Ambient-air ozonolysis of triglycerides in aged fingerprint residues

Abstract

In forensic science, reconstructing the timing of events occurring during a criminal offense is of great importance. In some cases, the time when particular evidence was left on a crime scene is a critical matter. The ability to estimate the fingerprint age would raise the evidentiary value of fingerprints tremendously. For this purpose the most promising approach is the analysis of changes in the chemical compositions of fingerprint residues in the course of aging. The focus of our study is the identification of human specific compounds in fingerprint residues, characterized by a significant aging behavior that could analytically be used for the age determination of fingerprints in future. The first challenge is the sensitive detection of trace amounts of relevant human specific fingerprint compounds. Highly sensitive LC-MS methods were developed for the reliable structure identification of unsaturated triglycerides and their natural degradation products in order to proof the aging mechanism that takes place in fingerprint residues. Thus our results build the fundamental basis for further forensic method development and potential application in forensic investigation. Ozonolysis was found to be one of the major lipid degradation pathways in fingerprint residues in ambient air. High-resolution tandem mass spectrometry (HRMS²) was carried out to identify the ozonolysis products (TG48:0-monoozonide) formed under exposure to the highly reactive ozone in atmospheric air. The obtained products were confirmed by matrix assisted laser desorption ionization mass spectrometry imaging (MALDI-MSI). Despite several challenges and limitations in the age estimation of fingerprints, the identification of individual degradation products of specific unsaturated lipids in aged fingerprint samples represents a significant analytical progress, resulting in a strong increase in the validity of chemical analysis of fingerprints.