Revealing hidden spectral information of chlorine and sulfur in data of a mobile Laser-induced Breakdown Spectroscopy system using chemometrics

Abstract For the damage assessment of reinforced concrete structures the quantified ingress profiles of harmful species like chlorides, sulfates and alkali need to be determined. In order to provide on-site analysis of concrete a fast and reliable method is necessary. Low transition probabilities as well as the high ionization energies for chlorine and sulfur in the near-infrared range makes the detection of Cl I and S I in low concentrations a difficult task. For the on-site analysis a mobile LIBS-system (λ = 1064 nm, Epulse ≤ 3 mJ, τ = 1.5 ns) with an automated scanner has been developed at BAM. Weak chlorine and sulfur signal intensities do not allow classical univariate analysis for process data derived from the mobile system. In order to improve the analytical performance multivariate analysis like PLS-R will be presented in this work. A comparison to standard univariate analysis will be carried out and results covering important parameters like detection and quantification limits (LOD, LOQ) as well as processing variances will be discussed (Allegrini and Olivieri, 2014 [1]; Ostra et al., 2008 [2]). It will be shown that for the first time a low cost mobile system is capable of providing reproducible chlorine and sulfur analysis on concrete by using a low sensitive system in combination with multivariate evaluation.

[1]  F. Marini,et al.  Validation of chemometric models - a tutorial. , 2015, Analytica chimica acta.

[2]  G. Wilsch,et al.  Laser-induced breakdown spectroscopy for on-line sulfur analyses of minerals in ambient conditions , 2009 .

[3]  Herbert Wiggenhauser,et al.  Determination of chloride content in concrete structures with laser-induced breakdown spectroscopy , 2005 .

[4]  N. B. Zorov,et al.  Determination of chlorine, sulfur and carbon in reinforced concrete structures by double-pulse laser-induced breakdown spectroscopy , 2014 .

[5]  Franco Allegrini,et al.  IUPAC-consistent approach to the limit of detection in partial least-squares calibration. , 2014, Analytical chemistry.

[6]  Jörg Henseler,et al.  Handbook of Partial Least Squares: Concepts, Methods and Applications , 2010 .

[7]  S. Wold,et al.  PLS-regression: a basic tool of chemometrics , 2001 .

[8]  C. Gottlieb,et al.  Laser Induced Breakdown Spectroscopy (LIBS) im Bauwesen – automatisierte Baustoffanalyse , 2015 .

[9]  Johannes D. Pedarnig,et al.  Boosting persistence time of laser-induced plasma by electric arc discharge for optical emission spectroscopy , 2015 .

[10]  F. Weritz,et al.  Quantitative determination of sulfur content in concrete with laser-induced breakdown spectroscopy ☆ , 2005 .

[11]  Gerd Wilsch,et al.  Detector comparison for sulfur and chlorine detection with laser induced breakdown spectroscopy in the near-infrared-region ☆ , 2007 .

[12]  M. Ostra,et al.  Detection limit estimator for multivariate calibration by an extension of the IUPAC recommendations for univariate methods. , 2008, The Analyst.

[13]  B. Kowalski,et al.  Partial least-squares regression: a tutorial , 1986 .