Michal Brokl

Characterization of Volatile Organic Compounds from Human Analogue Decomposition Using Thermal Desorption Coupled to Comprehensive Two-Dimensional Gas Chromatography-Time-of-Flight Mass Spectrometry

Complex processes of decomposition produce a variety of chemicals as soft tissues, and their component parts are broken down. Among others, these decomposition byproducts include volatile organic compounds (VOCs) responsible for the odor of decomposition. Human remains detection (HRD) canines utilize this odor signature to locate human remains during police investigations and recovery missions in the event of a mass disaster. Currently, it is unknown what compounds or combinations of compounds are recognized by the HRD canines. Furthermore, a comprehensive decomposition VOC profile remains elusive. This is likely due to difficulties associated with the nontarget analysis of complex samples. In this study, cadaveric VOCs were collected from the decomposition headspace of pig carcasses and were further analyzed using thermal desorption coupled to comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (TD-GC × GC-TOFMS). Along with an advanced data handling methodology, this approach allowed for enhanced characterization of these complex samples. The additional peak capacity of GC × GC, the spectral deconvolution algorithms applied to unskewed mass spectral data, and the use of a robust data mining strategy generated a characteristic profile of decomposition VOCs across the various stages of soft-tissue decomposition. The profile was comprised of numerous chemical families, particularly alcohols, carboxylic acids, aromatics, and sulfides. Characteristic compounds identified in this study, e.g., 1-butanol, 1-octen-3-ol, 2-and 3-methyl butanoic acid, hexanoic acid, octanal, indole, phenol, benzaldehyde, dimethyl disulfide, and trisulfide, are potential target compounds of decomposition odor. This approach will facilitate the comparison of complex odor profiles and produce a comprehensive VOC profile for decomposition.

Analysis of synthetic canine training aids by comprehensive two-dimensional gas chromatography-time of flight mass spectrometry.

Cadaver dogs are trained on a variety of materials, including artificial or pseudo scents. The chemical components of commercially available pseudo scents are not known, so their accuracy as a decomposition odour mimic and their effectiveness as a canine training aid have not been evaluated. Two pseudo scents that are commercially available and used for training cadaver dogs were analysed using comprehensive two-dimensional gas chromatography-time of flight mass spectrometry (GC×GC-TOFMS). The two formulations were determined to be simplistic in their composition, compared to real cadaveric volatile organic compound (VOC) mixtures, with only a few major components. The enhanced GC×GC-TOFMS peak capacity was nevertheless useful to discriminate less intense peaks from large overloaded peaks. The availability of both dimension retention times combined with the peak finding and deconvolution algorithm, enabled the chemical characterization of the two formulations. Additionally, high resolution (HR) TOFMS was used to extract molecular formulae and confirm identities of analytes. The seven compounds identified by this work have not been reported previously as volatile products of decomposition, indicating that these pseudo scents are not to be considered as an accurate representation of cadaveric decomposition odour. Further research on the olfaction of scent detection canines and the chemical composition of their target odourants needs to be conducted to develop improved canine training aids.

Multivariate analysis of mainstream tobacco smoke particulate phase by headspace solid-phase micro extraction coupled with comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry

A method involving headspace solid-phase microextraction (HS-SPME) and comprehensive two-dimensional gas chromatography (GC×GC) coupled to time-of-flight mass spectrometry (TOFMS) was developed and applied to evaluate profiles of volatile compounds present in mainstream tobacco smoke particulate matter trapped on glass fiber filters. Six SPME fibers were tested for the extraction capacities toward selected compounds, showing the best results for the polyacrylate fiber. The optimization of the extraction conditions was carried out using multivariate response surface methodology. Two cigarette types differing in a filter design were analyzed using optimized conditions. A template was built in order to generate comprehensive chemical information, which conceded obtaining consistent information across 24 chromatograms. Principal component analysis (PCA) allowed a clear differentiation of the studied cigarette types. Fisher ratio analysis allowed identification of compounds responsible for the chemical differences between the cigarette samples. Of the selected 143 most important ones, 134 analytes were reduced by the active carbon filter, while for nine, classical cellulose acetate filter was more efficient.

