Thermal Desorption Gas Chromatography Research Articles

Emission characteristics of volatile organic compounds from consumer spray products based on product type, spray method, and distance

Consumer spray products (CSPs) are widely used in daily life, yet it is challenging to find products that fully disclose all components posing health risks. Existing studies primarily focus on product components or VOC quantities emitted during use. Therefore, this study aimed to measure the VOC concentrations emitted by CSPs at varying distances. 47 CSPs available in the Korean market were selected, spanning three spray groups: antiseptics/insecticides (11), aromatic deodorants (16), and coating/polishing agents (20). VOC in air samples were collected using Tenax TA tube at a distance of 1 and 3 m from the sprayed CSPs and then analyzed by thermal desorption–gas chromatography–mass spectrometry system. Discrepancies were found between labeled and actual product components. Aromatic deodorants exhibited the highest total VOCs (TVOCs), while antiseptic/insecticide sprays exhibited the lowest. In the antiseptic/insecticide group and coating/polishing agent group, benzene as a propellant had a maximum concentration (30.9 ± 25.6 ppb), and as trigger, its concentration was 33.7 ± 30.7 ppb. Quantitative analysis using advanced analytical instruments only explained 26.1 ± 20.4% of toluene-equivalent TVOCs, suggesting the presence of additional substances. Concentrations varied by distance due to substance volatility and usage. Maintaining a distance of at least 1 m from CSPs is recommended.

Profiling of Organosulfur Compounds in Onions: A Comparative Study between LC-HRMS and DTD-GC-MS

Onions are known not only for their culinary importance but also for their nutritional and health-promoting properties. Both properties are closely linked to their content of organosulfur compounds, which account for up to 5% of the dry weight of an onion. Given the importance of these compounds, suitable analytical methods are required for their study. Two techniques should be highlighted in this context: gas chromatography coupled to mass spectrometry (GC-MS), and liquid chromatography coupled to mass spectrometry (LC-MS). In this study, eight different onion varieties were analyzed using two distinct analytical techniques: direct thermal desorption–gas chromatography–mass spectrometry (DTD-GC-MS) and high-resolution mass spectrometry (HRMS) on an LC-ESI-QqTOF instrument. Each method identified different organosulfur compounds, with LC-HRMS targeting 15 non-volatile compounds, such as cysteine sulfoxides, and GC-MS targeting 18 volatiles, such as disulfides and trisulfides. The results obtained were studied using Pearson correlations and principal component analysis. No precise correlation was found between the initial organosulfur compounds in onions and their hydrolysates. Consequently, although GC is one of the most employed techniques in the scientific literature, the use of LC-HRMS or a combination of both techniques may offer a more comprehensive and accurate description of the metabolomic profile of onions.

Emission of volatile organic compounds during open fire cooking with wood biomass: Traditional three-stone open fire vs. gasifier cooking stove in rural Kenya

Cooking with wood biomass fuels releases hazardous air pollutants, including volatile organic compounds (VOCs), that often disproportionally affect women and children. This study, conducted in Kwale and Siaya counties in Kenya, employed thermal desorption gas chromatography – mass spectrometry to analyse VOC emissions from cooking with a wood biomass three-stone open fire vs. top-lit updraft gasifier stove. In kitchens with adequate ventilation, total VOC levels increased from 35–252 μg∙m−3 before cooking to 2235–5371 μg∙m−3 during open fire cooking, whereas use of a gasifier stove resulted in reduced emissions from cooking by 48–77 % (506–2778 μg∙m−3). However, in kitchens with poor ventilation, there was only a moderate difference in total VOC levels between the two methods of cooking (9034–9378 μg∙m−3 vs. 6727–8201 μg∙m−3 for the three-stone open fire vs. gasifier stove, respectively). Using a non-target screening approach revealed significantly increased levels of VOCs, particularly benzenoids, oxygenated and heterocyclic compounds, when cooking with the traditional open fire, especially in closed kitchens, highlighting the effects of poor ventilation. Key hazardous VOCs included benzene, naphthalene, phenols and furans, suggesting potential health risks from cooking. In kitchens with good ventilation, use of the gasifier stove markedly reduced emissions of these priority toxic VOCs compared to cooking with an open fire. Thus, substituting open fires with gasifier stoves could help to improve household air quality and alleviate health risks. The study revealed that VOCs were present prior to cooking, possibly originating from previously cooked food (buildup) or the outside environment. VOC emissions were also exacerbated by reduced air flow in high humidity during rainfall, suggesting an area for further research. The findings underscore the importance of adopting cleaner cooking technologies and enhancing kitchen ventilation to mitigate the impacts of VOCs in developing countries.

Characterization of the SPIRITAS: A Disposable Sampling Setup for Volatile Organic Compound Collection and Analysis

Analyzing exhaled breath for volatile organic compounds (VOCs) using thermal desorption–gas chromatography–mass spectrometry (TD-GC-MS) offers a non-invasive diagnostic approach for various diseases. Despite its promise, the method faces challenges like sampling heterogeneity and high costs. Following the European Respiratory Society’s advocacy for methodological standardization, we developed the SPIRITAS (Standardized Product for Inexpensive Respiratory InvesTigation: A breath Sampler), a low-cost, disposable breath sampler. This study evaluates the SPIRITAS’s effectiveness in detecting targeted VOCs. We tested the SPIRITAS using the Peppermint Experiment, a standardized protocol that allows for comparison between different breath sampling and analytical practices by assessing the ability to detect five peppermint-specific VOCs after ingestion of a 200-milligram peppermint oil capsule. We included ten subjects and performed six breath samples per participant, including a baseline measurement taken before ingestion. We used the Wilcoxon signed-rank test to evaluate whether baseline values were significantly lower than the peak values of the targeted VOCs. Additionally, we conducted an experiment utilizing humidified medical-grade air to identify any VOCs attributable to the SPIRITAS setup itself. Results showed successful detection of four out of five targeted “peppermint-associated” VOCs: alpha-pinene (p ≤ 0.01), beta-pinene (p ≤ 0.01), menthone (p = 0.01), and menthol (p = 0.02), indicating significant differences between the baseline and peak values in the volunteers’ breath. However, detection of eucalyptol was inconsistent. In addition, we identified 16 VOCs that were released by the SPIRITAS, one of which remains unidentified. Our findings underscore the SPIRITAS’s potential for clinical applications, paving the way for broader biomarker research. The combination of ease of use, low cost, reduced risk of contamination, and standardization makes SPIRITAS very suitable for large-scale international studies. Furthermore, we have demonstrated the SPIRITAS’s effectiveness in detecting specific VOCs and identified 16 compounds originating from the SPIRITAS, ensuring that these compounds would not be mis-qualified as potential biomarkers in future clinical studies.

Research on loss rules of oil and gas in preserved shale cores after open air exposure

There is a large amount of oil and gas loss in traditional conventional core samples. Revealing the rules of oil and gas loss is of great significance for restore the pristine oil content and oil component in the shale. In this study, four preserved shale cores with different thermal maturity (Ro = 1.01–1.53%) and different total organic carbon content (TOC = 1.69–5.48 wt.%) were selected. The samples are obtained from the first member of the Qingshankou Formation in the Gulong Sag. Nuclear magnetic resonance (NMR) T1–T2 mapping and thermal desorption gas chromatography (TD–GC, at a constant temperature of 300°C for 3 min) were performed on the preserved cores and their replicas that were exposed in open air for different times, to study dynamic loss process and the molecular composition changes of shale oil. The results show that during exposure, shale experiences a large amount of oil loss, with a loss ratio of about 42%–78%, and the higher the maturity, the greater the loss ratio. The oil loss is mainly contributed by free oil, with a loss ratio as high as 88%. The adsorbed oil content, however, remains basically unchanged and has a good positive correlation with the TOC of shale. Once the cores were crushed, the gaseous hydrocarbon in oil was basically evaporated in just 5 min. After long-term storage, 90% of the C14- light hydrocarbon is lost, while the C14+ heavy hydrocarbon experiences basically no loss. Therefore, effective and timely analysis of preserved shales is extremely important. The oil content of uncrushed shale cores characterized by NMR T1–T2 mapping is much greater than that of the crushed sample measured by TD-GC, which means that NMR T1–T2 mapping can be important method to evaluate the original fluid saturation of shale.

