Calibration-free Laser-induced Breakdown Spectroscopy Method Research Articles

Rare earth elements and radioactive elements in black sands from the Konkan and Malabar coasts of India

ABSTRACT The objective of the present work is to demonstrate the ability of the laser-induced breakdown spectroscopy (LIBS) technique for quick detection and quantification of rare earth elements (REEs) and radioactive elements in the black sands at selected locations of the Konkan coast (Goa) and Malabar coast (Kerala) in India. Several REEs such as Ce, Nd, Sm, Dy, Ho, Tm, Gd, and Th have been detected in the LIBS spectra. Calibration-free LIBS method has been used to calculate the concentration of REEs and radioactive elements. The experimental result shows that the concentration of REEs such as Sm, Dy, Ho, and radioactive element Th is maximum in the sands collected from Thiruvananthapuram (Kerala) beach and minimum in the Baga (Goa) beach. The reliability of the results (qualitative and quantitative) obtained by the LIBS method has been examined by other spectroscopic techniques like XRF and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and found to be in close agreement. The multivariate approach (principal component analysis) has been applied to discern the samples based on their spectral data. Photoacoustic spectroscopy and XRD technique are used to detect compounds/minerals of REEs. The relative hardness, degree of crystallinity (DOC), and crystallite size have been calculated.

Characterization of impurity distribution and composition on the shutter plate for an optical diagnosis in EAST tokamak using laser-induced breakdown spectroscopy

The quantification of impurities in tokamak devices is of great significance as it allows for a better understanding of the plasma performance and the lifetime of plasma-facing components (PFCs). This study focuses on the characterization of the impurity distribution and composition on the surface of a shutter plate for an optical diagnosis in the Experimental Advanced Superconducting Tokamak (EAST) by Laser-Induced Breakdown Spectroscopy (LIBS). The primary impurity elements, including copper (Cu), tungsten (W), molybdenum (Mo), lithium (Li), and Sodium(Na), were identified by analyzing the LIBS spectra obtained from the surface of the shutter plate. The spatial distribution of these impurities on both sides of the plate was investigated. The analysis results indicate an increase in impurity content on the outer surface of the shutter plate as proximity to Last Closed Flux Surface (LCFS), followed by a near-linear decrease with the distance from the LCFS. The results of the inner ring on the inner side facing the glass window show fewer metal impurities than the outer rings on the edge for the inner side of the plate. Moreover, the thickness of the deposition layer was determined by estimating the Average Ablation Rate (AAR) through the measurement by confocal microscopy. In addition, Calibration-Free LIBS method were performed to determine the relative content of impurities. The results of this study provide valuable references for studying the migration and transportation of impurities.

New Insights on Modern Age Coins by Calibration-Free Laser-Induced Breakdown Spectroscopy Method and Chemometric Approaches

New Insights on Modern Age Coins by Calibration-Free Laser-Induced Breakdown Spectroscopy Method and Chemometric Approaches

Quantification of Aluminum Gallium Arsenide (AlGaAs) Wafer Plasma Using Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS).

