Determination of Rare Earth Elements in Geological Samples Using Laser-Induced Breakdown Spectroscopy (LIBS).

Laser-induced breakdown spectroscopy (LIBS) was used to detect rare earth elements (REEs) in natural geological samples. Low and high intensity emission lines of Ce, La, Nd, Y, Pr, Sm, Eu, Gd, and Dy were identified in the spectra recorded from the samples to claim the presence of these REEs. Multivariate analysis was executed by developing partial least squares regression (PLS-R) models for the quantification of Ce, La, and Nd. Analysis of unknown samples indicated that the prediction results of these samples were found comparable to those obtained by inductively coupled plasma mass spectrometry analysis. Data support that LIBS has potential to quantify REEs in geological minerals/ores.

Qualitative Analysis of Dairy and Powder Milk Using Laser-Induced Breakdown Spectroscopy (LIBS).

Laser-induced breakdown spectroscopy (LIBS) technique was used to compare various types of commercial milk products. Laser-induced breakdown spectroscopy spectra were investigated for the determination of the elemental composition of soy and rice milk powder, dairy milk, and lactose-free dairy milk. The analysis was performed using radiative transitions. Atomic emissions from Ca, K, Na, and Mg lines observed in LIBS spectra of dairy milk were compared. In addition, proteins and fat level in milks can be determined using molecular emissions such as CN bands. Ca concentrations were calculated to be 2.165 ± 0.203 g/L in 1% of dairy milk fat samples and 2.809 ± 0.172 g/L in 2% of dairy milk fat samples using the standard addition method (SAM) with LIBS spectra. Univariate and multivariate statistical analysis methods showed that the contents of major mineral elements were higher in lactose-free dairy milk than those in dairy milk. The principal component analysis (PCA) method was used to discriminate four milk samples depending on their mineral elements concentration. In addition, proteins and fat level in dairy milks were determined using molecular emissions such as CN band. We applied partial least squares regression (PLSR) and simple linear regression (SLR) models to predict levels of milk fat in dairy milk samples. The PLSR model was successfully used to predict levels of milk fat in dairy milk sample with the relative accuracy (RA%) less than 6.62% using CN (0,0) band.

Evaluation of Optical Depths and Self-Absorption of Strontium and Aluminum Emission Lines in Laser-Induced Breakdown Spectroscopy (LIBS).

Laser-induced breakdown spectroscopy (LIBS) is a widely used laser spectroscopic technique in various fields, such as material science, forensic science, biological science, and the chemical and pharmaceutical industries. In most LIBS work, the analysis is performed using radiative transitions from atomic emissions. In this study, the plasma temperature and the product [Formula: see text] (the number density N and the absorption path length [Formula: see text]) were determined to evaluate the optical depths and the self-absorption of Sr and Al lines. A binary mixture of strontium nitrate and aluminum oxide was used as a sample, consisting of variety of different concentrations in powder form. Laser-induced breakdown spectroscopy spectra were collected by varying various parameters, such as laser energy, gate delay time, and gate width time to optimize the LIBS signals. Atomic emission from Sr and Al lines, as observed in the LIBS spectra of different sample compositions, was used to characterize the laser induced plasma and evaluate the optical depths and self-absorption of LIBS.

Univariate and multivariate analyses of rare earth elements by laser-induced breakdown spectroscopy.

Univariate and multivariate analyses of six rare earth elements [cerium (Ce), europium (Eu), gadolinium (Gd), neodymium (Nd), samarium (Sm), and yttrium (Y)] have been performed using data from laser-induced breakdown spectroscopy (LIBS). Binary mixtures of oxide forms of each rare earth element in an Al2O3 matrix with their concentrations varying from 1% to 10% by weight in powder form were used as working samples for univariate analysis. For multivariate analysis, complex mixtures of oxides of all these six rare earth elements and Al2O3 in powder form, where the concentration of each element oxide was varied from 1% to 50% by weight one by one, were used to record LIBS spectra. Optimum values of gate delay, gate width, and laser energy were used to get spectra from these samples and spectra were used to develop calibration models. The limits of detection for Ce, Eu, Gd, Nd, Sm, and Y were calculated to be 0.098%, 0.052%, 0.077%, 0.047%, 0.250%, and 0.036%, respectively, from the calibration curves.

Comparative Study of Elemental Nutrients in Organic and Conventional Vegetables Using Laser-Induced Breakdown Spectroscopy (LIBS).

