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BackgroundSeveral studies suggest that far-field transmission (>6 ft) explains a significant number of COVID-19 superspreading outbreaks.ObjectiveTherefore, quantifying the ratio of near- and far-field exposure to emissions from a source is key to better understanding human-to-human airborne infectious disease transmission and associated risks.MethodsIn this study, we used an environmentally-controlled chamber to measure volatile organic compounds (VOCs) released from a healthy participant who consumed breath mints, which contained unique tracer compounds. Tracer measurements were made at 0.76 m (2.5 ft), 1.52 m (5 ft), 2.28 m (7.5 ft) from the participant, as well as in the exhaust plenum of the chamber.ResultsWe observed that 0.76 m (2.5 ft) trials had ~36-44% higher concentrations than other distances during the first 20 minutes of experiments, highlighting the importance of the near-field exposure relative to the far-field before virus-laden respiratory aerosol plumes are continuously mixed into the far-field. However, for the conditions studied, the concentrations of human-sourced tracers after 20 minutes and approaching the end of the 60-minute trials at 0.76 m, 1.52 m, and 2.28 m were only ~18%, ~11%, and ~7.5% higher than volume-averaged concentrations, respectively.SignificanceThis study suggests that for rooms with similar airflow parameters disease transmission risk is dominated by near-field exposures for shorter event durations (e.g., initial 20-25-minutes of event) whereas far-field exposures are critical throughout the entire event and are increasingly more important for longer event durations.Impact statementWe offer a novel methodology for studying the fate and transport of airborne bioaerosols in indoor spaces using VOCs as unique proxies for bioaerosols. We provide evidence that real-time measurement of VOCs can be applied in settings with human subjects to estimate the concentration of bioaerosol at different distances from the emitter. We also improve upon the conventional assumption that a well-mixed room exhibits instantaneous and perfect mixing by addressing spatial distances and mixing over time. We quantitatively assessed the exposure levels to breath tracers at alternate distances and provided more insights into the changes on "near-field to far-field" ratios over time. This method can be used in future to estimate the benefits of alternate environmental conditions and occupant behaviors.

Chili is a globally significant spice used fresh or dried for culinary, condiment, and medicinal purposes. Growing concerns about food safety have increased the demand for high-quality products and non-invasive tools for quality control like origin tracing and safety assurance. Volatile analysis offers a rapid, comprehensive, and safe method for characterizing various food products. Thus, this study aims to assess the impact of the drying process on the aromatic composition of various Capsicum species and to identify key compounds driving the aromatic complexity of each genetic makeup. To accomplish these objectives, the aroma was examined in fruits collected from 19 different pepper accessions (Capsicum sp.) belonging to four species: one ancestral (C. chacoense) and three domesticated pepper species (C. annuum, C. baccatum and C. chinense). Fresh and dried samples were analyzed using a headspace PTR-TOF-MS platform. Our findings reveal significant changes in the composition and concentration of volatile organic compounds (VOCs) from fresh to dried Capsicum. Notably, chili peppers of the species C. chinense consistently exhibited higher emission intensity and a more complex aroma compared to other species (both fresh and dried). Overall, the data clearly demonstrate that the drying process generally leads to a reduction in the intensity and complexity of the aromatic compounds emitted. Specifically, fresh peppers showed higher volatile organic compounds content compared to dried ones, except for the two sweet peppers studied, which exhibited the opposite behavior. Our analysis underscores the variability in the effect of drying on volatile compound composition among different pepper species and even among different cultivars, highlighting key compounds that could facilitate species classification in dried powder. This research serves as a preliminary guide for promoting the utilization of various pepper species and cultivars as powder, enhancing product valorization. [ABSTRACT FROM AUTHOR]

Nitrogen oxides (NOX) in the atmosphere cause oxidation reactions with photochemical radicals and volatile organic compounds, leading to the accumulation of ozone (O3). NOX constitutes a significant portion of the NOy composition, with nitrous acid (HONO) and nitric acid (HNO3) following. HONO plays a crucial role in the reaction cycle of NOX and hydrogen oxides. The majority of HNO3 reduction mechanisms result from aerosolization through heterogeneous reactions, having adverse effects on humans and plants by increasing secondary aerosol concentrations in the atmosphere. The investigation of the formation and conversion mechanisms of HONO and HNO3 is important; however, research in this area is currently lacking. In this study, we observed HONO, HNO3, and their precursor gases were observed in the atmosphere using parallel-plate diffusion scrubber-ion chromatography. A 0-D box model simulated the compositional distribution of NOy in the atmosphere. The formation reactions and conversion mechanisms of HONO and HNO3 were quantified using reaction equations and reaction coefficients. Among the various mechanisms, dominant mechanisms were identified, suggesting their importance. According to the calculation results, the produce of HONO was predominantly attributed to heterogeneous reactions, excluding an unknown source. The sink processes were mainly governed by photolysis during daytime and reactions with OH radicals during nighttime. HNO3 showed dominance in its production from N2O5, and in its conversion mechanisms primarily involving aerosolization and deposition. [ABSTRACT FROM AUTHOR]

Maize porridge, known as ''polenta'' in Italy, is a global staple food. This study aims to characterize the quality of four Italian flint maize landraces by investigating physical properties and macronutrients composition. By using SPME GC–MS and PTR-ToF-MS we analyzed the flours volatilome and changes in aroma profile post- cooking. Cooking induced the formation of 5 compounds and the loss of up to 25 compounds, primarily through evaporation. Post-cooking, the concentrations of some sulphur compounds (methanethiol, dimethyl sulfide and dimethyl trisulfide), lipid oxidation compounds (2-pentylfuran and hexanal) and Maillard reaction compounds including some aldehydes (nonanal, benzaldehyde, phenylacetaldheyde), pyridine and furans (furfural and furfuryl alcohol) increased. Differences in volatilome and macronutrients contents among landraces were also observed with Marano samples having on average a significantly higher concentration of proteins (13.67 %), while the Nostrano samples had the highest fat content (5.00 %). Fatty acid profile differences were mirrored in the volatilome. Spin flours had the highest level of linoleic acid, leading to elevated levels in cooked polenta due to linoleic acid oxidation. The differences in volatilome and macronutrients contents among the samples confirmed that local landraces are not only important for biodiversity and cultural heritage but also lead to unique aroma compounds profiles.

In this work, for the first time, a gruyt beer and the same one after the addition of Citrus aurantium essential oil (AEO), were investigated to determine the composition of the volatile fraction. The applied analytical techniques, such as Head Space/Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry (HS/SPME-GC-MS) and Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS), allowed us to identify the content of volatile organic compounds (VOCs). From the comparison between the two beer samples, it showed that the one after the addition of AEO was particularly richened in limonene and a series of minor terpene compounds. AEO was also characterized by GC/MS analysis and the results showed that limonene reached 95%. Confocal microscopy was used to look at riboflavin autofluorescence in yeast cells. It was found that beer with AEO had twice as much fluorescence intensity as the control. A spectrophotometric analysis of total polyphenols, tannins, and flavonoids, and a bioactivity screening, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-Azinobis-(3-Ethylbenzthiazolin-6-Sulfonic Acid) (ABTS) radical scavenger, chelating, reducing, antiglycative ones, were also carried out. Moreover, the tolerability of the tested samples in human H69 cholangiocytes and the cytoprotection towards the tert-butyl hydroperoxide (tBOOH)-induced oxidative damage were evaluated. Under our experimental conditions, the beers were found to be able to scavenge DPPH and ABTS radicals and chelate iron ions, despite weak antiglycative and reducing properties. The tested samples did not affect the viability of H69 cholangiocytes up to the highest concentrations; moreover, no signs of cytoprotection against the damage induced by tBOOH were highlighted. Adding AEO to beer resulted in a moderate enhancement of its DPPH scavenging and chelating abilities, without improvements in the other assays. Conversely, AEO and its major compound limonene were ineffective when assessed at the concentrations added to beer. This evidence suggests that the addition of AEO may enhance the organoleptic features of the beer and slightly potentiate some of its bioactivities. [ABSTRACT FROM AUTHOR]