In this work, we report the results of the compositional analysis of an aluminum gallium arsenide (AlGaAs) sample using the calibration-free laser-induced breakdown spectroscopy (CF-LIBS) technique. The AlGaAs sample was doped with three various concentrations of gallium (Ga), arsenic (As), and aluminum (Al), as reported by the manufacturer, and the CF-LIBS technique was employed to identify the doping concentration. A pulsed Q-switched Nd: YAG laser capable of delivering 200 and 400 mJ energy at 532 and 1064 nm, respectively, was focused on the target sample for ablation, and the resulting emission spectra were captured using a LIBS 2000+ spectrometer covering the spectral range from 200 to 720 nm. The emission spectra of the AlGaAs sample yielded spectral lines of Ga, As, and Al. These lines were further used to calculate the plasma parameters, including electron temperature and electron number density. The Boltzmann plot method was used to calculate the electron temperature, and the average electron temperature was found to be 5744 ± 500 K. Furthermore, the electron number density was calculated from the Stark-broadened line profile method, and the average number density was calculated to be 6.5 × 1017 cm−3. It is further observed that the plasma parameters including electron temperature and electron number density have an increasing trend with laser irradiance and a decreasing trend along the plume length up to 2 mm. Finally, the elemental concentrations in terms of weight percentage using the CF-LIBS method were calculated to be Ga: 94%, Al: 4.77% and As: 1.23% for sample-1; Ga: 95.63%, Al: 1.15% and As: 3.22% for sample-2; and Ga: 97.32%, Al: 0.69% and As: 1.99% for sample-3. The certified concentrations were Ga: 95%, Al: 3% and As: 2% for sample-1; Ga: 96.05%, Al: 1% and As: 2.95% for sample-2; and Ga: 97.32%, Al: 0.69% and As: 1.99% for sample-3. The concentrations measured by CF-LIBS showed good agreement with the certified values reported by the manufacturer. These findings suggest that the CF-LIBS technique opens up an avenue for the industrial application of LIBS, where quantitative/qualitative analysis of the material is highly desirable.

Characterization of toxic substances present in smoking tobacco using different spectroscopic techniques

Laser-induced breakdown spectroscopy (LIBS), a laser-based atomic spectroscopic technique, has been used to investigate the presence of toxic/heavy elements/compounds in various smoking tobacco samples. Based on the analysis of the LIBS spectra, the presence of toxic elements like Cr, Sb, Sr, Ni, and Ba, including organic elements C, H, N, O and other common elements like Fe, Mg, Na, and K, has been confirmed in the tobacco samples. Electronic bands of diatomic molecules such as CN and C2 are also observed in the LIBS spectra of the samples, which may be due to the presence of nicotine, chlorophyll, anthocyanin, etc., organic compounds. Calibration-free LIBS (CF-LIBS), a mathematical method, is used to determine the concentration of constituents using the intensity of the spectral lines of the species in the tobacco samples. Atomic absorption spectroscopy (AAS) technique is also used to determine the concentration of elements. The result obtained by AAS validates the result obtained using the CF-LIBS method. The presence of the organic compounds/molecules in the tobacco samples has been investigated using photoacoustic spectroscopy (PAS). Based on the analysis of the PAS spectrum, various organic compounds/molecules like nicotine, chlorophyll, pheophytin, β-carotenoid, anthocyanin, pheophytin, chlorophyllide, and bacteriochlorophy II are identified in the tobacco samples. UV-Visible absorption spectroscopy of these samples is used to compare the results obtained by PAS. Principal component analysis, a multivariate method, is applied to LIBS data to classify the various smoking tobacco samples based on their constituents. Our results show that ten smoking tobacco samples of different brands are forming three different clusters based on the similarity of their constituents.

Quantitative laser-induced breakdown spectroscopy for discriminating neoplastic tissues from non-neoplastic ones.

In this paper, we present a method to distinguish neoplastic tissues from non-neoplastic ones using calibration-free laser-induced breakdown spectroscopy (CF-LIBS). For this propose, plasma emission was collected from neoplastic and non-neoplastic tissues taken from the ovarian cancer mice models. Results were obtained by utilizing the characteristic plasma emission lines of different elements that have been confirmed in the investigated samples. From the temporal evolution of plasma emission, the optimum temporal-observation-windows are identified for LIBS investigation. The concentrations of the detected elements in tissues were measured by a calibration-free approach based on data process of plasma parameters at the local thermodynamic equilibrium. The neoplastic specimens provided more energetic plasma than non-neoplastic ones that resulting in higher peaks intensities, electron density and electron temperature especially in the early windows (between 0.1 µs to 0.8 µs). Results demonstrated higher concentrations of major and trace elements such as Mg, Fe, Ca, Na, and K in the neoplastic tissues. Finally, the results using CF-LIBS method were found to be in good agreement with that of Inductive coupled plasma-optical emission spectroscopy (ICP-OES).

