Quantitative assessment of zearalenone in maize using multivariate algorithms coupled to Raman spectroscopy.

Zearalenone is a contaminant in food and feed products which are hazardous to humans and animals. This study explored the feasibility of the Raman rapid screening technique for zearalenone in contaminated maize. For representative Raman spectra acquisition, the ground maize samples were collected by extended sample area to avoid the adverse effect of heterogeneous component. Regression models were built with partial least squares (PLS) and compared with those built with other variable selection algorithms such as synergy interval PLS (siPLS), ant colony optimization PLS (ACO-PLS) and siPLS-ACO. SiPLS-ACO algorithm was superior to others in terms of predictive power performance for zearalenone analysis. The best model based on siPLS-ACO achieved coefficients of correlation (Rp) of 0.9260 and RMSEP of 87.9132 µg/kg in the prediction set, respectively. Raman spectroscopy combined multivariate calibration showed promising results for the rapid screening large numbers of zearalenone maize contaminations in bulk quantities without sample-extraction steps.

Purity assessment of crystalline zearalenone.

Commercially available solid zearalenone (ZON) to be used as a certified liquid calibrant (BCR-699) in a project funded by the European Commission within the Standard Measurement and Testing program was characterized and its purity determined. The degree of purity of the ZON was examined by UV spectrophotometer, liquid chromatography (LC) with diode array and fluorescence detection, 1H and 13C-NMR spectrometry, LC-mass spectrometry (LC/MS/MS), ion chromatography (IC), and differential scanning calorimetry (DSC). The diagrams obtained from DSC analysis and the UV spectrum showed no detectable impurities. Likewise, no impurities were observed by LC analysis with both diode array and fluorescence detection. IC determination revealed negligible contamination of ZON with chloride of 0.020 +/- 0.005% and nitrate of 0.016 +/- 0.006%. Zearalanone (ZAN) was identified as one of 2 minor (0.2%) impurities by LC/MS/MS. The 1H-NMR measurements revealed an additional peak, which has not been previously reported in the literature. It could be identified as part of the ZON spectrum as the signal arising from the phenolic proton attached to C4'. The manufacturer states an additional contamination with 0.2% methylene chloride, which could be confirmed to an extent of 0.1% by 1H-NMR. Minor impurities, whose structures remain unknown, were discovered at 3.5 and < 1 ppm. Total percentage of impurities based on NMR measurement was estimated not to exceed 1%. A purity of 99.5% with a tolerance of +/- 0.5% was finally attributed to the ZON studied in this project.