Laser-induced Breakdown Spectrometer Research Articles

Mineralogy, provenance, and diagenesis of a potassic basaltic sandstone on Mars: CheMin X-ray diffraction of the Windjana sample (Kimberley area, Gale Crater).

The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X‐ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, ~Or95); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (~25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X‐ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations—like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser‐Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K‐rich targets have 5.6% K2O, ~1.8 times that of Windjana, implying a sediment component with >40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na2O, and is likely to be basaltic. The K‐rich sediment component is consistent with APXS and ChemCam observations of K‐rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. The presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g., mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar‐age terranes on Earth.

Detection of toxic elements using laser-induced breakdown spectroscopy in smokers' and nonsmokers' teeth and investigation of periodontal parameters.

A laser-induced breakdown spectrometer (LIBS) was built and optimized to detect levels of toxic elements such as lead, cadmium, and arsenic present in the roots of extracted teeth of smokers and nonsmokers. Sixty extracted teeth from patients having a history of chronic periodontitis were divided into two groups of 30 teeth each for smoker and nonsmoker patients and, as controls, a third group of 30 patients who did not have a history of chronic periodontitis. The respective elemental concentration (Pb, Cd, and As) 23-29, 0.26-0. 31, and 0.64-11ppm are for nonsmokers, 35-55, 0.33-0.51, and 0.91-1.5ppm are for smokers, and lastly 0.17-0.31, 0.01-0.05, and 0.05-0.09ppm are for control group. In order to test the validity of the results achieved using our LIBS system, a standard inductively coupled plasma (ICP) technique was also applied for the analysis of the same teeth samples, and ICP results were found to be in excellent agreement with our LIBS results. In addition to this, the gingival index, plaque index, clinical attachment loss (CAL) and probing pocket depth were also recorded. Our LIBS spectroscopic analysis showed high levels of lead, cadmium, and arsenic concentration on root surfaces of teeth, which may be due to CAL.

ChemCam: Chemostratigraphy by the First Mars Microprobe

The ChemCam laser-induced breakdown spectrometer on the rover Curiosity has provided more than 200,000 spectra from over 5000 different locations on Mars. This instrument is the first chemical microprobe on Mars and has an analytical footprint 0.3–0.6 mm in diameter. ChemCam has observed a measure of hydration in all the sedimentary materials encountered along the rover traverse in Gale Crater, indicating the ubiquity of phyllosilicates as a constituent of the analyzed sandstones, mudstones, and conglomerates. Diagenetic features, including calcium sulfate veins, millimeter-thick magnesium-rich diagenetic ridges, and manganese-rich rock surfaces, provide clues to water–rock interactions. Float clasts of coarse-grained igneous rocks are rich in alkali feldspars and some are enriched in fluorine, indicating greater magmatic evolution than expected on Mars. The identification of individual soil components has contributed to our understanding of the evolution of Martian soil. These observations have broadened our understanding of Mars as an active and once habitable planet.

Development of a deep-sea laser-induced breakdown spectrometer for in situ multi-element chemical analysis

Spectroscopy is emerging as a technique that can expand the envelope of modern oceanographic sensors. The selectivity of spectroscopic techniques enables a single instrument to measure multiple components of the marine environment and can form the basis for versatile tools to perform in situ geochemical analysis. We have developed a deep-sea laser-induced breakdown spectrometer (ChemiCam) and successfully deployed the instrument from a remotely operated vehicle (ROV) to perform in situ multi-element analysis of both seawater and mineral deposits at depths of over 1000m. The instrument consists of a long-nanosecond duration pulse-laser, a spectrometer and a high-speed camera. Power supply, instrument control and signal telemetry are provided through a ROV tether. The instrument has two modes of operation. In the first mode, the laser is focused directly into seawater and spectroscopic measurements of seawater composition are performed. In the second mode, a fiber-optic cable assembly is used to make spectroscopic measurements of mineral deposits. In this mode the laser is fired through a 4m long fiber-optic cable and is focused onto the target’s surface using an optical head and a linear stage that can be held by a ROV manipulator. In this paper, we describe the instrument and the methods developed to process its measurements. Exemplary measurements of both seawater and mineral deposits made during deployments of the device at an active hydrothermal vent field in the Okinawa trough are presented. Through integration with platforms such as underwater vehicles, drilling systems and subsea observatories, it is hoped that this technology can contribute to more efficient scientific surveys of the deep-sea environment.

