Calibration-free Laser-induced Breakdown Spectroscopy Technique Research Articles

Chemometrics and Spectroscopic Analyses of Peganum harmala Plant’s Seeds by Laser-Induced Breakdown Spectroscopy

In the present work, the rapid identification of elements and their relative chemical composition in various Peganum harmala seed samples were investigated using a calibration-free laser-induced breakdown spectroscopy technique (CF-LIBS). A pulsed Nd:YAG laser-source with a 5 ns pulse-duration, and 10 Hz pulse repetition rates providing 400 and 200 mJ energy at 1064 and 532 nm wavelength, respectively, was focused on the Peganum harmala seed samples for ablation. A LIBS 2000+ spectrometer within the wavelength range (200 to 720 nm), emission-spectra were recorded. The measured spectra of the Peganum harmala sample gives spectral lines of Carbon (C), Magnesium (Mg), Lithium (Li), Sodium (Na), Calcium (Ca), Silicon (Si), Iron (Fe), Strontium (Sr), Copper (Cu), Potassium (K), and Lead (Pb). A CF-LIBS technique has been employed for the compositional study of the elements exist in the Peganum harmala seed samples. The measured results demonstrate that C, Mg, and Ca are found to be major elements in the Peganum harmala seed samples with compositions of ~36.64%, ~24.09%, and ~19.03%, respectively. Along with the major elements, the elements including Li, Na, Si, K, Fe, and Sr were identified as minor elements with compositions of ~2.87%, ~2.33%, ~3.72%, ~7.17%, ~2.83%, and ~1.14%, respectively. Besides Cu (~8.07 μg/g), and Pb (~1.10 μg/g) elements were observed as trace elements exist in the Peganum harmala seed samples. Furthermore, the electron number density including the plasma excitation-temperature were calculated using the stark-broadening line profile method and the Saha–Boltzmann plot method, respectively. The plasma parameters versus laser-irradiance and the distance from the sample were further investigated. Moreover, a principal component analysis (PCA) method was also utilized to the spectral data obtained by using LIBS to discriminate various seed samples with four classes, namely, α, β, γ, and Δ. Three principal-components (PCs) calculated from eigenvalues of score matrix described 87.6%, 4.6%, and 2.5% of total variance for PC1, PC2, and PC3, respectively. The LIBS spectral data variance covered by the initial 3 PCS was found as ~94.7% of total variance. The PCA results have successfully demonstrated the different classes of the Peganum harmala seed samples based on the different doping compositional ratios of the Zn element. This study confirmed the feasibility and ability of LIBS and PCA for the rapid analysis of Peganum harmala seed samples. Finally, the results achieved using CF-LIBS were incorporated with those obtained from the XRF and EDX analytical techniques.

Elemental study of Devarda’s alloy using calibration free-laser induced breakdown spectroscopy (CF‒LIBS)

In the present study, we present the compositional analysis of a Devarda’s alloy using the calibration–free laser-induced breakdown spectroscopy (CF-LIBS) technique. A nanosecond pulsed Q-switched Nd:YAG laser was focused on the target-sample under investigation to ablate its surface and the measured emission spectrum was registered by using a spectrometer (LIBS2000+) having the optical spectral within a range from 200–720 nm. The analysis of the measured optical spectra confirms the presence of three major elements Aluminum (Al), Copper (Cu), and Zinc (Zn) in the target sample. The emission intensity line profiles of Zn, Cu, and Al were utilized to estimate the plasma-parameters consisting of excitation temperature, and the plasma number density. The plasma excitation temperature was investigated using the Boltzmann-plot technique, which yields the temperature for Cu and Zn as 8547 ± 5% K and 8100 ± 5%, respectively, while the electron plasma density was calculated from the Stark-broadening of individual neutral emission lines of Al, Cu, and Zn. For the quantitative analysis of the elements that exist in the target sample, a CF-LIBS technique was employed by assuming the condition of optically thin plasma as well as local thermodynamics equilibrium. Using the CF-LIBS technique, the relative composition in the form of weight percentage was estimated to be Zn: 57%, Al: 39%, and Cu: 4%, whereas, the certified concentration of Devarda’s alloy was 50% for Zn, 45% for Al, and 5% for Cu. These measured results reveal that the elemental concentration utilizing CF-LIBS shows a reasonable agreement with standard estimates illustrated by the manufacturer. This study further suggests that the CF-LIBS technique opens up an opportunity for engineering and industrial usage of LIBS where a quantifiable study of the substance is exceedingly advantageous.

Laser Spectroscopic Characterization for the Rapid Detection of Nutrients along with CN Molecular Emission Band in Plant-Biochar

We report a quantitative analysis of various plant-biochar samples (S1, S2 and S3) by utilizing a laser-induced breakdown spectroscopy (LIBS) technique. For LIBS analysis, laser-induced microplasma was generated on the target surface by using a focused beam through a high-power Nd: YAG laser and optical emission spectra were recorded using a charged coupled device (CCD) array spectrometer, with wavelength ranges from 200 nm to 720 nm. The spectroscopical analysis showed the existence of various ingredients, including H, Li, Ca, Na, Al, Zn, Mg, Sr, Si, and Fe, along with a CN molecular emission band due to B2Σ+ − X2Σ+ electronic transition. By assuming conditions of the plasma is optically thin and in LTE, calibration-free laser-induced breakdown spectroscopy (CF-LIBS) was utilized for the compositional analysis of the ingredients present in the three plant-biochar samples. To lower the uncertainties, we used an average composition (%) of the three plant-biochar samples. The quantitative study of the plant-biochar samples was also achieved using the energy dispersive X-ray (EDX) technique, showing good agreement with the CF-LIBS technique. In addition, statistical analysis, such as principal component analysis (PCA), was performed for the clustering and classification of the three plant-biochar samples. The first three PCs explained an overall ~91% of the variation in LIBS spectral data, including PC1 (58.71%), PC2 (20.9%), and PC3 (11.4%). These findings suggest that LIBS is a robust tool for rapid measurement of heavy as well as light elements, such as H, Li, and nutritional metals in plant-biochar samples.

