title: Classification of gasoline data obtained by gas chromatography using a piecewise alignment algorithm combined with feature selection and principal component analysis.
abstract: A fast and objective chemometric classification method is developed and applied to the analysis of gas chromatography (GC) data from five commercial gasoline samples. The gasoline samples serve as model mixtures, whereas the focus is on the development and demonstration of the classification method. The method is based on objective retention time alignment (referred to as piecewise alignment) coupled with analysis of variance (ANOVA) feature selection prior to classification by principal component analysis (PCA) using optimal parameters. The degree-of-class-separation is used as a metric to objectively optimize the alignment and feature selection parameters using a suitable training set thereby reducing user subjectivity, as well as to indicate the success of the PCA clustering and classification. The degree-of-class-separation is calculated using Euclidean distances between the PCA scores of a subset of the replicate runs from two of the five fuel types, i.e., the training set. The unaligned training set that was directly submitted to PCA had a low degree-of-class-separation (0.4), and the PCA scores plot for the raw training set combined with the raw test set failed to correctly cluster the five sample types. After submitting the training set to piecewise alignment, the degree-of-class-separation increased (1.2), but when the same alignment parameters were applied to the training set combined with the test set, the scores plot clustering still did not yield five distinct groups. Applying feature selection to the unaligned training set increased the degree-of-class-separation (4.8), but chemical variations were still obscured by retention time variation and when the same feature selection conditions were used for the training set combined with the test set, only one of the five fuels was clustered correctly. However, piecewise alignment coupled with feature selection yielded a reasonably optimal degree-of-class-separation for the training set (9.2), and when the same alignment and ANOVA parameters were applied to the training set combined with the test set, the PCA scores plot correctly classified the gasoline fingerprints into five distinct clusters.
authors.affiliation: Department of Chemistry, Box 351700, University of Washington, Seattle, WA 98195, USA.
authors.forename: Karisa M
authors.initials: KM
authors.lastname: Pierce
authors.forename: Janiece L
authors.initials: JL
authors.lastname: Hope
authors.forename: Kevin J
authors.initials: KJ
authors.lastname: Johnson
authors.forename: Bob W
authors.initials: BW
authors.lastname: Wright
authors.forename: Robert E
authors.initials: RE
authors.lastname: Synovec
mesh_terms: D000465:Algorithms; D000704:Analysis of Variance; D002849:Chromatography, Gas / Q000379:methods*; D005742:Gasoline / Q000032:analysis* / Q000145:classification*; D025341:Principal Component Analysis
chemical_list: D005742:Gasoline