Unravelling caramelization and Maillard reactions in glucose and glucose + leucine model cakes: Formation and degradation kinetics of volatile markers extracted during baking

A large number of volatile compounds are formed during the baking of foods by reactions such as caramelization and Maillard reactions. Elucidating the reaction mechanisms may be useful to predict and control food quality. Ten reaction volatile markers were extracted during baking of solid model cakes implemented with known amounts of precursors (glucose with or without leucine) and then quantified by Thermal desorption–Gas chromatography–Mass spectrometry. The kinetic data showed that the level of air convection in the oven had no significant influence on the reaction rates. In contrast, increasing baking temperatures had a nonlinear accelerating impact on the generation of newly formed volatile compounds with a bell–shaped kinetic curve found for most of the markers at 200 °C. The presence of leucine triggered the activation of the Maillard and Strecker routes with a specific and very rapid formation of 3–Methylbutanal and pyrazines. A dynamic model was developed, combining evaporation flow rate and kinetic formation and consumption of reaction markers. It can be used to describe, for two furanic compounds of different volatilities, the vapor concentrations in the oven from the concentrations measured in the model cakes.

Low-cost sensor-based investigation of CO2 and volatile organic compounds in classrooms: Exploring dynamics, ventilation effects and perceived air quality relations

Poor classroom air quality (CAQ) can have negative impacts on student health, well-being and performance. Although CO2 concentrations are the proxy most often applied when assessing classroom ventilation and air quality, volatile organic compounds (VOCs) are important contributors to classroom air pollution. However, little is known about the sources and dynamics of VOCs in classrooms and its relation to classroom occupancy, ventilation and perceived air quality. In this study, CAQ was investigated in 75 Danish classrooms throughout November 2021 using low-cost sensors for continuous measurements of occupancy, CO2- and total volatile organic compound (TVOC) concentrations in conjunction with thermal desorption gas chromatography mass spectrometry (TD-GC-MS) analysis of organic compounds. Measurements show significant increases in TVOC concentrations during school hours as well as a day-to-day increase in the morning TVOC levels from insufficient ventilation from preceding days. A weak (r = 0.21) but significant (p < 0.01) correlation was found between classroom CO2 and TVOC. However, unlike the CO2 concentrations, TVOC concentrations were affected by episodic emissions from classroom activities. Ventilation type was identified as a key factor influencing both CO2- and TVOC levels. Although mechanically ventilated classrooms experienced significantly lower CO2- and TVOC levels compared to naturally ventilated classrooms, all classrooms exceeded guideline values of 1000 ppm CO2 with 70% of the classrooms exceeding this more than half of the occupied time. In contrast to CO2, a positive correlation was identified between the median TVOC concentrations during occupancy and the reported perceived CAQ.

A novel coupling technique based on thermal desorption gas chromatography with mass spectrometry and ion mobility spectrometry for breath analysis

