Fast and sensitive trace metal analysis in aqueous solutions by laser-induced breakdown spectroscopy using wood slice substrates

To perform fast and sensitive trace metal analysis in aqueous solutions by laser-induced breakdown spectroscopy (LIBS) based on only one single-pulse laser system, a wood slice has been used as a liquid absorber to transform liquid sample analysis to solid sample analysis using LIBS. High detection sensitivity and good reproducibility can be achieved with this approach. Calibration curves for five metal elements, Cr, Mn, Cu, Cd, and Pb under trace concentrations, have been obtained, and the limits of their detection were determined to be in the range of 0.029–0.59 mg L^− 1, 2–3 orders better than those obtained by directly analyzing liquid samples where the laser was focused on a liquid surface. The wood slice was very easy to handle and thus, the whole analysis process took only 4–5 min for each sample. This approach provides a more practical approach for fast and sensitive metal element analysis in aqueous solutions using LIBS, which is especially useful for monitoring toxic heavy metals in water.     

Detection of heavy metals in Arabian crude oil residue using laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) was applied for the elemental analysis of Arabian crude oil residue samples. The spectra due to trace elements such as Ca, Fe, Mg, Cu, Zn, Na, Ni, K and Mo were recorded using this technique. The dependence of time delay and laser beam energy on the elemental spectra was also investigated. Prior to quantitative analysis, the LIBS system was calibrated using standard samples containing these trace elements. The results achieved through this method were compared with conventional technique like inductively coupled plasma.     

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.     

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.     

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.     

Mapping of different structures on large area of granite sample using laser-ablation based analytical techniques,an exploratory study

Laser-ablation based analytical techniques represent a simple way for fast chemical analysis of different materials. In this work, an exploratory study of multi-element (Ca, Al, Fe, Mn) mappings of a granite sample surface was performed by laser-induced breakdown spectroscopy (LIBS) and subsequently by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. The operating parameters (e.g. pulse energy, ablation-crater size) were optimized for both techniques in order to achieve the appropriate conditions for two-dimensional high-resolution compositional mappings of mineral microstructures in large sample areas. The sample was scanned with 100 × 100 individual sample points to map an area of 20 × 20 mm². The normalized signals were used for construct of contour plots which were colored according local distribution of the selected elements. The results of two laser-based methods were compared and found to be similar.     

LIBS for landmine detection and discrimination

The concept of utilizing laser-induced breakdown spectroscopy (LIBS) technology for landmine detection and discrimination has been evaluated using both laboratory LIBS and a prototype man-portable LIBS systems. LIBS spectra were collected for a suite of landmine casings, non-mine plastic materials, and ‘clutter-type’ objects likely to be present in the soil of a conflict area or a former conflict area. Landmine casings examined included a broad selection of anti-personnel and anti-tank mines from different countries of manufacture. Other materials analyzed included rocks and soil, metal objects, cellulose materials, and different types of plastics. Two ‘blind’ laboratory tests were conducted in which 100 broadband LIBS spectra were obtained for a mixed suite of landmine casings and clutter objects and compared with a previously-assembled spectral reference library. Using a linear correlation approach, ‘mine/no mine’ determinations were correctly made for more than 90% of the samples in both tests. A similar test using a prototype man-portable LIBS system yielded an analogous result, validating the concept of using LIBS for landmine detection and discrimination.     

Geochemistry study of soil affected catastrophically by tsunami disaster triggered by 2004 Indian Ocean earthquake using a fourth harmonics (λ = 266 nm) Nd:YAG laser induced breakdown spectroscopy

In this work, laser induced breakdown spectroscopy (LIBS) analysis of the soil samples collected from Aceh, a place in Indonesia worst affected by 2004 Indian Ocean tsunami, was conducted. In the LIBS experimental system, a high energy pulsed laser beam was focused on the tsunami affected soil samples and the atomic emission lines, originating from the laser induced plasma were recorded using locally developed laser induced breakdown spectrometer. Our results show that the concentrations of many elements especially terrestrial markers, namely titanium, iron, and carbonate marker such as magnesium, are higher in the tsunami-affected samples than that in the unaffected samples collected from the same neighborhood. The quantification of Ti, Fe and Mg were carried out using Ti II 334.94, Fe I 438.35, and Mg I 277.98 nm atomic transition lines respectively by drawing the calibration curve by preparing the samples of known concentrations in unaffected soil matrix. In order to ensure accurate quantification, the local thermal equilibrium of the laser-induced plasma was verified using Mc Writher criterion, for which the plasma temperature was estimated using linearized Boltzmann plot for six iron atomic transition lines and the electron number density in the plasma was estimated using Stark broadened Fe I 540.4 nm atomic lines. The estimated temperature and electron number density of the laser induced plasma are 9642 K and 3.5 × 10¹⁶ cm^?3 respectively. The concentrations of Ti, Fe and Mg in tsunami unaffected soil are 0.09, 3.2 and 0.02 w/w% and in tsunami affected soil are 0.14, 7.9 and 0.048 w/w% respectively. These values are in good agreement with XRF data. The elemental ratios extracted from LIBS signal intensity revealed that LIBS emission intensity ratios of several elements, such as Si/Ti, Al/Ti and Sr/Ba are potential candidates as the distinctive geochemical signature for identification the soil impacted and unimpacted by the 2004 Indian Ocean giant tsunami. The advantage of using LIBS for the elemental analysis is that the sample can be analyzed in its pristine form without any need cumbersome sample preparation method, which has the risk of bringing in external additives through chemicals used for the sample preparation. Other advantages of LIBS technique are that the analysis can be in situ and can be carried out remotely.     