In this study, the laser-induced breakdown spectroscopy (LIBS) technique was used to identify and compare the presence of major nutrient elements in organic and conventional vegetables. Different parts of cauliflowers and broccolis were used as working samples. Laser-induced breakdown spectra from these samples were acquired at optimum values of laser energy, gate delay, and gate width. Both univariate and multivariate analyses were performed for the comparison of these organic and conventional vegetable flowers. Principal component analysis (PCA) was taken into account for multivariate analysis while for univariate analysis, the intensity of selected atomic lines of different elements and their intensity ratio with some reference lines of organic cauliflower and broccoli samples were compared with those of conventional ones. In addition, different parts of the cauliflower and broccoli were compared in terms of intensity and intensity ratio of elemental lines.

Study of atomic and molecular emission spectra of Sr by laser induced breakdown spectroscopy (LIBS).

Laser Induced Breakdown Spectroscopy (LIBS) is an ideal analytical technique for in situ analysis of elemental composition. We have performed a comparative study of the quantitative and qualitative analysis of atomic and molecular emission from LIBS spectra. In our experiments, a mixture of SrCl2 and Al2O3 in powder form was used as a sample. The atomic emission from Sr and molecular emission from SrCl and SrO observed in LIBS spectra were analyzed. The optimum laser energies, gate delays, and gate widths for selected atomic lines and molecular bands were determined from spectra recorded at various experimental parameters. These optimum experimental conditions were used to collect calibration data, and the calibration curves were used to predict the Sr concentration. Limits of detection (LODs) for selected atomic and molecular emission spectra were determined.

Laser-induced breakdown spectroscopy (LIBS) of a high-pressure CO2-water mixture: application to carbon sequestration.

Geologic carbon storage in deep saline aquifers is considered a feasible and possible approach of mitigating the problem of increasing greenhouse gas emissions. However, there are latent risks in which carbon dioxide (CO2) could migrate from the deep saline formations to shallower aquifers. In the event of a significant CO2 leakage to an underground source of drinking water, CO2 will dissolve in the water, thereby increasing its acidity, which could potentially enhance the solubility of various aquifer constituents, including hazardous compounds, subsequently compromising groundwater quality due to increased concentration of aqueous metals. In this paper we explore the possibility of detecting such leakage by the use of laser-induced breakdown spectroscopy (LIBS). The experiments were conducted in calcium chloride solution at three pressures of 10, 50, and 120 bar. To evaluate the direct effect of elevated CO2 on the intensity of calcium emission lines (422.67 and 393.37 nm), we also performed experiments with pure nitrogen (N2) gas, offering large water solubility contrast. We found that when performed in presence of CO2, LIBS showed only a modest decrease in Ca emission intensity from 10 to 120 bar compared to N2. These results indicate that LIBS is a viable tool for measuring brine/water contents in high-pressure CO2 environment and can be applied for monitoring CO2 leakage and displaced brine migration.

Interferometric investigation of the influence of argon buffer gas on the characteristics of laser-induced aluminum plasmas.

An interferometric analysis was performed to investigate the influence of argon (Ar) buffer gas on the characteristics of laser-induced aluminum (Al) plasma at atmospheric pressure. The plasma was produced by focusing a Q-switched Nd:YAG laser pulse (λ=1064 nm, pulse duration ∼5 ns, E=6.0 mJ) onto an Al target. The interference patterns were constructed using a Nomarski interferometer incorporated with a frequency-doubled, Q-switched Nd:YAG laser (λ=532 nm, pulse duration ∼10 ns) that generates an interferometric probe beam. The interferometric measurements were carried out as a function of the elapsed time after the onset of breakdown under the conditions of open air and an Ar gas jet flow (5 l/min). With the injection of an Ar buffer gas jet in the ablation process, an increase in electron density and a preferential axial plasma expansion of the plasma plume were observed during the early stages of plasma formation as a consequence of increased inverse-Bremsstrahlung (IB) absorption efficiency.

Effect of sodium chloride concentration on elemental analysis of brines by laser-induced breakdown spectroscopy (LIBS).

Leakage of injected carbon dioxide (CO2) or resident fluids, such as brine, is a major concern associated with the injection of large volumes of CO2 into deep saline formations. Migration of brine could contaminate drinking water resources by increasing their salinity or endanger vegetation and animal life as well as human health. The main objective of this study was to investigate the effect of sodium chloride (NaCl) concentration on the detection of calcium and potassium in brine samples using laser-induced breakdown spectroscopy (LIBS). The ultimate goals were to determine the suitability of the LIBS technique for in situ measurements of metal ion concentrations in NaCl-rich solution and to develop a chemical sensor that can provide the early detection of brine intrusion into formations used for domestic or agricultural water production. Several brine samples of NaCl-CaCl2 and NaCl-KCl were prepared at NaCl concentrations between 0.0 and 3.0 M. The effect of NaCl concentration on the signal-to-background ratio (SBR) and signal-to-noise ratio (SNR) for calcium (422.67 nm) and potassium (769.49 nm) emission lines was evaluated. Results show that, for a delay time of 300 ns and a gate width of 3 µs, the presence of and changes in NaCl concentration significantly affect the SBR and SNR for both emission lines. An increase in NaCl concentration from 0.0 to 3.0 M produced an increase in the SNR, whereas the SBR dropped continuously. The detection limits obtained for both elements were in the milligrams per liter range, suggesting that a NaCl-rich solution does not severely limit the ability of LIBS to detect trace amount of metal ions.