Exhaled breath analysis is evolving into an increasingly important non-invasive diagnostic tool. Volatile organic compounds (VOCs) in breath contain information about health status and are promising biomarkers for several diseases, including respiratory infections caused by bacteria. To monitor the composition of VOCs in breath or the emission of VOCs from bacteria, sensitive analytical techniques are required. Next to mass spectrometry, ion mobility spectrometry (IMS) is considered a promising analytical tool for detecting gaseous analytes in the parts per billion by volume to parts per trillion by volume range. This work presents a new, dual coupling of thermal desorption gas chromatography to a quadrupole mass spectrometer (MS) and an IMS by operating a simple splitter. Nearly identical retention times can be reached in the range of up to 30 min with slight deviations of 0.06 min–0.24 min. This enables the identification of unknown compounds in the IMS chromatogram using unambiguous mass spectral identification, as there are still no commercially available databases for IMS. It is also possible to discriminate one of the detectors using the splitter to improve detection limits. Using a test liquid mixture of seven ketones, namely 2-butanone, 2-pentanone, 2-hexanone, 2-heptanone, 2-octanone, 2-nonanone, and 2-decanone with a concentration of 0.01 g l−1 reproducibilities ranging from 3.0% to 7.6% for MS and 2.2%–5.3%, for IMS were obtained, respectively. In order to test the system optimized here for the field of breath analysis, characteristic VOCs such as ethanol, isoprene, acetone, 2-propanol, and 1-propanol were successfully identified in exhaled air using the dual detector system due to the match of the corresponding IMS, and MS spectra. The presented results may be considered to be a starting point for the greater use of IMS in combination with MS within the medical field.

Impact of thermal desorption tubes on the variability of exhaled breath data

Due to the overall low abundance of volatile compounds in exhaled breath, it is necessary to preconcentrate the sample prior to traditional thermal desorption (TD) gas chromatography mass spectrometry analysis. While certain aspects of TD tubes, such as volatile storage, have been evaluated, many aspects remain uncharacterized. Two common TD tubes, Tenax TA and Biomonitoring 5TD tubes, were evaluated for background content and flow rate variability. The data illustrate that the Biomonitoring 5TD tubes have the highest number (23) and abundance of background contamination greater than 3x the mean noise when compared to Tenax TA (13) and empty tubes (9). Tentative identifications of the compounds in the background contamination experiment show that greater than 59% (16/27) of the compounds identified have been reported in the breath literature. The data illustrate the TD tube background abundance could account for more than 70% of the chromatographic signal from exhaled breath for these select compounds. Flow rate measurements of 200 Tenax TA and 200 Biomonitoring 5TD tubes show a large range in measured flow rates among the TD tubes (Tenax: 252.9–284.0 ml min−1, 5TD: 220.6–255.1 ml min−1). Finally, TD tubes of each type, Tenax TA and Biomonitoring 5TD, previously established to have high, medium, and low flow rates, show insignificant differences (p > 0.05) among the tubes of different flow rates, using both gas standards and an exhaled breath from a peppermint experiment. Collectively, these results establish overall background compounds attributed to each TD tube type tested. Additionally, while measured flow rate variability is present and plausibly impacts exhaled breath results, the data demonstrate no statistically significant difference was observed between tubes showing high, medium, and low flow rates from two separate sample types.

Direct quantification of 1,1-dimethylhydrazine transformation products in sandy soil by thermal desorption gas chromatography – Tandem mass spectrometry

The use of rocket propellants based on unsymmetrical dimethylhydrazine (UDMH) in launch vehicles and boosters poses a threat to the environment due to the release of UDMH into soils and its subsequent transformation into a variety of nitrogen-containing compounds, including toxic and carcinogenic ones. The present proof-of-concept study proposes a novel approach to screening and simultaneous determination of a wide range of nitrogen-containing UDMH transformation products in soils, based on direct thermal desorption (TD) as a solvent-free sample extraction technique coupled with GC–MS/MS analysis.Optimal TD conditions consisting of the incubation of 5 mg sample at 300 °C for 30 min, allowed attaining high recoveries (80–100 %) for the most tested compounds and developing the method for quantification of fifteen acyclic and heterocyclic UDMH transformation products in sandy soil with LODs of 0.3–7.8 µg kg−1. The matrix matched calibration and introduction of the internal standard (pyridine‑d5) ensured high accuracy (75–100 %) and precision (RSD < 15 %) of the analysis. Along with high sensitivity and accuracy, the main advantages of the developed method are exceptional simplicity of sample preparation, low amount of toxic sample, high automation degree, and environmental friendliness.The developed method was successfully tested in the analysis of seven real soil samples taken from the Baikonur cosmodrome operational zone (Kazakhstan). The use of TD-GC–MS analysis in full spectrum scanning mode allowed for tentative identification of 62 UDMH transformation products including several compounds not yet described in the literature.

