Fused glass sample preparation for quantitative laser-induced breakdown spectroscopy of geologic materials

Laser-induced breakdown spectroscopy is a powerful analytical method, but LIBS is subject to a matrix effect which can limit its ability to produce quantitative results in complex materials such as geologic samples. Various methods of sample preparation, calibration, and data processing have been attempted to compensate for the matrix effect and improve LIBS precision. This study focuses on sample preparation by comparing fused glass as a preparation for powdered material to the more commonly used method of pressing powder into pellets for LIBS analysis of major elements in complex geologic materials. Pelletizing powdered material is a common and convenient method for preparing samples but problems with the physical matrix brought on by inconsistencies in the homogeneity, density, and laser absorption, coupled with the chemical matrix problem lead to spectral peak responses that are not always consistent with the absolute concentration of representative elements. Twenty-two mineral and rock samples were analyzed for eight major oxide elements. Samples were prepared under both glass and pellet methods and compared for internal precision and overall accuracy. Fused glass provided a more consistent physical matrix and yielded more reliable peak responses in the LIBS analysis than did the pressed pellet preparation. Statistical comparisons demonstrated that the glass samples expressed stronger separability between different mineral species based on the eight elements than for the pressed pellets and showed better spot-to-spot repeatability. Regression models showed substantially better correlations and predictive ability among the elements for the glass preparation than did those for the pressed pellets.     

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.     

Elemental Analysis of Cement by Calibration-Free Laser Induced Breakdown Spectroscopy (CF-LIBS) and Comparison with Laser Ablation – Time-of-Flight – Mass Spectrometry (LA-TOF-MS), Energy Dispersive X-Ray Spectrometry (EDX), X-Ray Fluorescence Spectroscopy (XRF), and Proton Induced X-Ray Emission Spectrometry (PIXE)

The purpose of the present study is to determine the elemental composition of Pakistani cement brands using calibration-free laser induced breakdown spectroscopy (CF-LIBS) and to compare the obtained results with the other analytical techniques such as, laser ablation – time-of-flight – mass spectrometry (LA-TOF-MS), energy dispersive X-ray spectrometry (EDX), X-ray fluorescence spectroscopy (XRF) and proton induced X-ray emission spectrometry (PIXE). Compositional results reveal that all the cement brands are mainly composed of calcium, silicon, iron, aluminum, magnesium, potassium, sodium, titanium, lithium and strontium with varying concentrations. The compositions obtained by LIBS and LA-TOF-MS are in good agreement with results obtained by the other standard techniques and demonstrate the potential use of LIBS for the online monitoring of industrial cement production.     

Correction of self-absorption effect in calibration-free laser-induced breakdown spectroscopy by an internal reference method

A simplified procedure for correcting self-absorption effect was proposed in calibration-free laser-induced breakdown spectroscopy (CF-LIBS). In typical LIBS measurement conditions, the plasma produced is often optically thick, especially for the strong lines of major elements. The selection of self-absorption lines destroys the performance of CF-LIBS, and the familiar correction method based on the curve of growth is complex in implementation. The procedure we proposed, named internal reference for self-absorption correction (IRSAC), first chose an internal reference line for each species, then compared other spectral line intensity of the same species with the reference line to estimate the self-absorption degrees of other spectral lines, and finally achieved an optimal correction by a regressive algorithm. The self-absorption effect of the selected reference line can be ignored, since the reference line with high excitation energy of the upper level is slightly affected by the self-absorption. Through the IRSAC method, the points on the Boltzmann plot become more regular, and the evaluations of the plasma temperature and material composition are more accurate than the basic CF-LIBS.     

Calibration-Free Laser-Induced Breakdown Spectroscopy: State of the art

The aim of this paper is offering a critical review of Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS), the approach of multi-elemental quantitative analysis of LIBS spectra, based on the measurement of line intensities and plasma properties (plasma electron density and temperature) and on the assumption of a Boltzmann population of excited levels, which does not require the use of calibration curves or matrix-matched standards. The first part of this review focuses on the applications of the CF-LIBS method. Quantitative results reported in the literature, obtained in the analysis of various materials and in a wide range of experimental conditions, are summarized, with a special emphasis on the departure from nominal composition values. The second part is a discussion of the simplifying assumptions which lie at the basis of the CF-LIBS algorithm (stoichiometric ablation and complete atomization, thermal equilibrium, homogeneous plasma, thin radiation, detection of all elements). The inspection of the literature suggests that the CF-LIBS method is more accurate in analyzing metallic alloys rather than dielectrics. However, the full exploitation of the method seems to be still far to come, especially for the lack of a complete characterization of the effects of experimental constraints. However, some general directions can be suggested to help the analyst in designing LIBS measurements in a way which is more suited for CF-LIBS analysis.     