In this work, Arthrospira platensis grown in Tuscany, Italy, was investigated using different analytical approaches to characterize its volatile and non-volatile chemical composition. The results showed the presence of a high number of volatile organic compounds (VOCs) such as hydrocarbons, furans, sulfides, alkanes, aldehydes, alcohols, ketones, esters and compounds belonging to other chemical classes such as fatty acids, alcohols and sugars. Furthermore, a proximal composition analysis was also performed to determine the protein, fat, carbohydrate and ash content. Total antioxidant capacity (TAC) determined by FRAP and ABTS•+ methods (5.96 mmol TE/g DW; 5.28 mmol Fe2+E/g DW, respectively), showed good reducing power and comparable free radical scavenging activity. The antibacterial power of spirulina-based alcoholic macerate (AM) was also evaluated against Staphylococcus aureus (ATCC 29213), Escherichia coli (ATCC 25922), Pseudomonas aeruginosa (ATCC 060127853), Enterococcus faecalis (ATCC 29211), Klebsiella pneumoniae (ATCC 700603) and Candida albicans (ATCC 24433) and the obtained data have shown that it had no effect against pathogenic bacterial strains. On the contrary, at low concentrations, AM exerted a prebiotic effect on some probiotic strains such as L. casei if treated with AM concentrations ranging from 1.56% v/v and 3.12% v/v and L. rhamnosus if treated with AM concentrations lower than 0.78% v/v. In conclusion, this study highlighted how spirulina, based on the rich composition and its antioxidant and prebiotic effect, can represent a source of beneficial substances for human health. [ABSTRACT FROM AUTHOR]

Chili is a globally significant spice used fresh or dried for culinary, condiment, and medicinal purposes. Growing concerns about food safety have increased the demand for high-quality products and non-invasive tools for quality control like origin tracing and safety assurance. Volatile analysis offers a rapid, comprehensive, and safe method for characterizing various food products. Thus, this study aims to assess the impact of the drying process on the aromatic composition of various Capsicum species and to identify key compounds driving the aromatic complexity of each genetic makeup. To accomplish these objectives, the aroma was examined in fruits collected from 19 different pepper accessions (Capsicum sp.) belonging to four species: one ancestral (C. chacoense) and three domesticated pepper species (C. annuum, C. baccatum and C. chinense). Fresh and dried samples were analyzed using a headspace PTR-TOF-MS platform. Our findings reveal significant changes in the composition and concentration of volatile organic compounds (VOCs) from fresh to dried Capsicum. Notably, chili peppers of the species C. chinense consistently exhibited higher emission intensity and a more complex aroma compared to other species (both fresh and dried). Overall, the data clearly demonstrate that the drying process generally leads to a reduction in the intensity and complexity of the aromatic compounds emitted. Specifically, fresh peppers showed higher volatile organic compounds content compared to dried ones, except for the two sweet peppers studied, which exhibited the opposite behavior. Our analysis underscores the variability in the effect of drying on volatile compound composition among different pepper species and even among different cultivars, highlighting key compounds that could facilitate species classification in dried powder. This research serves as a preliminary guide for promoting the utilization of various pepper species and cultivars as powder, enhancing product valorization.

SPME-GC-MS and PTR-ToF-MS techniques were applied to describe the content of volatile flavor compounds in a craft beer before and after adding spirulina. The obtained results showed that the volatile profile of the two beer samples differed. Furthermore, to chemically characterize biomass spirulina, a derivatization reaction followed by GC-MS analysis was performed, highlighting a high content of molecules belonging to different chemical classes, such as sugars, fatty acids and carboxylic acids. A spectrophotometric analysis of total polyphenols and tannins, investigation into the scavenging activity towards DPPH and ABTS radicals and confocal microscopy of brewer's yeast cells were carried out. Moreover, the cytoprotective and antioxidant properties towards the oxidative damage induced by tert-butyl hydroperoxide (tBOOH) in human H69 cholangiocytes were investigated. Finally, the modulation of Nrf2 signaling under oxidative stress conditions was also evaluated. Both samples of beer were shown to contain similar levels of total polyphenols and tannins, with slightly increased levels in that containing spirulina 0.25% w/v. Moreover, the beers were found to be endowed with radical scavenging properties towards both DPPH and ABTS radicals, albeit with a weak contribution of spirulina; however, a higher riboflavin content was detected in spirulina-treated yeast cells. Conversely, the addition of spirulina (0.25% w/v) appeared to improve the cytoprotective properties of beer towards tBOOH-induced oxidative damage in H69 cells and reduce intracellular oxidative stress. Accordingly, the cytosolic Nrf2 expression was found to be increased. [ABSTRACT FROM AUTHOR]

Featured Application: First detailed reduced electric field selected reagent ion mass spectrometric study of propofol and its major metabolite for potential analytical breath test applications in the clinical environment. The first detailed selected reagent ion-time-of-flight-mass spectrometric fundamental investigations of 2,6-diisopropylphenol, more commonly known as propofol (C12H18O), and its metabolite 2,6-diisopropyl-1,4-benzoquinone (C12H16O2) using the reagent ions H3O+, H3O+.H2O, O2+• and NO+ are reported. Protonated propofol is the dominant product ion resulting from the reaction of H3O+ with propofol up to a reduced electric field strength (E/N) of about 170 Td. After 170 Td, collision-induced dissociation leads to protonated 2-(1-methylethyl)-phenol (C9H13O+), resulting from the elimination of C3H6 from protonated propofol. A sequential loss of C3H6 from C9H13O+ also through collision-induced processes leads to protonated phenol (C6H7O+), which becomes the dominant ionic species at E/N values exceeding 170 Td. H3O+.H2O does not react with propofol via a proton transfer process. This is in agreement with our calculated proton affinity of propofol being 770 kJ mol−1. Both O2+• and NO+ react with propofol via a charge transfer process leading to two product ions, C12H18O+ (resulting from non-dissociative charge transfer) and C11H15O+ that results from the elimination of one of the methyl groups from C12H18O+. This dissociative pathway is more pronounced for O2+• than for NO+ throughout the E/N range investigated (approximately 60–210 Td), which reflects the higher recombination energy of O2+• (12.07 eV) compared to that of NO+ (9.3 eV), and hence the higher internal energy deposited into the singly charged propofol. Of the four reagent ions investigated, only H3O+ and H3O+.H2O react with 2,6-diisopropyl-1,4-benzoquinone, resulting in only the protonated parent at all E/N values investigated. The fundamental ion-molecule studies reported here provide underpinning information that is of use for the development of soft chemical ionisation mass spectrometric analytical techniques to monitor propofol and its major metabolite in the breath. The detection of propofol in breath has potential applications for determining propofol blood concentrations during surgery and for elucidating metabolic processes in real time. [ABSTRACT FROM AUTHOR]

Hop-derived volatile organic compounds (VOCs) and their transformation products significantly impact beer flavour and aroma. Geraniol, a key monoterpene alcohol in hops, has been reported to undergo yeast-modulated biotransformation into various terpenoids during fermentation, which impacts the citrus and floral aromas of the finished beer. This study monitored the evolution of geraniol and its transformation products throughout fermentation to provide insight into differences as a function of yeast species and strain. The headspace concentration of VOCs produced during fermentation in model wort was measured using Solid-Phase Microextraction Gas Chromatography/Mass Spectrometry (SPME-GC/MS) and Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-ToF-MS). In the absence of yeast, only geraniol was detected, and no terpenoid compounds were detected in geraniol-free ferments. During fermentation, the depletion of geraniol was closely followed by the detection of citronellol, citronellyl acetate and geranyl acetate. The concentration of the products and formation behaviour was yeast strain dependent. SPME-GC/MS provided confidence in compound identification. PTR-ToF-MS allowed online monitoring of these transformation products, showing when formation differed between Saccharomyces cerevisiae and Saccharomyces pastorianus yeasts. A better understanding of the ability of different yeast to biotransform hop terpenes will help brewers predict, control, and optimize the aroma of the finished beer. [ABSTRACT FROM AUTHOR]

In this work, Arthrospira platensis grown in Tuscany, Italy, was investigated using different analytical approaches to characterize its volatile and non-volatile chemical composition. The results showed the presence of a high number of volatile organic compounds (VOCs) such as hydrocarbons, furans, sulfides, alkanes, aldehydes, alcohols, ketones, esters and compounds belonging to other chemical classes such as fatty acids, alcohols and sugars. Furthermore, a proximal composition analysis was also performed to determine the protein, fat, carbohydrate and ash content. Total antioxidant capacity (TAC) determined by FRAP and ABTS•+ methods (5.96 mmol TE/g DW; 5.28 mmol Fe2+E/g DW, respectively), showed good reducing power and comparable free radical scavenging activity. The antibacterial power of spirulina-based alcoholic macerate (AM) was also evaluated against Staphylococcus aureus (ATCC 29213), Escherichia coli (ATCC 25922), Pseudomonas aeruginosa (ATCC 060127853), Enterococcus faecalis (ATCC 29211), Klebsiella pneumoniae (ATCC 700603) and Candida albicans (ATCC 24433) and the obtained data have shown that it had no effect against pathogenic bacterial strains. On the contrary, at low concentrations, AM exerted a prebiotic effect on some probiotic strains such as L. casei if treated with AM concentrations ranging from 1.56% v/v and 3.12% v/v and L. rhamnosus if treated with AM concentrations lower than 0.78% v/v. In conclusion, this study highlighted how spirulina, based on the rich composition and its antioxidant and prebiotic effect, can represent a source of beneficial substances for human health.

In this work, for the first time, a gruyt beer and the same one after the addition of Citrus aurantium essential oil (AEO), were investigated to determine the composition of the volatile fraction. The applied analytical techniques, such as Head Space/Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry (HS/SPME-GC-MS) and Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS), allowed us to identify the content of volatile organic compounds (VOCs). From the comparison between the two beer samples, it showed that the one after the addition of AEO was particularly richened in limonene and a series of minor terpene compounds. AEO was also characterized by GC/MS analysis and the results showed that limonene reached 95%. Confocal microscopy was used to look at riboflavin autofluorescence in yeast cells. It was found that beer with AEO had twice as much fluorescence intensity as the control. A spectrophotometric analysis of total polyphenols, tannins, and flavonoids, and a bioactivity screening, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-Azinobis-(3-Ethylbenzthiazolin-6-Sulfonic Acid) (ABTS) radical scavenger, chelating, reducing, antiglycative ones, were also carried out. Moreover, the tolerability of the tested samples in human H69 cholangiocytes and the cytoprotection towards the tert-butyl hydroperoxide (tBOOH)-induced oxidative damage were evaluated. Under our experimental conditions, the beers were found to be able to scavenge DPPH and ABTS radicals and chelate iron ions, despite weak antiglycative and reducing properties. The tested samples did not affect the viability of H69 cholangiocytes up to the highest concentrations; moreover, no signs of cytoprotection against the damage induced by tBOOH were highlighted. Adding AEO to beer resulted in a moderate enhancement of its DPPH scavenging and chelating abilities, without improvements in the other assays. Conversely, AEO and its major compound limonene were ineffective when assessed at the concentrations added to beer. This evidence suggests that the addition of AEO may enhance the organoleptic features of the beer and slightly potentiate some of its bioactivities.

The application of direct-injection mass spectrometric (DI-MS) techniques, like Proton Transfer Reaction Time of Flight Mass Spectrometry (PTR-ToF-MS) has been suggested as a reliable phenotyping tool for fruit volatilome assessment in both genetic and quality-related studies. In this study the complexity of raspberry aroma was investigated by a comprehensive untargeted VOC analysis, done by combining SPME-GC-MS and PTR-ToF-MS assessments with multi-block discriminant analysis using the DIABLO mixOmics framework. The aim was to acquire an exhaustive characterization of the raspberry volatilome according to different fruit ripening stages (pink, ripe, and overripe) and genetic variances (50 accessions), as well as to investigate the potential of PTR-ToF-MS as a rapid and high throughput VOC phenotyping tool to address issues related to raspberry fruit quality. Results of this study demonstrated the complementarity between SPME-GC-MS and PTR-ToF-MS techniques to evaluate the raspberry aroma composition. PTR-ToF-MS generates reliable raspberry VOC fingerprints mainly due to a reduced compound fragmentation and precise content estimation. In addition, the high collinearity between isomers of monoterpenes and norisoprenoids, discovered by GC analysis, reduces the main analytic limitation of PTR-ToF-MS of not being able to separate isomeric molecules. The high similarity between the VOC matrices obtained by applying PTR-ToF-MS and SPME-GC-MS confirmed the possibility of using PTR-ToF-MS as a reliable high throughput phenotyping tool for raspberry volatiolome assessment. In addition, results provided by the germplasm collection investigation enabled to distinguish the best performing accessions, based on VOCs composition, to be used as superior parental lines for future breeding programs.

This work presents in vitro and in vivo aroma release analysis of three espresso coffees carried out by PTR-ToF-MS headspace and nosespace analysis, respectively. The products were C. arabica coffees prepared using an espresso coffee machine: a low-caffeine C. arabica var. laurina light roast, a low-caffeine C. arabica var. laurina dark roast, and a single-origin coffee from Ethiopia which were roasted to a medium roast degree. Headspace analysis allowed for discrimination between coffees with a prediction accuracy of 92% or higher. Relevant discriminating compounds were related to the roasting degree and varietal compounds. Coffee nosespace consisted of 35 mass peaks overall. Despite this relatively low number of detected peaks, coffee discrimination was still possible with ≥93% accuracy. The compounds most relevant to the discrimination were those related to the roasting degree. Major differences—both qualitative and quantitative—were found between headspace and nosespace profiles. [ABSTRACT FROM AUTHOR]

Objectives: Lung cancer (LC) is the largest single cause of death from cancer worldwide, and the lack of effective screening methods for early detection currently results in unsatisfactory curative treatments. We herein aimed to use breath analysis, a noninvasive and very simple method, to identify and validate biomarkers in breath for the screening of lung cancer. Materials and methods: We enrolled a total of 2308 participants from two centers for online breath analyses using proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS). The derivation cohort included 1007 patients with primary LC and 1036 healthy controls, and the external validation cohort included 158 LC patients and 107 healthy controls. We used eXtreme Gradient Boosting (XGBoost) to create a panel of predictive features and derived a prediction model to identify LC. The optimal number of features was determined by the greatest area under the receiver-operating characteristic (ROC) curve (AUC). Results: Six features were defined as a breath-biomarkers panel for the detection of LC. In the training dataset, the model had an AUC of 0.963 (95% CI, 0.941-0.982), and a sensitivity of 87.1% and specificity of 93.5% at a positivity threshold of 0.5. Our model was tested on the independent validation dataset and achieved an AUC of 0.771 (0.718-0.823), and sensitivity of 67.7% and specificity of 73.0%. Conclusion: Our results suggested that breath analysis may serve as a valid method in screening lung cancer in a borderline population prior to hospital visits. Although our breath-biomarker panel is noninvasive, quick, and simple to use, it will require further calibration and validation in a prospective study within a primary care setting. [ABSTRACT FROM AUTHOR]

Regional anaesthesia is well established as a standard method in clinical practice. Currently, the local anaesthetics of amino-amide types such as prilocaine are frequently used. Despite routine use, complications due to overdose or accidental intravenous injection can arise. A non-invasive method that can indicate such complications early would be desirable. Breath gas analysis offers great potential for the non-invasive monitoring of drugs and their volatile metabolites. The physicochemical properties of o-toluidine, the main metabolite of prilocaine, allow its detection in breath gas. Within this study, we investigated whether o-toluidine can be monitored in exhaled breath during regional anaesthesia in an animal model, if correlations between o-toluidine and prilocaine blood levels exist and if accidental intravenous injections are detectable by o-toluidine breath monitoring. Continuous o-toluidine monitoring was possible during regional anaesthesia of the cervical plexus and during simulated accidental intravenous injection of prilocaine. The time course of exhaled o-toluidine concentrations considerably differed depending on the injection site. Intravenous injection led to an immediate increase in exhaled o-toluidine concentrations within 2 min, earlier peak and higher maximum concentrations, followed by a faster decay compared to regional anaesthesia. The strength of correlation of blood and breath parameters depended on the injection site. In conclusion, real time monitoring of o-toluidine in breath gas is possible by means of PTR-ToF-MS. Since simulated accidental intravenous injection led to an immediate increase in exhaled o-toluidine concentrations within 2 min and higher maximum concentrations, monitoring exhaled o-toluidine may potentially be applied for the non-invasive real-time detection of accidental intravenous injection of prilocaine. [ABSTRACT FROM AUTHOR]

Abstract Isoprene synthase (IspS) is the sole enzyme in plants responsible for the yearly emission in the atmosphere of thousands of tonnes of the natural hydrocarbon isoprene worldwide. Species of the monocotyledonous family Arecaceae (palms) are among the highest plant emitters, but to date no IspS gene from this family has been identified. Here, we screened with PTR‐ToF‐MS 18 genera of the Arecaceae for isoprene emission and found that the majority of the sampled species emits isoprene. Putative IspS genes from six different genera were sequenced and three of them were functionally characterized by heterologous overexpression in Arabidopsis thaliana, demonstrating that they encode functional IspS genes. Site‐directed mutagenesis and expression in Arabidopsis demonstrated the functional relevance of a novel IspS diagnostic tetrad from Arecaceae, whose most variable amino acids could not preserve catalytic function when substituted by a putatively dicotyledonous‐specific tetrad. In particular, mutation of threonine 479 likely impairs the open–closed transition of the enzyme by altering the network of hydrogen bonds between helices H1α, H, and I. These results shed new light on the evolution of IspS in monocots, suggesting that isoprene emission is an ancestral trait within the Arecaceae family. The identification of IspS from Arecaceae provides promising novel enzymes for the production of isoprene in heterologous systems and allows the screening and selection of commercially relevant palm varieties with lower environmental impact.

SPME-GC-MS and PTR-ToF-MS techniques were applied to describe the content of volatile flavor compounds in a craft beer before and after adding spirulina. The obtained results showed that the volatile profile of the two beer samples differed. Furthermore, to chemically characterize biomass spirulina, a derivatization reaction followed by GC-MS analysis was performed, highlighting a high content of molecules belonging to different chemical classes, such as sugars, fatty acids and carboxylic acids. A spectrophotometric analysis of total polyphenols and tannins, investigation into the scavenging activity towards DPPH and ABTS radicals and confocal microscopy of brewer’s yeast cells were carried out. Moreover, the cytoprotective and antioxidant properties towards the oxidative damage induced by tert-butyl hydroperoxide (tBOOH) in human H69 cholangiocytes were investigated. Finally, the modulation of Nrf2 signaling under oxidative stress conditions was also evaluated. Both samples of beer were shown to contain similar levels of total polyphenols and tannins, with slightly increased levels in that containing spirulina 0.25% w/v. Moreover, the beers were found to be endowed with radical scavenging properties towards both DPPH and ABTS radicals, albeit with a weak contribution of spirulina; however, a higher riboflavin content was detected in spirulina-treated yeast cells. Conversely, the addition of spirulina (0.25% w/v) appeared to improve the cytoprotective properties of beer towards tBOOH-induced oxidative damage in H69 cells and reduce intracellular oxidative stress. Accordingly, the cytosolic Nrf2 expression was found to be increased.

The first detailed selected reagent ion-time-of-flight-mass spectrometric fundamental investigations of 2,6-diisopropylphenol, more commonly known as propofol (C12H18O), and its metabolite 2,6-diisopropyl-1,4-benzoquinone (C12H16O2) using the reagent ions H3O+, H3O+.H2O, O2+• and NO+ are reported. Protonated propofol is the dominant product ion resulting from the reaction of H3O+ with propofol up to a reduced electric field strength (E/N) of about 170 Td. After 170 Td, collision-induced dissociation leads to protonated 2-(1-methylethyl)-phenol (C9H13O+), resulting from the elimination of C3H6 from protonated propofol. A sequential loss of C3H6 from C9H13O+ also through collision-induced processes leads to protonated phenol (C6H7O+), which becomes the dominant ionic species at E/N values exceeding 170 Td. H3O+.H2O does not react with propofol via a proton transfer process. This is in agreement with our calculated proton affinity of propofol being 770 kJ mol−1. Both O2+• and NO+ react with propofol via a charge transfer process leading to two product ions, C12H18O+ (resulting from non-dissociative charge transfer) and C11H15O+ that results from the elimination of one of the methyl groups from C12H18O+. This dissociative pathway is more pronounced for O2+• than for NO+ throughout the E/N range investigated (approximately 60–210 Td), which reflects the higher recombination energy of O2+• (12.07 eV) compared to that of NO+ (9.3 eV), and hence the higher internal energy deposited into the singly charged propofol. Of the four reagent ions investigated, only H3O+ and H3O+.H2O react with 2,6-diisopropyl-1,4-benzoquinone, resulting in only the protonated parent at all E/N values investigated. The fundamental ion-molecule studies reported here provide underpinning information that is of use for the development of soft chemical ionisation mass spectrometric analytical techniques to monitor propofol and its major metabolite in the breath. The detection of propofol in breath has potential applications for determining propofol blood concentrations during surgery and for elucidating metabolic processes in real time.

Hop-derived volatile organic compounds (VOCs) and their transformation products significantly impact beer flavour and aroma. Geraniol, a key monoterpene alcohol in hops, has been reported to undergo yeast-modulated biotransformation into various terpenoids during fermentation, which impacts the citrus and floral aromas of the finished beer. This study monitored the evolution of geraniol and its transformation products throughout fermentation to provide insight into differences as a function of yeast species and strain. The headspace concentration of VOCs produced during fermentation in model wort was measured using Solid-Phase Microextraction Gas Chromatography/Mass Spectrometry (SPME-GC/MS) and Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-ToF-MS). In the absence of yeast, only geraniol was detected, and no terpenoid compounds were detected in geraniol-free ferments. During fermentation, the depletion of geraniol was closely followed by the detection of citronellol, citronellyl acetate and geranyl acetate. The concentration of the products and formation behaviour was yeast strain dependent. SPME-GC/MS provided confidence in compound identification. PTR-ToF-MS allowed online monitoring of these transformation products, showing when formation differed between Saccharomyces cerevisiae and Saccharomyces pastorianus yeasts. A better understanding of the ability of different yeast to biotransform hop terpenes will help brewers predict, control, and optimize the aroma of the finished beer.

The characterization of vehicle exhaust emissions of volatile organic compounds (VOCs) is essential to estimate their impact on the formation of secondary organic aerosol (SOA) and, more generally, air quality. This paper revises and updates non-methane volatile organic compounds (NMVOCs) tailpipe emissions of three Euro 5 vehicles during Artemis cold urban (CU) and motorway (MW) cycles. Positive matrix factorization (PMF) analysis is carried out for the first time on proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS) datasets of vehicular emission. Statistical analysis helped to associate the emitted VOCs to specific driving conditions, such as the start of the vehicles, the activation of the catalysts, or to specific engine combustion regimes. Merged PTR-ToF-MS and automated thermal desorption gas chromatography mass spectrometer (ATD-GC-MS) datasets provided an exhaustive description of the NMVOC emission factors (EFs) of the vehicles, thus helping to identify and quantify up to 147 individual compounds. In general, emissions during the CU cycle exceed those during the MW cycle. The gasoline direct injection (GDI) vehicle exhibits the highest EF during both CU and MW cycles (252 and 15 mg/km), followed by the port-fuel injection (PFI) vehicle (24 and 0.4 mg/km), and finally the diesel vehicle (15 and 3 mg/km). For all vehicles, emissions are dominated by unburnt fuel and incomplete combustion products. Diesel emissions are mostly represented by oxygenated compounds (65%) and aliphatic hydrocarbons (23%) up to C22, while GDI and PFI exhaust emissions are composed of monoaromatics (68%) and alkanes (15%). Intermediate volatility organic compounds (IVOCs) range from 2.7 to 13% of the emissions, comprising essentially linear alkanes for the diesel vehicle, while naphthalene accounts up to 42% of the IVOC fraction for the gasoline vehicles. This work demonstrates that PMF analysis of PTR-ToF-MS datasets and GC-MS analysis of vehicular emissions provide a revised and deep characterization of vehicular emissions to enrich current emission inventories. [ABSTRACT FROM AUTHOR]

Mosses inhabit nearly all terrestrial ecosystems and engage in important interactions with nitrogen‐fixing microbes, sperm‐dispersing arthropods, and other plants. It is hypothesized that these interactions could be mediated by biogenic volatile organic compounds (BVOCs). Moss BVOCs may play fundamental roles in influencing local ecologies, such as biosphere–atmosphere–hydrosphere communications, physiological and evolutionary dynamics, plant–microbe interactions, and gametophyte stress physiology. Further progress in quantifying the composition, magnitude, and variability of moss BVOC emissions, and their response to environmental drivers and metabolic requirements, is limited by methodological and analytical challenges. We review several sampling techniques with various analytical approaches and describe best practices in generating moss gametophyte BVOC measures. We emphasize the importance of characterizing the composition and magnitude of moss BVOC emissions across a variety of species to better inform and stimulate important cross‐disciplinary studies. We conclude by highlighting how current methods could be employed, as well as best practices for choosing methodologies. [ABSTRACT FROM AUTHOR]

The aim of this study was to investigate volatile organic compounds (VOCs) in exhaled breath as possible non-invasive markers to monitor the inflammatory response in inflammatory bowel disease (IBD) patients as a result of repeated and prolonged moderate-intensity exercise. We included 18 IBD patients and 19 non-IBD individuals who each completed a 30, 40, or 50 km walking exercise over three consecutive days. Breath and blood samples were taken before the start of the exercise event and every day post-exercise to assess changes in the VOC profiles and cytokine concentrations. Proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) was used to measure exhaled breath VOCs. Multivariate analysis, particularly ANOVA-simultaneous component analysis (ASCA), was employed to extract relevant ions related to exercise and IBD. Prolonged exercise induces a similar response in breath butanoic acid and plasma cytokines for participants with or without IBD. Butanoic acid showed a significant correlation with the cytokine IL-6, indicating that butanoic acid could be a potential non-invasive marker for exercise-induced inflammation. The findings are relevant in monitoring personalized IBD management. [ABSTRACT FROM AUTHOR]

Authentication of dairy systems is of growing interest for the dairy industry and we investigated the potentiality of using volatile fingerprinting of ripened cheeses by proton transfer reaction time-of-flight mass spectrometry. A total of 1,075 individual model cheeses made from milk of individual Brown Swiss cows of 72 farms were analysed. Using a linear discriminant analysis, cows and herds were assigned to 3 or 5 dairy systems differing in management, available facilities, and diets. We obtained variable discrimination abilities (up to 77% of correct classification of cheeses and 70% of farms with cross-validation). We found m/z 61,028 (acetic acid), 109,070 (pyrazine), and m/z 137,132 (terpene) characterising model cheeses from traditional dairy systems and m/z 71,086 (3-methyl-butan-1-ol, 3-methyl-3-buten-1-ol, pentan-1-ol), m/z 101,097 (hexan-2-one, hexanal), m/z 123,117 (nonenal), m/z 129,127 (octan-1-one, octanal), and two unidentified peaks m/z 83,071 and m/z 93,090 characterising model cheeses from the modern farms. In conclusion, it seems possible to discriminate between a range of dairy systems using fast volatile fingerprinting of ripened cheeses but a proper validation of results obtained is needed.Highlights Mass spectrometry technique (PTR-ToF-MS) was able to discriminate between dairy systems. We found m/z 61,028 (acetic acid), 109,070 (pyrazine), and m/z 137,132 (terpene) characterising model cheeses from traditional dairy systems. We found m/z 71,086 (3-methyl-butan-1-ol, 3-methyl-3-buten-1-ol, pentan-1-ol), m/z 101,097 (hexan-2-one, hexanal), m/z 123,117 (nonenal), m/z 129,127 (octan-1-one, octanal), and two unidentified peaks m/z 83,071 and m/z 93,090 characterising model cheeses from the modern farms.

Abstract Mosses inhabit nearly all terrestrial ecosystems and engage in important interactions with nitrogen‐fixing microbes, sperm‐dispersing arthropods, and other plants. It is hypothesized that these interactions could be mediated by biogenic volatile organic compounds (BVOCs). Moss BVOCs may play fundamental roles in influencing local ecologies, such as biosphere–atmosphere–hydrosphere communications, physiological and evolutionary dynamics, plant–microbe interactions, and gametophyte stress physiology. Further progress in quantifying the composition, magnitude, and variability of moss BVOC emissions, and their response to environmental drivers and metabolic requirements, is limited by methodological and analytical challenges. We review several sampling techniques with various analytical approaches and describe best practices in generating moss gametophyte BVOC measures. We emphasize the importance of characterizing the composition and magnitude of moss BVOC emissions across a variety of species to better inform and stimulate important cross‐disciplinary studies. We conclude by highlighting how current methods could be employed, as well as best practices for choosing methodologies.

The outbreak of COVID-19 promoted strict restrictions to human activities in China, which led to dramatic decrease in most air pollutant concentrations (e.g., PM2.5, PM10, NOx, SO2, and CO). However, abnormal increase of ozone (O3) concentrations was found during the lockdown period in most urban areas of China. In this study, we conducted a field measurement targeting ozone and its key precursors by utilizing a novel proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) in Changzhou, which is representative for the Yangtze River Delta (YRD) city cluster of China. We further applied the integrated methodology including machine learning, observation-based model (OBM), and sensitivity analysis to get insights into the reasons causing the abnormal increase of ozone. Major findings include: (1) By deweathered calculation, we found changes in precursor emissions contributed 5.1 ppbv to the observed O3 during the Full-lockdown period, while meteorological conditions only contributed 0.5 ppbv to the O3 changes. (2) By using an OBM model, we found that although significant reduction of O3 precursors was observed during Full-lockdown period, the photochemical formation of O3 was stronger than that during the Pre-lockdown period. (3) The NOx/VOCs ratio dropped dramatically from 1.84 during Pre-lockdown to 0.79 in Full-lockdown period, which switched O3 formation from VOCs-limited regime to the conjunction of NOx- and VOC-limited regime. Additionally, the decrease in NOx/VOCs ratio during Full-lockdown period was supposed to increase the MeanO3 by 2.4 ppbv. Results of this study investigate insights into the relationship between O3 and its precursors in urban area, demonstrating reasons causing the abnormal increase of O3 in most urban areas of China during the COVID-19 lock-down period. This study also underlines the necessity of controlling anthropogenic OVOCs, alkenes, and aromatics in the sustained campaign of reducing O3 pollution in China. [ABSTRACT FROM AUTHOR]

This work presents in vitro and in vivo aroma release analysis of three espresso coffees carried out by PTR-ToF-MS headspace and nosespace analysis, respectively. The products were C. arabica coffees prepared using an espresso coffee machine: a low-caffeine C. arabica var. laurina light roast, a low-caffeine C. arabica var. laurina dark roast, and a single-origin coffee from Ethiopia which were roasted to a medium roast degree. Headspace analysis allowed for discrimination between coffees with a prediction accuracy of 92% or higher. Relevant discriminating compounds were related to the roasting degree and varietal compounds. Coffee nosespace consisted of 35 mass peaks overall. Despite this relatively low number of detected peaks, coffee discrimination was still possible with ≥93% accuracy. The compounds most relevant to the discrimination were those related to the roasting degree. Major differences—both qualitative and quantitative—were found between headspace and nosespace profiles.

Regional anaesthesia is well established as a standard method in clinical practice. Currently, the local anaesthetics of amino-amide types such as prilocaine are frequently used. Despite routine use, complications due to overdose or accidental intravenous injection can arise. A non-invasive method that can indicate such complications early would be desirable. Breath gas analysis offers great potential for the non-invasive monitoring of drugs and their volatile metabolites. The physicochemical properties of o-toluidine, the main metabolite of prilocaine, allow its detection in breath gas. Within this study, we investigated whether o-toluidine can be monitored in exhaled breath during regional anaesthesia in an animal model, if correlations between o-toluidine and prilocaine blood levels exist and if accidental intravenous injections are detectable by o-toluidine breath monitoring. Continuous o-toluidine monitoring was possible during regional anaesthesia of the cervical plexus and during simulated accidental intravenous injection of prilocaine. The time course of exhaled o-toluidine concentrations considerably differed depending on the injection site. Intravenous injection led to an immediate increase in exhaled o-toluidine concentrations within 2 min, earlier peak and higher maximum concentrations, followed by a faster decay compared to regional anaesthesia. The strength of correlation of blood and breath parameters depended on the injection site. In conclusion, real time monitoring of o-toluidine in breath gas is possible by means of PTR-ToF-MS. Since simulated accidental intravenous injection led to an immediate increase in exhaled o-toluidine concentrations within 2 min and higher maximum concentrations, monitoring exhaled o-toluidine may potentially be applied for the non-invasive real-time detection of accidental intravenous injection of prilocaine.

Isoprene synthase (IspS) is the sole enzyme in plants responsible for the yearly emission in the atmosphere of thousands of tonnes of the natural hydrocarbon isoprene worldwide. Species of the monocotyledonous family Arecaceae (palms) are among the highest plant emitters, but to date no IspS gene from this family has been identified. Here, we screened with PTR‐ToF‐MS 18 genera of the Arecaceae for isoprene emission and found that the majority of the sampled species emits isoprene. Putative IspS genes from six different genera were sequenced and three of them were functionally characterized by heterologous overexpression in Arabidopsis thaliana, demonstrating that they encode functional IspS genes. Site‐directed mutagenesis and expression in Arabidopsis demonstrated the functional relevance of a novel IspS diagnostic tetrad from Arecaceae, whose most variable amino acids could not preserve catalytic function when substituted by a putatively dicotyledonous‐specific tetrad. In particular, mutation of threonine 479 likely impairs the open–closed transition of the enzyme by altering the network of hydrogen bonds between helices H1α, H, and I. These results shed new light on the evolution of IspS in monocots, suggesting that isoprene emission is an ancestral trait within the Arecaceae family. The identification of IspS from Arecaceae provides promising novel enzymes for the production of isoprene in heterologous systems and allows the screening and selection of commercially relevant palm varieties with lower environmental impact. [ABSTRACT FROM AUTHOR]

Characteristics and sources of volatile organic compounds (VOCs) were investigated with highly time-resolved measurements by a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) at an urban site in Beijing in winter 2017. During the measurement period, high mixing ratios of VOCs (48.9 ppbv) and trace gases were observed, with alternating episodes of strong haze pollution and clean air. Ten VOC families showed clear dependence on the VOC concentration. Aromatics increased the most during haze, with significantly elevated benzene concentration at high VOC concentration, while CxHyO3 and CxHy increased the least. The positive matrix factorization (PMF) receptor model was applied to the VOC mass spectra, yielding four major VOC factors: traffic emissions (21.0%), solid fuel combustion (SFC, 24.4%), and two oxygenated VOC (OVOC) factors (32.3% and 22.3%). Traffic and solid fuel combustion were dominant during the periods of high total VOC concentration, while the OVOC1 fraction was reduced. Comparisons with organic aerosol (OA) sources showed increased oxygenated organic aerosol (OOA) concentration during high VOC concentration periods, indicating the importance of OVOCs to secondary organic aerosol formation. Furthermore, trajectory analysis showed that most of the clean days were associated with northerly winds with high ratios of OVOC1. In contrast, the haze periods were not only due to high primary emissions under stagnant conditions, but also influenced by air masses from a more regional scale.

The aim of this study was to investigate volatile organic compounds (VOCs) in exhaled breath as possible non-invasive markers to monitor the inflammatory response in inflammatory bowel disease (IBD) patients as a result of repeated and prolonged moderate-intensity exercise. We included 18 IBD patients and 19 non-IBD individuals who each completed a 30, 40, or 50 km walking exercise over three consecutive days. Breath and blood samples were taken before the start of the exercise event and every day post-exercise to assess changes in the VOC profiles and cytokine concentrations. Proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) was used to measure exhaled breath VOCs. Multivariate analysis, particularly ANOVA-simultaneous component analysis (ASCA), was employed to extract relevant ions related to exercise and IBD. Prolonged exercise induces a similar response in breath butanoic acid and plasma cytokines for participants with or without IBD. Butanoic acid showed a significant correlation with the cytokine IL-6, indicating that butanoic acid could be a potential non-invasive marker for exercise-induced inflammation. The findings are relevant in monitoring personalized IBD management.

In ecology, Volatile Organic Compounds (VOCs) have a high bioactive and signaling potential. VOCs are not only metabolic products, but are also relevant in microbial cross talk and plant interaction. Here, we report the first large-scale VOC study of 13 different species of Mortierella sensu lato (s. l.) isolated from a range of different alpine environments. Proton Transfer Reaction–Time-of-Flight Mass Spectrometry (PTR–ToF–MS) was applied for a rapid, high-throughput and non-invasiveVOCfingerprintingof72Mortierellas. l. isolates growing understandardized conditions. Overall, we detected 139 mass peaks in the headspaces of all 13 Mortierellas. l. species studied here. Thus, Mortierella s. l. species generally produce a high number of different VOCs. Mortierella species could clearly bedis criminated basedon their volatilomes, evenifonly high-concentration mass peaks were considered. The volatilomes were partially phylogenetically conserved. There were no VOCs produced by only one species, but the relative concentrations of VOCs differed between species. From a univariate perspective, we detected mass peaks with distinctively high concentrations in single species. Here, we provide initial evidence that VOCs may provide a competitive advantage and modulate Mortierella s. l. species distribution on a global scale. [ABSTRACT FROM AUTHOR]

Authentication of dairy systems is of growing interest for the dairy industry and we investigated the potentiality of using volatile fingerprinting of ripened cheeses by proton transfer reaction time-of-flight mass spectrometry. A total of 1,075 individual model cheeses made from milk of individual Brown Swiss cows of 72 farms were analysed. Using a linear discriminant analysis, cows and herds were assigned to 3 or 5 dairy systems differing in management, available facilities, and diets. We obtained variable discrimination abilities (up to 77% of correct classification of cheeses and 70% of farms with cross-validation). We found m/z 61,028 (acetic acid), 109,070 (pyrazine), and m/z 137,132 (terpene) characterising model cheeses from traditional dairy systems and m/z 71,086 (3-methyl-butan-1-ol, 3-methyl-3-buten-1-ol, pentan-1-ol), m/z 101,097 (hexan-2-one, hexanal), m/z 123,117 (nonenal), m/z 129,127 (octan-1-one, octanal), and two unidentified peaks m/z 83,071 and m/z 93,090 characterising model cheeses from the modern farms. In conclusion, it seems possible to discriminate between a range of dairy systems using fast volatile fingerprinting of ripened cheeses but a proper validation of results obtained is needed. Mass spectrometry technique (PTR-ToF-MS) was able to discriminate between dairy systems. We found m/z 61,028 (acetic acid), 109,070 (pyrazine), and m/z 137,132 (terpene) characterising model cheeses from traditional dairy systems. We found m/z 71,086 (3-methyl-butan-1-ol, 3-methyl-3-buten-1-ol, pentan-1-ol), m/z 101,097 (hexan-2-one, hexanal), m/z 123,117 (nonenal), m/z 129,127 (octan-1-one, octanal), and two unidentified peaks m/z 83,071 and m/z 93,090 characterising model cheeses from the modern farms. [ABSTRACT FROM AUTHOR]

A second wave of coronavirus disease 2019 (COVID-19) infections emerged in Beijing in summer 2020, which provided an opportunity to explore the response of air pollution to reduced human activity. Proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) coupled with positive matrix factorization (PMF) source apportionment were applied to evaluate the pollution pattern and capture the detailed dynamic emission characteristics of volatile organic compounds (VOCs) during the representative period, with the occurrence of O _3 pollution episodes and the Beijing resurgence of COVID-19. The level of anthropogenic VOC was lower than during the same period in previous years due to the pandemic and emission reduction measures. More than two thirds of the days during the observation period were identified as high-O _3 days and VOCs exhibited higher mixing ratios and faster consumption rates in the daytime on high-O _3 days. The identified VOC emission sources and the corresponding contributions during the whole observation period included: vehicle + fuel (12.41 ± 9.43%), industrial process (9.40 ± 8.65%), solvent usage (19.58 ± 13.46%), biogenic (6.03 ± 5.40%), background + long-lived (5.62 ± 11.37%), and two groups of oxygenated VOC (OVOC) factors (primary emission and secondary formation, 26.14 ± 15.20% and 20.84 ± 14.0%, respectively). Refined dynamic source apportionment results show that the ‘stay at home’ tendency led to decreased emission (−34.47 ± 1.90%) and a weakened morning peak of vehicle + fuel during the Beijing resurgence. However, a growing emission of primary OVOCs (+51.10 ± 8.28%) with similar diurnal variation was observed in the new outbreak and afterwards, which might be related to the enhanced usage of products intended to clean and disinfect. The present study illustrated that more stringent VOC reduction measures towards pandemic products should be carried out to achieve the balanced emission abatement of NO _x and VOC when adhering to regular epidemic prevention and control measures.

Proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a powerful tool for real-time monitoring of trace concentrations of volatile organic compounds (VOCs). The sensitivity of PTR-ToF-MS also depends on the ability to effectively focus and transmit ions from the relatively high-pressure drift tube (DT) to the low-pressure mass analyzer. In the present study, a modular ion-funnel (IF) is placed adjacent to the DT of a PTR-ToF-MS instrument to improve the ion-focusing. IF consists of a series of electrodes with gradually decreasing orifice diameters. Radio frequency (RF) voltage and direct current (DC) electric field are then applied to the electrodes to get the ions focused. We investigated the effect of the RF voltage and DC field on the sensitivity of a pattern of VOCs including hydrocarbons, alcohols, aldehydes, ketones, and aromatic compounds. In a proof-of-concept study, the instrument operating both as normal DT (DC-mode) and at optimal IF conditions (RF-mode) was applied for the breath analysis of 21 healthy human subjects. For the range of investigated VOCs, an improvement of one order of magnitude in sensitivity was observed in RF-mode compared with DC-mode. Limits of detection could be improved by a factor of 2–4 in RF-mode compared with DC-mode. Operating the instrument in RF-mode allowed the detection of more compounds in the exhaled air compared with DC-mode. Incorporation of the IF considerably improved the performance of PTR-ToF-MS allowing the real-time monitoring of a larger number of potential breath biomarkers. [ABSTRACT FROM AUTHOR]

To improve the understanding of secondary organic aerosol (SOA) formation from the photo-oxidation of anthropogenic and biogenic precursors at the regional background station on Baengnyeong Island, Korea, gas phase and aerosol chemistries were investigated using the Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-ToF-MS) and the Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS), respectively. HR-ToF-AMS measured fine particles (PM1 diameter of particle matter less than 1 μm) at a 6-minute time resolution from February to November 2012, while PTR-ToF-MS was deployed during an intensive period from September 21 to 29, 2012. The one-minute time-resolution and high mass resolution (up to 4000 m Δm-1) data from the PTR-ToF-MS provided the basis for calculations of the concentrations of anthropogenic and biogenic volatile organic compounds (BVOCs) including oxygenated VOCs (OVOCs). The dominant BVOCs from the site are isoprene (0.23 ppb), dimethyl sulphide (DMS, 0.20 ppb), and monoterpenes (0.38 ppb). Toluene (0.45 ppb) and benzene (0.32 ppb) accounted for the majority of anthropogenic VOCs (AVOCs). OVOCs including acetone (3.98 ppb), acetaldehyde (2.67 ppb), acetic acid (1.68 ppb), and formic acid (2.24 ppb) were measured. The OVOCs comprise approximately 75% of total measured VOCs, suggesting the occurrence of strong oxidation processes and/or long-range transported at the site. A strong photochemical aging and oxidation of the atmospheric pollutants were also observed in aerosol measured by HR-ToF-AMS, whereby a high f44 : f43 value is shown for organic aerosols (OAs); however, relatively low f44 : f43 values were observed when high concentrations of BVOCs and AVOCs were available, providing evidence of the formation of SOA from VOC precursors at the site. Overall, the results of this study revealed several different SOA formation mechanisms, and new particle formation and particle growth events were identified using the powerful tools scanning mobility particle sizer (SMPS), PTR-ToF-MS, and HR-ToF-AMS.

Primary processing treatments are crucial to the flavor profile of coffee beans, which create the flavor precursors basis in coffee husks and diffuse into the beans, with satisfying outcomes. In this study, eleven coffee husks of Coffea arabica with different primary processing treatments (sun exposure, washing and honey treatment) from three latitudes of Yunnan were investigated by the combination of HS-SPME-GC-MS and PTR-TOF-MS. A total of 114 volatile organic compounds (VOCs) and 77 masses were identified. The characteristic compounds octanoic acid (S1) and methyl linoleate (S11) in sun-exposed, phenethyl alcohol (F4), methyl salicylate (F7), 3,5-dimethylbenzaldehyde (F9) and phytone (T9) in washed and n -hexadecanoic acid (S9) of honey-treated husks were recognized by the ions at m/z 33.032, m/z 68.049, m/z 83.049, m/z 67.054, m/z 57.034, m/z 41.030 and m/z 49.010, respectively. This study demonstrated the feasibility and complementarity of HS-SPME-GC-MS and PTR-TOF-MS in the rapid identification of VOCs in coffee husks. Meanwhile, the antioxidant capacities of the 11 husks were evaluated in vitro , and the sun-exposed samples exhibited most promising potency, in which methyl salicylate (F7), methyl linoleate (S11), methyl linolenate (S13), ethyl linoleate (S14), ethyl linolenate (S16), linalool (T1), citronellol (T2) and caffeine (J3) contributed mainly to the antioxidant capacities. • The volatile profiles of 3 primary processed coffee husks were recognized firstly. • HS-SPME-GC-MS and PTR-TOF-MS were first introduced to rapid analysis of coffee husks. • Sun-exposed coffee husks were potential antioxidants in future application. [ABSTRACT FROM AUTHOR]

Fire represents a major threat to Mediterranean terrestrial ecosystems because of the high temperatures reached during summer. While massive loads of organic, inorganic compounds and particulate matter are known to be emitted into the atmosphere from forest wildfires, less is known about the emission from vegetation surrounding fires where air temperatures higher than 100 °C can be reached. Little information exists on the emission from dead vegetation accumulated as litter over forest soils, from which fires often starts. In this study, the response of litter to heatwaves generated by nearby fires was investigated under controlled conditions. Litter samples collected in a Mediterranean maquis and a Holm oak stand during summer were placed in an enclosure flushed with a continuous flow of air, the temperature of the enclosure was progressively risen to 125 °C, until some smog developed but no flaming occurred. The gas from the enclosure was analysed for the content of CO 2 , H 2 O, and volatile organic compounds (VOC) to assess the dependence of emission from the air temperature. VOC emission was continuously determined by Proton-Transfer-Reaction mass spectrometry with time of flight (PTR-TOF-MS). Data obtained were complemented with those obtained by collecting VOC on traps that were later analysed by Gas chromatography–mass spectrometry (GC-MS). Results provided useful information to understand the emission mechanism of VOC and other gases from dead vegetation present in the litter of two Mediterranean ecosystems, both dominated by evergreen vegetation species. The study demonstrated that low molecular weight VOC and aromatic hydrocarbons (arenes) produced mostly by thermal oxidation of the wood biopolymers are emitted in addition to isoprenoids typically associated to storage organs and photosynthetic pathway. Moreover, our results support parameterization of litter VOC emission processes in air quality models. [Display omitted] • CO 2 and VOC emissions from litter of two Mediterranean ecosystems were measured. • Carbon emission from litter was found to strongly increase with temperature. • Low molecular weight oxygenated compounds dominated VOC emission. • Isoprenoid emissions were higher in the Mediterranean maquis than Holm oak litter. [ABSTRACT FROM AUTHOR]

This study addresses the characterization of volatile organic compounds (VOCs) emitted by samples of 13 different wood species, belonging to both softwoods and hardwoods groups, regularly measured at different intervals of time, after the first measurement on green wood. The same wood specimens were subjected to several cycles of water desorption and adsorption, assuming that moisture variation might play a role in both the formation and emission of VOCs. Proton Transfer Reaction-Time of Flight-Mass Spectrometry (PTR-TOF-MS) was used as a tool to characterize the emission of VOCs. Coupled with a multivariate class-modelling approach, this tool was able to discriminate between groups (softwood and hardwood) and in some cases between different species. However, results showed that the discriminant capacity of VOCs emission to separate species and families rapidly decreases after the first cycles of moisture variation in wood. The green wood was characterized by a richness of volatile compounds, whereas, after only the first dry cycle, wood emitted a more restricted group of compounds. We hypothesized that most of these VOCs might have originated from structural changes and degradation processes that involve the main polymers (particularly hemicellulose) constituting the cell wall of wooden cells. The results obtained are in agreement with the physical and chemical modification processes that characterize wood ageing.

The quality of coffee is linked to the aroma created by the chemical reactions that occur during the roasting process. While it is generally thought that roasted coffee is a stable product with a relatively long shelf-life, little information is available on the evolution (kinetic) of the volatile organic compounds (VOCs) in the days immediately following the process. The aim of this study is to determine the evolution of VOCs released by coffee beans, on samples of Coffea arabica (three different origins) and Coffea canephora (1 single origin), by using a Proton Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-ToF-MS) 24 hours after roasting, and for the next 9 days. Results confirmed the differences already highlighted in previous studies between the VOCs spectra of the two species. There were also significant differences in the intensity of emissions for the different origins of Coffea arabica, with the highest VOCs amount over time always detected in the Honduras Arabica samples. The involved detected protonated ions were grouped into three classes: compounds (ppbv) present with decreasing quantity ; weakly increasing; almost constant trend; or always increasing. A complex dynamic emerged for the different protonated ions over time, which not only affects the mass spectra of the different species but also influences the configuration of the mass spectra of the different geographical zones of production.

In this study, we present reactions of NH4+ with a series of analytes (A): acetone (C3H6O), methyl vinyl ketone (C4H6O), methyl ethyl ketone (C4H8O), and eight monoterpene isomers (C10H16) using a Selective Reagent Ionization Time-of-Flight Mass Spectrometer (SRI-ToF-MS). We studied the ion-molecule reactions at collision energies of 55 and 80 meV. The ketones, having a substantially lower proton affinity than NH3, produce only cluster ions NH4+(A) in detectable amounts at 55 meV. At 80 meV, no cluster ions were detected meaning that these adduct ions are formed by strongly temperature dependent association reactions. Bond energies of cluster ions and proton affinities for most monoterpenes are not known and were estimated by high level quantum chemical calculations. The calculations reveal monoterpene proton affinities, which range from slightly smaller to substantially higher than the proton affinity of NH3. Proton affinities and cluster bond energies allow to group the monoterpenes as a function of the enthalpy for the dissociation reaction NH4+A→AH++NH3. We find that this enthalpy can be used to predict the NH4+(A) cluster ion yield. The present study explains product ion formation involving NH4+ ion chemistry. This is of importance for chemical ionization mass spectrometry (CIMS) utilizing NH4+ as well as NH4+(H2O) as reagent ions to quantitatively detect atmospherically important organic compounds in real-time.

In this work, for the first time, a gruyt beer and the same one after the addition of Citrus aurantium essential oil (AEO), were investigated to determine the composition of the volatile fraction. The applied analytical techniques, such as Head Space/Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry (HS/SPME-GC-MS) and Proton Transfer Reaction-Time of Flight-Mass Spectrometer (PTR-ToF-MS), allowed us to identify the content of volatile organic compounds (VOCs). From the comparison between the two beer samples, it showed that the one after the addition of AEO was particularly richened in limonene and a series of minor terpene compounds. AEO was also characterized by GC/MS analysis and the results showed that limonene reached 95%. Confocal microscopy was used to look at riboflavin autofluorescence in yeast cells. It was found that beer with AEO had twice as much fluorescence intensity as the control. A spectrophotometric analysis of total polyphenols, tannins, and flavonoids, and a bioactivity screening, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-Azinobis-(3-Ethylbenzthiazolin-6-Sulfonic Acid) (ABTS) radical scavenger, chelating, reducing, antiglycative ones, were also carried out. Moreover, the tolerability of the tested samples in human H69 cholangiocytes and the cytoprotection towards the tert-butyl hydroperoxide (tBOOH)-induced oxidative damage were evaluated. Under our experimental conditions, the beers were found to be able to scavenge DPPH and ABTS radicals and chelate iron ions, despite weak antiglycative and reducing properties. The tested samples did not affect the viability of H69 cholangiocytes up to the highest concentrations; moreover, no signs of cytoprotection against the damage induced by tBOOH were highlighted. Adding AEO to beer resulted in a moderate enhancement of its DPPH scavenging and chelating abilities, without improvements in the other assays. Conversely, AEO and its major compound limonene were ineffective when assessed at the concentrations added to beer. This evidence suggests that the addition of AEO may enhance the organoleptic features of the beer and slightly potentiate some of its bioactivities.

Volatile organic compounds (VOCs) in exhaled breath provide insights into various metabolic processes and can be used to monitor physiological response to exercise and medication. We integrated and validated in situ a sampling and analysis protocol using proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) for exhaled breath research. The approach was demonstrated on a participant cohort comprising users of the cholesterol-lowering drug statins and non-statin users during a field campaign of three days of prolonged and repeated exercise, with no restrictions on food or drink consumption. The effect of prolonged exercise was reflected in the exhaled breath of participants, and relevant VOCs were identified. Most of the VOCs, such as acetone, showed an increase in concentration after the first day of walking and subsequent decrease towards baseline levels prior to walking on the second day. A cluster of short-chain fatty acids including acetic acid, butanoic acid, and propionic acid were identified in exhaled breath as potential indicators of gut microbiota activity relating to exercise and drug use. We have provided novel information regarding the use of breathomics for non-invasive monitoring of changes in human metabolism and especially for the gut microbiome activity in relation to exercise and the use of medication, such as statins.

Abstract In this study we examine the application of a factor analysis technique for datasets recorded by the chemical ionization instrument Proton Transfer Reaction - Time-of-Flight - Mass Spectrometer (PTR-ToF-MS). Numerical simulations were carried out to test and optimize the performance of the factorization method Multivariate Curve Resolution - Alternating Least Squares (MCR-ALS). The simulations demonstrated that the choice of initial estimates for the factor analysis are crucial for the outcome of the factorization. For this purpose we describe a new method based on the Pearson correlation coefficient which, compared to the other tested methods, yields the best factorization results. Overlapping contributions of different substances to a certain mass bin and large uncertainties in the data deteriorate the performance of the factor analysis. The deconvolution technique was also applied to data obtained with a PTR-ToF-MS employed at a smog chamber. The response from single substances (fragmentation patterns) such as α-pinene, α-pinene oxide and pinonaldehyde as well as a more complex experiment involving the ozonolysis of α-pinene are investigated. For the single substances, the factorization method points to the presence of impurities which could be differentiated from the masses affiliated with the actual substances. The α-pinene ozonolysis experiment was analysed with the factorization technique and yielded four factors, one representing the decay of the reactant and three different products. The matrix factorization technique appeared to be a valuable tool allowing for a detailed analysis of complex mass spectra without the need of any prior information. Highlights • Investigation of the suitability of factor analysis to interpret PTR-ToF-MS datasets. • Factor analysis performance tested on chemical model systems. • Measured fragmentation patterns of α-pinene, α-pinene oxide and pinonaldehyde. • Factor analysis of a smog chamber dark α-pinene ozonolysis experiment at 293 K. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Reactions of 9 D-labeled volatile compounds with H 3 O+ in PTR- MS were investigated. • Exothermic proton transfer was the dominant ionization mechanism. • Deuterium/hydrogen isotope exchange reactions with water in drift tube were noted. • D/H exchange led to generation of various isotopologue ions and complex spectra. Abstract Product ion distributions resulting from the primary reactions of H 3 O+ with nine D-labeled volatile organic compounds and the subsequent sequential reactions with H 2 O have been determined using a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF 8000 (IONICON Analytik GmbH)) at various reduced electric field (E/N) values ranging from 80 up to 150 Td and for two different absolute humidity levels of air sample < 0.1% and 5%. The specific D-labeled compounds used in this study are acetone-d 6 , toluene-d 8 , benzene-d 6 , ethanol-d (C 2 H 5 OD), ethanol-d 2 (CH 3 CD 2 OH), ethanol-d 6 , 2-propanol-d 8 , 2-propanol-d 3 (CD 3 CH(OH)CH 3), and isoprene-d 5 (CH 2 CHC(CD 2)CD 3). With the exception of the two 2-propanol compounds, non-dissociative proton transfer is the dominant primary reaction pathway. For 2-propanol-d 8 and 2-propanol-d 3 the major primary reaction channel involved is dissociative proton transfer. However, unlike their undeuterated counterparts, the primary product ions undergo subsequent deuterium/hydrogen isotope exchange reactions with the ever present water in the drift tube, the extent of which of course depends on the humidity within that tube. This exchange leads to the generation of various isotopologue product ions, the product ion branching percentages of which are also dependent on the humidity in the drift tube. This results in complex mass spectra and the distribution of product ions leads to issues of reduced sensitivity and accuracy. However, the effect of D/H exchange considerably varies between the compounds under study. In the case of acetone-d 6 it is very weak (< 1%), because the exchange process is not facile when the deuterium is in the methyl functional group. In comparison, the H 3 O+/ benzene-d 6 (C 6 D 6) reaction and sequential reactions with water result in the production of the isotopologue ions C 6 D n (H 7-n)+ (where n = 0–6). Changing the value of E/N and/or the humidity in the drift tube considerably affects the amount of the isotope exchange reactions and hence the resulting sequential product ion distributions. An important conclusion of the findings from this work is that care must be taken in the choice of an exogenous deuterated compound for use in breath pharmacokinetic studies using proton transfer reaction mass spectrometry; otherwise the resulting D/H exchange processes impose interpretative problems. [ABSTRACT FROM AUTHOR]