Inhibition effect of three types of biochar on volatile organic compounds from asphalt: Revealing chemical adsorption as the primary mechanism

For advancing sustainable and eco-friendly road materials, addressing the emissions of volatile organic compounds (VOCs) from asphalt binders is paramount. As an environment-friendly adsorbent, biochar is highly promising for mitigating such VOCs emissions. Herein, the feasibility and mechanism of using biochar to control VOCs emissions from asphalt were investigated. Biochar was derived from rice husk, straw and coffee grounds. The VOCs composition was analysed using thermal desorption–gas chromatography–mass spectrometry. Differential scanning calorimetry was employed to simulate asphalt VOCs release, while temperature-programmed desorption spectroscopy was employed to investigate biochar inhibition. Rice husk–derived biochar exhibited the highest inhibition effect on asphalt VOCs. The inhibitory effects of the three biochar samples were weakened with increasing number of carbon atoms in organic compounds, with less ideal inhibition efficiency for aromatic compounds. Chemical adsorption was the primary mechanism for the inhibition of VOCs emissions by biochar at high temperatures.

Determination of in situ hydrocarbon contents in shale oil plays: Part 3: Quantification of light hydrocarbon evaporative loss in old cores based on preserved shales

Petroleum resource assessment obtained from laboratory tests on old core samples shelved in the open environment tend to underestimate in situ resources. Therefore, hydrocarbon loss and its restoration need to be investigated. The hydrocarbon loss was studied via the difference of programmed pyrolysis parameter (Rock–Eval derived S1) between preserved/fresh cores and their replicas that had been long-term exposed to ambient conditions. However, the in situ hydrocarbon potential is still seemed to be underestimated, because the effect of sample crushing and crucible waiting on pristine S1 detection did not receive enough attention. To solve this issue, 50 preserved shale core samples with Ro from 1.00% to 1.51% were collected from the K1qn1 Formation of northern Songliao Basin, Eastern China. All the samples were subjected to four parallel experiments: Dean–Stark extraction and nuclear magnetic resonance (NMR) T1–T2 mapping, using large rock pieces 3–5 cm in size, and thermal desorption gas chromatography (TD–GC) and Rock–Eval analysis, using 60-mesh powdered samples. In addition, a time series of TD–GC and Rock–Eval analyses were conducted on a preserved shale sample to investigate hydrocarbon loss during sample crushing, Rock–Eval crucible waiting process, and elapse-time exposure to the open environment. Rock–Eval pyrolysis was also conducted on one month-exposed shale cores and solvent-extracted samples. The results show that the total hydrocarbon content of large rock pieces is significantly greater than that of powdered samples. Sample crushing or grinding leads C8− light hydrocarbons to evaporate, and results in a loss of approximately 35% of S1. Rock–Eval crucible waiting process causes C14− hydrocarbons to evaporate, and results in an additional 25% loss of S1. To compensate for the sample crush induced S1 loss, an exponential distribution model was proposed based on the C8+ hydrocarbons in the TD–GC S1 fingerprints. Sample maturity, pristine light hydrocarbon (C14−) proportions, organic matter richness, and oil-bearing pore size primarily control the hydrocarbon loss of old shale samples. The higher the proportion of C14− and the lower the abundance of organic matter, the higher the amount of hydrocarbon loss. Finally, S1 restoration coefficient charts for large rock pieces and powdered samples with Ro ranging from 1.00% to 1.42% are provided. It highlights that previous studies have severely underestimated the in situ S1 when using the Rock–Eval method. This research has great implication for estimating in situ hydrocarbon potential using conventional coring samples.

