm Ca I 430.77 nm Ca I 431.87 nm Ca I 445.48 nm Ca I 526.56 nm Ca I 559.45 nm Ca I 616.22 nm Ca II 315.89 nm Ca II 317.93 nm Ca I 370.54 nm Ca II 393.37 nm Ca II 396.85 nm Ca II 854.21 nm Ca II 866.21 nm

Lines [nm]:

Zr I 360.12 nm Zr I 458.23 nm Zr I 468.78 nm Zr I 471.01 nm Zr I 473.95 nm Zr I 477.23 nm Zr I 481.50 nm Zr I 482.43 nm Zr II 339.20 nm Zr II 343.82 nm Zr II 349.62 nm Zr II 357.69 nm Zr II 367.47 nm Zr II 369.82 nm

Lines [nm]:

Si I 288.16 nm Si I 243.51 nm Si I 250.69 nm Si I 251.61 nm Si I 251.92 nm Si I 252.41 nm Si I 252.85 nm Si I 263.13 nm Si I 612.50 nm Si II 413.09 nm Si II 637.14 nm

...

Emmision lines:
Fe II 235.45 nm
Fe II 240.49 nm
Si I 243.51 nm
C I 247.86 nm
Fe I 249.06 nm
Si I 250.69 nm
Si I 251.61 nm
Si I 251.92 nm
Si I 252.41 nm
Si I 252.85 nm
Mn II 257.61 nm
Fe II 258.59 nm
Fe II 259.94 nm
Fe II 261.19 nm
Si I 263.13 nm
Fe II 273.95 nm
Fe II 274.93 nm
Mg I 277.98 nm
Mg I 278.30 nm
Mg II 279.55 nm
Mg II 279.80 nm
Mg II 280.27 nm
Mg I 285.21 nm
Si I 288.16 nm
Fe I 302.06 nm
Fe I 306.72 nm
Al I 308.22 nm
Al I 309.27 nm
Ca II 315.89 nm
Ca II 317.93 nm
Ti II 323.90 nm
Zn I 330.26 nm
Ti I 334.19 nm
Ti II 334.94 nm
Ti II 336.12 nm
Ti II 337.28 nm
Ti II 338.38 nm
Zr II 339.20 nm
Zr II 343.82 nm
Zr II 349.62 nm
Fe I 357.01 nm
Zr II 357.69 nm
Al II 358.66 nm
Zr I 360.12 nm
Ti I 364.27 nm
Ti I 365.35 nm
Zr II 367.47 nm
Fe I 368.75 nm
Zr II 369.82 nm
Ca I 370.54 nm
Fe I 374.56 nm
Fe I 374.95 nm
Ti II 375.93 nm
Ti II 376.13 nm
Fe I 376.38 nm
Mg I 383.83 nm
Fe I 385.64 nm
Fe I 385.99 nm
Ti I 390.48 nm
Ca II 393.37 nm
Al I 394.40 nm
Al I 396.15 nm
Ca II 396.85 nm
Ti I 398.18 nm
Ti I 399.86 nm
Mn I 403.08 nm
Mn I 403.31 nm
Pb I 405.78 nm
Sr II 407.77 nm
Si II 413.09 nm
Ca I 422.67 nm
Ca I 430.77 nm
Ca I 431.87 nm
Fe I 432.58 nm
Fe I 438.35 nm
Fe I 440.48 nm
Ca I 445.48 nm
Ti I 453.48 nm
Ti I 454.88 nm
Ba II 455.40 nm
Zr I 458.23 nm
Sr I 460.73 nm
Zr I 468.78 nm
Zr I 471.01 nm
Zr I 473.95 nm
Zr I 477.23 nm
Zr I 481.50 nm
Zr I 482.43 nm
Sr I 486.87 nm
Sr I 489.20 nm
Ba II 493.41 nm
Ti I 498.17 nm
Ti I 499.11 nm
Ti I 499.95 nm
Ti I 500.72 nm
Ti I 501.42 nm
Ti I 503.84 nm
Mg I 516.73 nm
Mg I 518.36 nm
Ca I 526.56 nm
K I 533.97 nm
Ba I 553.55 nm
Ca I 559.45 nm
Na I 589.00 nm
Na I 589.59 nm
Si I 612.50 nm
Ba II 614.17 nm
Ca I 616.22 nm
Mg II 634.67 nm
Si II 637.14 nm
H I 656.28 nm
Li I 670.78 nm
N I 742.36 nm
N I 744.23 nm
N I 746.83 nm
K I 766.49 nm
K I 769.90 nm
O I 777.42 nm
O I 794.76 nm
N I 818.49 nm
N I 818.80 nm
Na I 819.48 nm
N I 824.24 nm
O I 844.64 nm
Ca II 854.21 nm
Ca II 866.21 nm
N I 868.61 nm

Stark width and shift for electron number density diagnostics of low temperature plasma: Application to silicon Laser Induced Breakdown Spectroscopy

Author: Lykovic, M. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals

DOI: 10.1016/j.sab.2017.03.015

Authors
Konjevic, N.

Keywords

Laser induced plasma spectroscopy; Spectroscopic plasma diagnostics; Stark broadening; Electron number density; Spectral line shapes and intensities;SINGLY IONIZED SILICON; VISIBLE SIII LINES; II SPECTRAL-LINES; EMISSION-SPECTROSCOPY; OPTICAL-EMISSION; THERMODYNAMIC-EQUILIBRIUM; BROADENING PARAMETERS; SELF-ABSORPTION; HYDROGEN-ATOMS; NEUTRAL ATOM

Abstract

In this work we summarize, analyze and critically evaluate experimental procedures and results of LIBS electron number density plasma characterization using as examples Stark broadened Si I and Si II line profiles. Selected publications are covering the time period from very beginning of silicon LIBS studies until the end of the year 2015. To perform the analysis of experimental LIBS data, the testing of available semiclassical theoretical Stark broadening parameters for Si I and Si II lines was accomplished first. This is followed by the description of experimental setups, results and details of experimental procedure relevant for the line shape analysis of spectral lines used for plasma characterization. Although most of results and conclusions of this analysis are related to the application of silicon lines for LIBS characterization they are of general importance and may be applied to other elements and different low-temperature plasma sources. The analysis of experimental procedures used for LIBS diagnostics from emission profiles of non-hydrogenic spectral lines is carried out in the following order: the influence of laser ablation and crater formation, spatial and temporal plasma observation, line self-absorption and experimental profile deconvolution, the contribution of ion broadening in comparison with electron impacts contributions to the line width in case of neutral atom line and some other aspects of line shape analysis are considered. The application of Stark shift for LIBS diagnostics is demonstrated and discussed. Finally, the recommendations for an improvement of experimental procedures for LIBS electron number density plasma characterization are offered. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Plasma diagnostics

Material:

Silicon

Elements:

Lines [nm]:

Si I 250.69 nm Si I 288.16 nm Si I 390.55 nm Si II 634.71 nm Si II 637.14 nm

Emmision lines:
Si I 250.69 nm
Si I 288.16 nm
Si I 390.55 nm
Si II 634.71 nm
Si II 637.14 nm

Application of laser-induced breakdown spectroscopy to zirconium in aqueous solution

Author: Ruas, A. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.03.014

Authors
Akaoka, K. ; Matsumoto, A. ; Ohba, H. ; Wakaida, I.

Keywords

LIBS; Solution; Zirconium; Fukushima Dai-chi decommissioning; Ultra-thin liquid jet;WATER-BASED LIQUIDS; QUANTITATIVE-ANALYSIS; METALLIC TRACES; SPECTROMETRY; SINGLE; CHROMIUM; PLASMA; SPECIATION; SODIUM; DEBRIS

Abstract

In the context of the Fukushima Dai-ichi Nuclear Power Plant (F1-NPP) decommissioning process, laser-induced breakdown spectroscopy (LIBS) has many advantages. The purpose of the present work is to demonstrate the on-line monitoring capability of the LIBS coupled with the ultra-thin liquid jet sampling method. The study focuses on zirconium in aqueous solution, considering that it is a major element in the F1-NPP fuel debris that has been subject to only a few LIBS studies in the past. The methodology of data acquisition and processing are described. In particular, two regions of interest with many high intensity zirconium lines have been observed around 350 nm in the case of the ionic lines and 478 nm in the case of atomic lines. The best analytical conditions for zirconium are different depending on the analysis of ionic lines or atomic lines. A low LOD of about 4 mg L-1 could be obtained, showing that LIBS coupled with the ultra-thin liquid jet sampling technique is a promising alternative for more complex solutions found in the F1-NPP, namely mixtures containing zirconium. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Aqueous solution

Elements:

Lines [nm]:

Zr II 339.20 nm Zr II 343.82 nm Zr II 347.94 nm Zr II 348.12 nm Zr II 349.62 nm Zr II 357.25 nm Zr II 361.31 nm Zr II 361.48 nm Zr I 468.78 nm Zr I 471.01 nm Zr I 473.95 nm Zr I 477.23 nm Zr I 481.56 nm

Lines [nm]:

H I 486.14 nm

Lines [nm]:

N I 821.63 nm

Emmision lines:
Zr II 339.20 nm
Zr II 343.82 nm
Zr II 347.94 nm
Zr II 348.12 nm
Zr II 349.62 nm
Zr II 357.25 nm
Zr II 361.31 nm
Zr II 361.48 nm
Zr I 468.78 nm
Zr I 471.01 nm
Zr I 473.95 nm
Zr I 477.23 nm
Zr I 481.56 nm
H I 486.14 nm
N I 821.63 nm

Dealloying evidence on corroded brass by laser-induced breakdown spectroscopy mapping and depth profiling measurements

Author: Cerrato, R. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2016.11.006

Authors
Casal, A. ; Mateo, M. P. ; Nicolas, G.

Keywords

Laser induced breakdown spectroscopy (LIBS); 3D chemical maps; Brass oxidation; Dealloying/dezincification;INDUCED PLASMA SPECTROMETRY; CHEMICAL MAPS; ALLOYS; DEZINCIFICATION

Abstract

The dealloying phenomenon, also called demetalification, is a; consequence of a corrosion problem found in binary alloys where an enrichment of one of the two main elements of the alloy is produced at the expense of the leaching of the other element. In the present work, the ability of laser induced breakdownspectroscopy (LIBS) for the detection and characterization of dealloying films formed on metal has been tested. For this purpose, specific areas of brass specimens have been subjected to a chemical attack of the surface in order to produce a selective leaching of zinc or dezincification. For the lateral and in-depth characterization of the dealloyed areas by LIES, depth profiles, 2D and 3D maps have been generated from the treated samples and from a reference non-treated sample. The differences in the maps and depth profiles between the corroded and non-corroded regions have allowed to reveal the localization and extension of the dealloying process along the brass sample surface and to estimate the thickness of the dezincification layers, demonstrating the capability of LIBS technique for the characterization of dealloying phenomena. (C) 2016 Published by Elsevier B.V.

Area:

Industry

Material:

Brass

Elements:

Lines [nm]:

Cu I 521.82 nm

Lines [nm]:

Zn I 481.05 nm

Emmision lines:
Zn I 481.05 nm
Cu I 521.82 nm

Surrogate measurement of chlorine concentration on steel surfaces by alkali element detection via laser-induced breakdown spectroscopy

Author: Xiao, X. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.02.011

Authors
Hartig, K. C. ; Jovanovic, I. ; Le Berre, S. ; Motta, A. T.

Keywords

Laser-induced breakdown spectroscopy; Stress corrosion cracking; Chlorine; Alkali elements;ATMOSPHERE

Abstract

Chlorine can play an important role in the process of stress corrosion cracking of dry cask storage canisters for used nuclear fuel, which are frequently located in marine environments. It is of significant interest to determine the surface concentration of chlorine on the stainless steel canister surface, but measurements are often limited by difficult access and challenging conditions, such as high temperature and high radiation fields. Laser-induced breakdown spectroscopy(LIBS) could enable chlorine concentration measurements while meeting the other constraints of this application, but suffers from high excitation energy of chlorine and the interference of the atomic emission lines of iron, thus limiting the sensitivity of detection, especially when LIBS has to be delivered over an optical fiber. We demonstrate that chlorine surface concentrations in the range of 0.5-100 mg/m(2) can be inferred by the detection and quantification of sodium contained in chlorine salts if the speciation and neutralization of salts are not of major concern, whereas minor components of sea salt such as magnesium and potassium are less attractive as surrogates for chlorine due to the lower sensitivity of LIBS for their detection and quantification. The limit of detection, measurement accuracy, and other features and limitations of this surrogate measurement approach are discussed. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Steel

Elements:

Lines [nm]:

Na I 589.00 nm Na I 589.59 nm Na I 818.33 nm Na I 819.48 nm

Lines [nm]:

Mg I 518.36 nm

Lines [nm]:

Cl I 837.59 nm

Lines [nm]:

K I 766.49 nm

Emmision lines:
Mg I 518.36 nm
Na I 589.00 nm
Na I 589.59 nm
K I 766.49 nm
Na I 818.33 nm
Na I 819.48 nm
Cl I 837.59 nm

Atomization efficiency and photon yield in laser-induced breakdown spectroscopy analysis of single nanoparticles in an optical trap

Author: Purohit, P. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.02.009

Authors
Fortes, F. J. ; Laserna, J. J.

Keywords

Laser-induced breakdown spectroscopy; LIBS; Solid aerosols; Single particle analysis; Optical catapulting; Optical trapping; Atomization efficiency; Photon yield;RADIATION PRESSURE; AEROSOL-PARTICLES; AIR-POLLUTION; BLACK CARBON; SIMULATION; LEVITATION; HEALTH; LIBS

Abstract

Laser-induced breakdown spectroscopy (LIBS) was employed for investigating the influence of particle size on the dissociation efficiency and the absolute production of photons per mass unit of airborne solid graphite spheres under single-particle regime. Particles of average diameter of 400 nm were probed and compared with 2 pm particles. Samples were first catapulted into aerosol form and then secluded in an optical trap set by a 532 nm laser. Trap stability was quantified before subjecting particles to LIBS analysis. Fine alignment of the different lines comprising the optical catapulting-optical trapping-laser-inducedbreakdown spectroscopy instrument and tuning of excitation parameters conditioning the LIBS signal such as fluence and acquisition delay are described in detail with the ultimate goal of acquiring clear spectroscopic data on masses as low as 75 fg. The atomization efficiency and the photon yield increase as the particle size becomes smaller. Time-resolved plasma imaging studies were conducted to elucidate the mechanisms leading to particle disintegration and excitation. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Environment ; Industry

Material:

Single nanoparticle

Elements:

Lines [nm]:

N II 399.50 nm

Lines [nm]:

Nb I 394.75 nm

Emmision lines:
Nb I 394.75 nm
N II 399.50 nm

Quantification of water content by laser induced breakdown spectroscopy on Mars

Author: Rapin, W. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.02.007

Authors
Beck, P. ; Bender, S. C. ; Beyssac, O. ; Cousin, A. ; Dehouck, E. ; Drouet, C. ; Forni, O. ; Gasnault, O. ; Chauvire, B. ; Laporte, D. ; Mangold, N. ; Maurice, S. ; Melikechi, N. ; Meslin, P. Y. ; Nachon, M. ; Rondeau, B. ; Schroder, S. ; Thomas, N. H. ; Wiens, R. C.

Keywords

Laser-induced breakdown spectroscopy; ChemCam; Hydrogen; Water; Hydration;CHEMCAM INSTRUMENT SUITE; GALE CRATER; OMEGA/MARS EXPRESS; CURIOSITY; HYDROGEN; CALIBRATION; ROVER; MINERALS; CHLORINE; REGOLITH

Abstract

Laser induced breakdown spectroscopy (LIBS), as performed by the ChemCam instrument, provides a new technique to measure hydrogen at the surface of Mars. Using a laboratory replica of the LIBS instrument onboard the Curiosity rover, different types of hydrated samples (basalts, calcium and magnesium sulfates, opals and apatites) covering a range of targets observed on Mars have been characterized and analyzed. A number of factors related to laserparameters, atmospheric conditions and differences in targets properties can affect the standoff LIBS signal, and in particular the hydrogen emission peak. Dedicated laboratory tests were run to identify a normalization of the hydrogen signal which could best compensate for these effects and enable the application of the laboratory calibration to Mars data. We check that the hydrogen signal increases linearly with water content; and normalization of the hydrogen emission peak using to oxygen and carbon emission peaks (related to the breakdown of atmospheric carbon dioxide) constitutes a robust approach. Moreover, the calibration curve obtained is relatively independent of the samples types. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Geology ; Mars

Material:

Water

Elements:

Lines [nm]:

O I 777.19 nm O I 777.42 nm O I 777.54 nm

Lines [nm]:

C I 247.86 nm C I 657.88 nm

Lines [nm]:

H I 656.28 nm

Emmision lines:
C I 247.86 nm
H I 656.28 nm
C I 657.88 nm
O I 777.19 nm
O I 777.42 nm
O I 777.54 nm

Measurement of Eu and Yb in aqueous solutions by underwater laser induced breakdown spectroscopy

Author: Bhatt, C. R. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.09.009

Authors
Goueguel, C. L. ; Jain, J. C. ; McIntyre, D. L. ; Singh, J. P.

Keywords

RARE-EARTH-ELEMENTS; COLLOIDS; LIQUIDS

Abstract

In this paper, we report the use of laser induced breakdown spectroscopy (LIBS) to detect dissolved Eu and Yb in bulk aqueous solutions. Ten strong emission lines of Eu and one strong emission line of Yb were identified in the underwater LIBS spectra obtained by using Czerny-Turner spectrometer within the wavelength range of 375-515 nm, Temporal evolution of plasma and the effect of laser pulse energy on the spectral emission were studied. Calibration curves using the concentration range from 500 to 10,000 ppm were developed and limits of detection for Eu and Yb were estimated to be 209 and 156 ppm, respectively. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Geology ; Industry

Material:

Aqueous solution

Elements:

Lines [nm]:

Eu II 381.97 nm Eu II 390.71 nm Eu II 393.05 nm Eu II 397.20 nm Eu II 412.97 nm Eu II 420.51 nm Eu II 443.56 nm Eu I 459.40 nm Eu I 462.72 nm Eu I 466.19 nm

Lines [nm]:

Yb I 398.80 nm

Emmision lines:
Eu II 381.97 nm
Eu II 390.71 nm
Eu II 393.05 nm
Eu II 397.20 nm
Yb I 398.80 nm
Eu II 412.97 nm
Eu II 420.51 nm
Eu II 443.56 nm
Eu I 459.40 nm
Eu I 462.72 nm
Eu I 466.19 nm

Roughness effects on the hydrogen signal in laser-induced breakdown spectroscopy

Author: Rapin, W. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.09.003

Authors
Bousquet, B. ; Cousin, A. ; Dehouck, E. ; Fabre, C. ; Forni, O. ; Frydenvang, J. ; Gasnault, O. ; Lacour, J. L. ; Lasue, J. ; Maurice, S. ; Meslin, P. Y. ; Wiens, R. C.

Keywords

LIBS; Water; Hydrogen; ChemCam; Mars; Low pressure; Roughness;CHEMCAM INSTRUMENT SUITE; QUANTITATIVE-ANALYSIS; INDUCED DESORPTION; SOLID-SURFACES; INDUCED PLASMA; LOW-PRESSURES; GALE CRATER; MARS; CONFINEMENT; IMPROVEMENT

Abstract

On Mars, Laser-Induced Breakdown Spectroscopy CUBS) as performed by the ChemCam instrument can be used to measure the hydrogen content of targets in situ, under a low pressure CO2 atmosphere. However, unexpected variations observed in the Martian dataset suggest an effect related to target roughness. Here, we present a series of laboratory experiments that reproduce the effect observed on Mars and explore possible causes. We show that the hydrogen peak intensity increases significantly with increasing exposure of the target surface to the LIBS plasma, and that these variations are specific to hydrogen, as other emission lines in the spectra are not affected. The increase of the signal could be related to an addition of hydrogen to the plasma due to interaction with the surrounding target surface, yet the exact physical process to explain such effect remains to be identified. More generally, this effect should be taken into account for the quantification of hydrogen in any LIBS applications where the roughness of the target is significant. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Mars

Material:

Aluminium ; Calcium sulfate

Elements:

Lines [nm]:

Ca II 854.21 nm Ca I 643.91 nm Ca I 644.98 nm Ca I 645.56 nm Ca II 645.69 nm Ca I 646.26 nm Ca I 647.17 nm Ca I 649.38 nm Ca I 649.97 nm

Lines [nm]:

O I 777.42 nm O I 777.54 nm

Lines [nm]:

C I 247.86 nm C II 657.81 nm

Lines [nm]:

Al II 705.66 nm Al II 706.36 nm

Lines [nm]:

H I 656.27 nm

Emmision lines:
C I 247.86 nm
Ca I 643.91 nm
Ca I 644.98 nm
Ca I 645.56 nm
Ca II 645.69 nm
Ca I 646.26 nm
Ca I 647.17 nm
Ca I 649.38 nm
Ca I 649.97 nm
H I 656.27 nm
C II 657.81 nm
Al II 705.66 nm
Al II 706.36 nm
O I 777.42 nm
O I 777.54 nm
Ca II 854.21 nm

Real-time qualitative study of forsterite crystal - Melt lithium distribution by laser-induced breakdown spectroscopy

Author: Lebedev, V. F. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.09.008

Authors
Makarchuk, P. S. ; Stepanov, D. N.

Keywords

Libs; Lithium; Forsterite; Real-time analysis;

Abstract

A factor of lithium distribution between single-crystal forsterite (Cai:Mg2SiO4) and its melt are studied by laser-induced breakdown spectroscopy. Lithium content in the crystalline phase is found to achieve a saturation at relatively low Li concentration in the melt (about 0.02%wt.). An algorithm and software are developed for real-time analysis of the studied spectra of lithium trace amounts at wide variation of the plasma radiation intensity. The analyzed plasma spectra processing method is based on the calculation of lithium emission part in the total emission of the target plasma for each recorded spectrum followed by the error estimation for the series of measurements in the normal distribution approximation. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Geology

Material:

Crystal ; Forsterite

Elements:

Lines [nm]:

Mg I 383.23 nm Mg I 517.27 nm Mg I 518.36 nm

Lines [nm]:

Li I 670.78 nm

Emmision lines:
Mg I 383.23 nm
Mg I 517.27 nm
Mg I 518.36 nm
Li I 670.78 nm

Calibration approach for extremely variable laser induced plasmas and a strategy to reduce the matrix effect in general

Author: Lazic, V. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals Applications

DOI: 10.1016/j.sab.2017.09.001

Authors
De Ninno, A.

Keywords

Laser induced breakdown spectroscopy LIBS; Plasma; Calibration; Matrix effect; Particles;INDUCED BREAKDOWN SPECTROSCOPY; ELEMENTAL ANALYSIS; QUANTITATIVE-ANALYSIS; SAMPLES; NORMALIZATION; PARAMETERS; AEROSOLS; LIBS

Abstract

The laser induced plasma spectroscopy was applied on particles attached on substrate represented by a silica wafer covered with a thin oil film. The substrate itself weakly interacts with a ns Nd:YAG laser (1064 nm) while presence of particles strongly enhances the plasma emission, here detected by a compact spectrometer array. Variations of the sample mass from one laser spot to another exceed one order of magnitude, as estimated by on-line photography and the initial image calibration for different sample loadings. Consequently, the spectral lines from particles show extreme intensity fluctuations from one sampling point to another, between the detection threshold and the detector's saturation in some cases. In such conditions the common calibration approach based on the averaged spectra, also when considering ratios of the element lines i.e. concentrations, produces errors too large for measuring the sample compositions. On the other hand, intensities of an analytical and the reference line from single shot spectra are linearly correlated. The corresponding slope depends on the concentration ratio and it is weakly sensitive to fluctuations of the plasma temperature inside the data set. A use of the slopes for constructing the calibration graphs significantly reduces the error bars but it does not eliminate the point scattering caused by the matrix effect, which is also responsible for large differences in the average plasma temperatures among the samples. Well aligned calibration points were obtained after identifying the couples of transitions less sensitive to variations of the plasma temperature, and this was achieved by simple theoretical simulations. Such selection of the analytical lines minimizes the matrix effect, and together with the chosen calibration approach, allows to measure the relative element concentrations even in highly unstable laserinduced plasmas. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Signal enhancement

Material:

Particles on surface ; Slica wafer

Elements:

Lines [nm]:

Ti II 308.80 nm Ti II 334.94 nm Ti II 336.12 nm

Lines [nm]:

O I 777.19 nm O I 777.42 nm O I 777.54 nm

Lines [nm]:

Fe I 372.26 nm Fe I 438.35 nm Fe II 259.94 nm

Lines [nm]:

Mg I 285.21 nm Mg II 266.08 nm

Lines [nm]:

Al I 309.27 nm Al I 394.40 nm

...

Emmision lines:
C I 247.86 nm
Mn II 257.61 nm
Fe II 259.94 nm
Mg II 266.08 nm
Mg I 285.21 nm
Si I 288.16 nm
Ti II 308.80 nm
Al I 309.27 nm
Cu I 324.75 nm
Ti II 334.94 nm
Ti II 336.12 nm
Fe I 372.26 nm
Al I 394.40 nm
Ca II 396.85 nm
Mn I 403.08 nm
Pb I 405.78 nm
Ca I 422.67 nm
Fe I 438.35 nm
Ba II 455.40 nm
Na I 589.59 nm
H I 656.27 nm
Li I 670.78 nm
N I 746.84 nm
K I 769.90 nm
O I 777.19 nm
O I 777.42 nm
O I 777.54 nm
Rb I 780.03 nm

On-line/on-site analysis of heavy metals in water and soils by laser induced breakdown spectroscopy

Author: Meng, D. S. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.09.011

Authors
Fang, L. ; Gu, Y. H. ; Jia, Y. ; Liu, J. G. ; Ma, M. J. ; Wang Y. Y. ; Zhao, N. J.

Keywords

Laser induced breakdown spectroscopy (LIBS); On-line analysis; Heavy metal; Enrichment; Instrument system;QUANTITATIVE-ANALYSIS; LIBS; CADMIUM; SAMPLES; LEAD

Abstract

The enrichment method of heavy metal in water with graphite and aluminum electrode was studied, and combined with plasma restraint device for improving the sensitivity of detection and reducing the limit of detection (LOD) of elements. For aluminum electrode enrichment, the LODs of Cd, Pb and Ni can be as low as several ppb. For graphite enrichment, the measurement time can be less than 3 min. The results showed that the graphite enrichment and aluminum electrode enrichment method can effectively improve the LIBS detection ability. The graphite enrichment method combined with plasma spatial confinement is more suitable for on-line monitoring of industrial waste water, the aluminum electrode enrichment method can be used for trace heavy metal detection in water. A LIBS method and device for soil heavy metals analysis was also developed, and a mobile LIBS system was tested in outfield. The measurement results deduced from LIES and ICP-MS had a good consistency. The results provided an important application support for rapid and on-site monitoring of heavy metals in soil. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Environment

Material:

Soil ; Water

Elements:

Lines [nm]:

Ni I 352.45 nm

Lines [nm]:

Cu I 324.75 nm

Lines [nm]:

Pb I 405.78 nm

Emmision lines:
Cu I 324.75 nm
Ni I 352.45 nm
Pb I 405.78 nm

Laser-induced breakdown spectra of rock powders at variable ablation and collection angles under Mars-analog conditions

Author: Breves, E. A. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Chemometrics

DOI: 10.1016/j.sab.2017.09.002

Authors
Bender, S. C. ; Boucher, T. ; Dyar, M. D. ; Lepore, K. H. ; Tokar, R. L.

Keywords

Laser-induced breakdown spectroscopy; LIBS; Variable angle; Incidence angle; Collection angle; Partial least-squares analysis; PLS;

Abstract

Laser-induced breakdown spectroscopy has become a popular tool for rapid elemental analysis of geological materials. However, quantitative applications of LIBS are plagued by variability in collected spectra that cannot be attributed to differences in geochemical composition. Even under ideal laboratory conditions, variability in LIBS spectra creates a host of difficulties for quantitative analysis. This is only exacerbated during field work, when both the laser-sample distance and the angle of ablation/collection are constantly changing. A primary goal of this study is to use empirical evidence to provide a more accurate assessment of uncertainty in LIBS-derived element predictions. We hope to provide practical guidance regarding the angles of ablation and collection that can be tolerated without substantially increasing prediction uncertainty beyond that which already exists under ideal laboratory conditions. Spectra were collected from ten geochemically diverse samples at angles of ablation and collection ranging from 0 degrees to +/- 60 degrees. Ablation and collection angles were changed independently and simultaneously in order to isolate spectral changes caused by differences in ablation angle from those due to differences in collection angle. Most of the variability in atomic and continuum spectra is attributed to changes in the ablation angle, rather than the collection angle. At higher angles, the irradiance of the laser beam is lower and produces smaller, possibly less dense plasmas. Simultaneous changes in the collection angle do not appear to affect the collected spectra, possibly because smaller plasmas are still within the viewing area of the collection optics, even though this area is reduced at higher collection angles. A key observation is that changes in the magnitude of atomic and total emission are <5% and 10%, respectively, in spectra collected with the configuration that most closely resembles field measurements (W) at angles <20 degrees. In addition, variability in atomic and continuum emission is strongly dependent upon sample composition. Denser, more Fe/Mg-rich rocks exhibited much less variability with changes in ablation and collection angles than Si-rich felsic rocks. Elemental compositions of our variable angle data that were predicted using a much larger but conventionally-collected calibration suite show that accuracy generally suffers when the incidence and collection angles are high. Prediction accuracy (for measurements acquired with varying collection and ablation angles) varies from +/- 1.28-1.86 wt% for Al2O3, +/- 1.25-1.66% wt for CaO, +/- 1.90-2.21 wt% for Fe2O3T, +/- 0.76-0.94 wt% for K2O, +/- 2.85-3.61 wt% MgO, +/- 0.15-0.17 wt% for MnO, +/- 0.68-0.78 wt% for Na2O, +/- 0.33-0.42 wt% for TiO2, and +/- 2.94-4.34 wt% SiO2. The ChemCam team is using lab data acquired under normal incidence and collection angles to predict the compositions of Mars targets at varying angles. Thus, the increased errors noted in this study for high incidence angle measurements are likely similar to additional, unacknowledged errors on ChemCam results for non-normal targets analyzed on Mars. Optimal quantitative analysis of LIBS spectra must include some knowledge of the angle of ablation and collection so the approximate increase in uncertainty introduced by a departure from normal angles can be accurately reported. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Geology ; Mars

Material:

Powder ; Rock

Elements:

Lines [nm]:

Mg II 280.27 nm Mg I 285.21 nm Mg II 279.11 nm

Lines [nm]:

Si I 288.16 nm Si II 634.71 nm

Lines [nm]:

Ca I 422.67 nm Ca II 393.37 nm

Emmision lines:
Mg II 279.11 nm
Mg II 280.27 nm
Mg I 285.21 nm
Si I 288.16 nm
Ca II 393.37 nm
Ca I 422.67 nm
Si II 634.71 nm

Practical soil analysis by laser induced breakdown spectroscopy employing subtarget supported micro mesh as a powder sample holder

Author: Suyanto, H. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.09.013

Authors
Kagawa, K. ; Kurniawan, K. H. ; Lie, T. J. ; Tija, M. O.

Keywords

Libs; Soil analysis; Practical powder sample holder; Quantitative powder analysis;ATOMIC EMISSION-SPECTROMETRY; SPECTROCHEMICAL ANALYSIS; PLASMA; LIBS; ABLATION; MATRIX; METALS; PB

Abstract

A practical alternative of sample preparation technique is proposed for direct powder analysis using laser-induced breakdown spectroscopy (LIBS) instead of the commonly adopted treatment of pelletizing the powder. The resulted pellet is known to suffer from reduced sensitivity of emission. Besides, it may also give rise to interfering effect from the binder emission. We introduce in this report a more practical technique of using a subtarget supported micro mesh (SSMM) powder sample holder. The LIBS spectrum of standard soil powder measured with 13 mJ 1064 nm Nd:YAG laser in 0.65 kPa ambient air is shown to exhibit the sharp emission lines of all the major elements in the sample. A comparison with the emission spectra measured from the pelletized powder, the spectrum obtained using the SSMM sample holder shows distinctly superior spectral quality marked by the absence of matrix effect found in pelletized powder samples, and the much stronger intensity due to the more effective shock wave plasma induced thermal excitation process produced by the hard subtarget in the sample holder. Repeating the measurement on a number of the standard soil samples of various Pb contents is shown to yield a linear calibration line with practically zero intercept and a detection limit of less than 10 ppm. We have thus demonstrated the viability of the proposed powder sample holder for the development of practical and quantitative powder analysis in the field. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Powder ; Soil

Elements:

Lines [nm]:

Ca II 393.37 nm Ca II 396.85 nm Ca I 422.67 nm

Lines [nm]:

Na I 589.00 nm Na I 589.59 nm

Lines [nm]:

Al I 394.40 nm Al I 396.15 nm

Lines [nm]:

K I 404.41 nm K I 404.72 nm

Lines [nm]:

Fe I 404.58 nm Fe I 406.36 nm

...

Emmision lines:
Si I 288.16 nm
Ca II 393.37 nm
Al I 394.40 nm
Al I 396.15 nm
Ca II 396.85 nm
K I 404.41 nm
Fe I 404.58 nm
K I 404.72 nm
Pb I 405.78 nm
Fe I 406.36 nm
Ca I 422.67 nm
Na I 589.00 nm
Na I 589.59 nm

Using laser-induced breakdown spectroscopy on vacuum alloys-production process for elements concentration analysis

Author: Zhao, T. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.09.014

Authors
Fan, Z. W. ; Li, X. ; Lian, F. Q. ; Lin, W. R. ; Liu, Y. ; Mo, Z. Q. ; Nie, S. Z. ; Wang, P. ; Xiao, H. ; Zhang, H. B. ; Zhong, Q. X.

Keywords

LIBS instrument design; Liquid steel analysis; On-line process monitoring; Vacuum alloys production; Laser-induced breakdownspectroscopy;LIBS; STEEL

Abstract

Laser-induced breakdown spectroscopy (LIBS) utilizing an echelle spectrograph-ICCD system is employed for online analysis of elements concentration in a vacuum induction melting workshop. Active temperature stabilization of echelle spectrometer is implemented specially for industrial environment applications. The measurement precision is further improved by monitoring laser parameters, such as pulse energy, spatial and temporal profiles, in real time, and post-selecting laser pulses with specific pulse energies. Experimental results show that major components of nickel-based alloys are stable, and can be well detected. By using internal standard method, calibration curves for chromium and aluminum are obtained for quantitative determination, with determination coefficient (relative standard deviation) to be 0.9559 (<22%) and 0.9723 (<2.8%), respectively. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Nickel-based alloy

Elements:

Lines [nm]:

Al I 396.15 nm

Lines [nm]:

Cr II 248.37 nm

Lines [nm]:

Ni II 230.30 nm

Emmision lines:
Ni II 230.30 nm
Cr II 248.37 nm
Al I 396.15 nm

Diagnostic study of laser-produced tungsten plasma using optical emission spectroscopy and time-of-flight mass spectroscopy

Author: Wu, D. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals

DOI: 10.1016/j.sab.2017.09.006

Authors
Ding, H. B. ; Hai, R. ; Liu, P. ; Sun L. Y. ; Zhang, L.