Plasma Diagnostic by Optical Emission Spectroscopy on Dolomite and Cross-Validation Using Scanning Electron Microscopy Coupled with Energy Dispersive X-ray Spectroscopy and Electron Probe Micro-Analysis

Dolomite [CaMg(CO3)2] is an important carbonate mineral mainly composed of calcium magnesium carbonate. The correct determination of magnesium content in carbonate rocks is important for accessing its suitability for different applications; however, presence of different phases with varying magnesium contents makes their analysis difficult. In the present work, a natural carbonate mineral dolomite is analyzed qualitatively and quantitatively using laser-induced breakdown spectroscopy along with X-ray diffraction, scanning electron microscopy coupled with energy dispersive spectroscopy and electron-probe microanalysis. The optical emission spectra recorded in 200–720 nm wavelength region revealed presence of emission lines for Ca, Mg, Al, Sr, and Na with varying intensities. We used two different techniques, that is, Boltzmann plot and Saha–Boltzmann plot methods to calculate the plasma temperature, and an average value of 4500 ± 450 K was deduced.The Stark broadening line profile method was exploited to calculate the electron number density using calcium and magnesium lines which resulted in 2.39 × 1017 cm–3. The quantitative compositional analysis was carried out using calibration-free laser-induced breakdown spectroscopy method for which the local thermodynamic equilibrium and optically thin plasma conditions were satisfied.The composition for dolomite major constituents calcium and magnesium were estimated as 68.58 and 31.41%, respectively.The results demonstrated the LIBS, EDS, and EPMA ability as an effective, powerful and complementary analytical techniques for the elemental composition analysis of carbonate minerals.

Quantitative elemental analysis of high silica bauxite using calibration-free laser-induced breakdown spectroscopy.

Bauxite is a primary ore of aluminum. Precise information about bauxite mineralogical composition is challenging and crucial for efficient aluminum extraction and for the determination of its appropriateness for different industrial applications. For the qualitative and quantitative analysis of bauxite ore, we performed laser-induced breakdown spectroscopy (LIBS) in conjunction with x-ray diffraction (XRD), x-ray fluorescence spectroscopy (XRF), scanning electron microscopy coupled with energy dispersive x-ray spectroscopy (SEM-EDS), and Fourier transform infrared spectroscopy (FTIR). Analysis of the acquired optical emission spectrum revealed the presence of Si, Al, Fe, K, Ti, Ca, Mg, Na, Cr, and Sr. The plasma temperature and electron number density values estimated using Boltzmann plot and Stark-broadening line profile methods were 5600K and 7.65×1017 cm-3, respectively. In the present study we show that a calibration-free LIBS method presents a powerful solution, enabling quantitative analysis of multi-element bauxite ore better than traditional analytical techniques. The bauxite quantification obtained using CF-LIBS under the assumption of local thermodynamic equilibrium and optically thin plasma was Si=47.31%, Al=31.90%, Fe=16.54%, K=2.45%, Ti=1.64%, and Ca=0.16%, and its comparison with the outcome from XRD, XRF, SEM-EDS, and FTIR not only assisted but potentially enhanced the mineralogical composition understanding of bauxite ore in the present study.

Spectral fitting approach for the determination of enrichment and contamination factors in mining sediments using laser-induced breakdown spectroscopy.

