Self-absorption reduction in laser-induced breakdown spectroscopy using laser-stimulated absorption: publisher's note.

This publisher's note contains corrections to Opt. Lett.40, 5224 (2015).OPLEDP0146-959210.1364/OL.40.005224.

Quantitative determination of tantalum and niobium in tantalum-niobium ore using laser-induced breakdown spectroscopy.

Tantalum-niobium (Ta-Nb) ore is the main source of two very important rare metals,Ta and Nb. However, it is still a challenge for laser-induced breakdown spectroscopy (LIBS) to quantitatively detect trace Ta and Nb elements in Ta-Nb ore samples. In this work, LIBS assisted with univariate and multivariate calibration methods that were used to quantitatively determine Ta and Nb elements under optimized experimental parameters, such as delay time, gate width, and analytical lines. The results show that LIBS with multivariate calibration methods is a feasible method, and the limit of detection of Ta and Nb elements was 59.21 and 8.02 µg g-1, respectively. It provides a promising way for the rapid and sensitive quantitative detecting of trace Ta and Nb elements in Ta-Nb ore samples.

Determination of Trace Available Heavy Metals in Soil Using Laser-Induced Breakdown Spectroscopy Assisted with Phase Transformation Method.

To detect available heavy metals in soil using laser-induced breakdown spectroscopy (LIBS) and improve its poor detection sensitivity, a simple and low cost sample pretreatment method named solid-liquid-solid transformation was proposed. By this method, available heavy metals were extracted from soil through ultrasonic vibration and centrifuging and then deposited on a glass slide. Utilization of this solid-liquid-solid transformation method, available Cd and Pb elements in soil were detected successfully. The results show that the regression coefficients of calibration curves for soil analyses reach to more than 0.98. The limits of detection could reach to 0.067 and 0.94 ppm for available Cd and Pb elements in soil under optimized conditions, respectively, which are much better than those obtained by conventional LIBS.

Spreading a water droplet through filter paper on the metal substrate for surface-enhanced laser-induced breakdown spectroscopy.

To improve the quantitative analysis accuracy of an aqueous solution using surface-enhanced laser-induced breakdown spectroscopy (SENLIBS), the filter paper was used as a transmission medium by placing it onto the surface of a metallic substrate to make the microdroplet spreading more uniform in a fixed region of the substrate surface. The trace elements (Cu, Pb, Cd, and Cr) in an aqueous solution were detected successfully using this method. The results showed that the sample preparation repeatability of SENLIBS was noticeably improved with the aid of filter paper. Moreover, the limit of detection (LoD) values was similar to those without filter paper. Furthermore, the R2 values were improved from 0.6192~0.9321 to 0.9481~0.9766, the RMSECV values were decreased from 0.53~1.95 µg/mL to 0.33~1.06 µg/mL, and the average relative error (ARE) values were decreased from 8.96~22.31% to 4.28~14.37% with the aid of filter paper. This demonstrated that the use of filter paper could improve the quantitative analysis accuracy of SENLIBS by increasing the sample preparation repeatability.

Classification accuracy improvement of laser-induced breakdown spectroscopy based on histogram of oriented gradients features of spectral images.

To improve the classification accuracy of laser-induced breakdown spectroscopy (LIBS), image histogram of oriented gradients (HOG) features method (IHFM) for materials analysis was proposed in this work. 24 rice (Oryza sativa L.) samples were carried out to verify the proposed method. The results showed that the classification accuracy of rice samples by the full-spectra intensities method (FSIM) and IHFM were 60.25% and 81.00% respectively. The classification accuracy was obviously improved by 20.75%. Universality test results showed that this method also achieved good results in the plastics, steel, rock and minerals classification. This study provides an effective method to improve the classification performance of LIBS.

Multielemental self-absorption reduction in laser-induced breakdown spectroscopy by using microwave-assisted excitation.

The self-absorption effect seriously affects the accuracy of determination in laser-induced breakdown spectroscopy (LIBS). In this work, we proposed to reduce multielemental self-absorption within a wide spectral range (200-900 nm) by using microwave-assisted excitation in LIBS (MAE-LIBS). Self-absorption reduction of sodium (Na), potassium (K), aluminum (Al), silicon (Si), and calcium (Ca) in potassium feldspar using MAE-LIBS was investigated. The mechanisms of self-absorption reduction in MAE-LIBS were also investigated. The results show that the serious self-absorption of spectral lines (Na and K) was reduced. The full widths at half maximum (FWHMs) of Na I 589.0 nm, Na I 589.6 nm, K I 766.5 nm, and K I 769.9 nm in potassium feldspar were reduced by 43%, 43%, 53%, and 47%, respectively. MAE-LIBS also has a little FWHM reduction for spectral lines with weak self-absorption. The results demonstrate that MAE-LIBS can simultaneously reduce multielemental self-absorption.

New spectral reduction algorithm for echelle spectrometer in laser-induced breakdown spectroscopy.

In this work, a new spectral reduction algorithm for the echelle spectrometer was proposed. Unlike conventional approaches, the key concept in this algorithm is to model the spectrogram rather the spectrometer, which makes the algorithm more adaptive to different designs. This algorithm also introduces a dynamic adjusting procedure for generating optimized spectra from laser-induced plasmas. This additional step improved the spectrum stability and absolute line intensity of the spectrum and yielded better quantification performance. Experimental results demonstrated that the quantification results of analyzing aluminum alloy samples were improved using this new algorithm.

Analytical-performance improvement of aqueous solution by chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy.

In this study, chemical replacement combined with surface-enhanced laser-induced breakdown spectroscopy (CR-SENLIBS) was introduced for detecting the trace chromium (Cr) element in an aqueous solution, which could use chemical replacement to change the sample from liquid to solid. In order to illustrate the analytical-performance of the CR-SENLIBS, the direct analysis of the liquid surface by LIBS (LSLIBS) was investigated for comparison. The results show that the spectral intensity of Cr I 357.86 nm, plasma lifetime, and spectral stability were improved. Moreover, the limit of detection of Cr I 357.86 nm was 0.018 µg/mL, which was lower than 1.814 µg/mL for LSLIBS. Furthermore, the accuracy and precision were improved more than 60% and 80%, respectively; for example, the root-mean-square error of cross-validation was improved from 1.09 to 0.75 µg/mL, and the average relative standard deviation of the predicted concentration of Cr was reduced from 22.89% to 4.53% by using CR-SENLIBS. These results suggest that CR-SENLIBS has good analytical-performance, which exhibits great potential in water quality monitoring.

Laser-induced breakdown spectroscopy assisted chemometric methods for rice geographic origin classification.

The problems of adulteration and mislabeling are very common in the food industry. Laser-induced breakdown spectroscopy (LIBS) coupled with chemometric methods has many intrinsic advantages on adulteration analysis of various materials. In this work, several chemometric algorithms, i.e., principal component analysis (PCA), decision tree (DT), random forest (RF), partial least squares discriminant analysis (PLS-DA), linear discriminant analysis (LDA), and support vector machine (SVM), were carried out assisted by LIBS technology to study the classification performances on rice geographic origins. A series of samples, including 20 kinds of rice samples from different geographic origins, was detected using LIBS with no pretreatment processes. For data analysis, PCA was employed to reduce the input variables, and to reduce the collinearity of LIBS spectral results as well. The results showed the classification accuracies of the mentioned chemometric algorithms of DT, RF, PLS-DA, LDA, and SVM with 89 input variables of 86.80%, 96.30%, 96.80%, 98.60%, and 99.20%, respectively. At the same time, the operation times of these algorithms were 3.81 s, 54.64 s, 3.63 s, 2.09 s, and 531.01 s, respectively. On the other hand, 30 principal components of input variables were also tested under the same conditions. The classification accuracies for the above algorithms were 81.60%, 98.00%, 95.70%, 98.40%, and 99.20%, respectively. The operation times were 2.01 s, 4.88 s, 3.67 s, 0.36 s, and 308.55 s, respectively. In addition, the five-fold cross-validation classification accuracies with 30 input variables for DT, RF, PLS-DA, LDA, and SVM were 83.75%, 97.95%, 94.75%, 98.35%, and 99.25%, respectively. As a result, LDA was demonstrated to be the best and most efficient tool for rice geographic origin classification assisted by LIBS with high accuracy and analytical speed, which has great potential for rapid identification of adulterated products in agriculture without use of any chemical reagent.

Determination of antimony in soil using laser-induced breakdown spectroscopy assisted with laser-induced fluorescence.

Antimony (Sb) in soil is attracting attention in the research community due to its potential toxicity and carcinogenicity. Traditional methods of detecting Sb lack the ability of rapid and nondigestion analysis, which hinders their development and application. Moreover, it is still a challenge for laser-induced breakdown spectroscopy (LIBS) to detect Sb in soil due to the weak intensities and intense interference of spectral lines. Here, LIBS, assisted with laser-induced fluorescence (LIBS-LIF), was used to selectively enhance the Sb's characteristic spectral lines under optimal parameters. The quantitative analysis performance was notably improved with a determination coefficient (R2) of 0.991, the limit of detection of 0.221 µg/g, and root mean square error of cross validation of 3.592 µg/g. These results demonstrate that LIBS-LIF has the potential to realize the rapid and accurate analysis of Sb in soil.