Time-resolved ultraviolet laser-induced breakdown spectroscopy for organic material analysis

Ultraviolet pulses (266 nm) delivered by a quadrupled Nd:YAG laser were used to analyze organic samples with laser-induced breakdown spectroscopy (LIBS). We present characteristics of the spectra obtained from organic samples with special attentions on the emissions of organic elements, O and N, and molecular bonds CN. The choice of these atomic or molecular species is justified on one hand, by the importance of these species to specify organic or biological materials; and on the other hand by the possible interferences with ambient air when laser ablation takes place in the atmosphere. Time-resolved LIBS was used to determine the time-evolution of line intensity emitted from these species. We demonstrate different kinetic behaviors corresponding to different origins of emitters: native atomic or molecular species directly vaporized from the sample or those generated through dissociation or recombination due to interaction between laser-induced plasma and air molecules. Our results show the ability of time-resolved UV-LIBS for detection and identification of native atomic or molecular species from an organic sample.     

Quantitative elemental analysis of nutritional,hazardous and pharmacologically active elements in medicinal Rhatany root using laser induced breakdown spectroscopy

Rhatany roots (RRs) have been used in indigenous systems of medicines to treat many common illnesses due to the presence of highly active astringent and antiviral biochemical constituents that possess strong therapeutic and pharmacological properties. Due to its widespread use, the accurate knowledge on the elemental composition of this medicinal plant can set a pharmacological research platform to investigate the effect of certain elements, and their ions in mediating the human metabolism and therapy. In this work calibration-free laser-induced breakdown spectroscopy (CF-LIBS) is used to detect the elements present in RRs sample, by analyzing the characteristic emission wavelengths and their respective intensities in the laser induced plasma, without the need for using any calibration standards or methods. Many nutritional elements, which are of human health significance and instrumental in mediating the established biological activities of RRs, were identified in a relative abundance. In addition to this, our analysis identified the trace level of a few toxic elements, whose overdose due to reckless intake wreaks havoc to human health and wellbeing. The reliability of qualitative and quantitative detection of the elements in RR by LIBS were validated by the standard inductively coupled plasma optical emission spectroscopy (ICP OES), the results of which are in good agreement with LIBS data with better relative accuracy. Also, in order to discriminate, and single out any two elements with the overlapping emission wavelength in LIBS, X-ray photoelectron spectroscopy was also carried out, which in its own right is in good agreement with the elemental analysis of LIBS in general.     

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.     

Analysis of Soil by Magnetic Field Assisted Calibration-Free Laser Induced Breakdown Spectroscopy (CF-LIBS) and Laser Ablation – Time-of-Flight Mass Spectrometry (LA-TOF-MS)

The qualitative and quantitative analysis of soil samples collected from Sialkot, Pakistan (which contains leather industrial plants), has been performed using laser-induced breakdown spectroscopy (LIBS) and laser ablation time of flight mass spectrometry (LA-TOF-MS). The focused beam of a Q-switched Nd: YAG laser (532?nm) was used to ablate the soil samples in air at atmospheric pressure. The optical emission spectra demonstrate the presence of the spectral lines of Si, Fe, Al, Ca, Ti, K, Cr, Mg, Na, Ba, and Li in all of the samples. The emission lines intensities, electron number densities, and excitation temperatures were significantly enhanced in the presence of an external 0.3 T magnetic field applied perpendicular to the plasma plume. A maximum enhancement factor of approximately 8 was observed in the emission intensity. The emergence of several additional lines has also been detected using the magnetic field-assisted LIBS approach. The elemental composition determined using calibration-free laser-induced breakdown spectroscopy (CF-LIBS), with and without magnetic field, reveals that the external magnetic field only adjusts the laser-generated plasma dynamics without affecting the quantitative analysis of the samples. Importantly, the toxic and heavy elements such as chromium and barium were detected and quantified in all of the soil samples by both of these techniques. The variations in the compositional analysis using CF-LIBS with and without the applied magnetic field and LA-TOF-MS were less than 10%.     

