Feasibility of laser-induced breakdown spectroscopy for the study of the temporal distribution of trace elements trapped in snow collected from greater himalayan range

The potential merit of laser-induced breakdown spectroscopy (LIBS) has been demonstrated for detection and quantification of trace pollutants trapped in snow/ice samples. In this technique, a high-power pulsed laser beam from Nd:YAG Laser (Model no. Surelite III-10, Continuum, Santa Clara, CA, USA) is focused on the surface of the target to generate plasma. The characteristic emissions from laser-generated plasma are collected and recorded by a fiber-coupled LIBS 2000+ (Ocean Optics, Santa Clara, CA, USA) spectrometer. The fingerprint of the constituents present in the sample is obtained by analyzing the spectral lines by using OOI LIBS software. Reliable detection of several elements like Zn, Al, Mg, Fe, Ca, C, N, H, and O in snow/ice samples collected from different locations (elevation) of Manali and several snow samples collected from the Greater Himalayan region (from a cold lab in Manali, India) in different months has been demonstrated. The calibration curve approach has been adopted for the quantitative analysis of these elements like Zn, Al, Fe, and Mg. Our results clearly demonstrate that the level of contamination is higher in those samples that were collected in the month of January in comparison to those collected in February and March.

Femtosecond laser induced breakdown spectroscopy of air-methane mixtures

Femtosecond laser pulses are used in order to induce dielectric breakdown in gaseous mixtures, namely in some reactive air-methane mixtures. The light emitted from the laser induced plasma was analyzed while the main emission features are identified and assigned. From the analysis of the emission spectra, a linear relationship was found to hold between the intensity of some spectral features and methane content. Finally, the use of femtosecond laser induced breakdown as a tool for the in situ determination of the composition of gaseous mixtures (e.g., equivalence ratio) is also discussed. © 2013 Elsevier B.V. All rights reserved.

Microelements in Potato and Lily Samples Studied by Laser-Induced Breakdown spectroscopy Technology

A LIBS setup was built in the Institute of Modern Physics. In our experiments, LIBS spectra produced by infrared radiation of Nd : YAG nanosecond laser with 100 and 150 mJ pulse energy, respectively, were measured by fiber optic spectrometer in the ranges of 230-430 run and 430-1080 nm with a delay time of 1.7 and gate width of 2 ms for potato and lily samples prepared by vacuum freeze-dried technique. The lines from different metal elements such as K, Ca, Na, Mg, Fe, Al, Mn and Ti, and nonmetal elements such as C, N, O and H, and some molecular spectra from C-2, CaO, and CN were identified according to their wavelengths. The relative content of the six microelements, Ca, Na, K, Fe, Al, and Mg in the samples were analyzed according to their representative line intensities. By comparison we found that there are higher relative content of Ca and Na in lily samples and higher relative content of Mg in potato samples. The experimental results showed that LIBS technique is a fast and effective means for measuring and comparing the contents of microelements in plant samples.

基于激光诱导击穿光谱技术的铝合金成分定量分析；Quantitative analysis of element concentration in Al alloy by using laser-induced breakdown spectroscopy

利用Nd:YAG激光器输出的532nm激光束对位于空气中的标准变形铝合金样品进行烧蚀产生了激光诱导等离子体.对测量的230—440nm波长范围的光谱进行了谱线标定,同时基于自由定标方法对样品成分进行了定量分析,确定了样品中的元素含量.分析结果与标准值具有较好的一致性.

Quantitative analysis analysis of element concentration in Al alloy by using laser-induced breakdown spectroscopy

Laser-induced breakdown plasma is produced by using Q-switched Nd: YAG laser operating at 532 nm, which interacts with the Al alloy sample target in air. The spectral lines in the 230-440 nm wavelength range have been identified, and based on the calibration-free method, the mass concentration of Al alloy are obtained, which is in good agreement with the standard value of the sample.

A Semi-Quantitative Analysis of Essential Micronutrient in Folium Lycii Using Laser-Induced Breakdown Spectroscopy Technique

In this paper, the capabilities of laser-induced break down spectroscopy (LIBS) for rapid analysis to multi-component plant are illustrated using a 1064 nm laser focused onto the surface of folium lycii. Based on homogeneous plasma assumption, nine of essential micronutrients in folium lycii are identified. Using Saha equation and Boltzmann plot method electron density and plasma temperature are obtained, and the irrelative concentration (Ca, Mg, Al, Si, Ti, Na, K, Li, and Sr) are obtained employing a semi-quantitative method.