Analytical-performance improvement of laser-induced breakdown spectroscopy for the processing degree of wheat flour using a continuous wavelet transform.

Quality and safety of food are two of the most important matters in our lives. Wheat is one of the most important products in the modern agricultural processing industry. Issues of mislabeling and adulteration are of increasingly serious concern in the grain market. They threaten the credibility of producers and traders and the rights of the consumers. Therefore, it is very significant to guarantee the processing degree of wheat flour. In this work, two different spectral peak recognition methods, i.e., artificial spectral peak recognition and automatic spectral peak recognition, are carried out to study the adulteration problem in the food industry. Three grades of the processing degree of wheat flour from northern China are classified by laser-induced breakdown spectroscopy (LIBS). To search for an automatic classification model, continuous wavelet transform is used for the automatic recognition of the LIBS spectrum peak. Principal component analysis is used to reduce the collinearity of LIBS spectra data. First, 20 principal components were selected to represent the spectral data for the following discrimination analysis by a support vector machine. The results showed that the classification accuracies of automatic spectral peak recognition are better than those of artificial spectral peak recognition. The classification accuracies of artificial spectral peak recognition and automatic spectral peak recognition are 95.33% and 98.67%; the fivefold cross-validation classification accuracies are 94.67% and 96.67%; and the operation times were 240 min and 2 min, respectively. It can be concluded that LIBS can provide simpler and faster classification without the use of any chemical reagent, which represents a decisive advantage for applications dedicated to rapidly detecting the processing degree of wheat flour and other cereals.

Identification of cervical cancer using laser-induced breakdown spectroscopy coupled with principal component analysis and support vector machine.

Cervical cancer is one of the most widespread diseases in women. Traditional cancer diagnosis is extremely complicated and relies on subjective interpretation of biopsy material. In this work, laser-induced breakdown spectroscopy (LIBS) was used in cervical cancer recognition. In order to improve identification accuracy of cervical cancer by LIBS, the chemometric methods of principal component analysis (PCA) and support vector machine (SVM) were combined. The results show that the content of trace elements in normal tissues and cervical cancer tissues was significantly different. Normalized peak intensities of Na, Mg, and K in the cervical cancer tissues were significantly higher than normal tissues, and the normalized peak intensities of Ca in the normal tissues were higher than cervical cancer tissues. The identification accuracies of PCA-SVM are better than SVM, with the achieved accuracies of 94.44% and 93.06%, respectively. It can be concluded that LIBS techniques coupled with chemometric method is a potential in cancer tissue identification, which provides a preliminary research basis for real-time diagnosis of cancer tissues using LIBS.

Spectral Interference Elimination in Soil Analysis Using Laser-Induced Breakdown Spectroscopy Assisted by Laser-Induced Fluorescence.

The complex and serious spectral interference makes it difficult to detect trace elements in soil using laser-induced breakdown spectroscopy (LIBS). To address it, LIBS-assisted by laser-induced fluorescence (LIBS-LIF) was applied to selectively enhance the spectral intensities of the interfered lines. Utilizing this selective enhancement effect, all the interference lines could be eliminated. As an example, the Pb I 405.78 nm line was enhanced selectively. The results showed that the determination coefficient (R2) of calibration curve (Pb concentration range = 14-94 ppm), the relative standard deviation (RSD) of spectral intensities, and the limit of detection (LOD) for Pb element were improved from 0.6235 to 0.9802, 10.18% to 4.77%, and 24 ppm to 0.6 ppm using LIBS-LIF, respectively. These demonstrate that LIBS-LIF can eliminate spectral interference effectively and improve the ability of LIBS to detect trace heavy metals in soil.

Spatially selective excitation in laser-induced breakdown spectroscopy combined with laser-induced fluorescence.

Spatially selective excitation was proposed to improve excitation efficiency in laser-induced breakdown spectroscopy combined with laser-induced fluorescence (LIBS-LIF). Taking chromium (Cr) and nickel (Ni) elements in steels as examples, it was discovered that the optimal excitation locations were the center of the plasmas for the matrix of the iron (Fe) element but the periphery for Cr and Ni elements. By focusing an excitation laser at the optimal locations, not only excitation efficiency but also the analytical accuracy and sensitivity of quantitative LIBS-LIF were better than those with excitation at the plasma center in conventional LIBS-LIF. This study provides an effective way to improve LIBS-LIF analytical performance.

