Mass spectrometry fingerprinting coupled to National Institute of Standards and Technology Mass Spectral search algorithm for pattern recognition

A new analytical strategy based on mass spectrometry fingerprinting combined with the NIST-MS search program for pattern recognition is evaluated and validated. A case study dealing with the tracing of the geographical origin of virgin olive oils (VOOs) proves the capabilities of mass spectrometry fingerprinting coupled with NIST-MS search program for classification. The volatile profiles of 220 VOOs from Liguria and other Mediterranean regions were analysed by secondary electrospray ionization-mass spectrometry (SESI-MS). MS spectra of VOOs were classified according to their origin by the freeware NIST-MS search v 2.0. The NIST classification results were compared to well-known pattern recognition techniques, such as linear discriminant analysis (LDA), partial least-squares discriminant analysis (PLS-DA), k-nearest neighbours (kNN), and counter-propagation artificial neural networks (CP-ANN). The NIST-MS search program predicted correctly 96% of the Ligurian VOOs and 92% of the non-Ligurian ones of an external independent data set; outperforming the traditional chemometric techniques (prediction abilities in the external validation achieved by kNN were 88% and 84% for the Ligurian and non-Ligurian categories respectively). This proves that the NIST-MS search software is a useful classification tool.     

A Bayesian Motivated Two-Sample Test Based on Kernel Density Estimates

A new nonparametric test of equality of two densities is investigated. The test statistic is an average of log-Bayes factors, each of which is constructed from a kernel density estimate. Prior densities for the bandwidths of the kernel estimates are required, and it is shown how to choose priors so that the log-Bayes factors can be calculated exactly. Critical values of the test statistic are determined by a permutation distribution, conditional on the data. An attractive property of the methodology is that a critical value of 0 leads to a test for which both type I and II error probabilities tend to 0 as sample sizes tend to ∞. Existing results on Kullback–Leibler loss of kernel estimates are crucial to obtaining these asymptotic results, and also imply that the proposed test works best with heavy-tailed kernels. Finite sample characteristics of the test are studied via simulation, and extensions to multivariate data are straightforward, as illustrated by an application to bivariate connectionist data.