Keywords

Time-of-flight mass spectroscopy; Laser induced breakdown spectroscopy; Tungsten plasma; Multi-charged ions; Dynamic plasma sheath;INDUCED-BREAKDOWN-SPECTROSCOPY; ABLATION; SPECTROMETRY; LIBS

Abstract

In this work, the plasma was produced by irradiating a tungsten target with an 8 ns pulsed Nd:YAG (lambda = 1064 nm) laser in a vacuum chamber under the pressure of 4 x 10(-4) Pa. The optical and particle emissions were systematically investigated using laser induced breakdown spectroscopy and time-of-flight mass spectroscopy respectively. The results showed that not only there were neutral and single ionized atoms in the laser induced plasma, but also quite a number of multi-charged ions were observed. The ion charge state was even up to 6 at the laser power density of similar to 11 GW/cm(2). Time and space resolved optical spectroscopy was investigated by using a bundle of lined fibers. Meanwhile, the time-resolved mass spectrometric study of laser produced tungsten plasma was carried out. The variation in intensities of the different species with time showed that higher charged ions reached their peak intensities earlier. This demonstrated that the higher charged ions had higher velocities and the different charged ions were separated during the expansion process. The kinetic energy corresponding to the velocity of the ions was found to increase exponentially with ionic charge state which was related to the acceleration of the dynamic plasma sheath. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Ions analysis

Material:

Tungsten

Elements:

Lines [nm]:

W I 429.46 nm W II 434.81 nm

Emmision lines:
W I 429.46 nm
W II 434.81 nm

Magnetic field selective enhancement of Li I lines comparing Li II line in laser ablated lithium plasma at 10(-2) mbar air ambient gas

Author: Liu, P. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals

DOI: 10.1016/j.sab.2017.09.004

Authors
Ding, H. B. ; Hai, R. ; Liu, J. M. ; Sun, L. Y. ; Wu, D.

Keywords

Magnetic field; Lithium plasma; Excited state; Recombination cross-section; Libs;INDUCED BREAKDOWN SPECTROSCOPY; OPTICAL-EMISSION SPECTROSCOPY

Abstract

In this paper, the effect of magnetic field (1.1 T) on the atomic and ionic spectral emission of a laser produced lithium plasma at low pressure has been investigated. The experimental results indicate that magnetic field enhances the intensities of Li I spectral lines but reduces the Li II spectral lines intensities. In this study, two narrowband filters were placed before the ICCD camera to observe the evolution feature of Li II spectral line (548.39 nm, 2p(3)P(2,1,0)-> 2s(3)S(1)) and Li I spectral line (610.30 nm, 3d(2)P(3/2,5/2) -> 2p(2)P(1/2,3/2)), respectively. The plasma dynamic images show that with the magnetic field, the number density of luminous Li atoms is higher, while the number density of luminous Li ions is lower in comparison to the field-free case. The reduced Li II spectral intensities indicate that the quenching rate of Li ions in the excited state is greater than that without the magnetic field. The enhanced impact frequency of recombination indicates that magnetic field increases the recombination process of electron and Li ions. All of these observations strongly suggest that magnetic confinement increases the recombination process of the electrons with Li ions in the plasma, which results in the decrease in the intensity of Li II line. The results are useful for applying laser-induced breakdown spectroscopy (LIBS) to in-situ diagnose the processes of lithium wall conditioning in EAST tokamak. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Aluminium-lithium alloy

Elements:

Lines [nm]:

Li II 548.57 nm Li I 670.78 nm Li II 548.36 nm

Emmision lines:
Li II 548.36 nm
Li II 548.57 nm
Li I 670.78 nm

Portable laser-induced breakdown spectroscopy/diffuse reflectance hybrid spectrometer for analysis of inorganic pigments

Author: Siozos, P. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.09.005

Authors
Anglos, D. ; Philippidis, A.

Keywords

LIBS; Diffuse reflectance; Portable instrument; Hybrid spectrometer; Pigments;IN-SITU; CULTURAL-HERITAGE; MULTITECHNIQUE APPROACH; WALL PAINTINGS; RAMAN ANALYSIS; LIBS; FIBER; ART; IDENTIFICATION; FLUORESCENCE

Abstract

A novel, portable spectrometer, combining two analytical techniques, laser-induced breakdown spectroscopy (LIBS) and diffuse reflectance spectroscopy, was developed with the aim to provide an enhanced instrumental and methodological approach with regard to the analysis of pigments in objects of cultural heritage. Technical details about the hybrid spectrometer and its operation are presented and examples are given relevant to the analysis of paint materials. Both LIBS and diffuse reflectance spectra in the visible and part of the near infrared, corresponding to several neat mineral pigment samples, were recorded and the complementary information was used to effectively distinguish different types of pigments even if they had similar colour or elemental composition. The spectrometer was also employed in the analysis of different paints on the surface of an ancient pottery sherd demonstrating the capabilities of the proposed hybrid diagnostic approach. Despite its instrumental simplicity and compact size, the spectrometer is capable of supporting analytical campaigns relevant to archaeological, historical or art historical investigations, particularly when quick data acquisition is required in the context of surveys of large numbers of objects and samples. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Cultural heritage

Material:

Inorganic pigment

Elements:

Emmision lines:

Hydrogen isotope detection in metal matrix using double-pulse laser-induced breakdown-spectroscopy

Author: Fantoni, R. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab2016.12.008

Authors
Almaviva, S. ; Caneve, L. ; Colao, F. ; Gasior, P. ; Kubkowska, M. ; Maddaluno, G.

Keywords

LIBS; Hydrogen isotopes; Plasma-facing-components; ITER; Laser diagnostics; Fusion reactors;EMISSION; PLASMA; ENHANCEMENT; TUNGSTEN; SAMPLES; LIBS; ABLATION; SPECTRA; TRITIUM; SPARK

Abstract

The amount of hydrogen isotopes retained in plasma facing components (PFCs) and the determination of their surface layer composition are among the most critical issues for the next generation fusion device, ITER, under construction in Cadarache (France). Laser Induced Breakdown Spectroscopy (LIBS) is currently under evaluation as a technique suitable for quantitative, in situ, non-invasive measurements of these quantities. In order to detect traces of contaminant in metallic samples and improve its limit of detection (LOD), the Double Pulse LIBS (DPLIBS) variant can be used instead of the standard Single Pulse LIBS (SP-LIBS), as it has been proven by several authors that DP-LIBS can considerably raise the analytical performances of the technique. In this work Mo samples coated with a 1.5-1.8 mu m thick W-Al mixed layer, contaminated with co-deposited deuterium (D) were measured by SP- and DP-LIBS under vacuum (p similar to 5 x 10(-5) mbar), with an experimental set-up simulating conditions that can be found in a real fusion device between plasma discharges. A partial Calibration Free procedure (pCF) was applied to the LIBS data in order to retrieve the relative concentration of W and Al in the mixed layer. The amount of deuterium was then inferred by using tungsten as internal standard, accounting for the intensity ratio between the D alpha line and nearby W I lines. The results are in satisfactory agreement with those obtained from preliminary Ion Beam Analysis measurements performed immediately after the specimen's realization. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Nuclear industry

Material:

Plasma facing component ; Tokamak

Elements:

Lines [nm]:

W I 234.80 nm W I 245.65 nm W I 283.14 nm W I 293.54 nm W I 331.14 nm W I 363.19 nm W I 376.01 nm W I 400.88 nm W I 411.06 nm W I 413.75 nm W II 232.83 nm W II 276.16 nm W II 361.38 nm W II 393.54 nm

Lines [nm]:

H I 656.28 nm

Lines [nm]:

Dy I 655.80 nm

Emmision lines:
W II 232.83 nm
W I 234.80 nm
W I 245.65 nm
W II 276.16 nm
W I 283.14 nm
W I 293.54 nm
W I 331.14 nm
W II 361.38 nm
W I 363.19 nm
W I 376.01 nm
W II 393.54 nm
W I 400.88 nm
W I 411.06 nm
W I 413.75 nm
Dy I 655.80 nm
H I 656.28 nm

Spectrochemical analysis of powdered biological samples using transversely excited atmospheric carbon dioxide laser plasma excitation

Author: Zivkovic, S. M. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2016.12.009

Authors
Momcilovic, M. ; Mutic, J. ; Savovic, J. J. ; Staicu, A. ; Trtica, M.

Keywords

Laser-induced breakdown spectroscopy (LIES); Transversely excited atmospheric carbon dioxide (TEA CO2) laser; Powdered organic samples; Spirulina; Quantitative analysis;INDUCED BREAKDOWN SPECTROSCOPY; INDUCED GAS PLASMA; PLANT MATERIALS; QUANTITATIVE-ANALYSIS; LIBS; EMISSION; MICRONUTRIENTS; OPTIMIZATION; SPECTROMETRY; CO2-LASER

Abstract

The aim of this study was to develop a simple laser induced breakdown spectroscopy (LIBS) method for quantitative elemental analysis of powdered biological materials based on laboratory prepared calibration samples. The analysis was done using ungated single pulse LIBS in ambient air at atmospheric pressure. Transversely-Excited Atmospheric pressure (TEA) CO2 laser was used as an energy source for plasma generation on samples. The material used for the analysis was a blue-green alga Spirulina, widely used in food and pharmaceutical industries and also in a few biotechnological applications. To demonstrate the analytical potential of this particular LIBS system the obtained spectra were compared to the spectra obtained using a commercial LIBS system based on pulsed Nd:YAG laser. A single sample of known concentration was used to estimate detection limits for Ba, Ca, Fe, Mg, Mn, Si and Sr and compare detection power of these two LIES systems. TEA CO2 laser based LIES was also applied for quantitative analysis of the elements in powder Spirulina samples. Analytical curves for Ba, Fe, Mg, Mn and Sr were constructed using laboratory produced matrix-matched calibration samples. Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used as the reference technique for elemental quantification, and reasonably well agreement between ICP and LIBS data was obtained. Results confirm that, in respect to its sensitivity and precision, TEA CO2 laser based LIBS can be successfully applied for quantitative analysis of macro and micro-elements in algal samples. The fact that nearly all classes of materials can be prepared as powders implies that the proposed method could be easily extended to a quantitative analysis of different kinds of materials, organic, biological or inorganic. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Biology

Material:

Plant ; Spirulina

Elements:

Lines [nm]:

Fe I 404.58 nm Fe I 406.36 nm Fe I 407.17 nm Fe II 258.26 nm Fe II 258.59 nm Fe II 259.15 nm Fe II 259.84 nm Fe II 259.94 nm Fe II 260.71 nm Fe II 261.19 nm Fe II 261.38 nm Fe II 261.76 nm Fe II 262.57 nm Fe II 262.83 nm

Lines [nm]:

Mg I 277.67 nm Mg I 277.83 nm Mg I 277.98 nm Mg I 278.14 nm Mg I 278.30 nm Mg I 285.21 nm Mg II 279.08 nm Mg II 279.55 nm Mg II 279.80 nm Mg II 280.27 nm

Lines [nm]:

Si I 250.69 nm Si I 251.43 nm Si I 251.61 nm Si I 251.92 nm Si I 252.41 nm Si I 252.85 nm

Lines [nm]:

K I 404.41 nm K I 404.72 nm K I 766.49 nm K I 769.90 nm

Lines [nm]:

Mn I 403.08 nm Mn I 403.45 nm Mn I 403.31 nm Mn I 404.14 nm

...

Emmision lines:
Si I 250.69 nm
Si I 251.43 nm
Si I 251.61 nm
Si I 251.92 nm
Si I 252.41 nm
Si I 252.85 nm
P I 253.40 nm
P I 253.56 nm
Fe II 258.26 nm
Fe II 258.59 nm
Fe II 259.15 nm
Fe II 259.84 nm
Fe II 259.94 nm
Fe II 260.71 nm
Fe II 261.19 nm
Fe II 261.38 nm
Fe II 261.76 nm
Fe II 262.57 nm
Fe II 262.83 nm
Mg I 277.67 nm
Mg I 277.83 nm
Mg I 277.98 nm
Mg I 278.14 nm
Mg I 278.30 nm
Mg II 279.08 nm
Mg II 279.55 nm
Mg II 279.80 nm
Mg II 280.27 nm
C II 283.67 nm
C II 283.76 nm
Mg I 285.21 nm
Mn I 403.08 nm
Mn I 403.31 nm
Mn I 403.45 nm
Mn I 404.14 nm
K I 404.41 nm
Fe I 404.58 nm
K I 404.72 nm
Fe I 406.36 nm
Fe I 407.17 nm
Sr II 407.77 nm
Ba II 455.40 nm
Sr I 460.73 nm
Na I 589.00 nm
Na I 589.59 nm
K I 766.49 nm
K I 769.90 nm

Laser-induced breakdown spectroscopy for the quantitative analysis of metals in sediments using natural zeolite matrix

Author: Austria, E. S. J. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Chemometrics

DOI: 10.1016/j.sab.2017.07.001

Authors
Fuentes, E. M. ; Lamorena R. B. ; Nuesca, G. M.

Keywords

Laser-induced breakdown spectroscopy; Matrix-match standard; Principal component analysis; Heat-treated natural zeolite; Sediment samples;HEAVY-METALS; ELEMENTAL ANALYSIS; LIBS LIMIT; SOILS; SAMPLES; SPECTROMETRY; ALLOYS; TOOL

Abstract

The dependence of laser-induced breakdown spectroscopy (LIBS) to the matrix of the sample remains an important consideration in performing quantitative analysis. In this study, a new matrix was introduced in the preparation of solid powder calibration curves. Heat-treated natural zeolite and KBr were mixed separately into high purity metal powders to generate calibration curves using a univariate approach. A LIBS technique was used in the detection and quantitative analysis of Cr, Cu and Pb in river sediment samples. The relative percent difference (RPD) was calculated to describe the variability measurements made using ICP/OES and LIBS as well as to evaluate the accuracy of the method. Calculated limits of detection in the matrices prepared were comparable with literature values and ranged from 0.41 to 6.1 ppm. The resulting metal concentrations indicate that the natural zeolite matrix were closer to the reference values compared to the KBr matrix. By employing principal component analysis (PCA), heat treated zeolite was shown as a potential diluent or binder for generating calibration curves and could provide matrix-matched standards in identification of target metals from unknown sediment samples. The natural zeolite appeared to closely simulate the ablation behavior and property of the samples, and it is found to be a potential suitable matrix for the quantitative LIBS analysis of sediments. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Environment

Material:

River sediment

Elements:

Lines [nm]:

Fe I 246.26 nm Fe I 249.06 nm Fe I 296.69 nm Fe II 249.12 nm Fe II 259.94 nm Fe I 344.06 nm Fe I 344.10 nm Fe I 347.55 nm Fe I 349.06 nm Fe I 358.12 nm Fe I 360.89 nm Fe I 361.88 nm Fe I 367.99 nm Fe I 374.56 nm Fe I 374.83 nm Fe I 374.95 nm Fe I 375.82 nm Fe I 376.38 nm Fe I 381.58 nm Fe I 382.04 nm Fe I 385.64 nm Fe I 385.99 nm Fe I 387.86 nm Fe I 388.63 nm Fe I 404.58 nm Fe I 406.36 nm Fe I 432.58 nm Fe I 438.35 nm

Lines [nm]:

Cr I 520.60 nm

Lines [nm]:

Cu I 324.75 nm

Lines [nm]:

Pb I 405.78 nm

Emmision lines:
Fe I 246.26 nm
Fe I 249.06 nm
Fe II 249.12 nm
Fe II 259.94 nm
Fe I 296.69 nm
Cu I 324.75 nm
Fe I 344.06 nm
Fe I 344.10 nm
Fe I 347.55 nm
Fe I 349.06 nm
Fe I 358.12 nm
Fe I 360.89 nm
Fe I 361.88 nm
Fe I 367.99 nm
Fe I 374.56 nm
Fe I 374.83 nm
Fe I 374.95 nm
Fe I 375.82 nm
Fe I 376.38 nm
Fe I 381.58 nm
Fe I 382.04 nm
Fe I 385.64 nm
Fe I 385.99 nm
Fe I 387.86 nm
Fe I 388.63 nm
Fe I 404.58 nm
Pb I 405.78 nm
Fe I 406.36 nm
Fe I 432.58 nm
Fe I 438.35 nm
Cr I 520.60 nm

Spatially resolved laser-induced breakdown spectroscopy in laminar premixed methane-air flames

Author: Tian, Z. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals Applications

DOI: 10.1016/j.sab.2017.08.001

Authors
Dong, M. R. ; Li, S. S. ; Lu, J. D.

Keywords

Laminar premixed methane-air flame; Laser-induced breakdown spectroscopy; Flames structure; Radial distribution;BURNING COAL PARTICLE; POLARIZATION SPECTROSCOPY; ANALYTICAL TOOL; ATOMIC SODIUM; JET FLAME; SPECTROMETRY; OH; TEMPERATURE; SPARK; RATIO

Abstract

Laser-induced breakdown spectroscopy was evaluated for the analysis of the structure of laminar premixed methane-air flames. Firstly, breakdown threshold pulse energy and plasma energy in different areas of the flame were measured simultaneously, and an approximate linear relation between them was detected. Secondly, a new approach was proposed to qualitatively characterize the flame temperature distributions based on the plasma energy distributions. Finally, combination of the spatial analysis of the spectrum intensity, plasma energy and equivalence ratio, the laminar premixed flames structure was investigated deeply, including the distribution of the flame temperature, the width and distribution of different flame region (e.g. premixed combustion regions, high temperature regions.),as well as the location of the flame front. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Methane-air flame

Elements:

Lines [nm]:

N I 742.36 nm N I 744.23 nm N I 746.83 nm

Lines [nm]:

H I 656.27 nm

Lines [nm]:

C I 247.86 nm

Lines [nm]:

O I 777.19 nm

Emmision lines:
C I 247.86 nm
H I 656.27 nm
N I 742.36 nm
N I 744.23 nm
N I 746.83 nm
O I 777.19 nm

Sensitive elemental detection using microwave-assisted laser-induced breakdown imaging

Author: Iqbal, A. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.07.008

Authors
Alwahabi, Z. T. ; Sun, Z. W. ; Wall, M.

