title: Comparison of sensitivity to artificial spectral errors and multivariate LOD in NIR spectroscopy - Determining the performance of miniaturizations on melamine in milk powder.
abstract: This study compared three commercially available spectrometers - whereas two of them were miniaturized - in terms of prediction ability of melamine in milk powder (infant formula). Therefore all spectra were split into calibration- and validation-set using Kennard Stone and Duplex algorithm in comparison. For each instrument the three best performing PLSR models were constructed using SNV and Savitzky Golay derivatives. The best RMSEP values were 0.28g/100g, 0.33g/100g and 0.27g/100g for the NIRFlex N-500, the microPHAZIR and the microNIR2200 respectively. Furthermore the multivariate LOD interval [LODmin, LODmax] was calculated for all the PLSR models unveiling significant differences among the spectrometers showing values of 0.20g/100g - 0.27g/100g, 0.28g/100g - 0.54g/100g and 0.44g/100g - 1.01g/100g for the NIRFlex N-500, the microPHAZIR and the microNIR2200 respectively. To assess the robustness of all models, artificial introduction of white noise, baseline shift, multiplicative effect, spectral shrink and stretch, stray light and spectral shift were applied. Monitoring the RMSEP as function of the perturbation gave indication of robustness of the models and helped to compare the performances of the spectrometers. Not taking the additional information from the LOD calculations into account one could falsely assume that all the spectrometers perform equally well which is not the case when the multivariate evaluation and robustness data were considered.
authors.affiliation: Institute of Analytical Chemistry and Radiochemistry, CCB-Center for Chemistry and Biomedicine, Leopold Franzens University, Innrain 80/82, 6020 Innsbruck, Austria. Electronic address: Raphael.henn@uibk.ac.at.
authors.forename: Raphael
authors.initials: R
authors.lastname: Henn
authors.affiliation: Institute of Analytical Chemistry and Radiochemistry, CCB-Center for Chemistry and Biomedicine, Leopold Franzens University, Innrain 80/82, 6020 Innsbruck, Austria. Electronic address: Christian.kirchler@uibk.ac.at.
authors.forename: Christian G
authors.initials: CG
authors.lastname: Kirchler
authors.affiliation: Institute of Analytical Chemistry and Radiochemistry, CCB-Center for Chemistry and Biomedicine, Leopold Franzens University, Innrain 80/82, 6020 Innsbruck, Austria. Electronic address: Maria-elisabeth.grossgut@student.uibk.ac.at.
authors.forename: Maria-Elisabeth
authors.initials: ME
authors.lastname: Grossgut
authors.affiliation: Institute of Analytical Chemistry and Radiochemistry, CCB-Center for Chemistry and Biomedicine, Leopold Franzens University, Innrain 80/82, 6020 Innsbruck, Austria. Electronic address: Christian.W.Huck@uibk.ac.at.
authors.forename: Christian W
authors.initials: CW
authors.lastname: Huck
mesh_terms: D000465:Algorithms; D005506:Food Contamination / Q000032:analysis*; D041943:Infant Formula / Q000737:chemistry*; D048088:Informatics; D057230:Limit of Detection; D008904:Miniaturization; D015999:Multivariate Analysis; D012044:Regression Analysis; D012107:Research Design; D019265:Spectroscopy, Near-Infrared / Q000379:methods*; D014227:Triazines / Q000032:analysis*
chemical_list: D014227:Triazines; C011907:melamine
keywords: Limit of Detection; Melamine; Miniaturization; NIR spectroscopy; PLSR; Robustness