Thermal Desorption-gas Chromatography-mass Spectrometry Research Articles

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.

VOC data-driven evaluation of vehicle cabin odor: from ANN to CNN-BiLSTM.

Emissions of volatile organic compounds (VOCs) in vehicles represent a significant problem, causing unpleasant odors. To mitigate VOCs and odors in vehicles, it is critical to choose interior parts with low odor and VOC emissions. However, prevailing odor evaluation methods are subjective, costly, and potentially harmful to the health of evaluators. In this study, we analyzed 139 automotive interior parts and 92 vehicles, establishing a cost-effective, data-driven method for odor evaluation. The contents of benzene, toluene, ethylbenzene, xylene, styrene, formaldehyde, acetaldehyde, acrolein, and total volatile organic compounds (TVOC) were detected by thermal desorption gas chromatography-mass spectrometry (TD-GC/MS) and high-performance liquid chromatography with an ultraviolet detector (HPLC-UV). Professional odor evaluators assessed the odors, identifying intensity levels from 2.0 to 4.5 in interior parts and 2.5 to 3.5 in whole vehicles. Leveraging this data, we applied four supervised learning algorithms to develop predictive models for the odor intensity of both interior parts and entire vehicles. During model training, we implemented early stopping techniques for the artificial neural network (ANN) and convolutional neural network-bidirectional long short-term memory (CNN-BiLSTM) models, while optimizing the support vector machine (SVM) and extreme gradient boosting (XGBoost) models using the GridSearch algorithm. The evaluation results reveal that the CNN-BiLSTM model performs the best, achieving an average accuracy of 89% for unknown samples within an odor intensity level of 0.5. The root mean square error (RMSE) is 0.24, and the mean absolute error (MAE) is 0.08. The model also underwent a sevenfold cross-validation, achieving an accuracy of 83.43%. Additionally, we employed SHapley Additive exPlanations (SHAP) for the interpretative analysis of the model, which confirmed the consistency of each VOC's odor contribution with human olfactory rules. By predicting odors based on VOCs through supervised learning, this study reduces the costs and enhances the efficiency and applicability of odor assessment across various vehicle interiors.

Unraveling the Enantiomeric Distribution of Glycosidically Bound Linalool in Teas (Camellia sinensis) and Their Acidolysis Characteristics and Pyrolysis Mechanism.

Glycosidically bound linalool plays important roles in the formation of excellent tea flavor, while their enantiomeric distribution in teas and the actual transformations with free linalool are still unclear. In this study, a novel chiral ultrahigh performance liquid chromatography-mass spectrometry/mass spectrometry approach to directly analyze linalyl-β-primeveroside and linalyl-β-d-glucopyranoside enantiomers in teas was established and then applied in 30 tea samples. A close transformation relationship existed between the two states of linalool for their consistent dominant configurations (most S-form) and corresponding distribution trend in most teas (r up to 0.81). The acidolysis characterization indicated that free linalool might be slowly released from linalyl-β-primeveroside with stable enantiomeric ratios during long-term withering of white tea in a weakly acidic environment, along with other isomerized products, e.g., geraniol, nerol, α-terpineol, etc. Furthermore, a novel online thermal desorption-gas chromatography-mass spectrometry approach was established to simulate the pyrolysis releasing of linalyl-β-primeveroside during tea processing. Interestingly, free linalool was not the selected pyrolysis product of linalyl-β-primeveroside but rather trans/cis-2,6-dimethyl-2,6-octadiene during the high-fire roasting or baking step of oolong and green teas. The identification of above high-fire chemical marks presented great potential to scientifically evaluate the proper thermal conditions in the practical production of tea.

Measuring aliphatic hydrocarbons in sediments by direct thermal desorption-gas chromatography-mass spectrometry: Matrix effects and quantification challenges