Keywords

Laser-induced breakdown spectroscopy (LIBS); Signal enhancement; Microwave assisted; Imaging;SPECTROSCOPY LIBS; PLASMA; ENHANCEMENT; DISCHARGE

Abstract

This study reports a sensitive spectroscopic method for quantitative elemental detection by manipulating the temporal and spatial parameters of laser-inducedplasma. The method was tested for indium detection in solid samples, in which laser ablation was used to generate a tiny plasma. The lifetime of the laser-induced plasma can be extended to hundreds of microseconds using microwave injection to remobilize the electrons. In this novel method, temporal integrated signal of indium emission was significantly enhanced. Meanwhile, the projected detectable area of the excited indium atoms was also significantly improved using an interference-, instead of diffraction-, based technique, achieved by directly imaging microwave-enhanced plasma through a novel narrow-bandpass filter, exactly centered at the indium emission line. Quantitative laser-induce breakdown spectroscopy was also recorded simultaneously with the new imaging method. The intensities recorded from both methods exhibit very good mutual linear relationship. The detection intensity was improved to 14-folds because of the combined improvements in the plasma lifetime and the area of detection. Crown Copyright (C) 2017 Published by Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Indium

Elements:

Lines [nm]:

In I 451.13 nm

Emmision lines:
In I 451.13 nm

Laser-induced breakdown spectroscopy thickness measurements of films thinner than ablation rate

Author: Nishijima, D. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.08.007

Authors
Doerner, R. P. ; Hollmann, E. M. ; Miyamoto, M.

Keywords

LIBS; Thin films; Thickness;

Abstract

A new laser-induced breakdown spectroscopy (LIES) technique is proposed to measure the thickness of films thinner than the ablation rate. The film thickness dependence of the signal intensity is used as a calibration curve. It is demonstrated that calibration curves are successfully made for thin W films and (Fe, Cr, Ni) mixed-material films produced in a magnetron sputtering device. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Magnetron produced thin film

Elements:

Lines [nm]:

Cr I 425.44 nm

Lines [nm]:

Fe I 438.35 nm

Lines [nm]:

Ni I 378.35 nm

Lines [nm]:

W I 429.46 nm

Emmision lines:
Ni I 378.35 nm
Cr I 425.44 nm
W I 429.46 nm
Fe I 438.35 nm

On the elemental analysis of different cigarette brands using laser induced breakdownspectroscopy and laser-ablation time of flight mass spectrometry

Author: Ahmed, N. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.08.006

Authors
Ahmed, R. ; Baig, M. A. ; Umar, Z. A.

Keywords

LIBS; Cigarette brands; Elemental composition; Plasma parameters; LA-TOF-mass spectrometry;TOBACCO; CRYSTAL; SAMPLES; PLASMA

Abstract

We present qualitative and quantitative analysis of the trace elements present in different brands of tobacco available in Pakistan using laser inducedbreakdown spectroscopy (LIBS) and Laser ablation Time of Flight Mass Spectrometer (LA-TOFMS). The compositional analysis using the calibration free LIBS technique is based on the observed emission spectra of the laser produced plasma plume whereas the elemental composition analysis using IA-TOFMS is based on the mass spectra of the ions produced by laser ablation. The optical emission spectra of these samples contain spectral lines of calcium, magnesium, sodium, potassium, silicon, strontium, barium, lithium and aluminum with varying intensities. The corresponding mass spectra of the elements were detected in LA-TOF-MS with their composition concentration. The analysis of different brands of cigarettes demonstrates that LIBS coupled with a LA-TOF-MS is a powerful technique for the elemental analysis of the trace elements in any solid sample. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Agriculture ; Industry

Material:

Cigarette

Elements:

Lines [nm]:

Ca I 428.94 nm Ca I 429.90 nm Ca I 431.87 nm Ca I 458.15 nm Ca I 487.81 nm Ca I 558.88 nm Ca I 559.85 nm Ca I 585.75 nm Ca I 612.22 nm Ca I 616.13 nm Ca I 644.98 nm Ca I 647.17 nm Ca I 649.38 nm Ca II 315.89 nm Ca II 317.96 nm Ca II 370.60 nm Ca II 373.69 nm Ca II 849.80 nm Ca II 854.21 nm

Lines [nm]:

Mg I 383.23 nm Mg II 280.27 nm Mg II 279.55 nm

Emmision lines:
Mg II 279.55 nm
Mg II 280.27 nm
Ca II 315.89 nm
Ca II 317.96 nm
Ca II 370.60 nm
Ca II 373.69 nm
Mg I 383.23 nm
Ca I 428.94 nm
Ca I 429.90 nm
Ca I 431.87 nm
Ca I 458.15 nm
Ca I 487.81 nm
Ca I 558.88 nm
Ca I 559.85 nm
Ca I 585.75 nm
Ca I 612.22 nm
Ca I 616.13 nm
Ca I 644.98 nm
Ca I 647.17 nm
Ca I 649.38 nm
Ca II 849.80 nm
Ca II 854.21 nm

Femtosecond laser-induced breakdown spectroscopy: Elemental imaging of thin films with high spatial resolution

Author: Ahamer, C. M. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.08.005

Authors
Huber, N. ; Pedarnig, J. D. ; Riepl, K. M.

Keywords

Femtosecond laser ablation; Laser induced breakdown spectroscopy (LIBS); Spectrochemical imaging; YBa2Cu3O7 (YBCO); Thin film;OPTICAL-EMISSION SPECTROMETRY; MASS-SPECTROMETRY; ABLATION; SURFACE; SAMPLES; LIBS; PULSES; IDENTIFICATION; METALS; DAMAGE

Abstract

We investigate femtosecond laser-induced breakdown-spectroscopy (fs-LIBS) for the spectrochemical imaging of thin films with high spatial resolution. Chemical images are obtained by recording LIBS spectra at each site of 2D raster-scans across the samples employing one fs-laser pulse per site. The diffraction images of the Echelle spectrometer are binned to reduce the read-out time of the intensified CCD detector and to increase the stability of the emission signals against peak drifts in the echellograms. For copper thin films on glass the intensities of Cu I emission lines and the size of ablation craters vary non-monotonously with the film thickness h(Cu) = 5-500 nm. The emission efficiency, defined as the Cu I line intensity per ablated volume, strongly decreases for films thicker than the optical penetration depth. The Na I line intensity from glass increases exponentially with decreasing Cu film thickness. For yttrium barium copper oxide (YBCO) thin films on MgO various atomic and molecular emission lines of the laser-induced plasma are measured (film thickness h(YBCO) = 200-1000 nm). The obtained element (Y, Ba, Cu, Mg) and molecular (Y-O) fs-LIBS images match the structure of the micro-patterned YBCO films very well. The achieved lateral resolution delta r = 6 mu m is among the best values reported for spectrochemical LIBS imaging. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Femtosecond ; Industry

Material:

Metal ; YBCO film

Elements:

Lines [nm]:

Cu I 458.70 nm Cu I 465.11 nm Cu I 510.55 nm Cu I 515.32 nm Cu I 521.82 nm Cu I 578.21 nm

Lines [nm]:

Na I 589.00 nm Na I 589.59 nm

Lines [nm]:

Mg I 517.27 nm Mg I 518.36 nm

Lines [nm]:

Ba II 455.40 nm Ba II 493.41 nm

Lines [nm]:

Mn I 482.35 nm

...

Emmision lines:
Ba II 455.40 nm
Cu I 458.70 nm
Cu I 465.11 nm
Y I 467.49 nm
Mn I 482.35 nm
Ba II 493.41 nm
Cu I 510.55 nm
Cu I 515.32 nm
Mg I 517.27 nm
Mg I 518.36 nm
Cu I 521.82 nm
Cu I 578.21 nm
Na I 589.00 nm
Na I 589.59 nm

Fast identification of steel bloom composition at a rolling mill by laser-induced breakdownspectroscopy

Author: Sturm, V. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.08.009

Authors
Eisbach, J. ; Fleige, R. ; Fricke-Begemann, C. ; Meinhardt, C.

Keywords

LIBS; Steel analysis; Material identification; Rolling mill; Production control;QUANTITATIVE-ANALYSIS; HIGH-TEMPERATURE; SAMPLES; SPECTROMETRY; LIBS

Abstract

Laser-induced breakdown spectroscopy (LIBS) is applied for the elemental analysis of steel blooms in a rolling mill. The 2-3 tons steel blooms with superficial scale are transported in a sequence on a roller table to successive processing steps. Laser ablation of the scale and the analysis of the subsurface bulk steel is carried out using the same laser in <50 s during scheduled stop times of the roller table. Up to 14 elements such as Ni, Cr, and Mo are measured for several hundreds of blooms of low and high alloy steel during routine production. The comparison of the measured with the nominal compositions, results in root mean square errors of prediction in the range of 0.01-0.2 m.-%. The rolling sequence is clearly reflected by the LIBS measurement of the individual blooms demonstrating the feasibility for material identification. Identification rates are estimated from computer simulations by permutation of the LIBS measured values and the reference values from the rolling sequence. (C) 2017 The Authors. Published by Elsevier B.V.

Area:

Industry

Material:

Steel

Elements:

Lines [nm]:

Fe II 273.07 nm Fe I 311.66 nm Fe I 328.68 nm Fe I 341.31 nm Fe I 352.13 nm

Lines [nm]:

Ni I 341.48 nm Ni I 352.45 nm

Lines [nm]:

Cr II 279.22 nm

Lines [nm]:

Cu II 212.60 nm

Lines [nm]:

Mo I 317.03 nm

Emmision lines:
Cu II 212.60 nm
Fe II 273.07 nm
Cr II 279.22 nm
Fe I 311.66 nm
Mo I 317.03 nm
Fe I 328.68 nm
Fe I 341.31 nm
Ni I 341.48 nm
Fe I 352.13 nm
Ni I 352.45 nm

Quantification of gold and silver in minerals by laser-induced breakdown spectroscopy

Author: Diaz, D. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.08.008

Authors
Hahn, D. W. ; Molina, A.

Keywords

Laser-induced breakdown spectroscopy (LIBS); Gold ore; Gold; Silver; Conditional analysis;INSTRUMENTAL NEUTRON-ACTIVATION; RAY-FLUORESCENCE ANALYSIS; LA-ICP-MS; INDUCED PLASMA; QUANTITATIVE-ANALYSIS; PRECIOUS METALS; SULFIDE ORES; SPECTROMETRY; ABLATION; PYRITE

Abstract

The performance of laser-induced breakdown spectroscopy (LIBS) to identify and quantify gold and silver in ore samples was evaluated. Ores from a gold-producing mine and samples artificially doped with Au and Ag solutions to previously defined concentrations (surrogates) were prepared as 50-mm pellets prior to LIBS analysis. Silver detection and intensity measurement was straightforward for concentrations from 0.4 to 43 mu g/g and from 1.1 to 375 mu/g in ore and surrogate samples, respectively. Au emission lines were not found after ensemble averageor accumulation of 100-single shot LIBS spectra of ore samples containing up to 9.5 mu/g Au. However, the Au signal was present in the spectra of surrogate samples, for which a detection limit of about 0.8 mu g/g was determined. When the number of sampling shots in ore samples increased, various single shot spectra registered Au emission lines. The number of spectra containing Au emission lines increased with the number of single shots. Those results, as well as scanning electron microscopy analysis of ore samples, suggest that the discrete analyte distribution as well as the inherent discrete characteristics associated to LIBS made the presence of gold in the LIBS spark an unlikely occurrence. The particle sampling rates (the percentage of laser pulses expected to sample at least one particle) were estimated for gold concentrations of 1.1 and 10.0 mu/g as 0.04% and 0.32%, respectively. A Monte Carlo simulation indicated that >100 gold-containing particles should be sampled to accurately represent the discrete character of gold in the ore. Sampling 100 such particles requires >10(5) laser pulses over a single pellet. Despite the fact that this rather large number of shots makes difficult to conduct conditional analysis on pellets, for some samples that withstood 5000 shots, gold quantification in ores was successfully achieved at concentrations as low as 1 mu/g. Results are encouraging and illustrate the applicability of LIBS to gold and silver in field semi-quantitative analysis. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Geology

Material:

Ore

Elements:

Lines [nm]:

Au I 267.60 nm Au I 274.83 nm Au I 280.09 nm Au I 312.28 nm Au II 401.61 nm

Lines [nm]:

Ag I 328.07 nm Ag II 258.06 nm Ag II 276.75 nm Ag II 318.07 nm Ag II 318.39 nm

Lines [nm]:

Cu I 324.75 nm Cu I 327.40 nm

Emmision lines:
Ag II 258.06 nm
Au I 267.60 nm
Au I 274.83 nm
Ag II 276.75 nm
Au I 280.09 nm
Au I 312.28 nm
Ag II 318.07 nm
Ag II 318.39 nm
Cu I 324.75 nm
Cu I 327.40 nm
Ag I 328.07 nm
Au II 401.61 nm

Quantification of trace metals in infant formula premixes using laser-induced breakdown spectroscopy

Author: Cama-Moncunill, R. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Chemometrics

DOI: 10.1016/j.sab.2017.06.014

Authors
Cama-Moncunill, X. ; Casado-Gavalda, M. P. ; Cullen, P. J. ; Dixit, Y. ; Markiewicz-Keszycka, M. ; Sullivan, C.

Keywords

LIBS; Trace-element premixes; Univariate analysis; Multivariate analysis; PLS;SPECTROCHEMICAL ANALYSIS; LIBS; ADULTERATION; COPPER; MILK; BEEF

Abstract

Infant formula is a human milk substitute generally based upon fortified cow milk components. In order to mimic the composition of breast milk, trace elements such as copper, iron and zinc are usually added in a single operation using a premix. The correct-addition of premixes must be verified to ensure that the target levels in infant formulae are achieved. In this study, a laser-induced breakdown spectroscopy (LIBS) system was assessed as a fast validation tool for trace element premixes. LIBS is a promising emission spectroscopic technique for elemental analysis, which offers real-time analyses, little to no sample preparation and ease of use. LIBS was employed for copper and iron determinations of premix samples ranging approximately from 0 to 120 mg/kg Cu/1640 mg/kg Fe. LIES spectra are affected by several parameters, hindering subsequent quantitative analyses. This work aimed at testing three matrix-matched calibration approaches (simple-linear regression, multi-linear regression and partial least squares regression (PLS)) as means for precision and accuracy enhancement of LIBS quantitative analysis. All calibration models were first developed using a training set and then validated with an independent test set. PLS yielded the best results. For instance, the PLS model for copper provided a coefficient of determination (R-2) of 0.995 and a root mean square error of prediction (RMSEP) of 14 mg/kg. Furthermore, LIBS was employed to penetrate through the samples by repetitively measuring the same spot. Consequently, LIBS spectra can be obtained as a function of sample layers. This information was used to explore whether measuring deeper into the sample could reduce possible surface-contaminant effects and provide better quantifications. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry ; Nutrition

Material:

Infant formula

Elements:

Lines [nm]:

Fe I 438.35 nm Fe II 259.94 nm Fe I 358.12 nm Fe I 373.49 nm Fe I 430.79 nm Fe I 432.58 nm

Lines [nm]:

N I 746.83 nm N I 818.49 nm N I 821.63 nm N I 868.03 nm

Lines [nm]:

O I 777.19 nm O I 777.19 nm O I 844.64 nm

Lines [nm]:

Ca I 422.67 nm Ca I 616.22 nm Ca II 393.37 nm

Lines [nm]:

Cu I 324.75 nm Cu I 327.40 nm

...

Emmision lines:
C I 247.86 nm
Fe II 259.94 nm
Cu I 324.75 nm
Cu I 327.40 nm
Fe I 358.12 nm
Fe I 373.49 nm
Ca II 393.37 nm
Ca I 422.67 nm
Fe I 430.79 nm
Fe I 432.58 nm
Fe I 438.35 nm
Na I 589.00 nm
Ca I 616.22 nm
H I 656.27 nm
N I 746.83 nm
K I 766.49 nm
O I 777.19 nm
O I 777.19 nm
N I 818.49 nm
N I 821.63 nm
O I 844.64 nm
N I 868.03 nm

Potential of Laser Induced Breakdown Spectroscopy for analyzing the quality of unroasted and ground coffee

Author: Silva, T. V. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Chemometrics

DOI: 10.1016/j.sab.2017.06.015

Authors
Ferreira, E. C. ; Ferreira, E. J. ; Hubinger, S. Z. ; Milori, D. M. B. P. ; Neto, J. A. G.

Keywords

Coffee global quality; BGS; Classes discrimination; NIRS; LIBS;NEAR-INFRARED SPECTROSCOPY; MARKER COMPOUNDS; CUP QUALITY; BEANS; DEFECTS

Abstract

Coffee is an important commodity and a very popular beverage around the world. Its economic value as well as beverage quality are strongly dependent of the quality of beans. The presence of defective beans in coffee blends has caused a negative impact on the beverage Global Quality (GQ) assessed by cupping tests. The main defective beans observed in the productive chain has been those Blacks, Greens and Sours (BGS). Chemical composition of BGS has a damaging impact on beverage GQ That is why analytical tools are needed for monitoring and controlling the GQ in coffee agro-industry. Near Infrared Spectroscopy (NIRS) has been successfully applied for assessment of coffee quality. Another potential technique for direct, clean and fast measurement of coffee GQ is Laser Induced Breakdown Spectroscopy (LIBS). Elements and diatomic molecules commonly present in organic compounds (structure) can be assessed by using LIBS. In this article is reported an evaluation of LIBS for the main interferents of GQ (BGS defects). Results confirm the great potential of LIBS for discriminating good beans from those with BGS defects by using emission lines of C, CN, C-2 and N. Most importantly, some emission lines presented strong linear correlation (r > 0.9) with NIRS absorption bands assigned to proteins, lipids, sugar and carboxylic adds, suggesting LIBS potential to estimate these compounds in unroasted and ground coffee samples. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Agriculture

Material:

Coffee

Elements:

Lines [nm]:

N I 742.36 nm N I 744.23 nm N I 746.83 nm

Lines [nm]:

H I 656.27 nm

Lines [nm]:

C I 193.09 nm

Lines [nm]:

O I 777.42 nm

Emmision lines:
C I 193.09 nm
H I 656.27 nm
N I 742.36 nm
N I 744.23 nm
N I 746.83 nm
O I 777.42 nm

Impact of oxygen chemistry on the emission and fluorescence spectroscopy of laser ablation plumes

Author: Hartig, K. C. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals

DOI: 10.1016/j.sab.2017.07.002

Authors
Brumfield, B. E. ; Harilal, S. S. ; Phillips, M. C.