The ChemCam Remote Micro-Imager at Gale crater: Review of the first year of operations on Mars

The Mars Science Laboratory rover, “Curiosity” landed near the base of a 5km-high mound of layered material in Gale crater. Mounted on the rover mast, the ChemCam instrument is designed to remotely determine the composition of soils and rocks located a few meters from the rover, using a Laser-Induced Breakdown Spectrometer (LIBS) coupled to a Remote Micro-Imager (RMI). We provide an overview of the diverse imaging investigations that were carried out by ChemCam’s RMI during the first year of operation on Mars. 1182 individual panchromatic RMI images were acquired from Sol 10 to Sol 360 to document the ChemCam LIBS measurements and to characterize soils, rocks and rover hardware. We show several types of derived imaging products, including mosaics of images taken before and after laser shots, difference images to enhance the most subtle laser pits, merges with color Mastcam-100 images, micro-topography using the Z-stack technique, and time lapse movies. The very high spatial resolution of RMI is able to resolve rock textures at sub-mm scales, which provides clues regarding the origin (igneous versus sedimentary) of rocks, and to reveal information about their diagenetic and weathering evolution. In addition to its scientific value over the range accessible by LIBS (1–7m), we also show that RMI can also serve as a powerful long distance reconnaissance tool to characterize the landscape at distances up to several kilometers from the rover.

Detection of trace elements in nondegradable organic spent clay waste using optimized dual-pulsed laser induced breakdown spectrometer

The detection of trace elements present in nondegradable organic spent clay waste has been carried out using an optimized dual-pulsed laser induced breakdown spectrometer. The two laser pulses at 1064 and 266 nm were collinearly collimated and focused on the sample surface in order to enhance the signal intensity. The atomic transition lines at 568.8 nm (Na-I), 504.2 nm (Pb-II), 405.8 nm (Pb -I), 443.56 nm (Ca-I), 469.41 nm (S-I), 520.8 nm (Cr-I), 643 nm (Cd-I), and 928.1 nm (Cl-I) were used as marker wavelengths, and the concentrations of 688, 300, 204, 460, and 2440 ppm of Pb, S, Cd, Cr, and Cl, respectively, were detected in the 5% spent clay in the binder. The limits of detection of Pb, S, Cd, Cr, and Cl were estimated to be 6.7, 17.2, 6.5, 5.1, and 14.8 ppm, respectively, from the calibration curve for each element. In order to confirm the reliability of our system, the concentrations of the reported elements detected using our system were compared to the ones obtained with inductively coupled plasma emission spectroscopy and found to be in good agreement.

Optimization of a Laser Induced Breakdown Spectroscopy Method for the Analysis of Liquid Samples

A laser-induced breakdown spectrometer has been developed and optimized for the measurement of trace content of metals in Zamzam and in water processed by a Leveluck water machine. Zamzam water was frozen into ice using liquid nitrogen to overcome the LIBS diffi culties, specifi c to the detection of LIBS signal in liquid samples. The laser-produced plasma from the frozen ice sample was then analyzed using this LIBS spectrometer. The important parameters that can influence the sensitivity of the LIBS system, including the laser pulse width and energy, the sample homogeneity and the sampling geometry were optimized.