A matrix effect and accuracy evaluation for the determination of elements in milk powder LIBS and laser ablation/ICP-OES spectrometry

Laser ablation coupled to inductively coupled plasma optical emission spectrometry (LA-ICP-OES) and laser-induced breakdown spectroscopy (LIBS) were investigated for the determination of Ca, Mg, Zn and Na in milk samples. The accuracy of both methods was evaluated by comparison of the concentration found using LA-ICP-OES and LIBS with classical wet digestion associated with ICP-OES determination. The results were not fully acceptable, with biases from less than 1% to more than 60%. Matrix effects were also investigated. The sample matrix can influence the temperature, electron number density (n _e) and other excitation characteristics in the ICP. These ICP characteristics were studied and evaluated during ablation of eight milk samples. Differences in n _e (from 8.9 to 13.8 × 10¹⁴ cm⁻³) and rotational temperature (ranging from 3,400 to 4,400 K) occurred with no correlation with trueness. LIBS results obtained after classical external calibration procedure gave degraded accuracy, indicating a strong matrix effect. The LIBS measurements clearly showed that the major problem in LA-ICP was related to the ablation process and that LIBS spectroscopy is an excellent diagnostic tool for LA-ICP techniques.     

The influence of laser-particle interaction in laser induced breakdown spectroscopy and laser ablation inductively coupled plasma spectrometry

Particles produced by previous laser shots may have significant influence on the analytical signal in laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma (LA-ICP) spectrometry if they remain close to the position of laser sampling. The effects of these particles on the laser-induced breakdown event are demonstrated in several ways. LIBS-experiments were conducted in an ablation cell at atmospheric conditions in argon or air applying a dual-pulse arrangement with orthogonal pre-pulse, i.e., plasma breakdown in a gas generated by a focussed laser beam parallel and close to the sample surface followed by a delayed crossing laser pulse in orthogonal direction which actually ablates material from the sample and produces the LIBS plasma. The optical emission of the LIBS plasma as well as the absorption of the pre-pulse laser was measured. In the presence of particles in the focus of the pre-pulse laser, the plasma breakdown is affected and more energy of the pre-pulse laser is absorbed than without particles. As a result, the analyte line emission from the LIBS plasma of the second laser is enhanced. It is assumed that the enhancement is not only due to an increase of mass ablated by the second laser but also to better atomization and excitation conditions favored by a reduced gas density in the pre-pulse plasma. Higher laser pulse frequencies increase the probability of particle-laser interaction and, therefore, reduce the shot-to-shot line intensity variation as compared to lower particle loadings in the cell. Additional experiments using an aerosol chamber were performed to further quantify the laser absorption by the plasma in dependence on time both with and without the presence of particles. The overall implication of laser-particle interactions for LIBS and LA-ICP-MS/OES are discussed.     

A comparison of laser ablation inductively coupled plasma mass spectrometry,micro X-ray fluorescence spectroscopy,and laser induced breakdown spectroscopy for the discrimination of automotive glass

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), micro X-ray fluorescence spectroscopy (μXRF), and laser induced breakdown spectroscopy (LIBS) are compared in terms of discrimination power for a glass sample set consisting of 41 fragments. Excellent discrimination results (> 99% discrimination) were obtained for each of the methods. In addition, all three analytical methods produced very similar discrimination results in terms of the number of pairs found to be indistinguishable. The small number of indistinguishable pairs that were identified all originated from the same vehicle. The results also show a strong correlation between the data generated from the use of µXRF and LA-ICP-MS, when comparing µXRF strontium intensities to LA-ICP-MS strontium concentrations. A 266 nm laser was utilized for all LIBS analyses, which provided excellent precision (< 10% RSD for all elements and < 10% RSD for all ratios, N = 5). The paper also presents a thorough data analysis review for forensic glass examinations by LIBS and suggests several element ratios that provide accurate discrimination results related to the LIBS system used for this study. Different combinations of 10 ratios were used for discrimination, all of which assisted with eliminating Type I errors (false exclusions) and reducing Type II errors (false inclusions). The results demonstrate that the LIBS experimental setup described, when combined with a comprehensive data analysis protocol, provides comparable discrimination when compared to LA-ICP-MS and μXRF for the application of forensic glass examinations. Given the many advantages that LIBS offers, most notably reduced complexity and reduced cost of the instrumentation, LIBS is a viable alternative to LA-ICP-MS and μXRF for use in the forensic laboratory.     