Keywords

Laser ablation (LA); Laser induced fluorescence (LIF); Laser-induced breakdown spectroscopy (UBS); Plasma chemistry; Combustion;INDUCED BREAKDOWN SPECTROSCOPY; EXCITED ATOMIC FLUORESCENCE; INDUCED ALUMINUM PLASMA; SELECTIVE EXCITATION; URANIUM; ALO; SOLIDS; SPECTROMETRY; EVOLUTION; DYNAMICS

Abstract

Oxygen present in the ambient gas medium may affect both laser-induced breakdown spectroscopy (LIBS) and laser-induced fluorescence (LIF) emission through a reduction of emission intensity and persistence. In this study, an evaluation is made on the role of oxygen in the ambient environment under atmospheric pressure conditions in LIBS and laser ablation (LA)-LIF emission. To generate plasmas, 1064 nm, 10 ns pulses were focused on an aluminum alloy sample. LIF was performed by frequency scanning a CW laser over the 396.15 nm (3s(2)4s S-2(1/2) -> 3s(2)3p P-2 degrees(3/2)) Al I transition. Time-resolved emission and fluorescence signals were recorded to evaluate the variation in emission intensity caused by the presence of oxygen. The oxygen partial pressure (p(o)) in the atmospheric pressure environment using N-2 as the makeup gas was varied from 0 to 400 Torr O-2. 2D-fluorescence spectroscopy images were obtained for various oxygen concentrations for simultaneous evaluation of the emission and excitation spectral features. Results showed that the presence of oxygen in the ambient environment reduces the persistence of the LIBS and LIF emission through an oxidation process that depletes the density of atomic species within the resulting laser-produced plasma (LPP) plume. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Chemistry

Material:

Alloy ; Aluminium

Elements:

Lines [nm]:

Al I 394.40 nm Al I 396.15 nm

Emmision lines:
Al I 394.40 nm
Al I 396.15 nm

Classification of wines according to their production regions with the contained trace elements using laser-induced breakdown spectroscopy

Author: Tian, Y. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Chemometrics

DOI: 10.1016/j.sab.2017.07.003

Authors
Bernard, J. ; Bockova, J. ; Delepine-Gilon, N. ; Chen, L. ; Chen, Y. P. ; Li, H. ; Martin, S. ; Tang, H. S. ; Veis, P. ; Yan, C. H. ; Yu, J. ; Yu, J. L. ; Zhang, T. L.

Keywords

Wines; LIBS; Classification; Principal component analysis; Random forest; Matrix effect;LIQUID-LIQUID MICROEXTRACTION; ICP-MS; GEOGRAPHICAL ORIGIN; PROTECTED DESIGNATION; MULTIELEMENT ANALYSIS; SINGLE-PULSE; IDENTIFICATION; SAMPLES; LIBS; METALS

Abstract

Laser-induced breakdown spectroscopy (LIBS) has been applied to classify French wines according to their production regions. The use of the surface-assisted (or surface-enhanced) sample preparation method enabled a sub-ppm limit of detection (LOD), which led to the detection and identification of at least 22 metal and nonmetal elements in a typical wine sample including majors, minors and traces. An ensemble of 29 bottles of French wines, either red or white wines, from five production regions, Alsace, Bourgogne, Beaujolais, Bordeaux and Languedoc, was analyzed together with a wine from California, considered as an outlier. A non-supervised classification model based on principal component analysis (PCA) was first developed for the classification. The results showed a limited separation power of the model, which however allowed, in a step by step approach, to understand the physical reasons behind each step of sample separation and especially to observe the influence of the matrix effect in the sample classification. A supervised classification model was then developed based on random forest (RF), which is in addition a nonlinear algorithm. The obtained classification results were satisfactory with, when the parameters of the model were optimized, a classification accuracy of 100% for the tested samples. We especially discuss in the paper, the effect of spectrum normalization with an internal reference, the choice of input variables for the classification models and the optimization of parameters for the developed classification models. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Agriculture

Material:

Wine

Elements:

Lines [nm]:

Si I 250.69 nm Si I 251.43 nm Si I 251.61 nm Si I 251.92 nm Si I 252.41 nm Si I 252.85 nm Si I 288.16 nm

Lines [nm]:

Fe I 248.33 nm Fe I 249.06 nm Fe I 249.12 nm Fe I 252.33 nm Fe I 344.06 nm

Lines [nm]:

P I 253.40 nm P I 253.56 nm P I 255.33 nm P I 255.49 nm

Lines [nm]:

B I 249.68 nm B I 249.77 nm

Lines [nm]:

Mg I 518.36 nm Mg II 279.55 nm

...

Emmision lines:
Fe I 248.33 nm
Fe I 249.06 nm
Fe I 249.12 nm
B I 249.68 nm
B I 249.77 nm
Si I 250.69 nm
Si I 251.43 nm
Si I 251.61 nm
Si I 251.92 nm
Fe I 252.33 nm
Si I 252.41 nm
Si I 252.85 nm
P I 253.40 nm
P I 253.56 nm
P I 255.33 nm
P I 255.49 nm
Mn II 259.37 nm
Mg II 279.55 nm
Si I 288.16 nm
Ca II 317.93 nm
Zn I 334.50 nm
Ti II 334.94 nm
Fe I 344.06 nm
Ca I 445.48 nm
Ba II 455.40 nm
Sr I 460.73 nm
Mg I 518.36 nm
Na I 589.59 nm
Li I 670.78 nm
K I 766.49 nm
Rb I 780.03 nm

Quantitative methods for compensation of matrix effects and self-absorption in Laser InducedBreakdown Spectroscopy signals of solids

Author: Takahashi, T. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals Applications Chemometrics Review

DOI: 10.1016/j.sab.2017.09.010

Authors
Thornton, B.

Keywords

Laser induced breakdown spectroscopy (LIBS); Quantitative analysis; Matrix effect; Self-absorption;INDUCED PLASMA SPECTROSCOPY; ARTIFICIAL NEURAL-NETWORK; LEAST-SQUARES REGRESSION; ELEMENTAL ANALYSIS; MULTIVARIATE-ANALYSIS; EMISSION-SPECTROSCOPY; SPECTRAL-LINE; SOIL SAMPLES; IRON-ORE; CHEMCAM INSTRUMENT

Abstract

This paper reviews methods to compensate for matrix effects and self-absorption during quantitative analysis of compositions of solids measured using LaserInduced Breakdown Spectroscopy (LIBS) and their applications to in-situ analysis. Methods to reduce matrix and self-absorption effects on calibration curves are first introduced. The conditions where calibration curves are applicable to quantification of compositions of solid samples and their limitations are discussed. While calibration-free LIBS (CF-LIBS), which corrects matrix effects theoretically based on the Boltzmann distribution law and Saha equation, has been applied in a number of studies, requirements need to be satisfied for the calculation of chemical compositions to be valid. Also, peaks of all elements contained in the target need to be detected, which is a bottleneck for in-situ analysis of unknown materials. Multivariate analysis techniques are gaining momentum in LIBS analysis. Among the available techniques, principal component regression (PCR) analysis and partial least squares (PLS) regression analysis, which can extract related information to compositions from all spectral data, are widely established methods and have been applied to various fields including in-situ applications in air and for planetary explorations. Artificial neural networks (ANNs), where non-linear effects can be modelled, have also been investigated as a quantitative method and their applications are introduced. The ability to make quantitative estimates based on LIBS signals is seen as a key element for the technique to gain wider acceptance as an analytical method, especially in in-situ applications. In order to accelerate this process, it is recommended that the accuracy should be described using common figures of merit which express the overall normalised accuracy, such as the normalised root mean square errors (NRMSEs), when comparing the accuracy obtained from different setups and analytical methods. (C) 2017 The Authors. Published by Elsevier B.V.

Area:

Matrix effect

Material:

Solid sample

Elements:

Emmision lines:

Correlating laser-induced breakdown spectroscopy with neutron activation analysis to determine the elemental concentration in the ionome of the Populus trichocarpa leaf

Author: Martin, M. Z. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Chemometrics

DOI: 10.1016/j.sab.2017.10.008

Authors
Engle, N. L. ; Glasgow, D. C. ; Gunter, L. E. ; Tschaplinski, T. J. ; Tuskan, G. A. ; Weston, D. J. ; Wymore, A. M.

Keywords

MULTIVARIATE-ANALYSIS; WOOD

Abstract

The black cottonwood poplar (Populus trichocarpa) leaf ionome (inorganic trace elements and mineral nutrients) is an important aspect for determining the physiological and developmental processes contributing to biomass production. A number of techniques are used to measure the ionome, yet characterizing the leaf spatial heterogeneity remains a challenge, especially in solid samples. Laser-induced breakdown spectroscopy (LIBS) has been used to determine the elemental composition of leaves and is able to raster across solid matrixes at 10 pm resolution. Here, we evaluate the use of LIBS for solid sample leaf elemental characterization in relation to neutron activation. In fact, neutron activation analysis is a laboratory-based technique which is used by the National Institute of Standards and Technology (NIST) to certify trace elements in candidate reference materials including plant leaf matrices. Introduction to the techniques used in this research has been presented in this manuscript Neutron activation analysis (NAA) data has been correlated to the LIBS spectra to achieve quantification of the elements or ions present within poplar leaves. The regression coefficients of calibration and validation using multivariate analysis (MVA) methodology for six out of seven elements have been determined and vary between 0.810 and 0.998. LIBS and NM data has been presented for the elements such as, calcium, magnesium, manganese, aluminum, copper, and potassium. Chlorine was also detected but it did not show good correlation between the LIBS and NAA techniques. This research shows that LIBS can be used as a fast, high-spatial resolution technique to quantify elements as part of large-scale field phenotyping projects. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Biology

Material:

Leaves

Elements:

Lines [nm]:

Pd I 340.46 nm Pd I 342.12 nm Pd I 348.12 nm Pd I 351.69 nm

Emmision lines:
Pd I 340.46 nm
Pd I 342.12 nm
Pd I 348.12 nm
Pd I 351.69 nm

Detection and correction of laser induced breakdown spectroscopy spectral background based on spline interpolation method

Author: Tan, B. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals

DOI: 10.1016/j.sab.2017.10.012

Authors
Guo, Y. ; Huang, M. ; Qin, J. W. ; Zhu, Q. B.

Keywords

LIBS; Continuous background; Interpolation method; Quantitative;MODEL-FREE ALGORITHM; QUANTITATIVE-ANALYSIS; TRACE-ELEMENTS; CU; REGRESSION; SAMPLES; METALS; LIBS

Abstract

Laser-induced breakdown spectroscopy (LIBS) is an analytical technique that has gained increasing attention because of many applications. The production of continuous background in LIES is inevitable because of factors associated with laser energy, gate width, time delay, and experimental environment. The continuous background significantly influences the analysis of the spectrum. Researchers have proposed several background correction methods, such as polynomial fitting, Lorenz fitting and model-free methods. However, less of them apply these methods in the field of LIBS Technology, particularly in qualitative and quantitative analyses. This study proposes a method based on spline interpolation for detecting and estimating the continuous background spectrum according to its smooth property characteristic. Experiment on the background correction simulation indicated that, the spline interpolation method acquired the largest signal-to-background ratio (SBR) over polynomial fitting, Lorenz fitting and model-free method after background correction. These background correction methods all acquire larger SBR values than that acquired before background correction (The SBR value before background correction is 10.0992, whereas the SBR values after background correction by spline interpolation, polynomial fitting, Lorentz fitting, and model-free methods are 26.9576, 24.6828,18.9770, and 25.6273 respectively). After adding random noise with different kinds of signal-to-noise ratio to the spectrum, spline interpolation method acquires large SBR value, whereas polynomial fitting and model-free method obtain low SBR values. All of the background correction methods exhibit improved quantitative results of Cu than those acquired before background correction (The linear correlation coefficient value before background correction is 0.9776. Moreover, the linear correlation coefficient values after background correction using spline interpolation, polynomial fitting, Lorentz fitting, and model-free methods are 0.9998, 0.9915, 0.9895, and 0.9940 respectively). The proposed spline interpolation method exhibits better linear correlation and smaller error in the results of the quantitative analysis of Cu compared with polynomial fitting, Lorentz fitting and model-free methods, The simulation and quantitative experimental results show that the spline interpolation method can effectively detect and correct the continuous background. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Background correction ; Spline

Material:

Copper ; Iron

Elements:

Lines [nm]:

Cu I 324.75 nm Cu I 327.40 nm

Emmision lines:
Cu I 324.75 nm
Cu I 327.40 nm

A novel baseline correction method using convex optimization framework in laser-inducedbreakdown spectroscopy quantitative analysis

Author: Yi, C. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals Applications

DOI: 10.1016/j.sab.2017.10.014

Authors
Ke, K. ; Lv, Y. ; Xiao, H. ; Yu, X.

Keywords

Laser-induced breakdown spectroscopy; Baseline correction; Asymmetric penalty; Convex optimization;PARTIAL LEAST-SQUARES; WAVELET-TRANSFORM; MODEL; LIBS; COAL

Abstract

For laser-induced breakdown spectroscopy (LIBS) quantitative analysis technique, baseline correction is an essential part for the LIBS data preprocessing. As the widely existing cases, the phenomenon of baseline drift is generated by the fluctuation of laser energy, inhomogeneity of sample surfaces and the background noise, which has aroused the interest of many researchers. Most of the prevalent algorithms usually need to preset some key parameters, such as the suitable spline function and the fitting order, thus do not have adaptability. Based on the characteristics of LIBS, such as the sparsity of spectral peaks and the low-pass filtered feature of baseline, a novel baseline correction and spectral data denoising method is studied in this paper. The improved technology utilizes convex optimization scheme to form a non-parametric baseline correction model. Meanwhile, asymmetric punish function is conducted to enhance signal-noise ratio (SNR) of the LIBS signal and improve reconstruction precision. Furthermore, an efficient iterative algorithm is applied to the optimization process, so as to ensure the convergence of this algorithm. To validate the proposed method, the concentration analysis of Chromium (Cr),Manganese (Mn) and Nickel (Ni) contained in 23 certified high alloy steel samples is assessed by using quantitative models with Partial Least Squares (PLS) and Support Vector Machine (SVM). Because there is no prior knowledge of sample composition and mathematical hypothesis, compared with other methods, the method proposed in this paper has better accuracy in quantitative analysis, and fully reflects its adaptive ability. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Background correction

Material:

Steel

Elements:

Lines [nm]:

Cr I 278.06 nm Cr I 305.39 nm Cr I 363.96 nm Cr I 388.33 nm Cr I 435.96 nm Cr I 454.60 nm Cr I 460.06 nm Cr I 465.46 nm Cr I 480.10 nm Cr I 526.19 nm Cr I 529.67 nm

Emmision lines:
Cr I 278.06 nm
Cr I 305.39 nm
Cr I 363.96 nm
Cr I 388.33 nm
Cr I 435.96 nm
Cr I 454.60 nm
Cr I 460.06 nm
Cr I 465.46 nm
Cr I 480.10 nm
Cr I 526.19 nm
Cr I 529.67 nm

Anomalous broadening and shift of emission lines in a femtosecond laser plasma filament in air

Author: Ilyin, A. A. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals

DOI: 10.1016/j.sab.2017.10.010

Authors
Golik, S. S. ; Mayor, A. Y. ; Proschenko, D. Y. ; Shmirko, K. A.

Keywords

Filament; AC Stark effect; Rabi sideband; Line broadening; Amplified spontaneous emission;INDUCED BREAKDOWN SPECTROSCOPY; SPECTRAL-LINES; RADIATION; SYSTEM

Abstract

he temporal evolution of the width and shift of NI746.8 and OI777.4 nm lines is investigated in a filament plasma produced by a tightly focused femtosecond laser pulse (0.9 mJ, 48 fs). The nitrogen line shift and width are determined by the joint action of electron impact shift and the far-off resonance AC Stark effect. The intensive (I = 1.2.10(10) W/cm(2)) electric field of ASE (amplified spontaneous emission) and post-pulses result in a possible LS coupling break for the OI3p P-5 level and the generation of Rabi sidebands. The blueshifted main femtosecond pulse and Rabi sideband cause the stimulated emission of the N-2 1(+) system. The maximal widths of emission lines are approximately 6.7 times larger than the calculated Stark widths. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Anomalous broadening ; Plasma diagnostics

Material:

Air ; Nitrogen ; Oxygen

Elements:

Lines [nm]:

N I 742.36 nm N I 744.23 nm N I 746.83 nm

Lines [nm]:

O I 777.42 nm O I 777.19 nm O I 777.54 nm

Emmision lines:
N I 742.36 nm
N I 744.23 nm
N I 746.83 nm
O I 777.19 nm
O I 777.42 nm
O I 777.54 nm

Phase discrimination of uranium oxides using laser-induced breakdown spectroscopy

Author: Campbell, K. R. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Chemometrics

DOI: 10.1016/j.sab.2017.05.007

Authors
Barefield, J. E. ; Clegg, S. M. ; Colgan, J. P. ; Czerwinski, K. R. L. ; Judge, E. J. ; Kilcrease, D. P. ; Wilkerson, M. P. ; Wozniak, N. R.