Direct sample introduction thermal desorption (TD) coupled to GC–MS was investigated for the analysis of paraffinic hydrocarbons (HCs) from polluted sediments. TD-GC–MS is sometimes used for analysing paraffinic HCs from atmospheric particles but rarely for their direct desorption from sediments. So, the new TD methodology, applied to sediments, required development, optimization and validation. A definitive screening experimental design was performed to discriminate the critical factors on TD efficiency, from model sediments containing various organic matter (OM) amounts. Low molecular weight HCs had extraction behaviours markedly different from high molecular ones (HMW-HCs), but a compromise was found using very few sediment amount (5 mg), high temperature rate (55 °C min−1) and final temperature (350 °C). Linear HCs (n-C10 to n-C40) could be quantified using the matrix-matched calibration method, with very low detection limits (3.8–13.4 ng). The amount of the overall paraffinic alkanes was also determined as a sum of unresolved components between predefined equivalent carbon ranges. The developed solventless methodology was compared to an optimized solvent microwave assisted extraction (MAE). Matrix effects could be higher for TD compared to MAE but it depended on sediment matrix. When matrix effect was strong, particularly on HMW-HCs signal depletion, a dilution with pure non-porous sand was favourable for accurate quantification. The sum of resolved and unresolved HCs gave comparable results between MAE and TD extractions, with an exception of alkanes greater than C30 which were less quantitatively extracted via TD. However, TD-GC–MS was more sensitive than MAE-GC–MS. So TD-GC–MS is useful for analyzing sediments containing a great range of paraffinic HCs (C9-C34) and it has the advantages of being fully automated, with few sample preparation and operator intervention, using very low amounts of solvent, and generating few wastes.

Identification of exhaled volatile organic compounds that characterize asthma phenotypes: A J-VOCSA study

BackgroundAsthma is characterized by phenotypes of different clinical, demographic, and pathological characteristics. Identifying the profile of exhaled volatile organic compounds (VOCs) in asthma phenotypes may facilitate establishing biomarkers and understanding asthma background pathogenesis. This study aimed to identify exhaled VOCs that characterize severe asthma phenotypes among patients with asthma. MethodsThis was a multicenter cross-sectional study of patients with severe asthma in Japan. Clinical data were obtained from medical records, and questionnaires were collected. Exhaled breath was sampled and subjected to thermal desorption gas chromatography-mass spectrometry (GC/MS). ResultsUsing the decision tree established in the previous nationwide asthma cohort study, 245 patients with asthma were divided into five phenotypes and subjected to exhaled VOC analysis with 50 healthy controls (HCs). GC/MS detected 243 VOCs in exhaled breath samples, and 142 frequently detected VOCs (50% of all samples) were used for statistical analyses. Cluster analysis assigning the groups with similar VOC profile patterns showed the highest similarities between phenotypes 3 and 4 (early-onset asthma phenotypes), followed by the similarities between phenotypes 1 and 2 (late-onset asthma phenotypes). Comparisons between phenotypes 1–5 and HC revealed 19 VOCs, in which only methanesulfonic anhydride showed p < 0.05 adjusted by false discovery rate (FDR). Comparison of these phenotypes yielded several VOCs showing different trends (p < 0.05); however, no VOCs showed p < 0.05 adjusted by FDR. ConclusionsExhaled VOC profiles may be useful for distinguishing asthma and asthma phenotypes; however, these findings need to be validated, and their pathological roles should be clarified.

Detection of Clostridioides difficile infection by assessment of exhaled breath volatile organic compounds

Clostridioides difficile infection (CDI) is the leading cause of hospital-acquired infective diarrhea. Current methods for diagnosing CDI have limitations; enzyme immunoassays for toxin have low sensitivity and Clostridioides difficile polymerase chain reaction cannot differentiate infection from colonization. An ideal diagnostic test that incorporates microbial factors, host factors, and host-microbe interaction might characterize true infection. Assessing volatile organic compounds (VOCs) in exhaled breath may be a useful test for identifying CDI. To identify a wide selection of VOCs in exhaled breath, we used thermal desorption-gas chromatography-mass spectrometry to study breath samples from 17 patients with CDI. Age- and sex-matched patients with diarrhea and negative C.difficile testing (no CDI) were used as controls. Of the 65 VOCs tested, 9 were used to build a quadratic discriminant model that showed a final cross-validated accuracy of 74%, a sensitivity of 71%, a specificity of 76%, and a receiver operating characteristic area under the curve of 0.72. If these findings are proven by larger studies, breath VOC analysis may be a helpful adjunctive diagnostic test for CDI.