Influence of Laser Wavelength on Laser-induced Breakdown Spectroscopy Applied to Semi-Quantitative Analysis of Trace-Elements in a Plant Sample

Laser-induced breakdown spectroscopy (LIBS) as a powerful analytical technique is applied to analyze trace-elements in fresh plant samples. We investigate the LIBS spectra of fresh holly leaves and observe more than 430 lines emitted from 25 elements and molecules in the region 230-438 nm. The influence of laser wavelength on LIBS applied to semi-quantitative analysis of trace-element contents in plant samples is studied. The results show that the UV laser has lower relative standard deviations and better repeatability for semi-quantitative analysis of trace-element contents in plant samples. This work may be helpful for improving the quantitative analysis power of LIBS applied to plant samples.

Femtosecond imaging-mode laser-induced breakdown spectroscopy

Many nonlinear optical microscopy techniques based on the high-intensity nonlinear phenomena were developed recent years. A new technique based on the minimal-invasive in-situ analysis of the specific bound elements in biological samples is described in the present work. The imaging-mode Laser-Induced Breakdown Spectroscopy (LIBS) is proposed as a combination of LIBS, femtosecond laser material processing and microscopy. The Calcium distribution in the peripheral cell wall of the sunflower seedling (Helianthus Annuus L.) stem is studied as a first application of the imaging-mode LIBS. At first, several nonlinear optical microscopy techniques are overviewed. The spatial resolution of the imaging-mode LIBS microscope is discussed basing on the Point-Spread Function (PSF) concept. The primary processes of the Laser-Induced Breakdown (LIB) are overviewed. We consider ionization, breakdown, plasma formation and ablation processes. Water with defined Calcium salt concentration is used as a model of the biological object in the preliminary experiments. The transient LIB spectra are measured and analysed for both nanosecond and femtosecond laser excitation. The experiment on the local Calcium concentration measurements in the peripheral cell wall of the sunflower seedling stem employing nanosecond LIBS shows, that nanosecond laser is not a suitable excitation source for the biological applications. In case of the nanosecond laser the ablation craters have random shape and depth over 20 µm. The analysis of the femtosecond laser ablation craters shows the reproducible circle form. At 3.5 µJ laser pulse energy the diameter of the crater is 4 µm and depth 140 nm for single laser pulse, which results in 1 femtoliter analytical volume. The experimental result of the 2 dimensional and surface sectioning of the bound Calcium concentrations is presented in the work.

Novel estimation of the humification degree of soil organic matter by laser-induced breakdown spectroscopy

Soil organic matter (SOM) constitutes an important reservoir of terrestrial carbon and can be considered an alternative for atmospheric carbon storage, contributing to global warming mitigation. Soil management can favor atmospheric carbon incorporation into SUM or its release from SOM to atmosphere. Thus, the evaluation of the humification degree (HD), which is an indication of the recalcitrance of SOM, can provide an estimation of the capacity of carbon sequestration by soils under various managements. The HD of SOM can be estimated by using various analytical techniques including fluorescence spectroscopy. In the present work, the potential of laser-induced breakdown spectroscopy (LIBS) to estimate the HD of SUM was evaluated for the first time. Intensities of emission lines of Al, Mg and Ca from LIBS spectra showing correlation with fluorescence emissions determined by laser-induced fluorescence spectroscopy (LIFS) reference technique were used to obtain a multivaried calibration model based on the k-nearest neighbor (k-NN) method. The values predicted by the proposed model (A-LIBS) showed strong correlation with LIFS results with a Pearson's coefficient of 0.87. The HD of SUM obtained after normalizing A-LIBS by total carbon in the sample showed a strong correlation to that determined by LIFS (0.94), thus suggesting the great potential of LIBS for this novel application. (C) 2014 Elsevier B.V. All rights reserved.

Physical and chemical matrix effects in soil carbon quantification using laser-induced breakdown spectroscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of pulse repetition rate and number of pulses in the analysis of polypropylene and high density polyethylene by nanosecond infrared laser induced breakdown spectroscopy

