Quantitative analysis of chromium in vegetable oil by collinear double pulse laser-induced breakdown spectroscopy combined with dual-line internal standard method

Abstract

The safety quality of vegetable oil is very important for human life. The objective of this research is to determine the content of heavy metal chromium (Cr) in each of three kinds of vegetable oils (soybean oil, peanut oil, and corn oil) quantitatively by collinear double pulse laser-induced breakdown spectroscopy (DP-LIBS). In this study, a total of 24 vegetable oil samples are prepared, and each kind of vegetable oil has 8 samples. Fortune paulownia wood chips with a diameter of 20 mm and thickness of 3 mm are placed into the vegetable oil samples to collect the Cr element. After that, the 24 samples (fortune paulownia wood chips that have enriched Cr element) are dried in the oven, and the LIBS spectra of samples are acquired in a wavelength range of 206.28-481.77 nm by a dual-channel high-precision spectrometer. The spectral line of Cr (Cr I 425.39 nm) is chosen as the quantitative analysis spectral line, while CN (CN 421.39 nm) molecular spectral line, Ca (Ca I 422.64 nm) atomic spectral line and the sum of their spectral line intensities are selected as the internal standard lines. Then the calibration curves of Cr are obtained by the basic calibration method, single-line internal standard method (CN 421.39 nm or Ca I 422.64 nm as the internal standard line) and dual-line internal standard method (CN 421.39 nm and Ca I 422.64 nm as the internal standard lines). Finally, the validation samples are used to verify the performances of the calibration curves of Cr element. The results show that the values of fitting degree (R2) of the basic calibration curves for three kinds of vegetable oils are all above 0.97, and the relative errors of validation samples with low concentration are bigger than those with high concentration. The values of (R2) of calibration curves obtained by single-line internal standard method are above 0.98, and the relative errors of validation samples are lower than those obtained using basic calibration method. And the values of (R2) of calibration curves for soybean oils, corn oils and peanut oils are 0.995, 0.992 and 0.996, respectively, with using dual-line internal standard method. The relative errors between the two validation samples are 12.8%, 1.73%, 9.19%, 6.05% and 6.23%, 6.69%, respectively. And the results obtained by the dual-line internal standard method are better than those obtained by the basic calibration method and single-line internal standard method. Thus it can be seen that the dual-line internal standard method can reduce the error of quantitative analysis effectively and improve the predicting ability of LIBS technique for Cr element detection in vegetable oil.