To promote the green development of agriculture by returning biochar to farmland, it is of great significance to simultaneously detect heavy and nutritional metals in agricultural biochar. This work aimed first to apply laser-induced breakdown spectroscopy (LIBS) for the determination of heavy (Pb, Cr) and nutritional (K, Na, Ca, Mg, Cu, and Zn) metals in agricultural biochar. Each batch of collected biochar was prepared to a standardized sample using the separating and milling method. Two types of univariate analysis model were developed using peak intensity and integration area of the sensitive emission lines, but the performance did not satisfy the requirements of practical application because of the poor correlations between the measured values and predicted values, as well as large relative standard deviation of the prediction (RSDP) values. An ensemble learning algorithm, adaboost backpropagation artificial neural network (BP-Adaboost), was then used to develop the multivariate analysis models, which had a more robust performance than traditional univariate analysis, partial least squares regression (PLSR), and backpropagation artificial neural network (BP-ANN). The optimized RSDP values for K, Ca, Mg, and Cu were less than 10%, while the RSDP values for Pb, Cr, Zn, and Na were in the range of 10–20%. Moreover, the pairwise t-test of its prediction set showed that there was no significant difference between the measurements of LIBS and ICP-MS. The promising results indicate that rapid and simultaneous detection of major heavy and nutritional metals in agricultural biochar can be achieved using LIBS and reasonable chemometric algorithms.
Artificial neural network for on-site quantitative analysis of soils using laser induced breakdown spectroscopy