Testing the veracity of LIBS analyses on Mars using the LIBSSIM program

The LIBSSIM program was developed to aid in understanding data returned by the laser-induced breakdown spectrometer (LIBS) on Mars Science Laboratory (MSL). The program models the effects of rock grain size, mineralogy, sampling density, and beam size on inferred bulk chemical analyses using Martian basaltic compositions. The relationship between grain size and beam size was found to be the most important factor in producing a representative LIBSSIM-predicted bulk composition. As grain size increases relative to beam size, accuracy of calculated bulk compositions decreases, but chemical information about the nature of the component grains is improved. Sampling density takes on greatest importance in coarse-grained samples with large compositional differences among grains, where many analyses are required to reduce standard deviations to acceptable levels. These results stress the importance of careful sampling strategies for the LIBS at the MSL landing site at Gale crater.

Studies on the feasibility of laser-induced breakdown spectroscopy in explosion proof atmospheres

One of the latest major innovations of the Institute for Mining and Metallurgical Machinery (IMR) is the adaption of a laser-induced breakdown spectrometer (LIBS) into the harsh conditions of surface mines. Usually working in the clean environment of laboratories, a compact analyzer consisting of a laser system and a spectrometer was developed to work in harsh environments which are affected by dust, mist, vibration and shock. Now, IMR is working on adjusting this laser system to underground conditions which are aggravated by the possibilities of methane explosions such as in hard coal mines. This project focusses on the conception of the enclosure and it's sampling for LIBS analysis. It is funded by the German Research Foundation (DFG).

The ChemCam Instrument Suite on the Mars Science Laboratory (MSL) Rover: Body Unit and Combined System Tests

The ChemCam instrument suite on the Mars Science Laboratory (MSL) rover Curiosity provides remote compositional information using the first laser-induced breakdown spectrometer (LIBS) on a planetary mission, and provides sample texture and morphology data using a remote micro-imager (RMI). Overall, ChemCam supports MSL with five capabilities: remote classification of rock and soil characteristics; quantitative elemental compositions including light elements like hydrogen and some elements to which LIBS is uniquely sensitive (e.g., Li, Be, Rb, Sr, Ba); remote removal of surface dust and depth profiling through surface coatings; context imaging; and passive spectroscopy over the 240–905 nm range. ChemCam is built in two sections: The mast unit, consisting of a laser, telescope, RMI, and associated electronics, resides on the rover’s mast, and is described in a companion paper. ChemCam’s body unit, which is mounted in the body of the rover, comprises an optical demultiplexer, three spectrometers, detectors, their coolers, and associated electronics and data handling logic. Additional instrument components include a 6 m optical fiber which transfers the LIBS light from the telescope to the body unit, and a set of onboard calibration targets. ChemCam was integrated and tested at Los Alamos National Laboratory where it also underwent LIBS calibration with 69 geological standards prior to integration with the rover. Post-integration testing used coordinated mast and instrument commands, including LIBS line scans on rock targets during system-level thermal-vacuum tests. In this paper we describe the body unit, optical fiber, and calibration targets, and the assembly, testing, and verification of the instrument prior to launch.

Comparison of partial least squares and lasso regression techniques as applied to laser-induced breakdown spectroscopy of geological samples

