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Fisher ratio feature selection by manual peak area calculations on comprehensive two-dimensional gas chromatography data using standard mixtures with variable composition, storage, and interferences

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Abstract

Comprehensive two-dimensional gas chromatography (GC×GC) is becoming increasingly more common for non-targeted characterization of complex volatile mixtures. The information gained with higher peak capacity and sensitivity provides additional sample composition information when one-dimensional GC is not adequate. GC×GC generates complex multivariate data sets when using non-targeted analysis to discover analytes. Fisher ratio (FR) analysis is applied to discern class markers, limiting complex GC×GC profiles to the most discriminating compounds between classes. While many approaches for feature selection using FR analysis exist, FR can be calculated relatively easily directly on peak areas after any native software has performed peak detection. This study evaluated the success rates of manual FR calculation and comparison to a critical F-value for samples analyzed by GC×GC with defined concentration differences. Long-term storage of samples and other spiked interferences were also investigated to examine their impact on analyzing mixtures using this FR feature selection strategy. Success rates were generally high with mostly 90–100% success rates and some instances of percentages between 80 and 90%. There were rare cases of false positives present and a low occurrence of false negatives. When errors were made in the selection of a compound, it was typically due to chromatographic artifacts present in chromatograms and not from the FR approach itself. This work provides foundational experimental data on the use of manual FR calculations for feature selection from GC×GC data.

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Data availability

The data sets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

SepSolve Analytical is acknowledged for assistance in data processing and troubleshooting of the GC×GC system setup. The researchers also acknowledge Hilary Corcoran from Chaminade University of Honolulu (CUH) for technical support.

Funding

This material is based upon work supported by the National Science Foundation under Grant Number 1752607. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. Additional funding was received from Restek Corporation through the Restek Academic Support Program.

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  1. Laboratory of Forensic and Bioanalytical Chemistry, Chaminade University of Honolulu, Honolulu, HI, 96815, USA

    Danson J. Oliva, Cynthia Cheung & Katelynn A. Perrault

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  1. Danson J. Oliva
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  2. Cynthia Cheung
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  3. Katelynn A. Perrault
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Correspondence to Katelynn A. Perrault.

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Published in the topical collection Comprehensive 2D Chromatography with guest editors Peter Q. Tranchida and Luigi Mondello.

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Oliva, D.J., Cheung, C. & Perrault, K.A. Fisher ratio feature selection by manual peak area calculations on comprehensive two-dimensional gas chromatography data using standard mixtures with variable composition, storage, and interferences. Anal Bioanal Chem 415, 2575–2585 (2023). https://doi.org/10.1007/s00216-022-04484-8

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