Non-targeted discovery-based analysis for gas chromatography with mass spectrometry: A comparison of peak table, tile, and pixel-based Fisher ratio analysis

Freye, Chris Edward; Bowden, Patrick Robert; Greenfield, Margo Torello; Tappan, Bryce C.

doi:10.1016/j.talanta.2019.120668

Title: Non-targeted discovery-based analysis for gas chromatography with mass spectrometry: A comparison of peak table, tile, and pixel-based Fisher ratio analysis

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Abstract

The ability to discover minute differences between samples or sample classes for gas chromatography coupled to mass spectrometry (GC-MS) can be a challenging endeavor, especially when those differences are not a priori. Fisher ratio (F-ratio) analysis is an apt technique to probe the differences between GC-MS chromatograms. F-ratio analysis is a supervised, non-targeted, discovery-based method that compares two different samples (or sample classes) to reduce the GC-MS dataset into a hit list composed of class distinguishing compounds. Three different F-ratio techniques, peak table, tile, and pixel-based were used to “discover” nine non-native analytes that were spiked into gasoline at four different nominal concentrations of 250, 85, 25, 5 parts-per-million (ppm). For the tile and pixel-based F-ratio calculations, a novel methodology is introduced to improve the sensitivity of the F-ratio calculations while reducing false positives. Furthermore, we use a combinatorial technique using null class comparisons, termed null distribution analysis, to determine a statistical F-ratio cutoff for analysis of the hit lists. The pixel-based algorithm was the most sensitive method and was able to “discover” all nine spiked analytes at a nominal concentration of 250 ppm albeit with one false positive interspersed towards the bottom of the hit list. The pixel-based softwaremore »« less

Authors:

Freye, Chris Edward ^[1];

^[1]; Greenfield, Margo Torello ^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Publication Date:: 2019-12-28

Research Org.:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1581579

Alternate Identifier(s):: OSTI ID: 1599914

Report Number(s):: LA-UR-19-28925
Journal ID: ISSN 0039-9140

Grant/Contract Number:: 89233218CNA000001

Resource Type:: Accepted Manuscript

Journal Name:: Talanta

Additional Journal Information:: Journal Volume: 211; Journal Issue: C; Journal ID: ISSN 0039-9140

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 47 OTHER INSTRUMENTATION; Gas chromatography; Mass spectrometry; GC-MS; Fisher ratio; ANOVA

Citation Formats


                    Freye, Chris Edward, Bowden, Patrick Robert, Greenfield, Margo Torello, and Tappan, Bryce C. Non-targeted discovery-based analysis for gas chromatography with mass spectrometry: A comparison of peak table, tile, and pixel-based Fisher ratio analysis.  United States: N. p., 2019. 
Web.  doi:10.1016/j.talanta.2019.120668.

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                    Freye, Chris Edward, Bowden, Patrick Robert, Greenfield, Margo Torello, & Tappan, Bryce C. Non-targeted discovery-based analysis for gas chromatography with mass spectrometry: A comparison of peak table, tile, and pixel-based Fisher ratio analysis.  United States.  https://doi.org/10.1016/j.talanta.2019.120668

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                    Freye, Chris Edward, Bowden, Patrick Robert, Greenfield, Margo Torello, and Tappan, Bryce C. Sat .  
"Non-targeted discovery-based analysis for gas chromatography with mass spectrometry: A comparison of peak table, tile, and pixel-based Fisher ratio analysis".  United States.  https://doi.org/10.1016/j.talanta.2019.120668.  https://www.osti.gov/servlets/purl/1581579.

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@article{osti_1581579,

  title        = {Non-targeted discovery-based analysis for gas chromatography with mass spectrometry: A comparison of peak table, tile, and pixel-based Fisher ratio analysis},

  author       = {Freye, Chris Edward and Bowden, Patrick Robert and Greenfield, Margo Torello and Tappan, Bryce C.},

  abstractNote = {The ability to discover minute differences between samples or sample classes for gas chromatography coupled to mass spectrometry (GC-MS) can be a challenging endeavor, especially when those differences are not a priori. Fisher ratio (F-ratio) analysis is an apt technique to probe the differences between GC-MS chromatograms. F-ratio analysis is a supervised, non-targeted, discovery-based method that compares two different samples (or sample classes) to reduce the GC-MS dataset into a hit list composed of class distinguishing compounds. Three different F-ratio techniques, peak table, tile, and pixel-based were used to “discover” nine non-native analytes that were spiked into gasoline at four different nominal concentrations of 250, 85, 25, 5 parts-per-million (ppm). For the tile and pixel-based F-ratio calculations, a novel methodology is introduced to improve the sensitivity of the F-ratio calculations while reducing false positives. Furthermore, we use a combinatorial technique using null class comparisons, termed null distribution analysis, to determine a statistical F-ratio cutoff for analysis of the hit lists. The pixel-based algorithm was the most sensitive method and was able to “discover” all nine spiked analytes at a nominal concentration of 250 ppm albeit with one false positive interspersed towards the bottom of the hit list. The pixel-based software was also able to “discover” more of the spiked analytes at the lower concentrations with seven of the spiked analytes “discovered” at 85 ppm, four of the spiked analytes “discovered” at 25 ppm, and one analyte “discovered” at 5 ppm.},

  doi          = {10.1016/j.talanta.2019.120668},

  journal      = {Talanta},

  number       = C,

  volume       = 211,

  place        = {United States},

  year         = {2019},

  month        = {12}

}

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