A remote laser-induced breakdown spectrometer (LIBS) designed to simulate the ChemCam instrument on the Mars Science Laboratory Rover Curiosity was used to probe 100 geologic samples at a 9-m standoff distance. ChemCam consists of an integrated remote LIBS instrument that will probe samples up to 7m from the mast of the rover and a remote micro-imager (RMI) that will record context images. The elemental compositions of 100 igneous and highly-metamorphosed rocks are determined with LIBS using three variations of multivariate analysis, with a goal of improving the analytical accuracy. Two forms of partial least squares (PLS) regression are employed with finely-tuned parameters: PLS-1 regresses a single response variable (elemental concentration) against the observation variables (spectra, or intensity at each of 6144 spectrometer channels), while PLS-2 simultaneously regresses multiple response variables (concentrations of the ten major elements in rocks) against the observation predictor variables, taking advantage of natural correlations between elements. Those results are contrasted with those from the multivariate regression technique of the least absolute shrinkage and selection operator (lasso), which is a penalized shrunken regression method that selects the specific channels for each element that explain the most variance in the concentration of that element. To make this comparison, we use results of cross-validation and of held-out testing, and employ unscaled and uncentered spectral intensity data because all of the input variables are already in the same units. Results demonstrate that the lasso, PLS-1, and PLS-2 all yield comparable results in terms of accuracy for this dataset.However, the interpretability of these methods differs greatly in terms of fundamental understanding of LIBS emissions. PLS techniques generate principal components, linear combinations of intensities at any number of spectrometer channels, which explain as much variance in the response variables as possible while avoiding multicollinearity between principal components. When the selected number of principal components is projected back into the original feature space of the spectra, 6144 correlation coefficients are generated, a small fraction of which are mathematically significant to the regression. In contrast, the lasso models require only a small number (<24) of non-zero correlation coefficients (β values) to determine the concentration of each of the ten major elements. Causality between the positively-correlated emission lines chosen by the lasso and the elemental concentration was examined. In general, the higher the lasso coefficient (β), the greater the likelihood that the selected line results from an emission of that element. Emission lines with negative β values should arise from elements that are anti-correlated with the element being predicted. For elements except Fe, Al, Ti, and P, the lasso-selected wavelength with the highest β value corresponds to the element being predicted, e.g. 559.8nm for neutral Ca. However, the specific lines chosen by the lasso with positive β values are not always those from the element being predicted. Other wavelengths and the elements that most strongly correlate with them to predict concentration are obviously related to known geochemical correlations or close overlap of emission lines, while others must result from matrix effects. Use of the lasso technique thus directly informs our understanding of the underlying physical processes that give rise to LIBS emissions by determining which lines can best represent concentration, and which lines from other elements are causing matrix effects.

Detection of chloride in reinforced concrete using a dualpulsed laser-induced breakdown spectrometer system: comparative study of the atomic transition lines of Cl I at 59485 and 83759 nm

The presence of chloride in reinforced concrete can cause severe damage to the strength and durability of buildings and bridges. The detection of chloride in concrete structures at early stages of the corrosion buildup process is, therefore, very important. However, detection of chlorine in trace amounts in concrete is not a simple matter. A dual-pulsed laser-induced breakdown spectrometer (LIBS) has been developed at our laboratory for the detection of chloride contents in reinforced concrete by using two atomic transition lines of neutral chlorine (Cl I) at 594.8 and 837.5 nm. A calibration curve was also established by using standard samples containing chloride in known concentration in the concrete. Our dual-pulsed LIBS system demonstrated a substantial improvement in the signal level at both wavelengths (594.8 and 837.5 nm). However, the new atomic transition line at 594.8 nm shows a significant improvement compared to the line at 837.5 nm in spite of the fact that the relative intensity of the former is 0.1% of the latter. This weak signal level of the 837.5 nm transition line of chlorine can be attributed to some kind of self-absorption process taking place in the case of the concrete sample.

Detection of hazardous pollutants in chrome-tanned leather using locally developed laser-induced breakdown spectrometer

