TY - JOUR

T1 - Partial least squares assisted influence coefficients concept improves accuracy in X-ray fluorescence analysis

AU - Aidene, Soraya

AU - Khaydukova, Maria

AU - Savinov, Sergey

AU - Semenov, Valentin

AU - Kirsanov, Dmitry

AU - Panchuk, Vitaly

N1 - Publisher Copyright: © 2022 Elsevier B.V.

PY - 2022/7

Y1 - 2022/7

N2 - Routine application of X-ray fluorescence (XRF) spectrometry in laboratory practice requires special procedures to correct for matrix effects. One of the most popular procedures is the influence coefficients method. In this method the regression equation relating analytical signal to the target element concentration is extended with empirical terms correcting the influence from particular matrix elements. While the influence coefficients method is quite accurate, it is rather laborious as it requires individual selection of matrix terms for each element under study. The influence coefficients method is based on the least squares regression technique, thus the number of matrix correction terms is limited by the number of available standard calibration samples. Here we propose a very simple technique that can take into account an unlimited number of terms in the influence coefficients method through the employment of partial least squares regression (PLS) where spectral intensities, their ratios and squared intensities are employed as variables. Unlike traditional application of PLS in XRF studies where the regression model is built using spectral intensities only, the proposed approach inspired by classic influence coefficients allows elimination of complex specific XRF matrix effects. The paper describes the suggested method and demonstrates its' performance in two EDXRF data sets with significant matrix effects (ore and steel samples).

AB - Routine application of X-ray fluorescence (XRF) spectrometry in laboratory practice requires special procedures to correct for matrix effects. One of the most popular procedures is the influence coefficients method. In this method the regression equation relating analytical signal to the target element concentration is extended with empirical terms correcting the influence from particular matrix elements. While the influence coefficients method is quite accurate, it is rather laborious as it requires individual selection of matrix terms for each element under study. The influence coefficients method is based on the least squares regression technique, thus the number of matrix correction terms is limited by the number of available standard calibration samples. Here we propose a very simple technique that can take into account an unlimited number of terms in the influence coefficients method through the employment of partial least squares regression (PLS) where spectral intensities, their ratios and squared intensities are employed as variables. Unlike traditional application of PLS in XRF studies where the regression model is built using spectral intensities only, the proposed approach inspired by classic influence coefficients allows elimination of complex specific XRF matrix effects. The paper describes the suggested method and demonstrates its' performance in two EDXRF data sets with significant matrix effects (ore and steel samples).

KW - Influence coefficients

KW - Matrix effects

KW - Partial least squares

KW - X-ray fluorescence spectrometry

UR - http://www.scopus.com/inward/record.url?scp=85130791934&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/34ee8c2f-c5ba-3a2c-a7c8-b980e02fc554/

U2 - 10.1016/j.sab.2022.106452

DO - 10.1016/j.sab.2022.106452

M3 - Article

AN - SCOPUS:85130791934

VL - 193

JO - SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY

JF - SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY

SN - 0584-8547

M1 - 106452

ER -