Fast detection of toxic metals in crops is important for monitoring pollution and ensuring food safety. In this study, laser-induced breakdown spectroscopy (LIBS) was used to detect the chromium content in rice leaves. We investigated the influence of laser wavelength (532 nm and 1064 nm excitation), along with the variations of delay time, pulse energy, and lens-to-sample distance (LTSD), on the signal (sensitivity and stability) and plasma features (temperature and electron density). With the optimized experimental parameters, univariate analysis was used for quantifying the chromium content, and several preprocessing methods (including background normalization, area normalization, multiplicative scatter correction (MSC) transformation and standardized normal variate (SNV) transformation were used to further improve the analytical performance. The results indicated that 532 nm excitation showed better sensitivity than 1064 nm excitation, with a detection limit around two times lower. However, the prediction accuracy for both excitation wavelengths was similar. The best result, with a correlation coefficient of 0.9849, root-mean-square error of 3.89 mg/kg and detection limit of 2.72 mg/kg, was obtained using the SNV transformed signal (Cr I 425.43 nm) induced by 532 nm excitation. The results indicate the inspiring capability of LIBS for toxic metals detection in plant materials.
Quick access to cadmium (Cd) contamination in lettuce is important to supervise the leafy vegetable growth environment and market. This study aims to apply laser-induced breakdown spectroscopy (LIBS) technology for fast determination of Cd content and diagnosis of the Cd contamination degree in lettuce. Emission lines Cd II 214.44 nm, Cd II 226.50 nm, and Cd I 228.80 nm were selected to establish the univariate analysis model. Multivariate analysis including partial least squares (PLS) regression, was used to establish Cd content calibration models, and PLS model based on 22 variables selected by genetic algorithm (GA) obtained the best performance with correlation coefficient in the prediction set Rp2 = 0.9716, limit of detection (LOD) = 1.7 mg/kg. K-Nearest Neighbors (KNN) and random forest (RF) were used to analyze Cd contamination degree, and RF model obtained the correct classification rate of 100% in prediction set. The preliminary results indicate LIBS coupled with chemometrics could be used as a fast, efficient and low-cost method to assess Cd contamination in the vegetable industry.
High-accuracy and fast detection of nutritive elements in traditional Chinese medicine Panax notoginseng (PN) is beneficial for providing useful assessment of the healthy alimentation and pharmaceutical value of PN herbs. Laser-induced breakdown spectroscopy (LIBS) was applied for high-accuracy and fast quantitative detection of six nutritive elements in PN samples from eight producing areas. More than 20,000 LIBS spectral variables were obtained to show elemental differences in PN samples. Univariate and multivariate calibrations were used to analyze the quantitative relationship between spectral variables and elements. Multivariate calibration based on full spectra and selected variables by the least absolute shrinkage and selection operator (Lasso) weights was used to compare the prediction ability of the partial least-squares regression (PLS), least-squares support vector machines (LS-SVM), and Lasso models. More than 90 emission lines for elements in PN were found and located. Univariate analysis was negatively interfered by matrix effects. For potassium, calcium, magnesium, zinc, and boron, LS-SVM models based on the selected variables obtained the best prediction performance with Rp values of 0.9546, 0.9176, 0.9412, 0.9665, and 0.9569 and root mean squared error of prediction (RMSEP) of 0.7704 mg/g, 0.0712 mg/g, 0.1000 mg/g, 0.0012 mg/g, and 0.0008 mg/g, respectively. For iron, the Lasso model based on full spectra obtained the best result with an Rp value of 0.9348 and RMSEP of 0.0726 mg/g. The results indicated that the LIBS technique coupled with proper multivariate chemometrics could be an accurate and fast method in the determination of PN nutritive elements for traditional Chinese medicine management and pharmaceutical analysis.
The presence of cadmium in rice stems is a limiting factor that restricts its function as biomass. In order to prevent potential risks of heavy metals in rice straws, this study introduced a fast detection method of cadmium in rice stems based on laser induced breakdown spectroscopy (LIBS) and chemometrics. The wavelet transform (WT), area normalization and median absolute deviation (MAD) were used to preprocess raw spectra to improve spectral stability. Principal component analysis (PCA) was used for cluster analysis. The classification models were established to distinguish cadmium stress degree of stems, of which extreme learning machine (ELM) had the best effect, with 91.11% of calibration accuracy and 93.33% of prediction accuracy. In addition, multivariate models were established for quantitative detection of cadmium. It can be found that ELM model had the best prediction effects with prediction correlation coefficient of 0.995. The results show that LIBS provides an effective method for detection of cadmium in rice stems. The combination of LIBS technology and chemometrics can quickly detect the presence of cadmium in rice stems, and accurately realize qualitative and quantitative analysis of cadmium, which could be of great significance to promote the development of new energy industry.