Pulse repetition rates and the number of laser pulses are among the most important parameters that do affect the analysis of solid materials by laser induced breakdown spectroscopy, and the knowledge of their effects is of fundamental importance for suggesting analytical strategies when dealing with laser ablation processes of polymers. In this contribution, the influence of these parameters in the ablated mass and in the features of craters was evaluated in polypropylene and high density polyethylene plates containing pigment-based PbCrO4. Surface characterization and craters profile were carried out by perfilometry and scanning electron microscopy. Area, volume and profile of craters were obtained using Taylor Map software. A laser induced breakdown spectroscopy system consisted of a Q-Switched Nd:YAG laser (1064 nm, 5 ns) and an Echelle spectrometer equipped with ICCD detector were used. The evaluated operating conditions consisted of 10, 25 and 50 laser pulses at 1, 5 and 10 Hz, 250 mJ/pulse (85 J cm(-2)), 2 mu s delay time and 6 mu s integration time gate. Differences in the topographical features among craters of both polymers were observed. The decrease in the repetition rate resulted in irregular craters and formation of edges, especially in polypropylene sample. The differences in the topographical features and ablated masses were attributed to the influence of the degree of crystallinity, crystalline melting temperature and glass transition temperature in the ablation process of the high density polyethylene and polypropylene. It was also observed that the intensities of chromium and lead emission signals obtained at 10 Hz were two times higher than at 5 Hz by keeping the number of laser pulses constant. (C) 2011 Elsevier B. V. All rights reserved.

Effects of laser focusing and fluence on the analysis of pellets of plant materials by laser-induced breakdown spectroscopy

The effects of laser focusing and fluence on LIBS analysis of pellets of plant leaves was evaluated. A Q-switched Nd:YAG laser (5ns, 10Hz, 1064nm) was used and the emission signals were collected by lenses into an optical fiber coupled to a spectrometer with Echelle optics and ICCD. Data were acquired from the accumulation of 20 laser pulses at 2.0 mu s delay and 5.0 mu s integration time gate. The emission signal intensities increased with both laser fluence and spot size. Higher sensitivities for Ca, K, Mg, P, Al, B, Cu, Fe, Mn, and Zn determinations were observed for fluences in the range from 25 to 60Jcm(-2). Coefficients of variation of site-to-site measurements were generally lower than 10% (n=30 sites, 20 laser pulses/site) for a fluence of 50Jcm(-2) and 750 mu m spot size. For most elements, there is an indication that accuracy is improved with higher fluences. (C) 2012 Elsevier B.V. All rights reserved.

Laser-induced breakdown spectroscopy quantitative analysis method via adaptive analytical line selection and relevance vector machine regression model

Abstract A new LIBS quantitative analysis method based on analytical line adaptive selection and Relevance Vector Machine (RVM) regression model is proposed. First, a scheme of adaptively selecting analytical line is put forward in order to overcome the drawback of high dependency on a priori knowledge. The candidate analytical lines are automatically selected based on the built-in characteristics of spectral lines, such as spectral intensity, wavelength and width at half height. The analytical lines which will be used as input variables of regression model are determined adaptively according to the samples for both training and testing. Second, an LIBS quantitative analysis method based on RVM is presented. The intensities of analytical lines and the elemental concentrations of certified standard samples are used to train the RVM regression model. The predicted elemental concentration analysis results will be given with a form of confidence interval of probabilistic distribution, which is helpful for evaluating the uncertainness contained in the measured spectra. Chromium concentration analysis experiments of 23 certified standard high-alloy steel samples have been carried out. The multiple correlation coefficient of the prediction was up to 98.85%, and the average relative error of the prediction was 4.01%. The experiment results showed that the proposed LIBS quantitative analysis method achieved better prediction accuracy and better modeling robustness compared with the methods based on partial least squares regression, artificial neural network and standard support vector machine.

A laser induced breakdown spectroscopy quantitative analysis method based on the robust least squares support vector machine regression model

Data fluctuation in multiple measurements of Laser Induced Breakdown Spectroscopy (LIBS) greatly affects the accuracy of quantitative analysis. A new LIBS quantitative analysis method based on the Robust Least Squares Support Vector Machine (RLS-SVM) regression model is proposed. The usual way to enhance the analysis accuracy is to improve the quality and consistency of the emission signal, such as by averaging the spectral signals or spectrum standardization over a number of laser shots. The proposed method focuses more on how to enhance the robustness of the quantitative analysis regression model. The proposed RLS-SVM regression model originates from the Weighted Least Squares Support Vector Machine (WLS-SVM) but has an improved segmented weighting function and residual error calculation according to the statistical distribution of measured spectral data. Through the improved segmented weighting function, the information on the spectral data in the normal distribution will be retained in the regression model while the information on the outliers will be restrained or removed. Copper elemental concentration analysis experiments of 16 certified standard brass samples were carried out. The average value of relative standard deviation obtained from the RLS-SVM model was 3.06% and the root mean square error was 1.537%. The experimental results showed that the proposed method achieved better prediction accuracy and better modeling robustness compared with the quantitative analysis methods based on Partial Least Squares (PLS) regression, standard Support Vector Machine (SVM) and WLS-SVM. It was also demonstrated that the improved weighting function had better comprehensive performance in model robustness and convergence speed, compared with the four known weighting functions.