Determination of elemental impurities in plastic calibration standards using laser-induced breakdown spectroscopy.

Dual-energy computed tomography (CT) scanning is a rapidly emerging imaging technique employed in nondestructive evaluation of various materials. CT has been used for characterizing rocks and visualizing multiphase flow through rocks for over 25 years. The most common technique for dual-energy CT scanning relies on homogeneous calibration standards to produce the most accurate decoupled data. However, the use of calibration standards with impurities increases the probability of error in the reconstructed data and results in poor rock characterization. Laser-induced breakdown spectroscopy was used to determine impurity concentration in a set of commercially purchased calibration standards used in dual-energy scanning for material identification with coal samples. Two calibration models were developed by using univariate calibration with the internal ratio method and multiple linear regression. Seven elements (Al, Fe, Mg, Na, Ni, Sr, and Ti) were examined in five different samples containing varying amounts of each ion to compare calibration from univariate data analysis and from multivariate data analysis. The contaminant concentrations were also measured by a commercially available inductively coupled plasma optical emission spectroscopy instrument, and the data were used as a reference in developing calibration curves for a modified version of the single linear regression model and the multiple linear regression model.

Application of laser-induced breakdown spectroscopy for total carbon quantification in soil samples.

The increase of greenhouse gas (i.e., CO(2)) levels in the atmosphere has caused noticeable climate change. Many nations are currently looking into methods of permanent underground storage for CO(2) in an attempt to mitigate this problem. The goal of this work is to develop a process for studying the total carbon content in soils before, during, and after CO(2) injection to ensure that no leakage is occurring or to determine how much is leaking if it is occurring and what effect it will have on the ecosystem between the injection formation and the atmosphere. In this study, we quantitatively determine the total carbon concentration in soil using laser-induced breakdown spectroscopy (LIBS). A soil sample from Starkville, Mississippi, USA was mixed with different amounts of carbon powder, which was used as a calibration for additional carbon in soil. Test samples were prepared by adding different but known amounts of carbon powder to a soil sample and then mixing with polyvinyl alcohol binder before being pressed into pellets. LIBS spectra of the test samples were collected and analyzed to obtain optimized conditions for the measurement of total carbon in soil with LIBS. The total carbon content in the samples was also measured by a carbon analyzer, and the data (average of triplicates) were used as a reference in developing calibration curves for a modified version of the single linear regression model and the multiple linear regression model. The calibration data were then used to determine the total carbon concentration of an unknown sample. This work is intended to be used in the initial development of a miniaturized, field-portable LIBS analyzer for CO(2) leak detection.

Helium detection in gas mixtures by laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) has been evaluated as a tool for monitoring trace levels of helium in gas mixtures consisting mostly of hydrogen. Calibration data for helium in hydrogen was investigated at different helium concentration levels. At high concentrations of helium (>7.25%), the LIBS signal is quenched due to Penning ionization. The hydrogen alpha line (656.28 nm) was observed to broaden as the concentration of helium impurities in the hydrogen gas mixture increased. The helium line at 587.56 nm was selected as the analyte line for helium impurity detection. The effects of laser energy, the delay time between the laser pulse and data acquisition, and the gas pressure on the LIBS signal of helium were investigated to determine the optimum conditions for helium detection. The LIBS signal from the helium line at 587.56 nm shows good linear correlation with helium concentration for He concentrations below 1%. Thus, LIBS can be reliably used to detect the low levels of helium. The limit of detection for helium was found to be 78 ppm.

North American Symposium on Laser Induced Breakdown Spectroscopy (NASLIBS): introduction to feature issue.

This feature issue highlights the topics of the 2011 North American Symposium on Laser Induced Breakdown Spectroscopy (NASLIBS). These include LIBS application to Security and Forensic, Biomedical and Environmental, Liquid Analysis and Fundamentals of LIBS, Instrumentation/Commercialization, Fusion with LIBS, and New Frontiers.