Parametric study of a fiber-optic laser-induced breakdown spectroscopy probe for analysis of aluminum alloys

In the present work we demonstrate a fiber-optic laser-induced breakdown spectroscopy (FO LIBS) system for delivering laser energy to a sample surface to produce a spark as well as to collect the resulting radiation from the laser-induced spark. In order to improve the signal/background (S/B) ratio, various experimental parameters, such as laser energy, gate delay and width, detector gain, lenses of different focal lengths and sample surface, were tested. In order to provide high reliability and repeatability in the analysis, we also measured plasma parameters, such as electron density and plasma temperature, and determined their influence on the measurement results. The performance of FO LIBS was also compared with that of a LIBS system that does not use a fiber to transmit the laser beam. LIBS spectra with a good S/B were recorded at 2-μs gate delay and width. LIBS spectra of six different Al alloy samples were recorded to obtain calibration data. We were able to obtain linear calibration data for numerous elements (Cr, Zn, Fe, Ni, Mn, Mg and Cu). A linear calibration curve for LIBS intensity ratio vs. concentration ratio reduces the effect of physical variables (i.e. shot-to-shot power fluctuation, sample-to-surface distance, and physical properties of the samples). Our results reveal that this system may be useful in designing a high-temperature LIBS probe for measuring the elemental composition of Al melt.     

基于黑体辐射提高自由定标激光诱导击穿光谱(CF-LIBS)定量精度的方法

自由定标激光诱导击穿光谱(Calibration-Free LIBS,CF-LIBS)技术是定量分析行业发展的主要趋势之一。该技术可直接基于局部热力学平衡等离子体模型,通过LIBS光谱数据和谱线参数计算出等离子体参数和各元素含量。且无需使用标准样品建立定标曲线,该技术不受基体效应的影响,非常适合实时、在线和多元素同时分析。但由光学厚而引起的自吸收效应是影响定量分析的重要因素。通过对比实验光谱数据与黑体辐射强度,研究等离子体温度,提高光学系统收集效率,抑制自吸收效应对CF-LIBS定量结果的影响。经过黑体辐射校正后,基体元素Fe的测定含量从88.700%提升到94.575%,相对误差(RE)从8.072%降低到1.984%。微量元素Cr、Mo和V的测定含量分别从0.635%、0.096%和0.023%降低至0.698%、0.143%和0.022%,相对误差(RE)从13.723%、45.455%和21.053%降低至5.163%、18.75%和15.789%。整体的平均绝对误差(MAE)从1.994%降低至0.497%。玻尔兹曼图拟合回归曲线有了更高的线性度。拟合系数R²     

The role of various binding materials for trace elemental analysis of powder samples using laser-induced breakdown spectroscopy

Study of various binding materials like potassium bromide, poly(vinyl alcohol), starch, silver and aluminum has been carried out using laser-induced breakdown spectroscopy (LIBS). The role of matrix effects using these five binders on LIBS signal intensity was investigated for better performance of LIBS technique as a quantitative analytical tool. For comparative study of different binders, the signal intensity of different Mg lines at 518.3, 517.2, 383.8 and 279.5 nm wavelengths were recorded for pellets prepared with known concentrations of Mg in these binders. The influence of laser energy on ablated mass under different binding materials and its correlation with LIBS signal intensity has been explored. Optical scanning microscopy images of the ablated crater were studied to understand the laser ablation process. The study revealed that the binding material plays an important role in the generation of LIBS signal. The relative signal intensity measured for a standard Mg line (at 518.3 nm) were 735, 538, 387, 227 and 130 for potassium bromide, starch, poly(vinyl alcohol), silver and aluminum as binders, respectively. This indicates clearly that potassium bromide is better as a binder for LIBS studies of powder samples.     

An evaluation of the analytical performance of collinear multi-pulse laser induced breakdown spectroscopy

A detailed study of the relevant analytical figures of merit for time- and spatially integrated multi-pulse laser induced breakdown spectroscopy (MP-LIBS) was performed. Laser bursts containing up to 6, ns-range duration collinear pulses, separated by 20–40 μs interpulse gaps were used in the experiments, and the effect of the number of pulses within the burst on the analytical parameters was investigated. Signal enhancement, repeatability, matrix effects, background signals, sensitivity, linear dynamic range and limits of detection were studied for 20 lines of 11 elements in different solid matrices. It was established that all analytical figures of merit significantly improved with respect to those of single- or double-pulse LIBS as a result of the use of multiple laser pulses. For example, six-pulse limits of detection values were found to be with a factor of 4.2–16.7 lower than for double-pulses and calibration plots were found to be linear up to several tens of percents concentrations in some alloys.     