Keywords

Laser-induced breakdown spectroscopy; Uranium; Phase identification;EMISSION; FEMTOSECOND; STRENGTHS; SPECTRA; PLASMA; LIBS

Abstract

Nuclear forensics goals for characterizing samples of interest include qualitative and quantitative analysis of major and trace elements, isotopic analysis, phase identification, and physical analysis. These samples may include uranium oxides UO2, U3O8, and UO3, which play an important role in the front end of the nuclear fuel cycle, from mining to fuel fabrication. The focus of this study is to compare the ratios of the intensities of uranium and oxygen emission lines which can be used to distinguish between different uranium oxide materials using Laser-Induced Breakdown Spectroscopy (LIBS). Measurements at varying laser powers were made under an argon atmosphere at 585 Torr to ensure the oxygen emission intensity was originating from the sample, and not from the atmosphere. Fifteen uranium emission lines were used to compare experimental results with theoretical calculations in order to determine the plasma conditions. Using a laser energy of 26 mJ, the uranium lines 591.539 and 682.692 nm provide the highest degree of discrimination between the uranium oxides. The study presented here suggests that LIBS is useful for discriminating uranium oxide phases, UO2, U3O8, and UO3. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Nuclear industry

Material:

Uranium oxide

Elements:

Lines [nm]:

U II 409.01 nm U II 417.16 nm U II 424.17 nm U II 424.44 nm U I 424.63 nm U II 434.17 nm U I 435.57 nm U II 454.36 nm U I 455.20 nm U I 462.02 nm U II 462.71 nm U I 463.16 nm U I 591.54 nm U I 639.54 nm U I 682.69 nm

Lines [nm]:

O I 777.19 nm O I 777.42 nm O I 777.54 nm

Emmision lines:
U II 409.01 nm
U II 417.16 nm
U II 424.17 nm
U II 424.44 nm
U I 424.63 nm
U II 434.17 nm
U I 435.57 nm
U II 454.36 nm
U I 455.20 nm
U I 462.02 nm
U II 462.71 nm
U I 463.16 nm
U I 591.54 nm
U I 639.54 nm
U I 682.69 nm
O I 777.19 nm
O I 777.42 nm
O I 777.54 nm

Laser Induced Breakdown Spectroscopy compared with conventional plasma optical emission techniques for the analysis of metals - A review of applications and analytical performance

Author: Bengston, A. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Review

DOI: 10.1016/j.sab.2017.05.006

Authors

Keywords

DEPTH-PROFILE ANALYSIS; VACUUM-ULTRAVIOLET; SURFACE-ANALYSIS; STEEL ANALYSIS; DISCHARGE; SPECTROMETRY; ABLATION; SAMPLES; LIBS; QUANTIFICATION

Abstract

This review is focused on a comparison of LIBS with the two most common plasma Optical Emission Spectroscopy (OES) techniques for analysis of metals; spark OES and glow discharge (GD) OES. It is shown that these two techniques have only minor differences in analytical performance. An important part of the paper reviews a direct comparison of the analytical figures of merit for bulk analysis of steels using spark and LIBS sources. The comparison was carried out using one instrument with interchangeable sources, eliminating differences related to the optical system and detectors. It was found that the spark provides slightly better analytical figures of merit. The spark analysis is considerably faster, the simple design of the spark stand has enabled complete automation, both properties of great importance in the metallurgical industry for routine analysis. The analysis of non-metallic inclusions (NMI) with spark and LIBS is presented, in the case of the spark this has become known as Pulse Distribution Analysis (FDA). A very significant difference between the techniques is that the electrical spark typically evaporates similar to 100 times more material than a single laser pulse, resulting in complete evaporation of an NMI present in the evaporated metal. The major advantage of LIBS is that it is localised with very good lateral resolution. The major advantages of spark is that it is much faster (can be done simultaneous with the bulk analysis) and easier to quantify. Compositional Depth Profiling (CDP) is compared for GD-OES and LIBS. It is shown that for applications where GD-OES is well suited, e.g. coated metallic sheet, GD-OES still performs slightly better than LIBS. Similar to the case of NMI analysis, the major advantage of LIBS is the great lateral resolution. This allows elemental surface mapping, as well as CDP of very small areas on pm scale. One further advantage of LIBS is that samples of almost any material, shape and size can be analysed, whereas GD-OES has only limited capabilities for non-flat and small samples. A general conclusion of this review is that LIBS is not likely to replace spark and GD-OES in the foreseeable future, for applications where these techniques are well suited. On the other hand several new applications, particularly in the field of on-line monitoring of industrial processes, are making great inroads for LIBS in the metallurgical and manufacturing industries. (C) 2017 Elsevier B.V. All rights reserved.

Area:

All themes

Material:

Metal

Elements:

Lines [nm]:

Fe II 180.77 nm Fe I 281.33 nm

Lines [nm]:

Al I 396.15 nm

Lines [nm]:

P I 178.28 nm

Lines [nm]:

S I 180.73 nm

Lines [nm]:

Cr I 175.13 nm

...

Emmision lines:
Co II 175.00 nm
Cr I 175.13 nm
P I 178.28 nm
S I 180.73 nm
Fe II 180.77 nm
Fe I 281.33 nm
Ni I 380.71 nm
Al I 396.15 nm

Three-dimensional compositional mapping using double-pulse micro-laser-induced breakdownspectroscopy technique

Author: Grassi, R. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2016.11.004

Authors
Grifoni, E. ; Gufoni, S. ; Legnaioli, S. ; Lorenzetti, G. ; Macro, N. ; Menichetti, L. ; Pagnotta, S. ; Palleschi, V. ; Poggialini, F. ; Schiavo, C.

Keywords

LIBS; Microscopy; Compositional mapping; 3D analysis; DP-mu LIBS; Euro coins;PLASMA-MASS SPECTROMETRY; LIBS

Abstract

In this communication, we present the development of the first double-pulse micro-LIBS (DP-mu LIBS) instrument for three-dimensional compositional mapping of materials. The system allows for high-resolution three-dimensional scanning of materials; its advantages with respect to conventional single-pulse micro-LIBS systems are described and discussed. As a test example, we analyzed three Euro coins to show the performances of the system on homogeneous samples (20 Eurocents), heterogeneous samples (1 Euro) and layered samples (5 Eurocents). DP-LIBS cannot provide isotopic information and has, typically, limits of detection for the elements of interest much higher with respect to Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (IA-ICP-MS). However, when the isotopic information and the extreme sensitivity to trace elements is not be necessary, the results obtained show that DP-mu LIBS can be a viable alternative to LA-ICP-MS for the acquisition of high resolution threedimensional compositional maps. (C) 2016 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Eurocoin

Elements:

Lines [nm]:

Mg I 285.21 nm

Lines [nm]:

Al I 308.22 nm

Lines [nm]:

Fe I 385.99 nm

Lines [nm]:

Ni I 361.94 nm

Lines [nm]:

Cu I 324.75 nm

...

Emmision lines:
Sn I 284.00 nm
Mg I 285.21 nm
Al I 308.22 nm
Cu I 324.75 nm
Zn I 334.50 nm
Ni I 361.94 nm
Fe I 385.99 nm

State-to-state modeling of ultrashort laser-induced plasmas

Author: Morel, V. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals

DOI: 10.1016/j.sab.2016.11.002

Authors
Bultel, A. ; Grisolia, C. ; Schneider, I.

Keywords

Aluminum; Tungsten; Collisional-radiative model; Laser-induced plasma; Non-equilibrium plasma; Ultrashort pulse;INDUCED BREAKDOWN SPECTROSCOPY; THERMODYNAMIC-EQUILIBRIUM; FACING COMPONENTS; FEMTOSECOND; ARGON; NANOSECOND; PICOSECOND; NITROGEN; LIBS; EXPANSION

Abstract

The question of the Local Thermodynamic Equilibrium (LTE) of laser-induced plasmas is crucial regarding the Laser-Induced Breakdown Spectroscopy (LIBS) technique. The most relevant way to assess theoretically the possible departure from LTE is to develop state-to-state models of the chemical species involved. The present paper illustrates such an elaboration in the case of aluminum and tungsten. Based on this state-to-state approach, the two collisional-radiative models CoRaM-Al and CoRaM-W are elaborated. They include elementary processes under electron and heavy particle impact in thermal non-equilibrium, spontaneous emission, radiative recombination and thermal Bremsstrahlung. These models are applied to the case of ultrashort laser-induced plasmas expanding in an argon gas at different pressure, for which a relevant collisional-radiative model is also elaborated to predict the propagation of the shock wave. The laser conditions are close to those used for a typical LIBS analysis under ultrashort regime. At high argon pressure (10(5) Pa), the relaxation of the plasma takes place according to a rather low departure from LTE, as revealed by the thorough examination of the Boltzmann plots derived from the state-to-state models. This relaxation occurs at temperature higher for aluminum than for tungsten, but close to 10,000 IC from 200 ns. Conversely, at low pressure (10 Pa), the extinction of the plasma is observed at similar to 500 ns, just after a phase corresponding to significant departure from equilibrium. These results support the idea of the choice of short gate delays close to the laser pulse for the LIBS characterization of tungsten matrices in tokamak-like conditions. (C) 2016 Elsevier B.V. All rights reserved.

Area:

Collisional-radiative models

Material:

Aluminium ; Tungsten

Elements:

Emmision lines:

Novel approach of signal normalization for depth profile of cultural heritage materials

Author: Syvilay, D. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2016.11.001

Authors
Detalle, V. ; Martinez, L. ; Serfaty, S. ; Texier, A. ; Wilkie-Chancellier, N.

Keywords

SNV; Cultural heritage; Stratigraphy; Raman; Libs; Luminescence background;INDUCED BREAKDOWN SPECTROSCOPY; RAMAN-SPECTROSCOPY; WAVELET TRANSFORM; SPECTRA; FLUORESCENCE; COPPER; ART; SUBTRACTION; ARCHAEOLOGY; MICROSCOPY

Abstract

The investigation of cultural heritage materials is always complex and specific because unique. Materials are most often heterogeneous and organized in several layers such as mural paintings or corrosion products. The characterization of a complete artwork's stratigraphy is actually one of the questions of science conservation. Indeed, the knowledge of these layers allows completing the history of the work of art and a better understanding of alteration processes in order to set up an appropriate conservation action. The LIBS technique has been employed to study the stratigraphy of an artwork thanks to the ablation laser. However, as we know, atomic information could be insufficient to characterize two materials composed by the same based elements. Therefore, an additional molecular analysis, like Raman spectroscopy; is sometimes necessary for a better identification of the material in particular for organic coatings in cultural heritage. We suggest in this study to use Standard Normal Variate (SNV) as a common normalization for different kinds of spectra (LIBS and Raman spectroscopy) combined with a 3D colour representation for stratigraphic identification of the different layers composing the complex material from artwork. So in this investigation, the SNV method will be applied on LIBS and Raman spectra but also on baseline Raman spectra often considering as nuisance. The aim of this study is to demonstrate the versatility of SNV applied on varied spectra like LIBS, Raman spectra as well as the luminescence background. This original work considers the SNV with a 3D colour representation as a probable new perspective for an easy recognition of a structure layered with a direct overview of the depth profile of the artwork. (C) 2016 Elsevier B.V. All rights reserved.

Area:

Cultural heritage

Material:

Artwork stratigraphy

Elements:

Lines [nm]:

Fe II 259.84 nm Fe II 261.19 nm Fe II 261.76 nm Fe II 273.95 nm Fe II 274.93 nm Fe II 275.57 nm

Lines [nm]:

Cu I 324.75 nm Cu I 327.40 nm Cu I 578.21 nm

Lines [nm]:

Ca II 315.89 nm Ca II 317.93 nm

Emmision lines:
Fe II 259.84 nm
Fe II 261.19 nm
Fe II 261.76 nm
Fe II 273.95 nm
Fe II 274.93 nm
Fe II 275.57 nm
Ca II 315.89 nm
Ca II 317.93 nm
Cu I 324.75 nm
Cu I 327.40 nm
Cu I 578.21 nm

Laser-induced breakdown spectroscopy of light water reactor simulated used nuclear fuel: Main oxide phase

Author: Campbell, K. R. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.04.006

Authors
Barefield, J. E. ; Clegg, S. M. ; Colgan, J. P. ; Czerwinski, K. R. L. ; Judge, E. J. ; Kilcrease, D. P.

Keywords

Matrix effects; Laser-induced breakdown spectroscopy; Uranium; Limit of detection;URANIA; WASTE; UO2; ZR

Abstract

The analysis of light water reactor simulated used nuclear fuel using laser-induced breakdown spectroscopy (LIBS) is explored using a simplified version of the main oxide phase. The main oxide phase consists of the actinides, lanthanides, and zirconium. The purpose of this study is to develop a rapid, quantitative technique for measuring zirconium in a uranium dioxide matrix without the need to dissolve the material. A second set of materials including cerium oxide is also analyzed to determine precision and limit of detection (LOD) using LIBS in a complex matrix. Two types of samples are used in this study: binary and ternary oxide pellets. The ternary oxide, (U,Zr,Ce)O-2 pellets used in this study are a simplified version the main oxide phase of used nuclear fuel. The binary oxides, (U,Ce)O-2 and (U,Zr)O-2 are also examined to determine spectral emission lines for Ce and Zr, potential spectral interferences with uranium and baseline LOD values for Ce and Zr in a UO2 matrix. In the spectral range of 200 to 800 nm, 33 cerium lines and 25 zirconium lines were identified and shown to have linear correlation values (R-2) >0.97 for both the binary and ternary oxides. The cerium LOD in the (U,Ce)O-2 matrix ranged from 034 to 1.08 wt% and 0.94 to 1.22 wt% in (U,Ce,Zr)O-2 for 33 of Ce emission lines. The zirconium limit of detection in the (U,Zr)O-2 matrix ranged from 0.84 to 1.15 wt% and 0.99 to 1.10 wt% in (U,Ce,Zr)O-2 for 25 Zr lines. The effect of multiple elements in the plasma and the impact on the LOD is discussed. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Nuclear industry

Material:

Nuclear fuel

Elements:

Lines [nm]:

Ce II 380.81 nm Ce II 407.35 nm Ce II 447.12 nm Ce II 457.23 nm Ce II 535.35 nm Ce I 571.90 nm Ce II 395.25 nm Ce II 395.63 nm Ce II 428.94 nm Ce II 444.44 nm Ce II 448.39 nm Ce II 404.08 nm Ce II 438.22 nm Ce II 507.97 nm Ce I 581.29 nm Ce II 401.24 nm Ce II 438.68 nm Ce II 439.17 nm Ce II 452.31 nm Ce II 452.85 nm Ce II 460.64 nm Ce II 488.25 nm Ce I 512.96 nm Ce II 394.28 nm Ce II 399.38 nm Ce II 416.99 nm Ce II 435.27 nm Ce II 441.88 nm Ce II 452.74 nm Ce I 522.35 nm Ce II 540.92 nm Ce II 547.23 nm Ce I 594.09 nm

Lines [nm]:

Zr II 244.99 nm Zr II 272.26 nm Zr II 273.49 nm Zr II 274.26 nm Zr II 275.22 nm Zr II 281.87 nm Zr II 282.56 nm Zr II 284.46 nm Zr II 305.48 nm Zr II 310.66 nm Zr II 316.60 nm Zr II 327.31 nm Zr II 332.68 nm Zr II 335.61 nm Zr II 335.73 nm Zr II 338.83 nm Zr II 339.20 nm Zr II 339.31 nm Zr II 340.48 nm Zr II 341.03 nm Zr II 348.12 nm Zr II 355.66 nm Zr II 357.25 nm Zr II 357.69 nm Zr I 360.12 nm Zr II 361.31 nm Zr II 383.68 nm Zr II 444.30 nm

Lines [nm]:

U I 339.04 nm U II 339.48 nm U II 424.44 nm

Lines [nm]:

O I 777.19 nm

Lines [nm]:

Si I 288.16 nm

Emmision lines:
Zr II 244.99 nm
Zr II 272.26 nm
Zr II 273.49 nm
Zr II 274.26 nm
Zr II 275.22 nm
Zr II 281.87 nm
Zr II 282.56 nm
Zr II 284.46 nm
Si I 288.16 nm
Zr II 305.48 nm
Zr II 310.66 nm
Zr II 316.60 nm
Zr II 327.31 nm
Zr II 332.68 nm
Zr II 335.61 nm
Zr II 335.73 nm
Zr II 338.83 nm
U I 339.04 nm
Zr II 339.20 nm
Zr II 339.31 nm
U II 339.48 nm
Zr II 340.48 nm
Zr II 341.03 nm
Zr II 348.12 nm
Zr II 355.66 nm
Zr II 357.25 nm
Zr II 357.69 nm
Zr I 360.12 nm
Zr II 361.31 nm
Ce II 380.81 nm
Zr II 383.68 nm
Ce II 394.28 nm
Ce II 395.25 nm
Ce II 395.63 nm
Ce II 399.38 nm
Ce II 401.24 nm
Ce II 404.08 nm
Ce II 407.35 nm
Ce II 416.99 nm
U II 424.44 nm
Ce II 428.94 nm
Ce II 435.27 nm
Ce II 438.22 nm
Ce II 438.68 nm
Ce II 439.17 nm
Ce II 441.88 nm
Zr II 444.30 nm
Ce II 444.44 nm
Ce II 447.12 nm
Ce II 448.39 nm
Ce II 452.31 nm
Ce II 452.74 nm
Ce II 452.85 nm
Ce II 457.23 nm
Ce II 460.64 nm
Ce II 488.25 nm
Ce II 507.97 nm
Ce I 512.96 nm
Ce I 522.35 nm
Ce II 535.35 nm
Ce II 540.92 nm
Ce II 547.23 nm
Ce I 571.90 nm
Ce I 581.29 nm
Ce I 594.09 nm
O I 777.19 nm

Multi-elemental imaging of paraffin-embedded human samples by laser-induced breakdownspectroscopy

Author: Moncayo, S. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.04.013

Authors
Busser, B. ; Charles, J. ; Motto-Ros, V. ; Pelascini, F. ; Pinel, N. ; Sabatier-Vincent, M. ; Sancey, L. ; Templier, I. ; Trichard, F.

Keywords

LIBS imaging; Elemental imaging; Human paraffin-embedded tissue; Skin cancer;PLASMA-MASS SPECTROMETRY; SQUAMOUS-CELL CARCINOMA; X-RAY MICROSCOPY; LA-ICP-MS; BIOLOGICAL TISSUE; NANOPARTICLES; SKIN; RESOLUTION; ELEMENTS; METALS

Abstract

Chemical elements play central roles for physiological homeostasis in human cells, and their dysregulation might lead to a certain number of pathologies. Novel imaging techniques that improve the work of pathologists for tissue analysis and diagnostics are continuously sought. We report the use of Laser-Induced Breakdown Spectroscopy (LIBS) to perform multi-elemental images of human paraffin-embedded skin samples on the entire biopsy scale in a complementary and compatible way with microscope histopathological examination. A specific instrumental configuration is proposed in order to detect most of the elements of medical interest (i.e. P, Al, Mg, Na, Zn, Si, Fe, and Cu). As an example of medical application, we selected and analysed skin biopsies, including healthy skin tissue, cutaneous metastasis of melanoma, Merkel-cell carcinoma and squamous cell carcinoma. Clear distinctions in the distribution of chemical elements are observed from the different samples investigated. This study demonstrates the high complementarity of LIBS elemental imaging with conventional histopathology, opening new opportunities for any medical application involving metals. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Health

Material:

Skin tumour

Elements:

Emmision lines:

Quantitative elemental imaging of heterogeneous catalysts using laser-induced breakdownspectroscopy

Author: Trichard, F. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.04.008

Authors
Blouet, Y. ; Lienemann, C. P. ; Moncayo, S. ; Motto-Ros, V. ; Sorbier, L.