Determinations of trace boron in superalloys and steels using laser-induced breakdown spectroscopy assisted with laser-induced fluorescence.

Boron (B) is widely applied in microalloying of metals. As a typical light element, however, determination of boron in alloys with complex matrix spectra is still a challenge for laser-induced breakdown spectroscopy (LIBS) due to its weak line intensities in the UV-visible-NIR range and strong spectral interference from the matrix spectra. In this study, a wavelength-tunable laser was used to enhance the intensities of boron lines selectively. The intensities of B I 208.96 nm from boron plasmas were enhanced approximately 3 and 5.8 times while the wavelength-tunable laser was tuned to 249.68 and 249.77 nm, respectively. Utilizing the selective enhancement effect, accurate determinations of trace boron in nickel-based superalloys and steels were achieved by laser-induced breakdown spectroscopy assisted by laser-induced fluorescence (LIBS-LIF), with limits of detection (LoDs) of 0.9 and 0.5 ppm, respectively. The results demonstrated that LIBS-LIF can hopefully be used in boron determinations and has great potential for improving the ability of LIBS to determine light elements in alloys with a complex matrix.

Laser-induced breakdown spectroscopy of liquid solutions: a comparative study on the forms of liquid surface and liquid aerosol.

Liquid surface and liquid aerosol as the traditional liquid forms for laser-induced breakdown spectroscopy (LIBS) and inductively coupled plasma (ICP), respectively, have been used to analyze chromium (Cr) and cadmium (Cd) elements using LIBS in a liquid solution. The spectral differences, the effects of laser energy and laser frequency, the accumulated number of laser pulses, gate delay time, and the quantitative analyses for a liquid surface and a liquid aerosol were compared. The results showed that the liquid surface demonstrated a lower plasma threshold, higher optical emission intensity, and higher single-to-noise ratio. Moreover, the relative standard deviations (RSDs) of the intensities of the liquid aerosol are better than those of the liquid surface. Furthermore, the results of the quantitative analyses of Cr I 357.86 nm and Cd I 361.05 nm of the liquid surface are close to those of the liquid aerosol. The limit of detections of Cr and Cd of the liquid surface were 2.764 and 86.869 µg/mL, which were close to those of liquid aerosol, 2.847 µg/mL of Cr and 97.635 µg/mL of Cd. For both the liquid surface and liquid aerosol, the coefficient of determination R2 of the calibration curve for Cr and Cd were above 0.99, and the average RSDs of Cr and Cd of the liquid surface were 0.027 and 0.054, which were similar to the 0.020 of Cr and 0.042 of Cd of the liquid aerosol. These results suggest that both the liquid surface and aerosol have similar detection abilities for water quality monitoring.

Characteristics of spectral lines with crater development during laser-induced breakdown spectroscopy.

To study the characteristics of spectral lines with crater development during laser-induced breakdown spectroscopy, the changes in the spectral line intensities of iron (Fe) and chromium (Cr) during the development of craters were investigated. Images of the plasmas formed during crater development were captured, and the temperatures and electron densities of the plasmas were calculated. The results showed that when a crater developed, the intensities of the ion lines decreased and the intensities of the atomic lines increased. This is because the plasmas generated in the crater have a higher initial emission intensity and experience more rapid cooling as the crater develops. These two effects lead to changes in the rates of decrease of ion and atomic line intensities over time. Therefore, the changes in intensities of ion lines caused by crater development differ from which of atomic lines.

[Mapping Applications in Laser-Induced Breakdown Spectroscopy].

LIBS mapping was used to analyze and detect the elemental distribution of iron ore surface with self-developed software and 532 nm Nd∶YAG laser. Firstly, in order to illustrate the relationship between element content and spectral intensity, the calibration curve was established by scanning the surface of standard sample. Then, a self-made sample was homogeneously divided into three parts that was pressed by three different standard iron ore powders. For the purpose of validating the mapping technology, a two-dimensional concentration distribution profile was generated after scanning the sample surface which was compared with surface morphology phase of the sample. Finally, with the resolution of 100 microns, the surface scanning analysis of the natural iron ore within the scope of 14 mm×11 mm was implemented. With this basis, the distribution profile of the elements Ca, Al, Ti and Mn were obtained, and the analysis results were compared with the surface morphology phase of the natural iron ore. The results showed that LIBS mapping technology could be used to achieve the qualitative analysis of component gradient distribution of the heterogeneous sample surface.