A Simple Laser-Induced Breakdown Spectroscopy Method for Quantification and Classification of Edible Sea Salts Assisted by Surface-Hydrophilicity-Enhanced Silicon Wafer Substrates.

Salt, one of the most commonly consumed food additives worldwide, is produced in many countries. The chemical composition of edible salts is essential information for quality assessment and origin distinction. In this work, a simple laser-induced breakdown spectroscopy instrument was assembled with a diode-pumped solid-state laser and a miniature spectrometer. Its performances in analyzing Mg and Ca in six popular edible sea salts consumed in South Korea and classification of the products were investigated. Each salt was dissolved in water and a tiny amount of the solution was dropped and dried on the hydrophilicity-enhanced silicon wafer substrate, providing homogeneous distribution of salt crystals. Strong Mg II and Ca II emissions were chosen for both quantification and classification. Calibration curves could be constructed with limits-of-detection of 87 mg/kg for Mg and 45 mg/kg for Ca. Also, the Mg II and Ca II emission peak intensities were used in a k-nearest neighbors model providing 98.6% classification accuracy. In both quantification and classification, intensity normalization using a Na I emission line as a reference signal was effective. A concept of interclass distance was introduced, and the increase in the classification accuracy due to the intensity normalization was rationalized based on it. Our methodology will be useful for analyzing major mineral nutrients in various food materials in liquid phase or soluble in water, including salts.

Highly Precise Laser-Induced Breakdown Spectroscopy Analysis of Major Mineral Nutrients in Edible Salts Using Miniaturized Salt Ponds and Alternating Laser-Ablation Data Sampling.

In this work, we applied a hydrophilicity-enhanced solid substrate and an alternating laser-ablation data sampling (ALADS) scheme to improve laser-induced breakdown spectroscopy (LIBS) measurement precision and demonstrated the performance in analyzing K, Mg, Ca, and S contained in commercially available edible salt products. Five edible salt products from Australia, Bolivia, France, and South Korea were dissolved in water and a tiny volume of each solution was dropped on the solid substrate, that is, a miniaturized salt pond. After being dried, the residual salt crystals distributed still inhomogeneously, but the homogeneity could be significantly improved in comparison with that from typical drop-and-dry methods. The ALADS scheme was applied to extract three precise measurements from 9798 single-shot LIBS spectra covering the entire salt pond. The measurements obtained by ALADS were found to agree well with one another regardless of the inhomogeneous distribution of salt crystals. As a result, the measurement precision was proved remarkably. Limits of detection for K, Mg, Ca, and S were estimated to be 0.64, 1.7, 14, and 530 mg/kg, respectively, which are enough to analyze those elements contained in salts typically at the level of 100 parts per million (ppm) to ∼3 wt% for the purpose of salt quality assessment.

Feasibility of a Low-Power, Low-Resolution Laser-Induced Breakdown Spectroscopy Instrument for Analysis of Nickel Alloys: Quantification of the Major Alloying Elements and Classification.

A simple cost-effective laser-induced breakdown spectroscopy (LIBS) instrument was used for quantification of major elements in several nickel alloys and also sorting them. A compact low-power diode-pumped solid-state laser and a miniature low-resolution spectrometer were assembled for the LIBS instrument. Material properties of the nickel alloys depend mainly on the composition of the major elements, Ni, Cr, and Fe, ranging from a few to ∼60 wt%. The emission peaks at 547.7 nm, 520.4 nm, and 438.1 nm for Ni, Cr, and Fe, respectively, were chosen for this analysis. The analytical performance was found to be enough for the quantification of Ni, Cr, and Fe in the nickel alloys. Limits of detection and accuracy were estimated to be a few weight percent (wt%) and measurement precisions were less than 10% in terms of relative standard deviation. The calibration performance of this intensity-based method was compared with that of the "ratio method" which is used in conventional optical emission spectroscopy analyses. The comparison indicates that the intensity-based method is more appropriate with the low-performance LIBS instrument that detects emission peaks of only a few major elements. Also, multivariate modeling of the six different nickel alloy samples based on the emission peak intensities of Ni, Cr, and Fe was performed using k-nearest neighbors (KNN) and linear discriminant analysis (LDA). The KNN and ordinary LDA models showed 95.0% and 98.3% classification correctness for the separate test data set, respectively. To improve classification performance further, the two-step LDA model was trained. In this approach, the two closest sample classes responsible for the decrease in the classification correctness were separately modeled in the second step to exploit their difference effectively. The two-step LDA model showed 100% correctness in classifying the test objects. Our results indicate that such a low-performance LIBS instrument can be effectively utilized for quantitative analysis of the major elements in the nickel alloys and their rapid identification or sorting in combination with an appropriate multivariate modeling algorithm.