Keywords

LIBS; Quantification; Elemental imaging; Elemental profile; Heterogeneous catalyst; Palladium;X-RAY-FLUORESCENCE; FLIGHT MASS-SPECTROMETRY; HIGH-SPEED; GEOLOGICAL SAMPLES; HIGH-RESOLUTION; TRACE-ELEMENTS; CONVERTERS; METALS; MICROANALYSIS; MICROPROBE

Abstract

Currently, the use of catalysis is widespread in almost all industrial processes; its use improves productivity, synthesis yields and waste treatment as well as decreases energy costs. The increasingly stringent requirements, in terms of reaction selectivity and environmental standards, impose progressively increasing accuracy and control of operations. Meanwhile, the development of characterization techniques has been challenging, and the techniques often require equipment with high complexity. In this paper, we demonstrate a novel elemental approach for performing quantitative space-resolved analysis with ppm-scale quantification limits and mu m-scale resolution. This approach, based on laser-induced breakdown spectroscopy (LIBS), is distinguished by its simplicity, all-optical design, and speed of operation. This work analyzes palladium-based porous alumina catalysts, which are commonly used in the selective hydrogenation process, using the LIBS method. We report an exhaustive study of the quantification capability of LIBS and its ability to perform imaging measurements over a large dynamic range, typically from a few ppm to wt. These results offer new (i)nsight into the use of LIBS-based imaging in the industry and paves the way for innumerable applications. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Catalyst

Elements:

Lines [nm]:

Pd I 340.46 nm Pd I 342.12 nm Pd I 343.34 nm Pd I 348.12 nm Pd I 348.98 nm Pd I 337.30 nm

Lines [nm]:

Al II 359.75 nm

Lines [nm]:

Fe I 360.67 nm

Emmision lines:
Pd I 337.30 nm
Pd I 340.46 nm
Pd I 342.12 nm
Pd I 343.34 nm
Pd I 348.12 nm
Pd I 348.98 nm
Al II 359.75 nm
Fe I 360.67 nm

Double pulse laser induced breakdown spectroscopy of a solid in water: Effect of hydrostatic pressure on laser induced plasma, cavitation bubble and emission spectra

Author: Lopez-Claros, M. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals Applications

DOI: 10.1016/j.sab.2017.02.010

Authors
De Giacomo, A. ; Dell'Aglio, M. ; Fortes, F. J. ; Gaudiuso, R. ; Laserna, J. J. ; Santagata, A.

Keywords

Laser-induced breakdown spectroscopy; Deep Sea; Double pulse; Cavitation bubble; High pressure;BULK AQUEOUS-SOLUTIONS; ELEMENTAL ANALYSIS; SINGLE-PULSE; SHOCK-WAVES; LIQUIDS; LIBS; EXCITATION; INTENSITY; ABLATION; INSIGHTS

Abstract

There is a growing interest in the development of sensors use in exploration of the deep ocean. Techniques for the chemical analysis of submerged solids are of special interest, as they show promise for subsea mining applications where a rapid sorting of materials found in the sea bottom would improve efficiency. Laser-Induced Breakdown Spectroscopy (LIBS) has demonstrated potential for this application thanks to its unique capability of providing the atomic composition of submerged solids. Here we present a study on the parameters that affect the spectral response of metallic targets in an oceanic pressure environment. Following laser excitation of the solid, the plasma persistence and the cavitation bubble size are considerably reduced as the hydrostatic pressure increases. These effects are of particular concern in dual pulse excitation as reported here, where a careful choice of the interpulse timing is required. Shadowgraphic images of the plasma demonstrate that cavitation bubbles are formed early after the plasma onset and that the effect of hydrostatic pressure is negligible during the early stage of plasma expansion. Contrarily to what is observed at atmospheric pressure, emission spectra observed at high pressures are characterized by self-absorbed atomic lines on continuum radiation resulting from strong radiative recombination in the electron-rich confined environment. This effect is much less evident with ionic lines due to the much higher energy of the levels involved and ionization energy of ions, as well as to the lower extent of absorption effects occurring in the inner part of the plasma, where ionized species are more abundant. As a result of the smaller shorter-lived cavitation bubble, the LIBS intensity enhancement resulting from dual pulse excitation is reduced when the applied pressure increases. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Geology ; Industry ; Mining

Material:

Mineral ; Rock

Elements:

Lines [nm]:

Al I 396.15 nm

Emmision lines:
Al I 396.15 nm

Analysis of simulated high burnup nuclear fuel by laser induced breakdown spectroscopy

Author: Singh, M. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.03.012

Authors
Banerjee, J. ; Bhagat, R. K. ; Sarkar, A.

Keywords

LIBS; SIMFUEL; AHWR; Argon; Nuclear;INDUCED PLASMAS; URANIUM; THORIUM; LIBS; SPECTROMETRY; EMISSION; GLASS

Abstract

Advanced Heavy Water Reactor (AHWR) grade (Th-U)O-2 fuel sample and Simulated High Burn-Up Nuclear Fuels (SIMFUEL) samples mimicking the 28 and 43 GWd/Fe irradiated burn-up fuel were studied using laser-induced breakdown spectroscopy (LIBS) setup in a simulated hot-cell environment from a distance of >1.5 m. Resolution of <38 pm has been used to record the complex spectra of the SIMFUEL samples. By using spectrum comparison and database matching >60 emission lines of fission products was identified. Among them only a few emission lines were found to generate calibration curves. The study demonstrates the possibility to investigate impurities at concentrations around hundreds of ppm, rapidly at atmospheric pressure without any sample preparation. The results of Ba and Mo showed the advantage of LIBS analysis over traditional methods involving sample dissolution, which introduces possible elemental loss. Limits of detections (LOD) under Ar atmosphere shows significant improvement, which is shown to be due to the formation of stable plasma. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Nuclear fuel

Elements:

Lines [nm]:

Mo II 253.85 nm Mo I 255.09 nm Mo II 259.37 nm Mo II 265.34 nm Mo II 266.06 nm Mo II 267.28 nm Mo II 267.33 nm Mo I 267.99 nm Mo II 268.32 nm Mo II 268.80 nm Mo II 270.14 nm Mo II 271.74 nm Mo II 274.63 nm Mo II 276.98 nm Mo II 277.54 nm Mo II 278.00 nm Mo II 281.62 nm Mo II 284.82 nm Mo II 285.32 nm Mo II 286.38 nm Mo II 287.15 nm Mo II 308.76 nm Mo II 312.20 nm Mo I 313.26 nm Mo I 320.88 nm Mo I 383.38 nm Mo I 390.30 nm Mo I 418.83 nm Mo I 470.72 nm

Lines [nm]:

Zr II 256.89 nm Zr II 257.14 nm Zr II 267.86 nm Zr II 270.01 nm Zr II 274.26 nm Zr II 274.59 nm Zr II 284.46 nm Zr II 327.31 nm Zr II 327.93 nm Zr II 328.47 nm Zr II 343.82 nm Zr I 386.39 nm Zr I 389.03 nm Zr I 468.78 nm Zr I 468.85 nm Zr I 471.01 nm Zr I 477.23 nm

Lines [nm]:

Th II 254.81 nm Th II 406.92 nm Th II 420.89 nm Th I 459.54 nm Th II 486.32 nm Th II 491.98 nm Th II 513.11 nm

Lines [nm]:

Ce II 276.14 nm Ce II 322.71 nm Ce I 513.78 nm Ce I 560.13 nm Ce I 569.70 nm

Lines [nm]:

Sr II 407.77 nm Sr II 421.55 nm Sr I 460.73 nm Sr I 496.23 nm

...

Emmision lines:
Mo II 253.85 nm
Th II 254.81 nm
Mo I 255.09 nm
Zr II 256.89 nm
Zr II 257.14 nm
Mo II 259.37 nm
Ba I 264.65 nm
Mo II 265.34 nm
Mo II 266.06 nm
Mo II 267.28 nm
Mo II 267.33 nm
Zr II 267.86 nm
Mo I 267.99 nm
Mo II 268.32 nm
Mo II 268.80 nm
Zr II 270.01 nm
Mo II 270.14 nm
Mo II 271.74 nm
Zr II 274.26 nm
Zr II 274.59 nm
Mo II 274.63 nm
Ce II 276.14 nm
Mo II 276.98 nm
Mo II 277.54 nm
Mo II 278.00 nm
Mo II 281.62 nm
Zr II 284.46 nm
Mo II 284.82 nm
Mo II 285.32 nm
Mo II 286.38 nm
Mo II 287.15 nm
Ru I 290.89 nm
Mo II 308.76 nm
Mo II 312.20 nm
Mo I 313.26 nm
Mo I 320.88 nm
Ce II 322.71 nm
Zr II 327.31 nm
Zr II 327.93 nm
Zr II 328.47 nm
Zr II 343.82 nm
Mo I 383.38 nm
Zr I 386.39 nm
Zr I 389.03 nm
Mo I 390.30 nm
Th II 406.92 nm
Sr II 407.77 nm
Mo I 418.83 nm
Th II 420.89 nm
Sr II 421.55 nm
Nd II 423.24 nm
Ba II 455.40 nm
Th I 459.54 nm
Sr I 460.73 nm
Y I 467.49 nm
Zr I 468.78 nm
Zr I 468.85 nm
Mo I 470.72 nm
Zr I 471.01 nm
Sm I 476.03 nm
Zr I 477.23 nm
Th II 486.32 nm
Nd I 488.38 nm
Y II 490.01 nm
Th II 491.98 nm
Ba II 493.41 nm
Nd I 494.48 nm
Sr I 496.23 nm
Th II 513.11 nm
Ce I 513.78 nm
Ce I 560.13 nm
Ce I 569.70 nm

Spectrochemical analysis of Cs in water and soil using low pressure laser induced breakdownspectroscopy

Author: Ramli, M. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications

DOI: 10.1016/j.sab.2017.03.017

Authors
Kagawa, K. ; Khumaeni, A. ; Kurniawan, K. H. ; Tija, M. O.

Keywords

Trace radioactive pollutant; Cs in water; Cs in soil; Low pressure plasma; ITO film;SHOCK-WAVE PLASMA; SAMPLES; LIBS

Abstract

An experimental study has been conducted for the practical and in situ application of laser-induced breakdown spectroscopy (LIBS) for the detection of Cs pollutant in water and soil in the nearby area of Fukushima Nuclear Power Station. The spectrochemical measurements were carried out by means of 355 nm Nd-YAG laser with N-2 and He ambient gases at atmospheric and low pressures. The soil samples were prepared by pelletizing the mixtures of 80% soil and 20% KBr while the aqueous samples were prepared as thin films electro deposited on indium tin oxide (ITO) glass. The resulted emission spectra using 0.5 kPa N-2 ambient gas shows the minimum detectable Cs concentration of 0.2 ppm and 0.3 ppm in the water and soil samples, respectively. The result of this experiment has thus demonstrated the viability of the LIBS equipment employed here as a more practical, in-situ and even mobile alternative to the standard use of gamma-ray spectroscopy using germanium detector. (C) 2017 Published by Elsevier B.V.

Area:

Environment ; Nuclear industry

Material:

Soil ; Water

Elements:

Lines [nm]:

Mg II 854.32 nm

Lines [nm]:

Al I 396.15 nm

Lines [nm]:

Ca II 396.85 nm

Lines [nm]:

In I 410.17 nm

Lines [nm]:

Cs I 852.11 nm

...

Emmision lines:
Al I 396.15 nm
Ca II 396.85 nm
Pb I 405.78 nm
In I 410.17 nm
Cs I 852.11 nm
Mg II 854.32 nm

Revealing hidden spectral information of chlorine and sulfur in data of a mobile Laser-inducedBreakdown Spectroscopy system using chemometrics

Author: Gottlieb, C. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Applications Chemometrics

DOI: 10.1016/j.sab.2017.04.001

Authors
Gunther, T. ; Millar, S. ; Wilsch, G.

Keywords

LIBS; Mobile LIBS; Chemometrics; PLS-R; Building materials;CONCRETE STRUCTURES; CALIBRATION; REGRESSION; TUTORIAL; LIMIT

Abstract

For the damage assessment of reinforced concrete structures the quantified ingress profiles of harmful species like chlorides, sulfates and alkali need to be determined. In order to provide on-site analysis of concrete a fast and reliable method is necessary. Low transition probabilities as well as the high ionization energies for chlorine and sulfur in the near-infrared range makes the detection of CI I and S I in low concentrations a difficult task. For the on-site analysis a mobile LIBS-system (lambda = 1064 nm, E-pulse <= 3 mJ, tau = 1.5 ns) with an automated scanner has been developed at BAM. Weak chlorine and sulfur signal intensities do not allow classical univariate analysis for process data derived from the mobile system. In order to improve the analytical performance multivariate analysis like PLS-R will be presented in this work. A comparison to standard univariate analysis will be carried out and results covering important parameters like detection and quantification limits (LOD, LOQ) as well as processing variances will be discussed (Allegrini and Olivieri, 2014 [1]; Ostra et al., 2008 [2]). It will be shown that for the first time a low cost mobile system is capable of providing reproducible chlorine and sulfur analysis on concrete by using a low sensitive system in combination with multivariate evaluation. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Industry

Material:

Building ; Concrete

Elements:

Lines [nm]:

S I 921.29 nm S I 922.81 nm S I 923.75 nm

Lines [nm]:

Cl I 833.33 nm Cl I 837.59 nm

Lines [nm]:

Na I 818.33 nm

Emmision lines:
Na I 818.33 nm
Cl I 833.33 nm
Cl I 837.59 nm
S I 921.29 nm
S I 922.81 nm
S I 923.75 nm

Doppler splitting generated by shock waves in laser induced breakdown spectroscopy

Author: Bukvic, S. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2017)

Fundamentals

DOI: 10.1016/j.sab.2017.04.002

Authors
Skocic, M.

Keywords

Laser Induced Plasma; LIBS; Radially resolved spectroscopy; Doppler broadening; Shock waves;EXPANSION DYNAMICS; ABLATION; PLASMA

Abstract

We present a classical spectroscopic approach for investigation of the fast plasma expansion present in Laser Induced Plasma. We show that characteristic form of the spectral lines, caused by significant Doppler effect, contains valuable information regarding the expansion velocity, plasma deceleration, emitters temperature, electron density and so on. The proposed numerical procedure is simple since the inverse Abel transform is not a necessary step. We illustrate this technique analyzing expansion of laser induced copper plasma in ambient gas at low (20Pa) pressure. (C) 2017 Elsevier B.V. All rights reserved.

Area:

Plasma diagnostics

Material:

Copper

Elements:

Lines [nm]:

Cu I 324.75 nm Cu I 327.40 nm

Emmision lines:
Cu I 324.75 nm
Cu I 327.40 nm

Multivariate approach to the chemical mapping of uranium in sandstone-hosted uranium ores analyzed using double pulse laser-induced breakdown spectroscopy

Author: Klus, J. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2016)

Applications Chemometrics

DOI: 10.1016/j.sab.2016.08.014

Authors
Kaiser, J. ; Mikysek, P. ; Novotný, J. ; Novotný, K. ; Pořízka, P. ; Prochazka, D. ; Prochazková, P. ; Slobodník, M. ; Trojek, T.

Keywords

Laser-Induced Breakdown Spectroscopy; Uranium; principal component analysis; Chemical mapping; Sandstone-hosted deposit; X-ray Fluorescence;

Abstract

The goal of this work is to provide high resolution mapping of uranium in sandstone-hosted uranium ores using Laser-Induced Breakdown Spectroscopy (LIBS) technique. In order to obtain chemical image with highest possible spatial resolution, LIBS system in orthogonal double pulse (DP LIBS) arrangement was employed. Owing to this experimental arrangement the spot size of 50 μm in diameter resulting in lateral resolution of 100 μm was reached. Despite the increase in signal intensity in DP LIBS modification, the detection of uranium is challenging. The main cause is the high density of uranium spectral lines, which together with broadening of LIBS spectral lines overreaches the resolution of commonly used spectrometers. It results in increased overall background radiation with only few distinguishable uranium lines. Three different approaches in the LIBS data treatment for the uranium detection were utilized: i) spectral line intensity, ii) region of apparent background and iii) multivariate data analysis. By utilizing multivariate statistical methods, a specific specimen features (in our case uranium content) were revealed by processing complete spectral information obtained from broadband echelle spectrograph. Our results are in a good agreement with conventional approaches such as line fitting and show new possibilities of processing spectral data in mapping. As a reference technique to LIBS was employed X-ray Fluorescence (XRF). The XRF chemical images used in this paper have lower resolution (approximately 1–2 mm per image point), nevertheless the elemental distribution is apparent and corresponds to presented LIBS experiments.

Area:

Geology ; Industry ; Mapping

Material:

Sandstone

Elements:

Lines [nm]:

U II 409.01 nm

Emmision lines:
U II 409.01 nm

Assessment of the most effective part of echelle laser-induced plasma spectra for further classification using Czerny-Turner spectrometer

Author: Pořízka, P. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2016)

Fundamentals Applications Chemometrics

DOI: 10.1016/j.sab.2016.09.004

Authors
Brada, M. ; Kaiser, J. ; Klus, J. ; Novotný, J. ; Novotný, K. ; Prochazka, D. ; Vítková, G.

