Calibration models have been developed for determination of trace elements, silver for instance, in soil using laser-induced breakdown spectroscopy (LIBS). The major concern is the matrix effect. Although it affects the accuracy of LIBS measurements in a general way, the effect appears accentuated for soil because of large variation of chemical and physical properties among different soils. The purpose is to reduce its influence in such way an accurate and soil-independent calibration model can be constructed. At the same time, the developed model should efficiently reduce experimental fluctuations affecting measurement precision. A univariate model first reveals obvious influence of matrix effect and important experimental fluctuation. A multivariate model has been then developed. A key point is the introduction of generalized spectrum where variables representing the soil type are explicitly included. Machine learning has been used to develop the model. After a necessary pretreatment where a feature selection process reduces the dimension of raw spectrum accordingly to the number of available spectra, the data have been fed in to a back-propagation neuronal networks (BPNN) to train and validate the model. The resulted soilindependent calibration model allows average relative error of calibration (REC) and average relative error of prediction (REP) within the range of 5-6%.
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