Determination and quantification of heavy metals in sediments through laser-induced breakdown spectroscopy and partial least squares regression

Conventional analysis techniques and sample preprocessing methods for identifying trace metals in soil and sediment samples are costly and time-consuming. This study investigated the determination and quantification of heavy metals in sediments by using a Laser-Induced Breakdown Spectroscopy (LIBS) system and multivariate chemometric analysis. Principle Component Analysis (PCA) was conducted on the LIBS spectra at the emission lines of 11 selected elements (Al, Ca, Cd, Cr, Fe, K, Mg, Na, Ni, Pb, and Si). The results showed apparent clustering of four types of sediment samples, suggesting the possibility of application of the LIBS technique for distinguishing different types of sediments. Mainly, the Cd, Cr, and Pb concentrations in the sediments were analyzed. A data-smoothing method—namely, the Savitzky–Golay (SG) derivative—was used to enhance the performance of the Partial Least Squares Regression (PLSR) model. The performance of the PLSR model was evaluated in terms of the coefficient of determination (R²), Root Mean Square Error of Calibration (RMSEC), and Root Mean Square Error of Cross Validation (RMSECV). The results obtained using the PLSR with the SG derivative were improved in terms of the R² and RMSECV, except for Cr. In particular, the results for Cd obtained with the SG derivative showed a decrease of 25% in the RMSECV value. This demonstrated that the PLSR model with the SG derivative is suitable for the quantitative analysis of metal components in sediment samples and can play a significant role in controlling and managing the water quality of rivers.