Method development of stir bar sportive extraction coupled with thermal desorption-gas chromatography-mass spectrometry for the analysis of phthalates in Peruvian pisco

In this work, for the first time, a stir bar sorptive extraction (SBSE) coupled with thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS) was developed and validated for the determination of seven phthalates in Peruvian pisco. The phthalate compounds considered were dimethyl phthalate (DMP), diethyl phthalate (DEP), bis(2-ethylhexyl) hexahydrophthalate (BEHP), benzyl butyl phthalate (BBP), di-n-butyl phthalate (DBP), di-isodecyl phthalate (DIDP) and di-isobutyl phthalate (DIBP). The best overall analytical conditions obtained from the optimization were as follow: extraction time of 120 min, size of polydimethylsiloxane (PDMS) twister (20 mm length x 1 mm thickness), NaCl content (20 %) and sample volume (40 mL). The in-house validation of SBSE/TD–GC–MS method was performed taking into account the ISO/IEC 17,025 requirements and EURACHEM/CITAC guideline. Under optimal conditions, very low limits of detection of 1.3–0.21 µg L−1 were obtained. Furthermore, the limits of quantification ranged from 4.2–70 µg L−1, and the correlation coefficients were found to be ≥ 0.991. The method was precise, with relative standard deviations (RSD, %) for inter twister repeatability and the inter day repeatability precisions from 1.1 to 11 and from 6.2 to 15.9, respectively. The pisco samples were analysed with recoveries between 91–124.4%, and DBP, BEHP, and BBP were the most commonly found compounds in the samples. The optimized methodology was also evaluated in terms of green character, and it obtained almost the best AGREE score when it was compared with other previous methods for the analysis of phthalates in alcoholic beverages. Therefore, the SBSE/TD–GC–MS method has proved to be suitable for routine practice because it is simple, less laborious, economical, precise, accurate and green, and it would be applicable for pisco safety regulations.

Determination of fipronil and its three degradates in water using stir bar sorptive extraction–thermal desorption–gas chromatography–tandem mass spectrometry

A method was developed for determination of fipronil (FIP) pesticide and its three major degradates (fipronil desulfinyl, fipronil sulfide, fipronil sulfone) in water at the levels required by the EU Commission in the Decision 2022/1307. The method combines solvent-free stir bar sorptive extraction (SBSE) with thermal desorption–gas chromatography–tandem mass spectrometry (TD–GC–MS/MS). Simple sample processing involves 16 h of stirring a 100 mL water sample with a polydimethylsiloxane-coated sorptive stir bar, followed by TD of the trapped analytes into the GC. The greenness assessment by analytical Eco-Scale approach resulted in classification of the entire analytical method as "an excellent green analysis". The obtained limits of quantification for all FIPs determined in tap, lake, MilliQ water and artificial seawater were in the range of 0.12–0.30 ng L–1. The recoveries ranged between 81.7 and 109% with relative standard deviations from 2.8 to 14%. The results show that the method is suitable for screening and monitoring the studied analytes in selected matrices.

Comparison of Seasonal and Diurnal Concentration Profiles of BVOCs in Coniferous and Deciduous Forests

Ambient atmospheric concentrations of isoprene and monoterpenes were measured at two forest sites, one deciduous and one coniferous, over the year 2022. Both sites in a regional area were sampled monthly between April and September. The samples were taken using sorbent tubes and analyzed with thermal desorption–gas chromatography–mass spectrometry. The highest concentrations were determined in August at both sites. While isoprene is the most abundant compound at the deciduous forest with an average concentration of 5.59 µg m−3 in August, α-pinene and β-pinene dominate throughout the year at the coniferous forest with the highest concentrations also in August (3.44 µg m−3 and 1.51 µg m−3). Because other monoterpenes (camphene, sabinene, 3-carene, p-cymene and limonene) are also emitted in significant amounts, the total concentration measured in the coniferous forest is higher (7.96 µg m−3 in August) in comparison to the deciduous forest (6.08 µg m−3). Regarding the detected monoterpenes in the deciduous forest, sabinene is the dominant monoterpene in addition to α-pinene and is sometimes present in higher (July) or equal (August) concentrations. The seasonal and diurnal concentrations of all monoterpenes correlate very well with each other at both sites. An exception is sabinene with a diurnal concentration profile similar to isoprene.