Highly toxic contaminants like Cr, As, and Pb were detected in chrome-tanning process of animal skin to produce leather by applying locally developed laser-induced breakdown spectrometer. An Nd-YAG laser with 1,064nm wavelength was focused on the surface of leather samples (natural and manufactured) to generate a plasma spark and spectrally resolved spectra were used for identification and quantification of contaminants. The leather samples were collected from a tannery located in industrial cities of Riyadh and Jeddah, Saudi Arabia. The study was carried out on fully, half manufactured (wet blue leather), and natural hide (skin). To the best of our knowledge, this is the first attempt where laser-induced breakdown spectroscopy (LIBS) technique has been applied for the analysis of leather before and after tanning process. The maximum concentration of different elements of environmental significance like chromium, lead, arsenic, sulfur, magnesium were 199, 289, 31, 38, and 39ppm, respectively, in one of the manufactured leather samples. The limit of detection (LOD) of our LIBS system for chromium, lead, arsenic, sulfur, and magnesium were 2, 3, 1.5,7, and 3ppm, respectively. The safe permissible limit for tanned leather for highly toxic elements like chromium, lead, and arsenic are 1, 0.5, 0.01ppm, respectively, as prescribed in Environmental Regulation Standards for Saudi Industries set by Royal Commission Jubail, Saudi Arabia. The LIBS technique is superior to other conventional techniques like ICP or atomic absorption that a little or no sample preparation is required, no chemicals are needed, multi-elemental analysis is possible for all kinds of samples (natural and anthropogenic materials), microgram of sample is essential, and LIBS could be applied for remote analysis. It is highly selective and sensitivity higher than ICP, and as no sample and chemicals are required, it is cost effective for multi-sample analysis per unit time as compared with other conventional techniques. The concentration of some toxic elements (Cr, Pb, As) is much higher than the safe permissible limits set by Occupational Safety and Health Administration in USA or Saudi environmental regulatory agencies. Results obtained with our LIBS systems were in close agreement with the results obtained using other standard analytical technique such as the inductively coupled plasma atomic emission spectroscopy.

Determination of trace elements in volcanic rock samples collected from cenozoic lava eruption sites using LIBS

Trace elements of environmental significance present in the volcanic rock samples collected from sites of the Cenozoic era flood basalt flows and eruptions were detected using locally developed laser-induced breakdown spectrometer. For spectro-chemical analysis of these samples, the plasma was generated by focusing a pulsed Nd: YAG laser radiation at 1064 nm wavelength on the target rock samples. These samples were collected from four widely separated locations surrounding the volcanic eruption sites belonging to the Harrat Hutaymah volcanic field in the vicinity of Taba town, situated to the east of Hail city of northern Saudi Arabia. These samples represent the scoria basalt lava flows as well as a large tuff-ring crater and it contains xenoliths. These flows occur widespread over the Earth's surface in this region, and their contained xenoliths are brought up from depths of a few tens of kilometers. This volcanic field has received much less attention in the previous geological studies; and consequently, its effects on the environment are not well defined. The concentration of different elements of environmental significance like Cr, Pb, Mn, Cd, Sr and other trace metals like Cu, Al, Ca, Mg, Zn, Ti and Fe in these rock samples were determined by spectral analysis. Parametric dependence for improvement of LIBS sensitivity for detection of these elements was also carried out. The highest concentration detected of environmentally significant elements like Cr, Mn, Pb, Sr and Ni are 1910, 1399, 90.5, 12412 and 461.5 ppm, respectively in four different lava samples which are considered to be much higher than the safe permissible limits. The LIBS results were compared with the results obtained using other analytical techniques such as the inductively coupled plasma atomic emission spectroscopy (ICP-AES).

Measurement of Carbon Content in Steel by LIBS Which Transmits a Laser Beam in Optical Fiber

Utilizing new laser transmission technology, we have developed a laser induced breakdown spectrometer (LIBS) that allows to obtain uniform energy profile by transmitting high-energy laser emitted from GP-YAG through optical fiber, implemented measurement of carbon content in steel and demonstrated its capability of accurate and fast measurement. The spectrometer made it possible to measure both carbon content distribution in the depth direction and average carbon content in steel at the same time by setting the diameter of the laser light with energy of 90 mJ to 0.9 mm on samples after transmitting it by the optical fiber. In addition, we were able to find carbon content in steel in a coefficient of correlation over 0.99 by using 50 shots average data after 3.6 μm from surface.

