A more comprehensive understanding of the variability of latent fingermark composition is essential to improving current fingermark detection capabilities in an informed manner. Gas chromatography-mass spectrometry was used to examine the composition of the lipid fraction of latent fingermarks collected from a population of over 100 donors. Variations in the appearances of chromatograms from different donors were apparent in the relative peak sizes of compounds including free fatty acids, squalene, cholesterol and wax esters. Principal component analysis was used as an exploratory tool to explore patterns in this variation, but no correlation to donor traits could be discerned. This study also highlights the practical and inherent difficulties in collecting reproducible samples.
In this paper, we report the results of our preliminary studies into chemical characterization of the fluids produced during decomposition in the absence of a soil matrix. Pig (Sus domestica) carcasses were used to model the human decomposition process in two separate locations, Western Australia (Perth) and Canada (Oshawa). Analysis involved simple dilution and filtration of the decomposition fluids followed by gas chromatography-mass spectrometry. Several previously unreported compounds were detected in the decomposition fluid samples during the trials, including benzeneacetic acid, benzenepropionic acid, 2-piperidone, and isocaproic acid. Possible biosynthetic pathways for some of the compounds produced are proposed. Further research trials are required, particularly in the presence of soil matrices.
3Characterising the changes in fingermark composition as a function of time is of great value for 4 improving fingermark detection capabilities by understanding the processes and circumstances under 5 which target compounds become degraded. In this study, gas chromatography-mass spectrometry 6 was used to monitor relative changes in the lipids from latent fingermarks over 28 days. Principal 7 component analysis of the relative composition of 15 lipids in fingermarks showed that fingermark 8 age was a significant contributor to the variability observed in the data, but that inter-donor variability 9 was also significant. This was attributed principally to changes in the relative amounts of squalene, 10 which rapidly decreased in the fingermarks. It was also observed, however, that most fingermarks 11 exhibited relatively small changes in composition during the first seven days, followed by more rapid 12 changes up to 28 days. Significant inter-donor variation of both initial fingermark composition and the 13 rates and nature of loss processes was observed, which was reflected in the relative projection of 14 samples from different donors. Finally, samples stored with no exposure to light or airflow for 28 days 15were projected significantly closer to the samples analysed on the day of deposition than those 16 exposed to light, due to the reduced photodegradation rate of squalene. 17
This paper describes the establishment of a robust method to determine compound specific δD and δ(13)C values of volatile organic compounds (VOCs) in a standard mixture ranging between C(6) and C(10) and was applied to various complex emission samples, e.g. from biomass combustion and car exhaust. A thermal desorption (TD) unit was linked to a gas chromatography isotope ratio mass spectrometer (GC-irMS) to enable compound specific isotope analysis (CSIA) of gaseous samples. TenaxTA was used as an adsorbent material in stainless steel TD tubes. We determined instrument settings to achieve a minimal water background level for reliable δD analysis and investigated the impact of storage time on δD and δ(13)C values of collected VOCs (176 days and 40 days of storage, respectively). Most of the standard compounds investigated showed standard deviations (SD)<6‰ (δD) when stored for 148 days at 4 °C. However, benzene revealed occasionally D depleted values (21‰ SD) for unknown reasons. δ(13)C analysis demonstrated that storage of 40 days had no effect on VOCs investigated. We also showed that breakthrough (benzene and toluene, 37% and 7%, respectively) had only a negligible effect (0.7‰ and 0.4‰, respectively) on δ(13)C values of VOCs on the sample tube. We established that the sample portion collected at the split flow effluent of the TD unit can be used as a replicate sample for isotope analysis saving valuable sampling time and resources. We also applied TD-GC-irMS to different emission samples (biomass combustion, petrol and diesel car engines exhaust) and for the first time δD values of atmospheric VOCs in the above range are reported. Significant differences in δD of up to 130‰ were observed between VOCs in emissions from petrol car engine exhaust and biomass combustion (Karri tree). However, diesel car emissions showed a high content of highly complex unresolved mixtures thus a baseline separation of VOCs was not achieved for stable hydrogen isotope analysis. The ability to analyse δD by TD-GC-irMS complements the characterisation of atmospheric VOCs and is maybe used for establishing further source(s).
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