Evaluation of grinding methods for pellets preparation aiming at the analysis of plant materials by laser induced breakdown spectrometry

It has been demonstrated that laser induced breakdown spectrometry (LIBS) can be used as an alternative method for the determination of macro (P, K, Ca, Mg) and micronutrients (B, Fe, Cu, Mn, Zn) in pellets of plant materials. However, information is required regarding the sample preparation for plant analysis by LIBS. In this work, methods involving cryogenic grinding and planetary ball milling were evaluated for leaves comminution before pellets preparation. The particle sizes were associated to chemical sample properties such as fiber and cellulose contents, as well as to pellets porosity and density. The pellets were ablated at 30 different sites by applying 25 laser pulses per site (Nd:YAG@1064 nm, 5 ns, 10 Hz, 25 J cm⁻²). The plasma emission collected by lenses was directed through an optical fiber towards a high resolution echelle spectrometer equipped with an ICCD. Delay time and integration time gate were fixed at 2.0 and 4.5 μs, respectively. Experiments carried out with pellets of sugarcane, orange tree and soy leaves showed a significant effect of the plant species for choosing the most appropriate grinding conditions. By using ball milling with agate materials, 20 min grinding for orange tree and soy, and 60 min for sugarcane leaves led to particle size distributions generally lower than 75 μm. Cryogenic grinding yielded similar particle size distributions after 10 min for orange tree, 20 min for soy and 30 min for sugarcane leaves. There was up to 50% emission signal enhancement on LIBS measurements for most elements by improving particle size distribution and consequently the pellet porosity.     

Evaluation of laser induced breakdown spectroscopy for the determination of micronutrients in plant materials

Laser induced breakdown spectroscopy (LIBS) has been evaluated for the determination of micronutrients (B, Cu, Fe, Mn and Zn) in pellets of plant materials, using NIST, BCR and GBW biological certified reference materials for analytical calibration. Pellets of approximately 2 mm thick and 15 mm diameter were prepared by transferring 0.5 g of powdered material to a 15 mm die set and applying 8.0 tons cm^− 2. An experimental setup was designed by using a Nd:YAG laser operating at 1064 nm (200 mJ per pulse, 10 Hz) and an Echelle spectrometer with ICCD detector. Repeatability precision varied from 4 to 30% from measurements obtained in 10 different positions (8 laser shots per test portion) in the same sample pellet. Limits of detection were appropriate for routine analysis of plant materials and were 2.2 mg kg^− 1 B, 3.0 mg kg^− 1 Cu, 3.6 mg kg^− 1 Fe, 1.8 mg kg^− 1 Mn and 1.2 mg kg^− 1 Zn. Analysis of different plant samples were carried out by LIBS and results were compared with those obtained by ICP OES after wet acid decomposition.     

Laser-induced breakdown spectroscopy for simultaneous determination of Sm, Eu and Gd in aqueous solution

This paper reports studies on the determination of trace levels of samarium, europium and gadolinium in aqueous samples by laser-induced breakdown spectroscopy (LIBS). In this work, a membrane-based filter paper was used as a sample support for the liquid samples. The laser-induced plasma was produced in air at atmospheric pressure, using a pulsed Nd:YAG laser. Calibration standards and synthetic mixtures of these lanthanides were prepared using solutions prepared from respective high purity oxides. Linear calibration was obtained for Sm, Eu and Gd by normalizing the intensities of lanthanides emission lines with respective to C(I) 193.029 nm emission line. The concentrations of Sm, Eu and Gd were then determined in a solution containing a mixture of these lanthanides. The concentrations of individual lanthanides were obtained within 5% of the expected values. Limits of detection were found to be 1.3 ppmw (Sm), 1.9 ppmw (Eu) and 2.3 ppmw (Gd).     