Cooperative combination of LIBS-based elemental analysis and near-infrared molecular fingerprinting for enhanced discrimination of geographical origin of soybean paste.

Laser-induced breakdown spectroscopy (LIBS) and near-infrared (NIR) spectroscopy were combined to enhance discrimination of soybean paste samples according to geographical origin. Since element and organic component compositions of soybean pastes depend on soybean cultivation areas and fermentation conditions, utilization of two complementary spectroscopic signatures would be synergetic for the discrimination. When the areas of C (AC) and Ca (ACa) peaks in the LIBS spectra were used as the inputs for linear discriminant analysis, the accuracy was 95.4%. The accuracy became 92.1%, when the principal component (PC) scores obtained by principal component analysis of the NIR spectra were employed. To enhance NIR discrimination, two-trace two-dimensional (2T2D) correlation analysis was adopted to recognize minute spectral differences. With using the 1st/2nd PC scores of 2T2D slice spectra, accuracy increased to 95.0%. When the ratios of ACa/AC and the 2nd PC scores of the samples were combined together, the accuracy improved to 99.6%.

Combination of LIBS-based elemental analysis and near-infrared molecular fingerprinting of bile juice to enhance identification of gallbladder cancer.

Laser-induced breakdown spectroscopy (LIBS) and near-infrared (NIR) spectroscopy, enabling the measurement of raw bile directly without sample pretreatment, were cooperatively combined to enhance the discrimination of gallbladder cancer (GBC) from other diseases of gallstone and gallbladder (GB) polyp. Since elemental contents and metabolite compositions of bile vary according to the pathological conditions of pancreaticobiliary patients, the use of complementary information could be synergetic to improve disease identification accuracy. The ratios of Mg and Na peak areas (AMg/ANa) and Na and K peak areas (ANa/AK) in the LIBS spectra of GBC samples were different from those of the remaining samples. Also, the intensity ratios of main NIR peaks differed in GBC. Nonetheless, the use of only element peak area ratio or NIR peak intensity ratio was not sufficient to clearly discriminate GBC. On the other hand, when the ANa/AK values and second NIR principal component scores were combined, the discrimination of GBC from normal/gallstone/GB polyp was substantially enhanced owing to incorporation of both complementary GBC-discriminant spectroscopic signatures.

Two-Step Partial Least Squares-Discriminant Analysis Modeling for Accurate Classification of Edible Sea Salt Products Using Laser-Induced Breakdown Spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) has been widely applied to material classification in various fields, and partial least squares-discriminant analysis (PLS-DA) is one of the frequently used classical multivariate statistics to construct classification models based on the LIBS spectra. However, classification accuracy of the PLS-DA model is sensitive to the number of classes and their similarities. Considering this characteristic of PLS-DA, we suggest a two-step PLS-DA modeling approach to improve the classification accuracy. This strategy was demonstrated for a six-class problem in which six commercial edible sea salts produced in Japan, South Korea, and France are classified using their LIBS spectra. At the first step, test spectra were sorted into four classes and one extended class, composed of the two other most confusing classes, and then the test spectra in the extended class were further classified into each of the two constituent classes which were modeled separately from the other four classes. This two-step classification has been found to remarkably improve the PLS-DA classification accuracy by maximizing the difference between the confusing classes in the second-step modeling.

Quantitative analysis of ceria co-doped with samarium and gadolinium using laser-induced breakdown spectroscopy.

