关键词: 气相色谱-质谱联用, 免疫算法, 重叠峰解析, 农药混合物

Chemometric methods have been proved to be a powerful tool for resolution of overlapping signals. Immune algorithm (IA) is one of the chemometric approaches for analyzing multi-component GC-MS signals. The method extracts the information of the components by iteratively eliminating standard information (chromatogram or mass spectrum) from overlapping GC-MS signals. In the primary IA, however, the standard signal of each component possibly contained in the mixture must be provided by measuring the standard or by theoretical simulation. When there is difference between the measured signals of the standards and the mixture, distortion and negative values will appear in the resolved chromatograms. In order to conquer the problem, an algorithm based on an alternative iteration of least squares fitting and IA was proposed in this work. In the method, the measurement of GC-MS was achieved with a very fast temperature program to make the analytes to elute within a short retention time period, and then the chromatographic and mass spectral information of the components in the overlapping signal is calculated with the proposed algorithm. In the calculation, the algorithm takes random mass spectra of the components as the starting input, and then the information of each component is obtained with an alternating iterative process. In the iteration, the mass spectra are calculated by using the least squares fitting and the chromatographic profiles are resolved by IA. Furthermore, the non-negative and unimodality constraints are adopted in the calculation for improving the resolved results. The iteration stops when the remaining signal does not change. The feasibility of the method was validated by using a simulated GC-MS data matrix of a three-component mixture, and the practicability of the method was proved by resolving the GC-MS data of the 40-pesticide mixture. The results show that both the mass spectra and the chromatographic information of the components were extracted from the overlapping signals, and the pesticide mixture was analyzed within 10 min elution with the help of the proposed method.

Key words: gas chromatography-mass spectrometry, immune algorithm, resolution of overlapping peak, pesticide mixture