Impacts on Urban VOCs and PM2.5 during a Wildfire Episode

This study focuses on the impact of wildfire smoke emissions on regional, urban air quality during a wildfire event. We measured volatile organic compounds (VOCs) and fine particulate matter (PM2.5) in the San Francisco Bay Area to assess air quality during a wildfire event and compared them to those in a later non-wildfire period. VOCs were collected using thermal desorption tubes and quantified using thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Elevated concentrations of VOCs such as 1,3,5-trimethylbenzene (0.33 ± 0.01 µg/m3), benzene (1.03 ± 0.02 µg/m3), toluene (2.15 ± 0.04 µg/m3), ethylbenzene (0.60 ± 0.02 µg/m3), and m, p-xylene (0.77 ± 0.07 µg/m3) were observed in the wildfire event. Compared with that in the non-wildfire season, the toluene concentration during the wildfire period was more than three times the non-wildfire concentration. Similarly, the benzene concentration during the wildfire was almost four times higher, and that of p, m-xylene was three times higher. The higher wildfire levels were statistically significant for sec-butylbenzene, 1,2,4-trimethylbenzene, n-propylbenzene, o-xylene, styrene, 1,3,5-trimethylbenzene, benzene, toluene, ethylbenzene, and p,m-xylene (p &lt; 0.00001). These higher VOC levels compared with those for the non-fire period may potentially pose a public health concern. Open face passive sampler (OFPS)-collected PM was analyzed using scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) and revealed organic carbon tar balls. The highest daily average beta-attenuation-monitored PM2.5 during the fire period was 200 µg/m3 and the highest hourly average was 270 µg/m3. Monitoring gas phase species in addition to PM concentrations is useful during wildfire season to inform public health guidance.

Investigation on the source of VOCs emission from indoor construction materials using electronic sensors and TD-GC-MS

Indoor air quality (IAQ) is critical to the health and wellbeing of people. As the majority of people spend greater amounts of time indoors, either in office spaces or households, the level of air pollutants in such environments is critical. Building materials and furniture are known sources of air pollutants such as Volatile Organic Compounds (VOCs) and may be associated with discomfort, detrimental health of the occupants, etc. In this study, the VOCs found in a brand new office complex were monitored over a period of 6 months, with an emphasis on monitoring and quantifying harmful VOCs and identifying their emission source. Air samples were taken from a closed, unoccupied office space on a weekly basis and analysed using Thermal Desorption-Gas Chromatography-Mass Spectrometry (TD-GC-MS), while continuous monitoring of the air quality was performed using two commercially available IAQ sensors. To identify the source of the emitted VOCs, pieces of all construction material that were used in the office, including flooring, finished wall material, and adhesive glues, were removed, and placed in air-tight glass containers prior to analysis confirming that the source of VOCs is indeed the flooring. Identified compounds included mainly material origin VOCs such as BTEX (benzene, toluene, ethylbenzene, xylene) and styrene, but also common VOCs such as acetone and propan-2-ol. Of significant importance was the concentration of toluene that was found to be the most abundant VOC in both the flooring material and the indoor air.

Appropriate control measure design by rapidly identifying risk areas of volatile organic compounds during the remediation excavation at an organic contaminated site.

Many organic contaminated sites require on-site remediation; excavation remediation processes can release many volatile organic compounds (VOCs) which are key atmospheric pollutants. It is therefore important to rapidly identify VOCs during excavation and map their risk areas for human health protection. In this study, we developed a rapid analysis and assessment method, aiming to and reveal the real-time distribution of VOCs, evaluate their human health risks by quantitative models, and design appropriate control measures. Through on-site diagonal distribution sampling and analysis, VOCs concentration showed a decreasing trend within 5 m from the excavation point and then increased after 5 m with the increase in distance from the excavation point (p < 0.05). The concentrations of VOCs near the dominant wind direction were higher than the concentrations of surrounding pollutants. In contrast with conventional solid-phase adsorption (SPA) and thermal desorption gas chromatography-mass spectrometry (TD-GC/MS) methods for determining the composition and concentration of VOCs, the rapid measurement of VOCs by photo-ionization detector (PID) fitted well with the chemical analysis and modeling assessment of cancer/non-cancer risk. The targeting area was assessed as mild-risk (PID < 10ppm), moderate-risk (PID from 10 to 40ppm), and heavy-risk (PID > 40ppm) areas. Similarly, the human health risks also decreased gradually with the distance from the excavation point, with the main risk area located in the dominant wind direction. The results of rapid PID assessment were comparable to conventional risk evaluation, demonstrating its feasibility in rapidly identifying VOCs releases and assessing the human health risks. This study also suggested appropriate control measures that are important guidance for personal protection during the remediation excavation process.

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.

Chemical characterization, source identification and potential health effects of PM2.5-bound non-polar organic compounds over a COALESCE network site - Bhopal, India

Year-long (2019) measurements of carbonaceous aerosols were performed at Bhopal, a regionally representative site as a part of the COALESCE (Carbonaceous Aerosol Emissions, Source apportionment and Climate Impacts) campaign. Aerosol-associated non-polar organic compounds (NPOCs) were analysed using thermal desorption (TD) Gas chromatography/Mass spectrometry (TD-GC/MS). The annual average of the total organic carbon (OC), elemental carbon (EC), and analysed PAHs (Polycyclic Aromatic Hydrocarbons), and n-alkanes were, 9.74 ± 9.47 μg m−3, 2.13 ± 3.12 μg m−3, 10.43 ± 5.49 ng m−3, and 114.93 ± 49.24 ng m−3, respectively. PAHs diagnostic ratios suggested emissions from petroleum, grass, wood, and coal combustion. Combustion derived PAHs (CombPAHs) accounted for 72.5 % of the total measured PAHs. During wintertime, based on Pyr/BaP ratio (∼0.6), gasoline exhaust emissions were higher compared to diesel exhaust emissions. The weak correlations between PAHs and meteorological parameters suggested that variations in PAH levels are primarily driven by alterations in emission sources. Total PAHs were correlated moderately with BrC (r2 = 0.60). The estimated lifetime lung cancer risk (LLCR) values on exposure to 16 USEPA priority PAHs (5 × 10−5) demonstrated that PAH levels in this region pose moderate health risks. Given observations from only campaign mode short-term measurements of NPOCs over India, this work provides a more comprehensive understanding of the concentrations, seasonal variations, and sources of n-alkanes and health risk associated with particle bound PAHs over the data-poor central Indian region.

Metabolic insights at the finish line: deciphering physiological changes in ultramarathon runners through breath VOC analysis

Exhaustive exercise can induce unique physiological responses in the lungs and other parts of the human body. The volatile organic compounds (VOCs) in exhaled breath are ideal for studying the effects of exhaustive exercise on the lungs due to the proximity of the breath matrix to the respiratory tract. As breath VOCs can originate from the bloodstream, changes in abundance should also indicate broader physiological effects of exhaustive exercise on the body. Currently, there is limited published data on the effects of exhaustive exercise on breath VOCs. Breath has great potential for biomarker analysis as it can be collected non-invasively, and capture real-time metabolic changes to better understand the effects of exhaustive exercise. In this study, we collected breath samples from a small group of elite runners participating in the 2019 Ultra-Trail du Mont Blanc ultra-marathon. The final analysis included matched paired samples collected before and after the race from 24 subjects. All 48 samples were analyzed using the Breath Biopsy Platform with GC-Orbitrap™ via thermal desorption gas chromatography-mass spectrometry. The Wilcoxon signed-rank test was used to determine whether VOC abundances differed between pre- and post-race breath samples (adjusted P-value < .05). We identified a total of 793 VOCs in the breath samples of elite runners. Of these, 63 showed significant differences between pre- and post-race samples after correction for multiple testing (12 decreased, 51 increased). The specific VOCs identified suggest the involvement of fatty acid oxidation, inflammation, and possible altered gut microbiome activity in response to exhaustive exercise. This study demonstrates significant changes in VOC abundance resulting from exhaustive exercise. Further investigation of VOC changes along with other physiological measurements can help improve our understanding of the effect of exhaustive exercise on the body and subsequent differences in VOCs in exhaled breath.

Advanced micro-extraction techniques (SPME, HiSorb) for the determination of goat cheese whey wastewater VOCs

HiSorb and solid-phase microextraction (SPME), two environmentally friendly micro-extraction techniques based on the same fundamental principles, were evaluated for their extraction efficiency of volatile organic compounds (VOCs) from goat cheese whey wastewater. For this purpose, a sample preparation method based on the headspace-HiSorb technique was developed and evaluated for its efficiency in terms of the amount of extracted compounds and reproducibility of results. Thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) and GC/MS analytical methods were used to perform the wastewater analysis, respectively. The experimental parameters of HiSorb were evaluated in terms of probe coating, extraction time, stirring speed, sample volume, extraction temperature and salt addition. Under optimal extraction conditions, it was observed that the use of the divinylbenzene/carbon wide range/polydimethylsiloxane (DVB/CWR/PDMS) triple coating for HiSorb and DVB/Carboxen (CAR)/PDMS for SPME, was best suited to extract a broader range of VOCs with higher peak intensities. A total of 34 VOCs were extracted and determined with the DVB/CWR/PDMS HiSorb probe, while only 23 VOCs were determined with the conventional DVB/CAR/PDMS SPME fiber. The DVB/CWR/PDMS HiSorb probe has a higher adsorbent capacity which results in a higher sensitivity for VOCs compared to the DVB/CAR/PDMS SPME fiber. Furthermore, the HiSorb technique exhibits better reproducibility, as indicated by the lower relative standard deviation (RSD) of 3.7% compared to 7.1% for SPME. Therefore, the HiSorb technique is an effective method for detecting VOCs in complex matrices, such as wastewater.

Breath Analysis for Lung Cancer Early Detection-A Clinical Study.

