Abstract

Selective reagent ionization time-of-flight mass spectrometry with NO+ as the reagent ion (SRI-TOF-MS (NO+)) was applied for near real-time monitoring of selected skin-borne constituents which are potential markers of human presence. The experimental protocol involved a group of 10 healthy volunteers enclosed in a body plethysmography chamber mimicking the entrapment environment. A total of 12 preselected omnipresent in human scent volatiles were quantitatively monitored. Among them there were six aldehydes (n-propanal, n-hexanal, n-heptanal, n-octanal, n-nonanal, and 2 methyl 2-propenal), four ketones (acetone, 2-butanone, 3-buten-2-one, and 6-methyl-5-hepten-2-one), one hydrocarbon (2-methyl 2-pentene), and one terpene (DL-limonene). The observed median emission rates ranged from 0.28 to 44.8 nmol × person–1 × min–1 (16–1530 fmol × cm–2 × min–1). Within the compounds under study, ketones in general and acetone in particular exhibited the highest abundances. The findings of this study provide invaluable information about formation and evolution of a human-specific chemical fingerprint, which could be used for the early location of entrapped victims during urban search and rescue operations (USaR).

Highlights

  • H undreds of volatile organic compounds (VOCs) are emitted through breath, urine, and skin emanations by a human body.[1,2] This specific chemical fingerprint mirrors human physiology and can be used as a noninvasive biochemical probe capable of tracing normal and disease processes occurring in the organism, environmental exposure to pollutants and/or toxins, or microorganisms’ activity.[3]

  • We identified and quantified 33 volatile organic compounds omnipresent in forearm skin emanations of healthy volunteers.[8]

  • For this purpose selective reagent ionization time-of-flight mass spectrometry operating in NO+ mode and a bodyplethysmography chamber mimicking the entrapment scene were applied

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Summary

Introduction

H undreds of volatile organic compounds (VOCs) are emitted through breath, urine, and skin emanations by a human body.[1,2] This specific chemical fingerprint mirrors human physiology and can be used as a noninvasive biochemical probe capable of tracing normal and disease processes occurring in the organism, environmental exposure to pollutants and/or toxins, or microorganisms’ activity.[3]. Recent employing of a time-offlight (TOF) mass filter in the proton transfer reaction-mass spectrometry (PTR-MS) instruments considerably increased. Article their resolving power (up to 5000 m/Δm) and, thereby, the separation and identification of isobaric compounds.[14,15] the analytical power of the PTR-TOF-MS can be further enhanced by employing different precursor ions instead of H3O+ such as NO+, O2+, or Kr+ (selective reagent ionization time-of-flight mass spectrometry (SRI-TOF-MS)).[15,16] Such an approach can help in many cases to separate functional isomers. Volatiles were quantified using the SRI-TOF-MS in conjunction with NO+ as the reagent ion The selection of this reactant ion arose from two reasons. The reference substances with purities ranging from 95 to 99.8% were purchased from Sigma-Aldrich (Austria) and Fluka (Switzerland)

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