Monitoring of pollution index values in sediments is crucial in assessing the environmental impacts of toxic metals in a given location. These indices are typically acquired using elaborate and tedious calibration curve-dependent techniques such as (inductively coupled plasma - optical emission spectroscopy) ICP-OES and (atomic absorption spectroscopy) AAS. In this study, laser-induced breakdown spectroscopy (LIBS) was used as a simple and fast alternative method for estimating enrichment factor (EF) and contamination factor (CF) of the sediment samples obtained from selected mining sites. Quantitative analyses of three metal targets (Cd, Pb, and Zn) were done using a calibration-free LIBS method based on the Boltzmann population distribution. Both the EF and CF values calculated from classical ICP-OES method provided significantly high correspondence with the respective EF (R2 = 0.8862-0.9770, p < 0.01-0.05) and CF (R2 = 0.9454-0.9714, p < 0.01) obtained from the developed LIBS method. The intensity-based LIBS approach identified samples AC2 and CCC as the ones with the highest and lowest pollution index values, respectively. The same observation was seen using the concentration-based ICP-OES technique which showed good correlation between the two methods. The correlation results showed the potential of the curve-fitting LIBS analysis in evaluating the level of metal contamination in an area without the preparation of matrix-matched calibration curves.

Laser-induced breakdown spectroscopy measurement of a small fraction of rhenium in bulk tungsten

Laser-induced breakdown spectroscopy (LIBS) of bulk rhenium (Re) and tungsten (W)-Re alloy has been performed using a Q-switched Nd:YAG laser (wavelength = 1064 nm, pulse width ∼4–6 ns, laser energy = 115 mJ). It is found that the electron temperature, Te, of laser-induced Re plasma is lower than that of W plasma, and that Te of W-Re plasma is in between Re and W plasmas. This indicates that material properties affect Te in a laser-induced plasma. For analysis of W-3.3%Re alloy, only the strongest visible Re I 488.9 nm line is found to be used because of the strong enough intensity without contamination with W lines. Using the calibration-free LIBS method, the atomic fraction of Re, cRe, is evaluated as a function of the ambient Ar gas pressure, PAr. At PAr < 10 Torr, LIBS-measured cRe agrees well with that from EDX (energy-dispersive X-ray micro-analysis), while cRe increases with an increase in PAr at >10 Torr due to spectral overlapping of the Re I 488.9 nm line by an Ar II 488.9 nm line.

Determination of toxic and essential metals in rock and sea salts using pulsed nanosecond laser-induced breakdown spectroscopy.

A spectrometer based on pulsed nanosecond laser-induced breakdown spectroscopy (LIBS) was employed for the quantitative determination of heavy and essential metals in salts from various sources available in Pakistan. Six salt samples were collected from sea salt and rock salt. Toxic metals (Cu, Cd, and Ni) and other microessentials (Fe, Ca, Co, Mg, Mn, S, and Zn) were investigated from the recorded spectra. The detection system was calibrated using a parametric dependence study. The quantitative analyses were accomplished under the assumption of local thermodynamic equilibrium and optically thin plasma. The results by the LIBS technique were in agreement with the outcomes of the same samples studied using a more standard approach like inductively coupled plasma-atomic emission spectroscopy (ICP-AES). When the concentrations of heavy and essential metals were calculated using a calibration-free LIBS method that does not need a standard salt specimen and dilution, both LIBS and ICP-AES were also in good agreement. The limit of detection of the experimental set up was determined for the observed heavy metals in the studied samples.

Analysis of LiSn alloy at several depths using LIBS

The difference between the composition of the surface and the inner part of the LiSn sample was studied using Calibration Free Laser Induced Breakdown Spectroscopy (CF-LIBS) method. The sample was analysed under the low pressure (1330Pa) in Ar atmosphere. The spectra were record using Echelle spectrometer (Mechelle ME5000). Gate delay and gate width was optimised and set to 300ns. In order to analyse depth profile the LIBS spectra was recorded after each laser shot. The electron density analysed by laser induced plasma was determined separately for each laser shot, which means for each ablated layer of investigated sample. The difference between the individual shots taken at distinct sites of the sample are shown. The CF-LIBS method was used to determine the elemental composition near the surface and in the central part of the LiSn sample.

A Comparative Study of Calibration Free Methods for the Elemental Analysis by Laser Induced Breakdown Spectroscopy

We have used two calibration free laser induced breakdown spectroscopy (CF-LIBS) methods for the quantitative analysis of Pb–Sn alloys with different compositions. The first method is based on Boltzmann plots where the elemental concentration is determined from the intercept along the y-axis whereas the second method is the electron density conservation method, in which elemental compositions are determined by comparing the experimentally measured number density with the theoretical results obtained by CF-LIBS. The neutral spectral lines of lead and tin have been used for the estimation of plasma temperature by the Boltzmann plot method whereas the Saha–Boltzmann equation has been used to calculate the electron number density. By comparing the results of both CF-LIBS methods, it is concluded that the CF-LIBS (electron number density conservation) method is more appropriate than the CF-LIBS (Boltzmann plot method) for the quantitative elemental analysis.

Use of the near vacuum UV spectral range for the analysis of W-based materials for fusion applications using LIBS

The vacuum UV (VUV)-near Infrared (NIR) laser induced breakdown spectroscopy (LIBS) technique was applied to investigate the composition of W-based samples with a protective carbon layer. The sample was analyzed under pressures from 5 to 105 Pa and atmosphere (air, He). The spectra were recorded with three spectrometers at delays from 200 ns to 10 μs at atmospheric pressures and from 100 to 500 ns at low pressures. The electron density was determined from the measured spectra using Stark broadening and the electron temperature from the W I–W III Saha–plot in the VUV–NIR spectral range. The better precision was achieved due to usage W III spectral lines of tungsten. The achieved results are more reliable than results obtained without W III spectral lines. The calibration free LIBS method was then applied to determine the W and C contents of the analyzed sample.

Calibration-free analysis of immersed brass alloys using long-ns-duration pulse laser-induced breakdown spectroscopy with and without correction for nonstoichiometric ablation

Long-ns-duration, single pulse laser-induced breakdown spectroscopy (LIBS) is known to be an effective method to observe well resolved spectra from samples immersed in water at high hydrostatic pressures. The aim of this study is to investigate whether the signals obtained using this method are suitable for quantitative analysis of chemical composition. Six certified brass alloys consisting of copper (Cu), zinc (Zn) and lead (Pb) were measured underwater using a laser pulse of duration 250ns, and their compositions were determined using calibration-free LIBS (CF-LIBS) and corrected CF-LIBS (CCF-LIBS) methods. The mass fractions of Cu and Zn calculated using CF-LIBS showed better agreement with the certified values than those determined using CCF-LIBS, with relative errors of Cu 4.2±3.3 % and Zn 7.2±6.4 %. From the results, it can be said that the difference of preferential evaporation and ablation among elements does not need to be considered for underwater measurements with the long-pulse LIBS setup used in this work. While the results indicate that the CF-LIBS method can be applied for in situ quantitative analysis of major elements with concentrations>~10 %, the mass fractions determined for Pb, with concentrations<5 % had large relative errors, suggesting that an alternative method is required to quantify minor elements.

Influence of sample temperature on the expansion dynamics and the optical emission of laser-induced plasma

We investigate the influence of sample temperature on the dynamics and optical emission of laser induced plasma for various solid materials. Bulk aluminum alloy, silicon wafer, and metallurgical slag samples are heated to temperature TS≤500°C and ablated in air by Nd:YAG laser pulses (wavelength 1064nm, pulse duration approx. 7ns). The plasma dynamics is investigated by fast time-resolved photography. For laser-induced breakdown spectroscopy (LIBS) the optical emission of plasma is measured by Echelle spectrometers in combination with intensified CCD cameras. For all sample materials the temporal evolution of plume size and broadband plasma emission vary systematically with TS. The size and brightness of expanding plumes increase at higher TS while the mean intensity remains independent of temperature. The intensity of emission lines increases with temperature for all samples. Plasma temperature and electron number density do not vary with TS. We apply the calibration-free LIBS method to determine the concentration of major oxides in slag and find good agreement to reference data up to TS=450°C. The LIBS analysis of multi-component materials at high temperature is of interest for technical applications, e.g. in industrial production processes.