Aroma Components Analysis and Origin Differentiation of Black Tea Based on ATD-GC-MS and E-Nose

Black tea (Fuyun 6) samples collected from three regions, Youxi, Fu’an, and Datian, were analysed by automatic thermal desorption-gas chromatography–mass spectrometry (ATD-GC–MS) combined with the electronic nose (E-nose) technique to investigate the aroma composition differences between black teas from different regions. The response surface methodology was used to optimize the ATD conditions for extracting the aroma components from the black tea. The results revealed that the optimal conditions for aroma component accumulation from black tea samples included a sample weight of 2.8 g, an adsorption time of 39 min, an adsorption temperature of 75 °C, and a cold trap temperature of −30 °C. The ATD-GC–MS analyses identified a total of 71 aroma components in the black tea samples, of which 31 were utilized to differentiate the origins of the black teas. Additional aroma activity analyses indicated that benzyl alcohol, linalool, hexanal, octanal, and nonanal had odour activity values (OAVs) greater than 10. Additionally, the OAV of decanal exceeded 100, indicating its significant contribution to the aroma profile of Fuyun 6 black tea. The E-nose results demonstrated the ability to differentiate the black tea samples from the three different origins. This study successfully identified the specific aroma substances associated with different tea origins, providing valuable insights into the aroma characteristics of black teas from various regions.

Aromatic profiling of Murraya koenigii leaves by Thermal Desorption Gas chromatography-Mass Spectroscopy (TD-GC-MS)

The germplasms of the Murraya koenigii were collected from Rajahmundry, Annur, Kollihills, Suvashini, Bhavanisagar, Karamadai (KMM5, KMM6, KMM7, KMM8 and KMM14) and the Kerala Agricultural University (KAU). The fresh leaves were analyzed for its volatile organic compounds by Thermal Desorption Gas chromatography–Mass Spectroscopy (TD-GC-MS) to obtain germplasm specific volatile fingerprinting. The correlation between genotypes based on volatile profiles has been analyzed using principal component analysis (PCA) and hierarchical cluster analysis (HCA). A wide variety of volatile compounds identified in the eleven M. koenigii genotypes belongs to terpenoids, monoterpenes, sesquiterpenes, aldehyde, ketones, benzenes, azulenes and other minor compounds. The α-pinene and β-pinene content is high in Suvashini and Bhavanisagar (BSR) genotypes respectively. The monoterpenes such as γ-terpinene, α-myrcene and terpinolene are high in Karamadai variety (KMMK8), whereas caryophyllene content is high in the Rajahmundry. The results of PCA revealed that significant variances with 45.47% (PC 1) and 21.40% (PC 2). In AHC, the α-pinene and chloral hydrate forms the one major cluster. Additionally, α-fenchene and α-caryophyllene has observed forming second major cluster with significant magnitude. The cluster formed by sesquiterpenes are observed high in Annur (65.34%), followed by KMMK8 (48.01%), Kollihills (39.89%) and Rajahmundry (39.27%). The PCA and AHC combined with the fingerprint of TD-GC-MS have discriminated qualitative volatile profile and indicated that major changes VOCs emitted are highly attributed to the genetic factors.

Sterilization and reuse of masks for a standardized exhaled breath collection device by autoclaving