Ceria doped with low-valence lanthanide cations has been introduced for use as an electrolyte in solid oxide fuel cells (SOFCs). Improving the performance of SOFCs using doped ceria requires an increase in ion mobility across the solid electrolyte. Recently, ceria doped with multiple low-valence lanthanide ions has been found to show better ion mobility than that of the singly doped one. In this work, the feasibility of laser-induced breakdown spectroscopy (LIBS) for stoichiometric analysis of doubly doped ceria, SmxGd0.1-xCe0.9O2-δ, was investigated. The three lanthanide elements pouring out plenty of emission lines made identifying the well-resolved single emission line of the dopants (Sm and Gd) rarely feasible. However, the spectral feature of the dopants could be extracted from the unresolved spectra successfully by partial least squares-regression (PLS-R). The PLS-R model performance calibrating the LIBS spectra to the concentration of Sm or Gd was dependent on the contribution of the matrix element (Ce) to the latent variable chosen for modeling. The residual feature of Ce in the latent variable could be reduced further by smoothing LIBS spectra using a moving average. The best model showed dependable detection limit (0.83 mol% of Sm) and accuracy (0.24 mol% of Sm) performances. Spectral denoising by moving average and PLS-R modeling based on LIBS spectra can be used as a rapid and reliable methodology for the multiply doped ceria and assist the manufacturing and recycling processes of SOFCs.

Laser-induced breakdown spectroscopy for rapid accurate analysis of Mg, Ca, and K in edible sea salts.

A compact laser-induced breakdown spectroscopy (LIBS) instrument and a simple sample preparation method were developed for rapid on-site analysis of Mg, Ca, and K in edible sea salt products. The LIBS instrument was assembled using a small diode-pumped solid-state laser and a handheld spectrometer. Aqueous solutions of salts were prepared and sampled by using pieces of filter papers. The dried filter paper was attached on the flat surface of a silicon wafer and then analyzed by LIBS. Calibration curves were obtained using binary mixtures of ${\rm NaCl} {-} {{\rm MgSO}_4}$NaCl-MgSO4, ${\rm NaCl} {-} {{\rm CaCl}_2}$NaCl-CaCl2, and NaCl-KCl and used to estimate the concentrations of Mg, Ca, and K in 13 edible sea salt products. Matrix effects on the results from LIBS were identified in comparison with those from inductively coupled plasma optical emission spectroscopy. This indicates that the matrix of sea salt samples is significantly different from that of the binary mixture standards. The sea salts with known concentrations of Mg, Ca, and K were employed to match the matrices of samples and standards. This improved analysis accuracy remarkably. Furthermore, an alternative indirect method for estimating the concentration of K was suggested on the basis of the strong positive correlations observed between the concentrations of Mg and K in the sea salt samples.

Feasibility of Quantitative Analysis of Magnesium and Calcium in Edible Salts Using a Simple Laser-Induced Breakdown Spectroscopy Device.

Feasibility of a simple laser-induced breakdown spectroscopy (LIBS) device has been investigated for the analysis of Mg and Ca in edible salts. The LIBS spectrometer was assembled with a compact low-power diode-pumped solid-state laser (DPSSL) and a non-gated low-resolution handheld spectrometer. A simple sampling process was employed for on-site application. A piece of filter paper was dipped in the aqueous solution of a sample salt and dried for analysis using LIBS. Maintaining the sample surface height at the optimum position was critical to generate plasmas persistently due to the low pulse energy of the DPSSL. The varying height of the filter paper surface was monitored and compensated, while the sample stage was translated to collect spectra from different positions. The variation of line intensities of Mg and Ca could be attributed to the inhomogeneous distribution of dry residues. To correct this, the peak that consists of the Na(I) and C(II) lines at 568 nm was employed as a reference signal for intensity normalization of the analyte Mg(II) and Ca(II) lines. For edible salt products, the normalized Mg(II) and Ca(II) line intensities could be well correlated with the concentrations of Mg and Ca determined using inductively coupled plasma optical emission spectroscopy. Our results indicate that a simple LIBS device in combination with the simple sampling method is promising as an on-site salt quality assessment methodology.

