Laura McGregor

Blood is a matrix with high potential for forensic investigations and human rescue. Its volatile signature can be used in search exercises to locate injured or deceased individuals. Little is known, however, about the volatile organic compound (VOC) profile of blood, except that it is complex and varies while blood ages. In the present study, we used thermal desorption (TD) and comprehensive two-dimensional gas chromatography (GCxGC) coupled to variable-energy electron ionization time-of-flight mass spectrometry (TOFMS) to monitor VOC signatures of human blood. A highly complex reference standard (Century Mix) containing 108 compounds of various chemical functionalities and several homologue series of compounds was used for the purpose of transposing our previously developed cryogenically modulated GCxGC-TOFMS methods into the use of a reverse fill/flush (RFF) flow modulator. The average peak width at half height was 340 ms and the average tailing factor was 1.16. Light VOCs (down to C4) were effectively flow modulated and exhibited minimal breakthrough over a large dynamic range spanning four orders of magnitude. Mass spectrometric detection was performed using electron impact ionization (EI) carried out at 70 eV and lower energies (12, 14, and 16 eV). The use of variable-energy (ve) EI allowed mass spectra to be produced with less fragmentation and an increased presence of structurally significant ions and the molecular ion. This provided additional confidence in peak assignments, especially for closely eluting isomers often observed in the profiling of the headspace of blood. Variable-energy EI TD-GCxGC-TOFMS blood data sets were statistically processed using principal component analyses (PCA) and hierarchical cluster analyses (HCA). These techniques demonstrated that the effect of aging was greater than the inter-individual variation on the blood VOC profile. The combination of retention indices, low and high EI MS spectra served as a strong basis to gain more confidence in analytical identification by excluding identities proposed by mass spectral databases (70 eV) for compounds contributing to the separation of blood of different ages.

Summary The purpose of this study was to investigate the correlation between the Voice Handicap Index (VHI) and the Voice-Related Quality of Life Measure (V-RQOL), and to test conversion of scores between the two instruments. Understanding the relationship between instruments will facilitate comparison of voice outcome studies using different measures. A retrospective medical chart review of 140 consecutive patients with a chief complaint related to their voice presenting for speech pathology voice evaluation following laryngology evaluation and diagnosis was adopted. Each patient who filled out the VHI and V-RQOL within a 2-week period with no intervening treatment was included in the study. Correlation analysis for total scores was performed for the patients meeting inclusion criteria (n=132). Correlations were also performed as a function of diagnosis. Calculated VHI score based on measured V-RQOL score was compared to measured VHI score. Pearson correlation between scores on the VHI and V-RQOL was −0.82. There was no significant difference between the mean measured and mean calculated VHI scores. For individual scores, however, regression analysis did reveal a significant difference between calculated and measured VHI. The VHI and V-RQOL are highly correlated; however, this study suggests that the two instruments are not interchangeable for individuals. The purpose of this study was to investigate the correlation between the Voice Handicap Index (VHI) and the Voice-Related Quality of Life Measure (V-RQOL), and to test conversion of scores between the two instruments. Understanding the relationship between instruments will facilitate comparison of voice outcome studies using different measures. A retrospective medical chart review of 140 consecutive patients with a chief complaint related to their voice presenting for speech pathology voice evaluation following laryngology evaluation and diagnosis was adopted. Each patient who filled out the VHI and V-RQOL within a 2-week period with no intervening treatment was included in the study. Correlation analysis for total scores was performed for the patients meeting inclusion criteria (n=132). Correlations were also performed as a function of diagnosis. Calculated VHI score based on measured V-RQOL score was compared to measured VHI score. Pearson correlation between scores on the VHI and V-RQOL was −0.82. There was no significant difference between the mean measured and mean calculated VHI scores. For individual scores, however, regression analysis did reveal a significant difference between calculated and measured VHI. The VHI and V-RQOL are highly correlated; however, this study suggests that the two instruments are not interchangeable for individuals.