Study of matrix effects in laser plasma spectroscopy by shock wave propagation

The origin of analytical matrix effects in laser plasma spectroscopy was investigated. We focused on matrix effects in sand/soil mixtures and attempted to explain the increase in the spectral response of trace elements (at constant concentration) with sand percentage. First, it was found that the energy coupled in the plasma, and which can be calculated from the propagation of the laser induced shock wave, indeed characterizes the matrix. A simple experimental setup for such measurements was suggested. Our results indicate that previous explanations of the matrix effects in this system may not be correct. We suggested that the main matrix effects were attributed to the depth of the laser-induced crater, which was correlated to a portion of the laser energy that penetrates into sand particulates and does not cause direct ablation. This explanation holds when no other effects are present (e.g. grain size distribution). The hypothesis was validated by experimental data.     

Characterization and forensic analysis of soil samples using laser-induced breakdown spectroscopy (LIBS)

A method for the quantitative elemental analysis of surface soil samples using laser-induced breakdown spectroscopy (LIBS) was developed and applied to the analysis of bulk soil samples for discrimination between specimens. The use of a 266 nm laser for LIBS analysis is reported for the first time in forensic soil analysis. Optimization of the LIBS method is discussed, and the results compared favorably to a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method previously developed. Precision for both methods was <10% for most elements. LIBS limits of detection were <33 ppm and bias <40% for most elements. In a proof of principle study, the LIBS method successfully discriminated samples from two different sites in Dade County, FL. Analysis of variance, Tukey’s post hoc test and Student’s t test resulted in 100% discrimination with no type I or type II errors. Principal components analysis (PCA) resulted in clear groupings of the two sites. A correct classification rate of 99.4% was obtained with linear discriminant analysis using leave-one-out validation. Similar results were obtained when the same samples were analyzed by LA-ICP-MS, showing that LIBS can provide similar information to LA-ICP-MS. In a forensic sampling/spatial heterogeneity study, the variation between sites, between sub-plots, between samples and within samples was examined on three similar Dade sites. The closer the sampling locations, the closer the grouping on a PCA plot and the higher the misclassification rate. These results underscore the importance of careful sampling for geographic site characterization.     

Self-absorption model in quantitative laser induced breakdown spectroscopy measurements on soils and sediments

Application of laser induced breakdown spectroscopy (LIBS) in the quantitative analysis of elemental composition of soils with different origins and Antarctic marine sediments has been considered. The analytical method followed includes the usual plasma modeling at local thermal equilibrium (LTE) based on average temperature and electron density values, as well as spectra normalization, introduced in order to reduce the effects related both to the substrate optical and thermal properties and to the influence of laser parameters on quantitative data. The computational algorithm takes into account only atomic species and their first ionization states, which is sufficient at the plasma temperature measured in the experiments. Calibration curves are finally generated for each element of interest measured on certified samples with different provenience and matrix composition. In this paper a model is developed which takes into account the effects responsible for non-linearities in the relationship between line intensity and elemental concentration. The model properly includes line re-absorption and contributions from space regions with different plasma densities. Its application permits us to obtain the correlation coefficients between the LIBS measured and certified concentration of each element analyzed. These coefficients, specific for a given experimental layout and atomic lines data base, are successively applied in analytical LIBS measurements allowing for the direct determination of a single element concentration in any sample, regardless of its unknown matrix composition. The LIBS method presented here was tested on a priori unknown samples, and gave uncertainties in concentration varying from 15 to 40% over a large concentration range covering several orders of magnitude. The measuring error depends on element type, on the concentration value and also on the number of certified samples used for the initial calibration. The present results are already significant for some field application, such as on-board marine sediment analysis where a significant matrix variation with layer depth is common.     

Determination of poisonous metals in wastewater collected from paint manufacturing plant using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) system was developed for determination of toxic metals in wastewater collected from local paint manufacturing plant. The plasma was generated by focusing a pulsed Nd:YAG laser at 1064 nm on the solid residue from wastewater collected from paint industry. The concentration of different elements of environmental significance like, lead, copper, chromium, calcium, sulphur, magnesium, zinc, titanium, strontium, nickel, silicone, iron, aluminum, barium, sodium, potassium and zirconium, in paint wastewater were 6, 3, 4, 301, 72, 200, 20, 42, 4, 1, 35, 120, 133, 119, 173, 28 and 12 mg kg⁻¹, respectively. The evaluation of potential and capabilities of LIBS as a rapid tool for paint industry effluent characterization is discussed in detail. Optimal experimental conditions were evaluated for improving the sensitivity of our LIBS system through parametric dependence study. The laser-induced breakdown spectroscopy (LIBS) results were compared with the results obtained using standard analytical technique such as inductively coupled plasma emission spectroscopy (ICP). The relative accuracy of our LIBS system for various elements as compared with ICP method is in the range of 0.03-0.6 at 2.5% error confidence. Limits of detection (LOD) of our LIBS system were also estimated for the above mentioned elements.