Quantitative determination of element concentrations in industrial oxide materials by laser-induced breakdown spectroscopy

Calibration-free laser-induced breakdown spectroscopy (CF-LIBS) method is employed for quantitative determination of oxide concentrations in multi-component materials. Industrial oxide materials from steel industry are laser ablated in air, and the optical plasma emission is collected by spectrometers and gated detectors. The temperature and electron number density of laser-induced plasma are determined from measured LIBS spectra. Emission lines of aluminium (Al), calcium (Ca), iron (Fe), manganese (Mn), magnesium (Mg), silicon (Si), titanium (Ti), and chromium (Cr) of low self-absorption are selected, and the concentration of oxides CaO, Al(2)O(3), MgO, SiO(2), FeO, MnO, TiO(2), and Cr(2)O(3) is calculated by CF-LIBS analysis. For all sample materials investigated, we find good match of calculated concentration values (C(CF)) with nominal concentration values (C(N)). The relative error in oxide concentration, e(r) = |C(CF) - C(N)|/C(N), decreases with increasing concentration and it is e(r) ≤ 100% for concentration C(N) ≥ 1 wt.%. The CF-LIBS results are stable against fluctuations of experimental parameters. The variation of laser pulse energy over a large range changes the error by less than 10% for major oxides (C(N) ≥ 10 wt.%). The results indicate that CF-LIBS method can be employed for fast and stable quantitative compositional analysis of multi-component materials.

Application of LIBS in Detection of Antihyperglycemic Trace Elements in Momordica charantia

The present study exploits the information based on concentration of trace elements and minerals in understanding the role/mechanism of action of freeze-dried fruit powder suspended in distilled water of Momordica charantia (family: Cucurbitaceae) in diabetes treatment. Laser-induced break down spectroscopy (LIBS) spectra of plant product was recorded under optimized experimental conditions and analyzed. Several atomic lines such as Na, K, Mg, Ca, Fe, Al, etc. have been observed in the LIBS spectra of the above plant product. The concentrations of these minerals are determined by using calibration-free LIBS method. Correlation between the concentration of these elements/minerals and their defined role in diabetes management was studied in normal as well as diabetic animal models.

Investigation of common Indian edible salts suitable for kidney disease by laser induced breakdown spectroscopy

Salt is an essential and important dietary mineral for maintaining life. Currently, the issue of the potential benefit or damage from salt intake in chronic kidney disease patients is controversial. The attempt of this article is to bring into focus the potential role of elements particularly sodium, Na, and potassium, K, which are the main constituents of dietary salts, in kidney patients by using laser-induced breakdown spectroscopy (LIBS). LIBS spectra of different salt samples have been recorded in the spectral region 200-500 nm with spectral resolution 0.1 nm and in the spectral region 200-900 nm with spectral resolution 0.75 nm. Quantitative elemental study was carried out to determine the constituents of different types of common Indian edible salts by using the calibration-free LIBS method. Our experimental results demonstrate that Saindha salt (commonly known as rock salt) is more beneficial than other edible salts for patients suffering from chronic kidney disease. The results of the quantitative elemental analysis of the salts obtained from LIBS measurements are also compared to atomic absorption spectroscopy (AAS).

Quantitative analysis of gallstones using laser-induced breakdown spectroscopy

The utility of laser-induced breakdown spectroscopy (LIBS) for categorizing different types of gallbladder stone has been demonstrated by analyzing their major and minor constituents. LIBS spectra of three types of gallstone have been recorded in the 200-900 nm spectral region. Calcium is found to be the major element in all types of gallbladder stone. The spectrophotometric method has been used to classify the stones. A calibration-free LIBS method has been used for the quantitative analysis of metal elements, and the results have been compared with those obtained from inductively coupled plasma atomic emission spectroscopy (ICP-AES) measurements. The single-shot LIBS spectra from different points on the cross section (in steps of 0.5 mm from one end to the other) of gallstones have also been recorded to study the variation of constituents from the center to the surface. The presence of different metal elements and their possible role in gallstone formation is discussed.