TY - JOUR A1 - Dietz, T. A1 - Gottlieb, Cassian A1 - Kohns, P. A1 - Ankerhold, G. T1 - Comparison of atomic and molecular emission in LIBS for the quantification of harmful species in cement-based materials JF - Spectrochimica Acta Part B N2 - Due to the penetration of harmful chlorides into concrete, e.g. from de-icing salt, damage processes such as chloride-related pitting corrosion can occur if critical values are exceeded. In this study, multiphase materials such as chloride-contaminated concrete are examined in detail. A direct comparison is made by analyzing the spectroscopic information of simultaneously measured atomic and molecular emissions with laser-induced breakdown spectroscopy (LIBS). In addition, the influence on the calibration is examined on the basis of the combined spectral information of both reaction paths of the penetrated chlorides. The calibration models of univariate and multivariate methods were validated using reference samples with wet chemical analysis. The results are applied to a concrete sample of a parking deck, which was also analyzed by potentiometric wet chemistry. In order to account for the heterogeneity of concrete, spatially (200 μm) and spectroscopically (0.1 nm) resolved LIBS measurements were performed using a fully automated laboratory system. Simultaneous measurements with three spectrometers allow the analysis of the emission processes of several elements such as Cl, Ca, O, Si and Mg as well as the newly formed molecules CaO and CaCl. The evaluation of the molecular emission in combination with atomic lines extends the analytical performance, since different concrete phases such as aggregates and cement matrix can be better represented. The measurements were carried out in ambient air and with helium purge gas. The limit of detection (LOD) achieved for a combined evaluation of atomic and molecular emission was determined to be 0.028 wt%. KW - Laser-induced breakdown spectroscopy (LIBS) KW - Cement-based materials KW - Atomic and molecular mapping KW - Chemometrics PY - 2019 DO - https://doi.org/10.1016/j.sab.2019.105707 SN - 0584-8547 VL - 161 SP - 105707 PB - Elsevier B.V. AN - OPUS4-50438 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -