Comprehensive Two-Dimensional Gas Chromatography with Mass Spectrometry: Toward a Super-Resolved Separation Technique.

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.

PFAS emissions from functional textiles using micro-chamber and thermal desorption coupled to two-dimensional gas chromatography-time of flight mass spectrometry (TD-GC×GC-TOF MS).

Per- and polyfluoroalkyl substances (PFAS), in the polymeric form, have been used extensively in functional textiles, including firefighter's turnout gear (e.g., jackets and pants), where PFAS are applied to confer oil and water resistance. However, growing concerns over the persistence, potential toxicity, and environmental impact of PFAS have prompted a thorough assessment of potential exposure pathways. Here, we report the emission of PFAS from three firefighter turnout gear jackets at 38 °C. Volatile emissions from the three layers (outer layer, moisture barrier, and thermal liner) were collected onto sorbent tubes via dynamic headspace sampling using a micro-scale chamber device kept at 38 °C for one hour. The emission was characterized using thermal desorption (TD) coupled to two-dimensional gas chromatography - time-of-flight mass spectrometry (GC×GC-TOF MS). The enhanced separation capacity of GC×GC was essential due to the high number of compounds present in each sample, especially for the fabrics from used turnout gear jackets. Based on the filtering expressions, including two-dimensional retention time (1tr and 2tr) and PFAS diagnostic fragment ions (m/z 69, 95, and 131), fluorotelomer alcohols (FTOHs) and fluorotelomer acrylates were identified using standards and spectral matching with the NIST database. After conducting a non-targeted tile-based workflow, jackets (both used and unused) and layers were compared, resulting in the identification of the top 15 discriminating features from over 400 chromatographic peaks. Finally, preliminary FTOH emission experiments showed some usage and layers trends that are aligned with those reported using solvent extraction. Highest levels of FTOHs were found in the moisture barrier, followed by the outer layer and the thermal liner. Older jackets emitted higher levels of 8:2 FTOH and 10:2 FTOH than a newer jacket. In contrast, a newer jacket used for one year had emissions containing higher levels of 6:2 FTOH. Investigating routes of exposure and identifying new PFAS targets are critical steps in evaluating the environmental and health impacts of these persistent chemicals.

Multivariate statistical methods for the environmental forensic classification of coal tars from former manufactured gas plants.

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.

Exploring multiple-cumulative trapping solid-phase microextraction coupled to gas chromatography-mass spectrometry for quality and authenticity assessment of olive oil.

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.

Renal Disease in Primary Sjögren's Syndrome.

Primary Sjögren's syndrome (pSS) is a chronic autoimmune disorder characterised by lymphocytic infiltration of the exocrine glands, predominantly the salivary and lacrimal glands, leading to sicca symptoms. Patients may have extraglandular disease involving multiple organs, including the kidneys. 5% of patients with pSS can have renal involvement. Kidney disease in pSS presents a diagnostic challenge, as clinical symptoms are often insidious and can precede sicca symptoms. pSS affects the kidney through lymphocytic infiltration of renal tubules or immune complex deposition, leading to an array of clinical features. Tubulointerstitial nephritis is the most common histological pattern of kidney disease. Other tubular injuries include renal tubular acidosis with hypokalaemia, Fanconi's syndrome and diabetes insipidus. Glomerular disease is less common and typically involves an immune complex-mediated process. Optimal treatment for kidney diseases in pSS is not established, and treatment is guided by the pattern of disease. For tubulointerstitial nephritis, management involves electrolyte imbalance correction and the use of immunosuppression, including steroids. Treatment of glomerular disease is targeted to the histological pattern, and often requires a combination of immunosuppressive agents. The risk of end-stage kidney disease is low. Nevertheless, patients with pSS and kidney disease have significantly reduced quality of life.

In the beginning: a Canadian ethnographic study on sources and definitions of spiritual reflection used by health care professionals who are not chaplains.

This qualitative study presents a literature review, methodology, findings and discussion from a sample of 20 health care professional around their experiences of sources and definitions of spiritual reflection. The sample includes nursing, social work, occupational therapy, medicine, physiotherapy, music therapy, psychology and recreational therapy. Major sources are music, poetry, stories and sacred texts. Definitions are meaning making and encountering the divine along with personal reflection on values and assumptions. Limitations of the research and recommendations for education, practice and future research are also presented.

STOP5: a hot debrief model for resuscitation cases in the emergency department.

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.

Fruit volatilome profiling through GC × GC-ToF-MS and gene expression analyses reveal differences amongst peach cultivars in their response to cold storage.

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.

Correlation of the Voice Handicap Index (VHI) and the Voice-Related Quality of Life Measure (V-RQOL).

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.

Thermal desorption comprehensive two-dimensional gas chromatography coupled to variable-energy electron ionization time-of-flight mass spectrometry for monitoring subtle changes in volatile organic compound profiles of human blood.

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 340ms 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 70eV and lower energies (12, 14, and 16eV). 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 (70eV) for compounds contributing to the separation of blood of different ages.

Environmental and toenail metals concentrations in copper mining and non mining communities in Zambia.

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.

Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids from manufactured gas plants by reversed phase comprehensive two-dimensional gas chromatography.

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.