Field experiments were devised to mimic the entrapment conditions under the rubble of collapsed buildings aiming to investigate the evolution of volatile organic compounds (VOCs) during the early dead body decomposition stage. Three pig carcasses were placed inside concrete tunnels of a search and rescue (SAR) operational field terrain for simulating the entrapment environment after a building collapse. The experimental campaign employed both laboratory and on-site analytical methods running in parallel. The current work focuses only on the results of the laboratory method using thermal desorption coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (TD-GC×GC-TOF MS). The flow-modulated TD-GC×GC-TOF MS provided enhanced separation of the VOC profile and served as a reference method for the evaluation of the on-site analytical methods in the current experimental campaign. Bespoke software was used to deconvolve the VOC profile to extract as much information as possible into peak lists. In total, 288 unique VOCs were identified (i.e., not found in blank samples). The majority were aliphatics (172), aromatics (25) and nitrogen compounds (19), followed by ketones (17), esters (13), alcohols (12), aldehydes (11), sulfur (9), miscellaneous (8) and acid compounds (2). The TD-GC×GC-TOF MS proved to be a sensitive and powerful system for resolving the chemical puzzle of above-ground "scent of death".

This study explores the potential of an innovative multi-cumulative trapping headspace solid-phase microextraction approach coupled with untargeted data analysis to enhance the information provided by aroma profiling of virgin olive oil. Sixty-nine samples of different olive oil commercial categories (extra-virgin, virgin and lampante oil) and different geographical origins were analysed using this novel workflow. The results from each sample were aligned and compared using for the first time a tile-based approach to enable the mining of all of the raw data within the chemometrics platform without any pre-processing methods. The data matrix obtained allowed the extraction of multiple-level information from the volatile profile of the samples. Not only was it possible to classify the samples within the commercial category that they belonged to, but the same data also provided interesting information regarding the geographical origin of the extra-virgin olive oil.

Compositional disparity within a set of 23 coal tar samples (obtained from 15 different former manufactured gas plants) was compared and related to differences between historical on-site manufacturing processes. Samples were prepared using accelerated solvent extraction prior to analysis by two-dimensional gas chromatography coupled to time-of-flight mass spectrometry. A suite of statistical techniques, including univariate analysis, hierarchical cluster analysis, two-dimensional cluster analysis, and principal component analysis (PCA), were investigated to determine the optimal method for source identification of coal tars. The results revealed that multivariate statistical analysis (namely, PCA of normalized, preprocessed data) has the greatest potential for environmental forensic source identification of coal tars, including the ability to predict the processes used to create unknown samples.

Copper mining contributes to increased concentrations of metals in the environment, thereby increasing the risk of metals exposure to populations living in and around mining areas. This study investigated environmental and toenail metals concentrations of non-occupational human exposure to metals in 39 copper-mining town residents and 47 non-mining town residents in Zambia. Elevated environmental concentrations were found in samples collected from the mining town residents. Toenail concentrations of cobalt (GM 1.39 mg/kg), copper (GM 132 mg/kg), lead (21.41 mg/kg) selenium (GM 0.38 mg/kg) and zinc (GM 113 mg/kg) were significantly higher in the mining area and these metals have previously been associated with copper mining. Residence in the mining area, drinking water, dust and soil metals concentrations were the most important contributors to toenail metals concentrations. Further work is required to establish the specific pathways of exposure and the health risks of elevated metals concentrations in the copper mining area.

Abstract Peaches have a short shelf life and require chilling during storage and transport. Peach aroma is important for consumer preference and determined by underlying metabolic pathways and gene expression. Differences in aroma (profiles of volatile organic compounds, VOCs) have been widely reported across cultivars and in response to cold storage. However, few studies used intact peaches, or used equilibrium sampling methods subject to saturation. We analysed VOC profiles using TD-GC × GC-ToF-MS and expression of 12 key VOC pathway genes of intact fruit from six cultivars (three peaches, three nectarines) before and after storage at 1 °C for 7 days including 36 h shelf life storage at 20 °C. Two dimensional GC (GC × GC) significantly enhances discrimination of thermal desorption gas chromatography time-of-flight mass spectrometry (TD-GC-ToF-MS) and detected a total of 115 VOCs. A subset of 15 VOCs from analysis with Random Forest discriminated between cultivars. Another 16 VOCs correlated strongly with expression profiles of eleven key genes in the lipoxygenase pathway, and both expression profiles and VOCs discriminated amongst cultivars, peach versus nectarines and between treatments. The cultivar-specific response to cold storage underlines the need to understand more fully the genetic basis for VOC changes across cultivars.

Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids (DNAPLs) from former manufactured gas plants (FMGPs) was investigated using comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GC×GC TOFMS). Reversed phase GC×GC (i.e. a polar primary column coupled to a non-polar secondary column) was found to significantly improve the separation of polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues. Sample extraction and cleanup was performed simultaneously using accelerated solvent extraction (ASE), with recovery rates between 76% and 97%, allowing fast, efficient extraction with minimal solvent consumption. Principal component analysis (PCA) of the GC×GC data was performed in an attempt to differentiate between twelve DNAPLs based on their chemical composition. Correlations were discovered between DNAPL composition and historic manufacturing processes used at different FMGP sites. Traditional chemical fingerprinting methods generally follow a tiered approach with sample analysis on several different instruments. We propose ultra resolution chemical fingerprinting as a fast, accurate and precise method of obtaining more chemical information than traditional tiered approaches while using only a single analytical technique.

Objective Team-based resuscitation in emergency departments (EDs) is an excellent opportunity for hot debriefs (HDBs). In creating a bespoke HDB model for emergency medicine resuscitations, we sought to optimize learning from clinical experience, identify team strengths, challenges, encourage honest reflection and focus on ways of improving future performance. Methods Multidisciplinary ED focus groups reviewed existing models, identified benefits/barriers and created new frame works, testing and adapting further using fottage of a simulated complex resuscitation case. The new HDB tool was coined: "STOP5" (STOP for 5 minutes). Cases targeted were prehospital retrievals, major trauma, cardiac arrests, deaths in resuscitation, and staff-triggered. The framework details included a specifically scripted introduction followed by core elements that were S: summarize the case; T: things that went well; O: opportunities to improve; P: points to action and responsibilities. Staffs were surveyed at 1 month prior then 6 and 18 months post-introduction. Data collection forms were used to identify and track hard outcomes/system improvements resulting directly from HDBs. Results Potential benefits identified by respondents included: improved staff morale; team cohesion; improved care for future patients; promoting a culture for learning, patient safety and quality improvement. Ten process and equipment changes resulted directly from STOP5 over 12 months. Conclusion We anticipate the STOP5 framework to be globally generalizable and effective for many ED teams. Keywords: Emergencies; Resuscitation; Clinical competence; Feedback; Education

Comprehensive two-dimensional gas chromatography (GC×GC) is a mature analytical technique with a far greater separation capability than conventional one-dimensional methods. Atmospheric organic aerosols are comprised of a diverse range of substances which challenge one-dimensional analysis, and for which the two-dimensional method has proved very suitable. The review outlines the basic principles of the two-dimensional separation, and the instrumentation, including detectors. Time-of-flight mass spectrometry offers many advantages, especially with unknown mixtures, and has included use of low and high energy electron impact ionisation. The available methods of data reduction and analysis are outlined. GC×GC may be used in either targeted or untargeted modes, and studies have covered a very wide range of analytes, including many compound groups. Most common are studies of hydrocarbons, including polycyclic aromatic hydrocarbons (PAH), but other work has included oxygenates, chlorinated and nitrogen compounds, and diverse industrial chemicals and consumer products sampled across a range of environments.

A data interpretation and processing approach for improved compound identification and data presentation in comprehensive two-dimensional gas chromatography (GC×GC) is described. A footprint peak of a compound in 2D space can be represented by a centroid or peak apex, similar to the data-reduced histogram spectra used in mass spectrometry. The workflow was demonstrated on data from GC×GC-TOFMS. Peaks in a modulated chromatogram were initially detected by conventional chromatographic integration, followed by a curve-fitting approach, which interpolated high-precision, absolute retention times for all modulated peaks. First dimension retention time (1tR) was obtained by using an exponentially modified Gaussian (EMG) fitting model for near-Gaussian distributed subpeaks, polynomial fitting for highly asymmetrical peaks, and parabolic fitting for under-sampled peaks, which allows determination of a precise 1tR, considering the dwell-time arising from modulation and 2tR. Area summation of the modulated peaks belonging to the same compound was then performed to yield the total peak area. Each compound in the GC×GC-MS result was then represented by its position at the intersecting coordinates, (1tR, 2tR), in the 2D separation plane, having a height of the same magnitude as the total component summed area. This results in a novel and uncluttered GC×GC output convention based on the scripted total ion chromatogram (TIC) data with precise 1tR, 2tR, and area. Comparison between the contour plots from the scripted and conventional TIC revealed improved data presentation, accompanied by an apparent enhanced resolution. The described approach was applied to the identification of 177 aroma compounds from peaches as indicators of fruit quality.

A dense non-aqueous phase liquid sample formed by release of coal tar into the environment was derivatised by trimethylsilylation using the reagent N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and extracted in hexane using accelerated solvent extraction. This procedure enables comprehensive extraction of an extensive suite of organic compounds from tar, which has not previously been described. Comprehensive two dimensional gas chromatography coupled to time of flight mass spectrometry (GC×GC–TOFMS) was used for the analysis of the sample for concurrent evaluation of –OH functional group-containing compounds along with aliphatics, polycyclic aromatic hydrocarbons and other typical tar compounds normally determined via classic gas chromatography. Using statistically designed experiments, a range of conditions were tested for complete recovery of four different surrogates. The robustness and repeatability of the optimised derivatisation/extraction method was demonstrated. Finally, more than a hundred and fifty derivatised compounds were identified using mass spectra elucidation and GC×GC logical order of elution.

Abstract Accuracy is the most important issue when performing compound‐specific stable isotope analysis of polycyclic aromatic hydrocarbons (PAHs) extracted from complex samples. It depends on two main factors: the possible isotopic fractionation of the compounds during extraction and the potential co‐elution with interfering compounds with different isotopic signatures. Herein, a simplified pressurised liquid extraction method for compound‐specific stable isotope analysis of PAHs in non‐aqueous‐phase liquids of coal tar is presented. Samples extracted using the new method and by fractionation on a silica gel column were analysed by comprehensive two‐dimensional gas chromatography. It was possible to evaluate the effect of co‐elution on the carbon and hydrogen stable isotope signatures of the 16 US EPA priority PAHs in coal tars with various proportions of aromatic and aliphatic content. Even in samples that presented a good baseline resolution, the PAHs of interest co‐eluted with other aromatic compounds with a notable effect on their stable isotope values; this demonstrated the necessity to check the quality of all extraction and clean‐up methods (either the simplified pressurised liquid extraction or more traditional labour‐intensive methods) for more complex samples prior to data interpretation. Additionally, comprehensive two‐dimensional gas chromatography enabled visualisation of the suspected co‐elution for the first time.

Abstract The issue of urban air quality has received increased attention in recent years due to increased awareness of the potential health risks associated with particulate matter (PM) concentrations. Airborne particulate matter is composed of solid and/or liquid materials of various sizes, but the fine particles with diameters of <2.5 μm (so-called PM2.5) are of most concern, as long-term exposure to PM2.5 is thought to have the biggest impact on public health. PM2.5 consists of a wide range of components, from both primary emissions (e.g. vehicle exhausts or forest fires) and secondary reactions (i.e. compounds formed in the atmosphere by chemical reactions). It is important to have robust analysis of PM2.5 as the composition can give an indication of its source. PM2.5 is typically trapped onto quartz fibre filters and the semi-volatile organic compounds (SVOCs) are extracted using a solvent. Direct thermal desorption (TD) of the filter avoids this time-consuming sample preparation, for simple, yet sensitive, analysis of particulate matter. However, their identification and quantitation remains a challenge due to sample complexity. Analysts may attempt to address this using longer columns and/or slower oven temperature ramps, but this inevitably leads to longer analysis times. In recent years, the complexity of such samples has been revealed using the improved separation of comprehensive two-dimensional GC coupled with time-of-flight mass spectrometry (GC×GC–TOF MS). Here, we demonstrate the enhanced performance of a TD-GC×GC–TOF MS through analysis of a number of real-world PM2.5 filters.