Analysis of mainstream tobacco smoke particulate phase using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry.

Comprehensive 2D GC coupled to time-of-flight mass spectrometry was applied for the characterization of the particulate phase of mainstream tobacco smoke particulate. Five 3R4F research cigarettes were smoked on a rotary smoking machine under standardized conditions, total particular matter was collected on Cambridge filter pads and extracted using methanol-based liquid extraction and dynamic headspace (DHS) approaches. Automated peak finding and mass spectral deconvolution combined with scripting and manual revision of library hits were used to evaluate the library search results. The revised peak table contained nearly 1800 individual compounds for the DHS sample and over 900 for the solvent extracted sample. These methods of extraction were shown to be complementary, leading to only 11% of repeated analytes, and their combination gave rise to a list of almost 2500 individual compounds.

Improvement of ylang-ylang essential oil characterization by GC×GC-TOFMS.

A single fraction of essential oil can often contain hundreds of compounds. Despite of the technical improvements and the enhanced selectivity currently offered by the state-of-the-art gas chromatography (GC) and mass spectrometry (MS) instruments, the complexity of essential oils is frequently underestimated. Comprehensive two-dimensional GC coupled to time-of-flight MS (GC×GC-TOFMS) was used to improve the chemical characterization of ylang-ylang essential oil fractions recently reported in a previous one-dimensional (1D) GC study. Based on both, the enhanced chromatographic separation and the mass spectral deconvolution, 161 individual compounds were identified and labeled as potentially characteristic analytes found in both low and high boiling fractions issued from distillation of mature ylang-ylang flowers. Compared to the most recent full GC-MS characterization, this represents 75 new compounds, essentially consisting of terpenes, terpenoid esters, and alcohols.

Separation of Disaccharides by Comprehensive Two-Dimensional Gas Chromatography−Time-of-Flight Mass Spectrometry. Application to Honey Analysis

A new method based on comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-ToF MS) has been developed for the first time for the analysis of complex mixtures of disaccharides previously converted to their trimethylsilyl oximes (TMSO). Among the different experimental parameters considered for optimization, both the column set combination and the dimensions of the second-dimension column were found to be the most significant with regard to the complete resolution of structurally similar disaccharides. Application of the optimized method to honey analysis allowed the separation of most of the honey disaccharides previously described in the literature. Furthermore, 12 other unknown disaccharides have been separated by this method and characterized from their mass spectral data.

Comprehensive comparative compositional study of the vapour phase of cigarette mainstream tobacco smoke and tobacco heating product aerosol

A simple direct sample collection/dilution and introduction method was developed using quartz wool and Tenax/sulficarb sorbents for thermal desorption and comprehensive two-dimensional gas chromatography (TD-GC × GC) analyses of volatile organic compounds from vapour phase (VP) fractions of aerosol produced by tobacco heating products (THP1.0) and 3R4F mainstream tobacco smoke (MTS). Analyses were carried out using flame ionisation detection (FID) for semi-quantification and both low and high resolution time-of-flight mass spectrometry (LR/HR-TOFMS) for qualitative comparison and peak assignment. Qualitative analysis was carried out by combining identification data based on linear retention indices (LRIs) with a match window of ±10 index units, mass spectral forward and reverse library searches (from LR and HRTOFMS spectra) with a match factor threshold of >700 (both forward and reverse), and accurate mass values of ± 3 ppm for increased confidence in peak identification. Using this comprehensive approach of data mining, a total of 79 out of 85 compounds and a total of 198 out of 202 compounds were identified in THP1.0 aerosol and in 3R4F MTS, respectively. Among the identified analytes, a set of 35 compounds was found in both VP sample types. Semi-quantitative analyses were carried out using a chemical class-based external calibration method. Acyclic, alicyclic, aromatic hydrocarbons and ketones appeared to be prominent in 3R4F MTS VP, whereas larger amounts of aldehydes, ketones, heterocyclic hydrocarbons and esters were present in THP1.0 aerosol VP. The results demontsrate the capability and versatility of the method for the characterization and comparison of complex aerosol samples and highlighted the relative chemical simplicity of THP1.0 aerosol in comparison to MTS.