Influence of pulse-to-pulse delay for 532 nm double-pulse laser-induced breakdown spectroscopy of technical polymers

Laser induced breakdown spectroscopy (LIBS) is an emerging technique for fast and accurate compositional analysis of many different materials. We present a systematic study of collinear double-pulse LIBS on different technical polymers such as polyamide, polyvinyl chloride, polyethylene etc. Polymer samples were ablated in air by single-pulse and double-pulse Nd:YAG laser radiation (8 ns pulse duration) and spectra were recorded with an Echelle spectrometer equipped with an ICCD camera. We investigated the evolution of atomic and ionic line emission intensities for different delay times between the laser pulses (from 20 ns to 500 μs) at a laser wavelength of 532 nm. We observed double-pulse LIBS signals that were enhanced as compared to single-pulse measurements depending on the delay time and the type of polymer material investigated. LIBS signals of polymer materials that are enhanced by double-pulse excitation may be useful for monitoring the concentration of heavy metals in polymer materials.     

Evaluation of laser induced breakdown spectroscopy for the determination of macronutrients in plant materials

Laser induced breakdown spectroscopy (LIBS) has become an analytical tool for the direct analysis of a large variety of materials in order to provide qualitative and/or quantitative information. However, there is a lack of information for LIBS analysis of agricultural and environmental samples. In this work a LIBS system has been evaluated for the determination of macronutrients (P, K, Ca, Mg) in pellets of vegetal reference materials. An experimental setup was designed by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with ICCD detector. The plasma temperature was estimated by Boltzmann plots and instrumental parameters such as delay time, lens-to-sample distance and pulse energy were evaluated. Certified reference materials as well as reference materials were used for analytical calibrations of P, K, Ca, and Mg. Most results of the direct analysis of plant samples by LIBS were in reasonable agreement with those obtained by ICP OES after wet acid decomposition.     

Assessment of statistical uncertainty in the quantitative analysis of solid samples in motion using laser-induced breakdown spectroscopy

Statistical uncertainty in the quantitative analysis of solid samples in motion by laser-induced breakdown spectroscopy (LIBS) has been assessed. For this purpose, a LIBS demonstrator was designed and constructed in our laboratory. The LIBS system consisted of a laboratory-scale conveyor belt, a compact optical module and a Nd:YAG laser operating at 532 nm. The speed of the conveyor belt was variable and could be adjusted up to a maximum speed of 2 m s^− 1. Statistical uncertainty in the analytical measurements was estimated in terms of precision (reproducibility and repeatability) and accuracy. The results obtained by LIBS on shredded scrap samples under real conditions have demonstrated that the analytical precision and accuracy of LIBS is dependent on the sample geometry, position on the conveyor belt and surface cleanliness. Flat, relatively clean scrap samples exhibited acceptable reproducibility and repeatability; by contrast, samples with an irregular shape or a dirty surface exhibited a poor relative standard deviation.     

Signal enhancement of lead and arsenic in soil using laser ablation combined with fast electric discharge

In comparison to the traditional single pulse laser induced breakdown spectroscopy (SP-LIBS), a significant enhancement of atomic emission of lead and arsenic from laser plasma of soil has been demonstrated by the use of a laser ablation and fast pulse discharge plasma spectroscopy technique (LA-FPDPS). In this technique, a specifically designed high voltage and rapid discharge circuit was used to reheat the laser plasma and to enhance the plasma emission. A rapid and time damped alternating discharge current was observed with a short oscillating period ∼ 0.6 μs and sustained for about 6 μs. The peak intensities of Pb (283.31 nm) and As (286.04 nm) lines from soil plasma emission were greatly enhanced when compare to the traditional single pulse (SP) LIBS system. In addition, the precision of measurements in terms of the relative standard deviation (RSD) and the signal to noise (S/N) ratios were also improved. Scanning electron microscopy (SEM) images of the laser ablation regions indicated that the plasma reheating by the discharge spark was presumably the main mechanism for observed signal enhancement in the LA-FPDPS technique.     

Review: Applications of single-shot laser-induced breakdown spectroscopy

As applications for laser-induced breakdown spectroscopy (LIBS) become more varied with a greater number of field and industrial LIBS systems developed and as the technique evolves to be more quantitative that qualitative, there is a more significant need for LIBS systems capable of analysis with the use of a single laser shot. In single-shot LIBS, a single laser pulse is used to form a single plasma for spectral analysis. In typical LIBS measurements, multiple laser pulses are formed and collected and an ensemble-averaged method is applied to the spectra. For some applications there is a need for rapid chemical analysis and/or non-destructive measurements; therefore, LIBS is performed using a single laser shot. This article reviews in brief several applications that demonstrate the applicability and need for single-shot LIBS.     