Determining the Lifetime of Detectable Amounts of Gunshot Residue on the Hands of a Shooter Using Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been used to determine the period of time that a shooter will test positive for gunshot residue (GSR) after firing a revolver. Multiple rounds of primer were fired and samples collected at multiple hour intervals using an adhesive tape pressed against the skin. Samples were analyzed directly using a commercially available laser-induced breakdown spectrometer where barium emission (originating from barium nitrate in the primer) was observed. Population statistics were used to compare suspected GSR to a library of blank samples from which a threshold value was established. Statistically significant results, positive for GSR, are obtained 5.27 days after a firearm discharge using these techniques.

Detection of indoor biological hazards using the man-portable laser induced breakdown spectrometer

The performance of a man-portable laser induced breakdown spectrometer was evaluated for the detection of biological powders on indoor office surfaces and wipe materials. Identification of pure unknown powders was performed by comparing against a library of spectra containing biological agent surrogates and confusant materials, such as dusts, diesel soot, natural and artificial sweeteners, and drink powders, using linear correlation analysis. Simple models constructed using a second technique, partial least squares discriminant analysis, successfully identified Bacillus subtilis (BG) spores on wipe materials and office surfaces. Furthermore, these models were able to identify BG on materials not used in the training of the model.

Use of Chemometrics and Laser-Induced Breakdown Spectroscopy for Quantitative Analysis of Major and Minor Elements in Aluminum Alloys

In the present work, quantitative analysis of major and minor elements in aluminum alloys is investigated using chemometrics and laser-induced plasma spectroscopy with a commercially available laser-induced breakdown (LIBS) spectrometer. Multivariate calibrations use the entire signal matrix for all elements in a single multivariate regression model. This enables accounting for the correlation between variables often referred to as matrix effects in conventional univariate modeling. Modeling the entire signal matrix improves robustness over traditional univariate calibration since it can compensate for matrix effects. Several nonlinear data pretreatment methods have been used to correct for nonlinear behaviors of the analytical signals prior to performing the multivariate calibration. The use of multivariate calibration in combination with cubic implicit nonlinear data pretreatment showed the most accurate results. The accuracy reported with the developed multivariate calibration is better than 5% for the major alloying elements. Based on the results obtained, the use of chemometrics and laser-induced plasma spectroscopy have been successfully applied to the quantitative analysis of major and minor alloying elements in aluminum.

Laser-induced breakdown spectroscopy for quantitative spectrochemical analysis of geological materials: Effects of the matrix and simultaneous determination

A microscopic laser-induced breakdown spectrometer was used to evaluate the analytical matrix effect commonly observed in the analysis of geological materials. Samples were analyzed in either the powder or pressed pellet forms. Calibration curves of a number of iron and aluminum compounds showed a linear relationship between the elemental concentration and peak intensity. A direct determination of elemental content can thus be made from extrapolation on these calibration curves. To investigate matrix effects, synthetic model samples were prepared from various iron and aluminum compounds spiked with SiO 2 and CaCO 3. The addition of these matrices had a pronounced analytical effect on those compounds prepared as pressed pellets. However, results indicated the absence of matrix effects when the samples were presented to the laser as loose powders on tape and results were compared to certified values, indicating the reliability of this approach for accurate analysis, provided the sample particle diameters are greater than ≈100 μm. Finally, the simultaneous analysis of two different elements was demonstrated using powders on tape.

Design, construction and assessment of a field-deployable laser-induced breakdown spectrometer for remote elemental sensing

A field-deployable laser-induced breakdown spectrometer for measurements in the hundreds of meters range has been presented. The system is capable of elemental analysis with no previous preparation and in near real time, with the only requirement of a free line-of-sight between the instrument and the sample. Main factors influencing LIBS performance at stand-off distances are outlined. LIBS signal is shown to depend on range of analysis, peak power, beam quality, laser wavelength and optics dimensions. A careful control of focusing conditions has been shown to be of importance to avoid interferences from air breakdown by the stand-off focused beam.