An integrated laser Raman optical sensor for fast detection of nitrogen and oxygen in a cryogenic mixture.

An integrated fiber optic Raman sensor was designed for real-time, nonintrusive detection of liquid nitrogen (LN(2)) in liquid oxygen (LO(2)) at high pressures and high flow rates. This was intended to monitor the quality of LO(2) in oxidizer feed lines during the ground testing of rocket engines. Various issues related to optical diagnosis of cryogenic fluids (LN(2)/LO(2)) in supercritical environment of rocket engine test facility, such as fluorescence from impurity in optical window of feed line, signal-noise ratio, and fast data acquisition time, etc., are well addressed. The integrated sensor employed a frequency doubled 532-nm continuous wave Nd:YAG laser as an excitation light source. The other optical components included were InPhotonics Raman probes, spectrometers, and photomultiplier tubes (PMTs). The spectrometer was used to collect the Raman spectrum of LN(2) and LO(2). The PMT detection unit was integrated with home-built LABVIEW software for fast monitoring of concentration ratios LN(2) and LO(2). Prior to designing an integrated sensor system, its optical components were also tested with gaseous nitrogen (GN(2)) and oxygen (GO(2)).

Vibrationally selective radiative and non-radiative transitions in gaseous hydrogen molecules.

An efficient vibrationally selective technique to build-up the v″=1 vibrational levels in gaseous hydrogen is demonstrated using stimulated Raman pumping (SRP). Both photo-acoustic Raman spectroscopy (PARS) and coherent anti-Stokes Raman spectroscopy (CARS) are used to study non-radiative and radiative (v″=0 and v″=1) transitions in gaseous H(2) molecules. The population fraction in the v″=1 vibrational level has been estimated using combined photo-acoustic and coherent anti-Stokes Raman spectroscopy with stimulated Raman pumping.

Quantitative analysis of slurry sample by laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) has been employed for the analysis of slurry samples. Quantitative analysis of slurry samples is crucial and challenging. The problems associated with slurry samples include splashing, surface turbulence, and the difficulties of obtaining reproducible samples due to sedimentation. The LIBS analysis has achieved limited success due to inherent disadvantages when applied to slurry samples. In order to achieve improved measurement precision and accuracy, a spin-on-glass sampling method was evaluated. Five elements (Al, Ca, Fe, Ni, and Si) were examined in five slurry simulants containing varying amounts of each ion. Three calibration models were developed by using univariate calibration, multiple linear regression, and partial least square regression. LIBS analysis results obtained from the partial least square regression model were determined to be the best fit to results obtained from inductively coupled plasma optical emission spectroscopy analysis.

Photo-fragmentation cross-section of gaseous 2,4,6-trinitrotoluene at different ultraviolet wavelengths.

The photo-fragmentation cross-section of 2,4,6-trinitrotoluene (TNT) vapor at room temperature was determined at different ultraviolet wavelengths (254, 300, 340, and 400 nm) by measuring the concentration of NO molecule with cavity ring down spectroscopy and correcting for the photo-fragmentation cross-section of NO(2). Nitric oxide (NO) molecules are produced by the TNT photo-fragmentation processes via an intermediate production of NO(2). Our results reveal that the photo-fragmentation cross-section of TNT changes appreciably with change in wavelength with xenon arc lamp illumination, increasing with decreasing excitation wavelength. The maximum value of cross-section was observed at the shortest photo-fragmentation wavelength studied (254 nm), which is closest to the wavelength of an absorption peak of TNT near 220 nm.

Optimized fiber optic bioprobe with high spectral contrast exploiting laser-induced fluorescence for malignancy diagnosis.

A high spectral contrast is expected to be very important when laser-induced fluorescence (LIF) is employed for cancer diagnosis. We developed a LIF optical fiber sensor to achieve a very high spectral contrast between normal and malignant tissues. A comprehensive experimental investigation was carried out to study the role of two critically important parameters for sensor design, namely, the excitation-collection geometry and the excitation wavelength, and their effect on the autofluorescence spectral contrast. An optimum sensing configuration was determined in order to enhance the small, but consistent, spectral difference between the normal and the malignant tissue for improving the accuracy of LIF-based cancer diagnosis. With the optimum sensor configuration, we realized a spectral contrast of more than 22 times between normal and malignant tissue sample spectra.

Three new cyclopeptide alkaloids from Zizyphus species.

Two new cyclopeptide alkaloids, xylopyrine-D and xylopyrine-E, from Zizyphus xylopyra and a new alkaloid, jubanine-E, from Zizyphus jujuba have been isolated and their structures were established by chemical and spectral evidences.