Multi-element Quantitative Analysis of Single Micro-sized Suspended Particles in Air with High Accuracy Based on Random Forest and Variable Selection Strategies.

Abstract

The chemical compositions of atmospheric particles have been studied for several decades, and the traditional techniques for particle analysis usually require time-consuming sample preparation. Within this study, simultaneous quantitative detection of multiple metallic species (Zn, Cu, and Ni) in single micro-sized suspended particles was investigated by combining random forest (RF) and variable selection strategies. Laser-induced breakdown spectra of 15 polluted black carbon samples were applied for establishing the RF model, and the movmean smoothing spectral pretreatment method and variable selection methods [variable importance measurement (VIM), genetic algorithm (GA), and variable importance projection (VIP)] were proposed. Finally, the optimized RF calibration model with the evaluation indicators of mean relative error (MRE), root-mean-square error (RMSE), and coefficient of determination (R2) was constructed based on the optimal input variables and model parameters. Compared with the univariate regression method, the VIP-RF (Zn) and VIM-RF (Cu and Ni) models showed a better correlation relationship (Rp2 = 0.9662 for Zn, Rp2 = 0.9596 for Cu, and Rp2 = 0.9548 for Ni). For Zn, Cu, and Ni, the values of RMSEP (RMSE of prediction) decreased by 116.44, 68.94, and 102.10 ppm, while the values of MREP (MRE of prediction) decreased by 67, 55, and 48%, respectively. The values of ratio of prediction to deviation (RPD) of VIP-RF (Zn), VIM-RF (Cu), and VIM-RF (Ni) models were 5.4, 5.0, and 4.7, respectively. The performance of this combined approach displays a notable accuracy improvement in the quantitative analysis of single particles, suggesting that it is a promising tool for real-time air particulate matter pollution monitoring and control in the future.