An alternative analytical method for determining arsenic species in rice by using ion chromatography and inductively coupled plasma-mass spectrometry.

Qualitative and quantitative determination of total arsenic content and arsenic species in rice is very important because rice is one of the main sources of human arsenic intake. However, extraction and determination of arsenic species in rice has been very difficult due to severe matrix interference. An alternative analytical method was developed in this study to determine arsenic species in rice by using ion chromatography coupled to inductively coupled plasma-mass spectrometry. Two internal standards were used. The first internal standard was injected before sample introduction to correct signal change with time. The second internal standard was spiked into the sample to reduce matrix interference. Using the developed method, recoveries of dimethylarsinic acid, monomethylarsonic acid, and inorganic arsenic compared to certified values (NIST SRM 1568b rice flour) were 116%, 107%, and 92%, respectively.

Soft Independent Modeling of Class Analogy (SIMCA) Modeling of Laser-Induced Plasma Emission Spectra of Edible Salts for Accurate Classification.

We report soft independent modeling of class analogy (SIMCA) analysis of laser-induced plasma emission spectra of edible salts from 12 different geographical origins for their classification model. The spectra were recorded by using a simple laser-induced breakdown spectroscopy (LIBS) device. Each class was modeled by principal component analysis (PCA) of the LIBS spectra. For the classification of a separate test data set, the SIMCA model showed 97% accuracy in classification. An additional insight could be obtained by comparing the SIMCA classification result with that of partial least squares discriminant analysis (PLS-DA). Different from SIMCA, the PLS-DA classification accuracy seems to be sensitive to addition of new sample classes to the whole data set. This indicates that the individual modeling approach (SIMCA) can be an alternative to global modeling (PLS-DA), particularly for the classification problems with a relatively large number of sample classes.

Effects of repetitive photodynamic therapy using indocyanine green for acne vulgaris.

BACKGROUND: Indocyanine green (ICG) is a photosensitizer recently introduced for the treatment of acne. OBJECTIVE: To evaluate the efficacy and safety of photodynamic therapy (PDT) using ICG in subjects with acne vulgaris and to evaluate whether there was a difference in the efficacy of ICG-PDT between different numbers of treatment. MATERIALS AND METHODS: Subjects with acne on the face were included. ICG lotion (0.1%) was applied for 30 minutes, and a long pulse diode laser was used. Three or five treatments per subject were performed over 2 weeks. Acne lesion counts and Leeds revised acne grades were evaluated at baseline and 2 weeks after the last treatment. RESULTS: In total, 47 subjects completed the study. After both three and five ICG-PDT sessions, a significant reduction in acne lesions and significant improvement in Leeds revised acne grades were found in all treated subjects compared to baseline. In the subjects receiving five ICG-PDT sessions, the reduction of papules/pustules was greater than in the subjects receiving three ICG-PDT sessions (P < 0.01, respectively). However, there was no significant change in the count of nodules/cysts, although it is a negative trend (P = 0.066). Adverse effects were minimal. CONCLUSION: ICG-PDT using long-pulsed diode laser can be a safe and effective tool for acne vulgaris. Moreover, repetitive treatments of five can cause further improvement of inflammatory acne lesions.

Laser-induced breakdown spectroscopy (LIBS) analysis of calcium ions dissolved in water using filter paper substrates: an ideal internal standard for precision improvement.