Comparison of Mg/Ca concentration series from Patella depressa limpet shells using CF-LIBS and LA-ICP-MS

The elemental composition of marine mollusk shells can offer valuable information about environmental conditions experienced by a mollusk during its lifespan. Previous studies have shown significant correlations between Mg/Ca concentration ratios measured on biogenic carbonate of mollusk shells and sea surface temperature (SST). Here we propose the use of Laser-Induced Breakdown Spectroscopy (LIBS) and the validation of the Calibration-Free LIBS (CF-LIBS) approach for the rapid measurement and estimation of Mg/Ca molar concentration profiles within Patella depressa Pennant, 1777 limpet shells. To achieve these objectives, results derived from CF-LIBS methodology are compared with those obtained from an established analytical technique for this purpose, such as Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Concentration series obtained with both methodologies show defined temporal patterns and reflect the season-of-capture in each specimen. The results evidence a significant correlation (R2 = 0.63–0.81) between CF-LIBS and LA-ICP-MS Mg/Ca molar concentration profiles within four live-collected P. depressa shells. Averaged error for the molar concentration estimated with CF-LIBS was lower than 10% in every specimen. The comparison between the results obtained from two techniques used in this study has allowed us to demonstrate for the first time that Mg/Ca molar concentration measured in biogenic carbonates were accurately inferred using CF-LIBS technique. The CF-LIBS approach validation represents great potential for the rapid and large-scale paleoenvironmental and archaeological analysis of this mollusk species, which is frequently found in archaeological sites.

Analytical Analysis of Different Karats of Gold Using Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Time of Flight Mass Spectrometer (LA-TOF-MS)

Laser induced breakdown spectroscopy (LIBS) coupled with a laser ablation time of flight mass spectrometer (LA-TOF-MS) has been developed for discrimination/analysis of the precious gold alloys cartage. Five gold alloys of Karats 18K, 19K, 20K, 22K and 24K having certified composition of gold as 75, 79, 85, 93 and 99.99% were tested and their precise elemental compositions were determined using the laser produced plasma technique. The plasma was generated by focusing beam of a Nd:YAG laser on the target in air and its time integrated emission spectra were registered in the range 250–870 nm. The calibration free LIBS technique (CF-LIBS) was used for the quantitative determination of the constituent elements present in different Karats of gold. Elemental compositions of these gold alloys were also determined using a Laser Ablation time of flight mass spectrometer (LA-TOF-MS). The LIBS limit of detection was calculated from the calibration curves for copper, silver and gold. Results of CF-LIBS and LA-TOF-MS are in excellent agreement with the certified values. It is demonstrated that LIBS coupled with LA-TOF-MS is an efficient technique that can be used to analyze any precious alloys in a fraction of a second.

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

We present qualitative and quantitative analysis of the trace elements present in different brands of tobacco available in Pakistan using laser induced breakdown 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 LA-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.

Quantitative Analysis of Metallic Elements in Tobacco and Tobacco Ash by Calibration Free Laser-Induced Breakdown Spectroscopy

Cigarette smoking may be a substantial source of intake of some hazardous elements to the human health. In this work calibration-free laser-induced breakdown spectroscopy technique was employed to investigate the trace metallic elements (Fe, Ca, Al, Cu, K, Li, Mg, Mn, Na, Sr, Ti, and Zn) concentration in tobacco and tobacco ash. Moreover, variation of metallic elements mass concentration between tobacco and tobacco ash has been observed.

LIBS: A Quality Control Tool for Food Supplements

In the present paper the ability of calibration free laser induced breakdown spectroscopy (CF-LIBS) as a quality control tool to monitor the composition of different minerals present in food supplement samples belonging to Indian brands (brand-A and brand-B) has been demonstrated. LIBS spectra of these two food supplements (brand-A and brand-B) available in the form of tablet have been recorded. As reported by manufacturers of these two food supplements, LIBS spectra of brand-A contains the spectral signatures of minerals like Ca, Mg, C, P, Zn, Fe, Cu, and Cr whereas LIBS spectra of brand-B shows the presence of spectral lines like Ca, Mg and C. The spectral signatures of Na and K are also found in both brands whereas spectral signature of Ti is observed only in brand-B but these elements are not mentioned on the nutritional label of the brands. The quantitative analysis of mineral contents in food supplements has been done using CF-LIBS for brand A and brand B to verify the content of the minerals reported by the manufacturer of the food supplements. Our results show that Ca and Mg are the main matrix elements of these brands. The concentration of minor and trace elements estimated using CF-LIBS technique is found in agreement with the reported nutritional values of both the brands. The concentration of major elements Ca and Mg are also estimated from Atomic Absorption Spectroscopy which is in close agreement with CF-LIBS result.