Keywords

Laser-Induced Breakdown Spectroscopy; Multivariate classification; Echelle spectrometer; Czerny-Turner spectrometer;

Abstract

The objective of this work was to assess a part of echelle Laser-Induced Plasma spectra (ranging from 200 to 1000 nm) that could be most effectively employed for rocks classification. Therefore, a 60 nm wide spectral window mask was iteratively moved over the broadband echelle spectra. Each created narrow artificial spectral windows (60 nm) was used for the classification of rock samples using various Multivariate Data Analysis (MVDA) algorithms, reaching more than 99% of the overall accuracy in certain cases. Afterwards, the Czerny-Turner spectrometer (having higher sensitivity compared to the echelle spectrometer) was aligned to the a priori selected and the most effective spectral regions and rocks samples were re-measured. Consequently the MVDA analyses were utilized again, providing also satisfying classification results yielding more than 99% of the overall accuracy. Measurements of 28 sedimentary ores (certified reference materials) were done utilizing commercially available X-Trace device (AtomTrace), where spectrometers in both configurations (echelle and Czerny-Turner) were exploited.

Area:

Geology

Material:

Massive sulphide ; Mineralized ultramafic ; Siliceous dolomite ; Siltstone

Elements:

Lines [nm]:

Fe I 302.06 nm Fe I 304.76 nm Fe I 305.74 nm Fe I 404.58 nm Fe I 406.36 nm Fe I 407.17 nm Fe I 423.59 nm Fe I 425.08 nm Fe I 426.05 nm

Lines [nm]:

Mg I 285.21 nm Mg I 383.23 nm Mg I 383.83 nm Mg II 279.55 nm Mg II 280.27 nm

Lines [nm]:

Al I 308.22 nm Al I 309.27 nm Al I 394.40 nm Al I 396.15 nm

Lines [nm]:

Ca I 422.67 nm Ca II 393.37 nm Ca II 396.85 nm

Lines [nm]:

Si I 390.55 nm Si I 288.16 nm

...

Emmision lines:
Mg II 279.55 nm
Mg II 280.27 nm
Mg I 285.21 nm
Si I 288.16 nm
Fe I 302.06 nm
Fe I 304.76 nm
Fe I 305.74 nm
Al I 308.22 nm
Al I 309.27 nm
Cu I 324.75 nm
Cu I 327.40 nm
Mg I 383.23 nm
Mg I 383.83 nm
Si I 390.55 nm
Ca II 393.37 nm
Al I 394.40 nm
Al I 396.15 nm
Ca II 396.85 nm
Fe I 404.58 nm
Fe I 406.36 nm
Fe I 407.17 nm
Ca I 422.67 nm
Fe I 423.59 nm
Fe I 425.08 nm
Fe I 426.05 nm

Effect of experimental parameters and resulting analytical signal statistics in laser-induced breakdown spectroscopy

Author: Klus, J. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2016)

Fundamentals

DOI: 10.1016/j.sab.2016.10.002

Authors
Kaiser, J. ; Novotný, J. ; Novotný, K. ; Pořízka, P. ; Prochazka, D.

Keywords

Laser-induced breakdown spectroscopy; Generalized extreme value distribution; shot-to-shot statistics ;

Abstract

The purpose of this work is to provide detailed study of statistical behavior of different types of analytical signals in typical of Laser-Induced Breakdown Spectroscopy (LIBS) measurements. The main goal of this work is to justify usage of arithmetic mean and standard deviation as statistical estimates of expected value of selected analytical signal. In contrary to the general assumption that LIBS data show Gaussian distribution, this paper deals with the hypothesis that the data rather demonstrate Generalized Extreme Value Distribution. The study is realized on 10 selected lines measured on NIST glass standard. In order to cover wide range of possible applications three different spectra internal standardization techniques and their influence on distribution were studied. Finally, assuming that the data comes from a single distribution and the central limit theorem is valid, the influence of accumulations on the line distribution is examined and discussed. Statistical tools used and described in this paper can be utilized by other researchers to confirm their hypotheses and verify utilization of Gaussian distribution or even novel data processing methods.

Area:

LOD

Material:

Soft borosilicate glass

Elements:

Lines [nm]:

Mg II 279.55 nm Mg II 280.27 nm

Lines [nm]:

Ca II 393.37 nm Ca II 396.85 nm

Lines [nm]:

Na I 589.00 nm

Lines [nm]:

Al I 309.27 nm

Lines [nm]:

Si I 288.16 nm

...

Emmision lines:
Mg II 279.55 nm
Mg II 280.27 nm
Si I 288.16 nm
Al I 309.27 nm
Ca II 393.37 nm
Ca II 396.85 nm
Sr II 421.55 nm
Ba II 493.41 nm
Na I 589.00 nm
K I 766.49 nm

Laser-Induced Breakdown Spectroscopy coupled with chemometrics for the analysis of steel: The issue of spectral outliers filtering

Author: Pořízka, P. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2016)

Fundamentals Applications Chemometrics

DOI: 10.1016/j.sab.2016.08.008

Authors
Hrdlička, A. ; Kaiser, J. ; Képeš, E. ; Klus, J. ; Novotný, J. ; Novotný, K. ; Prochazka, D.

Keywords

Laser-Induced Breakdown Spectroscopy, LIBS; Outlier filtering; Principal Component Analysis, PCA; Linear correlation; Total spectral intensity; Soft Independent Modelling of Class Analogies, SIMCA;

Abstract

In this manuscript we highlight the necessity of outlier filtering prior the multivariate classification in Laser-Induced Breakdown Spectroscopy (LIBS) analyses. For the purpose of classification we chose to analyse BAM steel standards that possess similar composition of major and trace elements. To assess the improvement in figures of merit we compared the performance of three outlier filtering approaches (based on Principal Component Analysis, linear correlation and total spectral intensity) already separately discussed in the LIBS literature. The truncated data set was classified using Soft Independent Modelling of Class Analogies (SIMCA). Yielded results showed significant improvement in the performance of multivariate classification coupled to filtered data. The best performance was observed for the total spectral intensity filtering approach gaining the analytical figures of merit (overall accuracy, sensitivity, and specificity) over 98%. It is noteworthy that the results showed relatively low sensitivity and high specificity of the SIMCA algorithm regardless of the presence of outliers in the data sets. Moreover, it was shown that the variance in the data topology of training and testing data sets has a great impact on the consequent data classification.

Area:

Industry ; Outliers filtering

Material:

Steel

Elements:

Lines [nm]:

Cr II 284.98 nm Cr II 313.21 nm Cr II 336.80 nm Cr I 425.44 nm Cr I 427.48 nm Cr I 428.97 nm Cr I 520.45 nm Cr I 520.60 nm Cr I 520.84 nm Cr I 540.98 nm

Lines [nm]:

Fe I 381.58 nm Fe I 382.04 nm Fe I 382.59 nm Fe I 404.58 nm Fe I 432.58 nm Fe I 438.35 nm Fe I 489.15 nm Fe I 492.05 nm Fe I 495.76 nm

Lines [nm]:

Ni I 341.48 nm Ni I 349.30 nm Ni I 351.51 nm Ni I 352.45 nm

Lines [nm]:

Mn I 403.08 nm

Lines [nm]:

Mo I 550.65 nm

Emmision lines:
Cr II 284.98 nm
Cr II 313.21 nm
Cr II 336.80 nm
Ni I 341.48 nm
Ni I 349.30 nm
Ni I 351.51 nm
Ni I 352.45 nm
Fe I 381.58 nm
Fe I 382.04 nm
Fe I 382.59 nm
Mn I 403.08 nm
Fe I 404.58 nm
Cr I 425.44 nm
Cr I 427.48 nm
Cr I 428.97 nm
Fe I 432.58 nm
Fe I 438.35 nm
Fe I 489.15 nm
Fe I 492.05 nm
Fe I 495.76 nm
Cr I 520.45 nm
Cr I 520.60 nm
Cr I 520.84 nm
Cr I 540.98 nm
Mo I 550.65 nm

Detection of visually unrecognizable braking tracks using Laser-Induced Breakdown Spectroscopy, a feasibility study

Author: Prochazka, D. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2016)

Applications

DOI: 10.1016/j.sab.2016.02.013

Authors
Bilík, M. ; Brada, M. ; Bradáč, A. ; Kaiser, J. ; Klus, J. ; Novotný, J. ; Novotný, K. ; Pořízka, P. ; Prochazková, P. ; Semela, M. ; Ticová, B.

Keywords

Braking tracks; Forensic; LIBS; Tire treads; Laser-Induced Breakdown Spectroscopy;

Abstract

Identification of the position, length and mainly beginning of a braking track has proven to be essential for determination of causes of a road traffic accident. With the introduction of modern safety braking systems and assistance systems such as the Anti-lock Braking System (ABS) or Electronic Stability Control (ESC), the visual identification of braking tracks that has been used up until the present is proving to be rather complicated or even impossible. This paper focuses on identification of braking tracks using a spectrochemical analysis of the road surface. Laser-Induced Breakdown Spectroscopy (LIBS) was selected as a method suitable for fast in-situ element detection. In the course of detailed observations of braking tracks it was determined that they consist of small particles of tire treads that are caught in intrusions in the road surface. As regards detection of the “dust” resulting from wear and tear of tire treads in the environment, organic zinc was selected as the identification element in the past. The content of zinc in tire treads has been seen to differ with regard to various sources and tire types; however, the arithmetic mean and modus of these values are approximately 1% by weight. For in-situ measurements of actual braking tracks a mobile LIBS device equipped with a special module was used. Several measurements were performed for 3 different cars and tire types respectively which slowed down with full braking power. Moreover, the influence of different initial speed, vehicle mass and braking track length on detected signal is discussed here.

Area:

Industry ; LOD ; Traffic

Material:

Braking track

Elements:

Lines [nm]:

Zn I 328.23 nm Zn I 330.26 nm

Emmision lines:
Zn I 328.23 nm
Zn I 330.26 nm

Detection of tire tread particles using laser-induced breakdown spectroscopy

Author: Prochazka, D. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2015)

Applications

DOI: 10.1016/j.sab.2015.03.011

Authors
Bilík, M. ; Bradáč, A. ; Kaiser, J. ; Klus, J. ; Novotný, J. ; Novotný, K. ; Pořízka, P. ; Prochazková, P. ; Semela, M. ; Ticová, B.

Keywords

LIBS; Laser-induced breakdown spectroscopy; Tire tread; Optimization ;

Abstract

The objective of this paper is a study of the potential of laser induced breakdown spectroscopy (LIBS) for detection of tire tread particles. Tire tread particles may represent pollutants; simultaneously, it is potentially possible to exploit detection of tire tread particles for identification of optically imperceptible braking tracks at locations of road accidents. The paper describes the general composition of tire treads and selection of an element suitable for detection using the LIBS method. Subsequently, the applicable spectral line is selected considering interferences with lines of elements that might be present together with the detected particles, and optimization of measurement parameters such as incident laser energy, gate delay and gate width is performed. In order to eliminate the matrix effect, measurements were performed using 4 types of tires manufactured by 3 different producers. An adhesive tape was used as a sample carrier. The most suitable adhesive tape was selected from 5 commonly available tapes, on the basis of their respective LIBS spectra. Calibration standards, i.e. an adhesive tape with different area content of tire tread particles, were prepared for the selected tire. A calibration line was created on the basis of the aforementioned calibration standards. The linear section of this line was used for determination of the detection limit value applicable to the selected tire. Considering the insignificant influence of matrix of various types of tires, it is possible to make a simple recalculation of the detection limit value on the basis of zinc content in a specific tire.

Area:

Industry ; LOD ; Traffic

Material:

Braking track ; Tire

Elements:

Lines [nm]:

Zn I 328.23 nm Zn I 330.26 nm Zn I 334.50 nm

Emmision lines:
Zn I 328.23 nm
Zn I 330.26 nm
Zn I 334.50 nm

Comparative study on fast classification of brick samples by combination of principal component analysis and linear discriminant analysis using stand-off and table-top laser-induced breakdown spectroscopy

Author: Vítková, G. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2014)

Chemometrics

DOI: 10.1016/j.sab.2014.08.036

Authors
Čelko, L. ; Kaiser, J. ; Novotný, J. ; Novotný, K. ; Pořízka, P. ; Prokeš, L. ; Všianský, D.

Keywords

Stand-off LIBS; Laser-induced breakdown spectroscopy; Classification; PCA; LDA; Cultural heritage;

Abstract

Focusing on historical aspect, during archeological excavation or restoration works of buildings or different structures built from Brick it is important to determine, preferably in-situ and in real-time, the locality of Brick origin. Fast classification of Brick on the base of Laser-Induced Breakdown Spectroscopy (LIBS) spectra is possible using multivariate statistical methods. Combination of principal component analysis (PCA) and linear discriminant analysis (LDA) was applied in this case. LIBS was used to classify altogether the 29 brick samples from 7 different localities. Realizing comparative study using two different LIBS setups — stand-off and table-top it is shown that stand-off LIBS has a big potential for archeological in-field measurements.

Area:

Archaeology ; Classification ; Cultural heritage ; Industry

Material:

Brick

Elements:

Emmision lines:

Identification of quantum dots labeled metallothionein by fast scanning laser-induced breakdown spectroscopy

Author: Konečná, M. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2014)

Applications

DOI: 10.1016/j.sab.2014.08.037

Authors
Adam, V. ; Blažková, I. ; Hodek, P. ; Kaiser, J. ; Kizek, R. ; Kopel, P. ; Křížková, S. ; Novotný, K.

Keywords

Laser-induced breakdown spectroscopy; Cadmium; Quantum dot; Metallothionein; Immunoassay;

Abstract

The technique described in this paper allows detection of quantum dots (QDs) specifically deposited on the polystyrene surface by laser-induced breakdown spectroscopy (LIBS). Using LIBS, the distribution of QDs or their conjugates with biomolecules deposited on the surface can be observed, regardless of the fact if they exhibit fluorescence or not. QDs deposited on the specific surface of polystyrene microplate in the form of spots are detected by determination of the metal included in the QDs structure. Cd-containing QDs (CdS, CdTe) stabilized with mercaptopropionic (MPA) or mercaptosuccinic (MSA) acid, respectively, alone or in the form of conjugates with metallothionein (MT) biomolecule are determined by using the 508.58 nm Cd emission line. The observed absolute detection limit for Cd in CdTe QDs conjugates with MT in one spot was 3 ng Cd. Due to the high sensitivity of this technique, the immunoanalysis in combination with LIBS was also investigated. Cd spatial distribution in sandwich immunoassay was detected.

Area:

Biology

Material:

Polystyrene ; Quantum dot

Elements:

Lines [nm]:

Cd I 508.58 nm

Emmision lines:
Cd I 508.58 nm

Fast identification of biominerals by means of stand-off laser-induced breakdown spectroscopy using linear discriminant analysis and artificial neural network

Author: Vítková, G. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2012)

Applications Chemometrics

DOI: 10.1016/j.sab.2012.05.010

Authors
Hrdlička, A. ; Kaiser, J. ; Malina, R. ; Novotný, J. ; Novotný, K. ; Prochazka, D. ; Prokeš, L.

Keywords

Stand‐off LIBS; Laser-induced breakdown spectroscopy; PCA; LDA; ANN; Biomineral; Geomaterial; Archaeology;

Abstract

The goal of this paper is to compare two selected statistical techniques used for identification of archeological materials merely on the base of their spectra obtained by stand-off laser-induced breakdown spectroscopy (stand-off LIBS). Data processing using linear discriminant analysis (LDA) and artificial neural networks (ANN) were applied on spectra of 18 different samples, some of them archeological and some recent, containing 7 types of material (i.e. shells, mortar, Brick, soil pellets, ceramic, teeth and bones). As the input data PCA scores were taken. The intended aim of this work is to create a database for simple and fast identification of archeological or paleontological materials in situ. This approach can speed up and simplify the sampling process during archeological excavations that nowadays tend to be quite damaging and time-consuming.

Area:

Archaeology ; Classification ; Cultural heritage

Material:

Bone ; Brick ; Mortar ; Potsherd ; Shell ; Soil ; Tile ; Tooth

Elements:

Emmision lines:

Correlation of acoustic and optical emission signals produced at 1064 and 532 nm laser-induced breakdown spectroscopy (LIBS) of glazed wall tiles

Author: Hrdlička, A. ; et. al.

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy (2009)

Fundamentals Applications

DOI: 10.1016/j.sab.2008.10.043

Authors
Čtvrtníčková, T. ; Galiová, M. ; Kaiser, J. ; Kanický, V. ; Krásenský, P. ; Malina, R. ; Novotný, K. ; Otruba, V. ; Páleníková, K. ; Zaorálková, L.

Keywords

laser induced breakdown spectroscopy; LIBS; Acoustic signal; Normalization; Internal standard; Ceramic tile; Depth profiling;

Abstract

An acoustic signal was used for the internal standardization of laser-induced breakdown spectroscopy (LIBS) of a glazed wall tile. For the LIBS analyses, 1064 nm and 532 nm wavelengths of the Nd:YAG laser were utilized. The tile was depth profiled by a single-spot ablation from the glaze into the substrate. Some lines of major elements Si(I) 252.418, Si(I) 252.851, Al(I) 257.509, Cr(I) 295.368, Al(I) 309.271 nm and Ti(II) 334.904 nm were monitored. The decrease in the optical emissions during the ablation was successfully compensated for by normalization to the square power of the acoustic signal in the interval of 290–340 nm. This approach failed for the lines between 250–270 nm. The results were the same for both lasing wavelengths despite different irradiances. The acquired profiles are in good agreement with the reference X-ray fluorescence measurement.

Area:

Acoustics ; Industry

Material:

Ceramic tile ; Glaze ; Tile

Elements:

Lines [nm]:

Al I 257.51 nm Al I 309.27 nm

Lines [nm]:

Si I 252.41 nm Si I 252.85 nm

Lines [nm]:

Ti II 394.90 nm

Lines [nm]:

Cr I 295.37 nm

Emmision lines:
Si I 252.41 nm
Si I 252.85 nm
Al I 257.51 nm
Cr I 295.37 nm
Al I 309.27 nm
Ti II 394.90 nm

Journal: Spectrochimica Acta Part B: Atomic Spectroscopy

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