Use of LIBS for rapid characterization of parchment

Parchment from different sources has been analyzed by laser-induced breakdown spectroscopy (LIBS) for determination of Ca, Na, K, Mg, Fe, Cu, and Mn. The LIBS results were compared with results from inductively coupled plasma spectroscopy (ICP) and good correlation was obtained. Rapid distinction between modern and historical samples was achieved by discriminant analysis of the LIBS data. Animal type recognition was also possible on the basis of Mg/Cu emission peak ratio and Mg depth profiling.     

Laser-induced breakdown spectroscopy for detection of explosives residues: a review of recent advances, challenges, and future prospects

In this review we discuss the application of laser-induced breakdown spectroscopy (LIBS) to the problem of detection of residues of explosives. Research in this area presented in open literature is reviewed. Both laboratory and field-tested standoff LIBS instruments have been used to detect explosive materials. Recent advances in instrumentation and data analysis techniques are discussed, including the use of double-pulse LIBS to reduce air entrainment in the analytical plasma and the application of advanced chemometric techniques such as partial least-squares discriminant analysis to discriminate between residues of explosives and non-explosives on various surfaces. A number of challenges associated with detection of explosives residues using LIBS have been identified, along with their possible solutions. Several groups have investigated methods for improving the sensitivity and selectivity of LIBS for detection of explosives, including the use of femtosecond-pulse lasers, supplemental enhancement of the laser-induced plasma emission, and complementary orthogonal techniques. Despite the associated challenges, researchers have demonstrated the tremendous potential of LIBS for real-time detection of explosives residues at standoff distances. Figure This review discusses the application of laser-induced breakdown spectroscopy (LIBS) to the problem of explosive residue detection. LIBS offers the capability for real-time, standoff detection of trace amounts of residue explosives on various surfaces     

Evaluation of laser induced breakdown spectroscopy for cadmium determination in soils

Cadmium is known to be a toxic agent that accumulates in the living organisms and present high toxicity potential over lifetime. Efforts towards the development of methods for microanalysis of environmental samples, including the determination of this element by graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma optical emission spectrometry (ICP OES), and inductively coupled plasma-mass spectrometry (ICP-MS) techniques, have been increasing. Laser induced breakdown spectroscopy (LIBS) is an emerging technique dedicated to microanalysis and there is a lack of information dealing with the determination of cadmium. The aim of this work is to demonstrate the feasibility of LIBS for cadmium detection in soils. The experimental setup was designed using a laser Q-switched (Nd:YAG, 10 Hz, λ = 1064 nm) and the emission signals were collimated by lenses into an optical fiber coupled to a high-resolution intensified charge-coupled device (ICCD)-echelle spectrometer. Samples were cryogenically ground and thereafter pelletized before LIBS analysis. Best results were achieved by exploring a test portion (i.e. sampling spots) with larger surface area, which contributes to diminish the uncertainty due to element specific microheterogeneity. Calibration curves for cadmium determination were achieved using certified reference materials. The metrological figures of merit indicate that LIBS can be recommended for screening of cadmium contamination in soils.     

Laser-induced breakdown spectroscopy of γ-Fe2O3 nanoparticles in a biocompatible alginate matrix

An intensive multi-disciplinary research effort is underway at Wayne State University to synthesize and characterize magnetic nanoparticles in a biocompatible matrix for biomedical applications. The particular system being studied consists of 3–10 nm γ-Fe₂O₃ nanoparticles in an alginate matrix, which is being studied for applications in targeted drug delivery, as a magnetic-resonance imaging (MRI) contrast agent, and for hyperthermic treatments of malignant tumors. In the present work we report on our efforts to determine if laser-induced breakdown spectroscopy (LIBS) can offer a more accurate and substantially faster determination of iron content in such nanoparticle-containing materials than competing technologies such as inductively-coupled plasma (ICP). Standardized samples of -Fe₂O₃ nanoparticles (5–25 nm diameter) and silver micropowder (2–3.5 μm diameter) were created with thirteen precisely known concentrations and pressed hydraulically to create solid “pellets” for LIBS analysis. The ratio of the intensity of an Fe(I) emission line at 371.994 nm to that of an Ag(I) line at 328.069 nm was used to create a calibration curve exhibiting an exponential dependence on Fe mass fraction. Using this curve, an “unknown” γ-Fe₂O₃/alginate/silver pellet was tested, leading to a measurement of the mass fraction of Fe in the nanoparticle/alginate matrix of 51 ± 3 wt.%, which is in very good agreement with expectations and previous determinations of its iron concentration.