Exhaled breath research has been hindered by a lack of standardization in collection and analysis methodologies. Recently, the Respiration Collector for In Vitro Analysis (ReCIVA) sampling device has illustrated the potential to provide a consistent and convenient method for exhaled breath collection onto adsorbent media. However, the significant costs, compared to exhaled breath bags, associated with the standardized collector is believed to be the reason for limited widespread use by researchers in the exhaled breath field. For example, in addition to the sampling hardware, a single-use disposable silicon mask affixed with a filter is required for each exhaled breath collection. To reduce the financial burden, streamline device upkeep, reduce waste material, and ease the logistical burden associated with the single use masks, it is hypothesized that the consumable masks and filters could be sterilized by autoclaving for reuse. The masks were contaminated, autoclaved, and then tested for any surviving pathogens with spore strip standards and by measuring the optical density of cultures. The compound background collected when using the ReCIVA with new masks was compared to that collected with repeatedly autoclaved masks via thermal desorption gas chromatography mass spectrometry (TD-GC-MS). The capacity to block particulate matter of new filters was tested against that of autoclaved filters by introducing an aerosol and comparing pre-filter and post-filter particle counts. Finally, breath samplings were conducted with new masks and autoclaved masks to test for changes in measurements by TD-GC-MS of exogenous and endogenous compounds. The data illustrate the autoclave cycle sterilizes masks spiked with saliva to background levels (p = 0.2527). The results indicate that background levels of siloxane compounds are increased as masks are repetitively autoclaved. The data show that mask filters have significant breakthrough of 1 μm particles after five repetitive autoclaving cycles compared to new filters (p = 0.0219). Finally, exhaled breath results utilizing a peppermint ingestion protocol indicate two compounds associated with peppermint, menthone and 1-Methyl-4-(1-methylethyl)-cyclohexanol, and an endogenous exhaled breath compound, isoprene, show no significant difference if sampled with a new mask or a mask autoclaved five times (p > 0.1063). Collectively, the data indicate that ReCIVA masks and filters can be sterilized via autoclave and reused. The results suggest ReCIVA mask and filter reuse should be limited to three times to limit potentially problematic background contaminants and filter dysfunction.

Formation of secondary organic aerosols from the ozonolysis of Cis-3-hexenyl acetate: The effect of acidic seed particles and SO2

Cis-3-hexenyl acetate (cis-HXAC) is a major green leaf volatile released by plants, and its atmospheric degradation by O3 may play an important role in the formation of secondary organic aerosol (SOA). In this study, indoor smog chamber experiments were carried out to investigate the effects of particle acidity and SO2 on the formation of secondary organic aerosols (SOA) from the ozonolysis of cis-HXAC. Particle formation and growth were characterized using a scanning mobility particle sizer, and the chemical composition of the particles was analyzed by thermal-desorption gas chromatography mass spectrometry, with the main products and reaction pathways of cis-HXAC ozonolysis being identified. The results revealed that acidic seed particles inhibited SOA formation compared to non-acidic seed particles, and SO2 was considered to play a catalytic role in cis-HXAC ozonolysis, showing a good positive correlation with SOA generation. The results of this study provide new information on the ozonolysis of cis-HXAC, confirm the important role of anthropogenic pollution, and help to further elucidate the potential of green leaf volatiles ozonolysis to generate SOA under complex pollution conditions.

Application of Direct Thermal Desorption-Gas Chromatography-Mass Spectrometry for Determination of Volatile and Semi-Volatile Organosulfur Compounds in Onions: A Novel Analytical Approach.

The population is now more aware of their diets due to the connection between food and general health. Onions (Allium cepa L.), common vegetables that are minimally processed and grown locally, are known for their health-promoting properties. The organosulfur compounds present in onions have powerful antioxidant properties and may decrease the likelihood of developing certain disorders. It is vital to employ an optimum approach with the best qualities for studying the target compounds to undertake a thorough analysis of these compounds. In this study, the use of a direct thermal desorption-gas chromatography-mass spectrometry method with a Box-Behnken design and multi-response optimization is proposed. Direct thermal desorption is an environmentally friendly technique that eliminates the use of solvents and requires no prior preparation of the sample. To the author's knowledge, this methodology has not been previously used to study the organosulfur compounds in onions. Likewise, the optimal conditions for pre-extraction and post-analysis of organosulfur compounds were as follows: 46 mg of onion in the tube, a desorption heat of 205 °C for 960 s, and a trap heat of 267 °C for 180 s. The repeatability and intermediate precision of the method were evaluated by conducting 27 tests over three consecutive days. The results obtained for all compounds studied revealed CV values ranging from 1.8% to 9.9%. The major compound reported in onions was 2,4-dimethyl-thiophene, representing 19.4% of the total area of sulfur compounds. The propanethial S-oxide, the principal compound responsible for the tear factor, accounted for 4.5% of the total area.