We report an approach for selecting an internal standard to improve the precision of laser-induced breakdown spectroscopy (LIBS) analysis for determining calcium (Ca) concentration in water. The dissolved Ca(2+) ions were pre-concentrated on filter paper by evaporating water. The filter paper was dried and analyzed using LIBS. By adding strontium chloride to sample solutions and using a Sr II line at 407.771 nm for the intensity normalization of Ca II lines at 393.366 or 396.847 nm, the analysis precision could be significantly improved. The Ca II and Sr II line intensities were mapped across the filter paper, and they showed a strong positive shot-to-shot correlation with the same spatial distribution on the filter paper surface. We applied this analysis approach for the measurement of Ca(2+) in tap, bottled, and ground water samples. The Ca(2+) concentrations determined using LIBS are in good agreement with those obtained from flame atomic absorption spectrometry. Finally, we suggest a homologous relation of the strongest emission lines of period 4 and 5 elements in groups IA and IIA based on their similar electronic structures. Our results indicate that the LIBS can be effectively applied for liquid analysis at the sub-parts per million level with high precision using a simple drying of liquid solutions on filter paper and the use of the correct internal standard elements with the similar valence electronic structure with respect to the analytes of interest.

Feasibility of laser-induced breakdown spectroscopy (LIBS) for classification of sea salts.

We have investigated the feasibility of laser-induced breakdown spectroscopy (LIBS) as a fast, reliable classification tool for sea salts. For 11 kinds of sea salts, potassium (K), magnesium (Mg), calcium (Ca), and aluminum (Al), concentrations were measured by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and the LIBS spectra were recorded in the narrow wavelength region between 760 and 800 nm where K (I), Mg (I), Ca (II), Al (I), and cyanide (CN) band emissions are observed. The ICP-AES measurements revealed that the K, Mg, Ca, and Al concentrations varied significantly with the provenance of each salt. The relative intensities of the K (I), Mg (I), Ca (II), and Al (I) peaks observed in the LIBS spectra are consistent with the results using ICP-AES. The principal component analysis of the LIBS spectra provided the score plot with quite a high degree of clustering. This indicates that classification of sea salts by chemometric analysis of LIBS spectra is very promising. Classification models were developed by partial least squares discriminant analysis (PLS-DA) and evaluated. In addition, the Al (I) peaks enabled us to discriminate between different production methods of the salts.

Aging risk and health care expenditure in Korea.

This paper analyzes the impact of population aging on health care expenditures in Korea. Examination of the age-expenditure profile reveals that health care resources are allocated more for the older cohort of population over time, suggesting significant growth of health care expenditures due to population aging. We contend, however, that population aging is considered as a parameter rather than an independent variable to explain rising health care expenditures. This paper shows that population aging is not found to be a significant determinant of health care expenditures according to the econometric analysis using OECD health data and time-series data for Korea. Using the components decomposition method, which measures the contribution of each component of health care expenditure, we estimate that population aging contributes only less than 10 percent.

Isomeric discrimination and quantification of thyroid hormones, T3 and rT3, by the single ratio kinetic method using electrospray ionization mass spectrometry.

The single ratio kinetic method is applied to the discrimination and quantification of the thyroid hormone isomers, 3,5,3'-triiodothyronine and 3,3',5'-triiodothyronine, in the gas phase, based on the kinetics of the competitive unimolecular dissociations of singly charged transition-metal ion-bound trimeric complexes [M(II)(A)(ref*)(2)-H](+) (M(II) = divalent transition-metal ion; A = T(3) or rT(3); ref* = reference ligand). The trimeric complex ions are generated using electrospray ionization mass spectrometry and the ions undergo collisional activation to realize isomeric discrimination from the branching ratio of the two fragment pathways that form the dimeric complexes [M(II)(A)(ref*)-H](+) and [M(II)(ref*)(2)-H](+). The ratio of the individual branching ratios for the two isomers R(iso) is found strongly dependent on the references and the metal ions. Various sets are tried by choosing the reference from amino acids, substituted amino acids, and dipeptides in combination with the central metal ion chosen from five transition-metal ions (Co(II), Cu(II), Mn(II), Ni(II), and Zn(II)) for the complexes in this experiment. The results are compared in terms of the isomeric discrimination for the T(3)/rT(3) pair. Calibration curves are constructed by relating the ratio of the branching ratios against the isomeric composition of their mixture to allow rapid quantitative isomer analysis of the sample pair. Furthermore, the instrument-dependence of this method is investigated by comparing the two sets of results, one obtained from a quadrupole ion trap mass spectrometer and the other from a quadrupole time-of-flight mass spectrometer.