Second-order calibration high-resolution continuum source graphite furnace molecular absorption spectrometry-based...

In this study, we report the simultaneous determination of bromine and fluorine using Second-Order Calibration High-Resolution Continuum Source Graphite Furnace Molecular Absorption Spectrometry (HR CS MAS). The instrumental data acquired correspond to the time versus wavelength matrix per sample that were analyzed using Parallel Factor Analysis (PARAFAC), along with Unfold and N-way Partial Least Squares combined with a post-calibration step known as Residual Bilinearization (U and N PLS/RBL). Despite the significant difference in sensitivity between bromine and fluorine, all approaches provided reasonably accurate results when predicting both analytes in synthetic mixtures within a controlled environment. The relative prediction error (REP) values for bromine were 29.8 % (PARAFAC), 23.6 % (N-PLS/RBL), and 13.1 % (U-PLS/RBL), while for fluorine, the REP values were 3.4 % (PARAFAC), 3.5 % (N-PLS/RBL), and 3.2 % (U-PLS/RBL). When applying this approach to predict unknown samples, a comparison was made between the estimated nominal concentrations of fluorine and bromine obtained using either a reference method or based on labeled values or spiked mass, and those obtained using the proposed method. It was observed that PARAFAC was unable to predict the samples accurately, whereas the REP values for the prediction of bromine and fluorine using N-PLS/RBL and U-PLS/RBL methods were 19.3 %/19.2 % and 13.6 %/13.1 %, respectively.