This clinical study presents a comprehensive investigation into the utility of breath analysis as a non-invasive method for the early detection of lung cancer. The study enrolled 14 lung cancer patients, 14 non-lung cancer controls with diverse medical conditions, and 3 tuberculosis (TB) patients for biomarker discovery. Matching criteria including age, gender, smoking history, and comorbidities were strictly followed to ensure reliable comparisons. A systematic breath sampling protocol utilizing a BIO-VOC sampler was employed, followed by VOC analysis using Thermal Desorption-Gas Chromatography-Mass Spectrometry (TD-GC/MS). The resulting VOC profiles were subjected to stringent statistical analysis, including Orthogonal Projections to Latent Structures-Discriminant Analysis (OPLS-DA), Kruskal-Wallis test, and Receiver Operating Characteristic (ROC) analysis. Notably, 13 VOCs exhibited statistically significant differences between lung cancer patients and controls. The combination of eight VOCs (hexanal, heptanal, octanal, benzaldehyde, undecane, phenylacetaldehyde, decanal, and benzoic acid) demonstrated substantial discriminatory power with an area under the curve (AUC) of 0.85, a sensitivity of 82%, and a specificity of 76% in the discovery set. Validation in an independent cohort yielded an AUC of 0.78, a sensitivity of 78%, and a specificity of 64%. Further analysis revealed that elevated aldehyde levels in lung cancer patients' breath could be attributed to overactivated Alcohol Dehydrogenase (ADH) pathways in cancerous tissues. Addressing methodological challenges, this study employed a matching of physiological and pathological confounders, controlled room air samples, and standardized breath sampling techniques. Despite the limitations, this study's findings emphasize the potential of breath analysis as a diagnostic tool for lung cancer and suggest its utility in differentiating tuberculosis from lung cancer. However, further research and validation are warranted for the translation of these findings into clinical practice.

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.

Improvement of the quantitativeness of the thermal desorption-GC/MS method and development of polystyrene certified reference material for the quantification of decabromodiphenyl ether (BDE 209) by using isotope dilution mass spectrometry.

A polystyrene (PS) certified reference material (CRM) for the analysis of decabromodiphenyl ether (BDE 209) was issued. PS disk was prepared by injection molding of the mixture of versine PS and BDE 209. The certification of the PS CRM was conducted by two analytical methods with different sample preparation methods using isotope dilution mass spectrometry (IDMS). The certified value, wCRM, was 978 mg/kg, and this value coincided with the regulation value of BDE 209 in the Restriction of Hazardous Substances directive (1000 mg/kg). The uncertainties related to certification, uwmean, inhomogeneity, uhom, and long- and short-term instability, usts and ults, respectively, were evaluated based on the mass fraction of BDE 209. The uwmean, uhom, usts, and ults were 0.0265, 0.0046, 0.0061, and 0.0099 (relative), respectively, and the expanded uncertainty for this CRM was determined as 57 mg/kg (coverage factor is 2). Additionally, the quantitative capability of the thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was evaluated. In TD-GC/MS, the analytical values of the developed CRM obtained by the external and internal standard methods with matrix-free calibrants were out of the range of the wCRM (almost 10% larger or smaller), whereas those with matrix-matched calibrants agreed with the wCRM. In contrast to these results, the analytical values obtained by TD-GC/MS using IDMS were consistent with the wCRM no matter if matrix-free or matrix-matched calibrants were used. These results indicated that, for quantification of BDE 209 in PS, the trueness and precision of TD-GC/MS can be enhanced by applying IDMS without matrix-matched calibrants.

Air monitoring with passive samplers for volatile organic compounds in atmospheres close to petrochemical industrial areas. The case study of Tarragona (2019–2021)

This study reports a three-year monitoring campaign of 62 volatile organic compounds (VOCs) of increasing concern in urban atmospheres near petrochemical industrial areas. A total of 770 air samples were taken during the sampling campaigns conducted monthly between January 2019 and December 2021. The analytical method applied involved a 14-day passive sampling in Carbopack X tubes followed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). To gain insight into the correlations between VOCs, multivariate data analysis was used to assess the similarities and differences between datasets. Special attention was paid to benzene, 1,3-butadiene and 1,2-dichloroethane, because they are carcinogenic and are produced, handled and stored in the petrochemical industrial areas studied. The compounds found in the highest concentrations were alkanes, which were 21–66% of the total. Aromatic hydrocarbons and solvents were also detected at all the sampling sites, with BTEX and ethanol as the most prevalent compounds. Various concentration peaks of up to 4.8 μg m−3 for benzene and up to 4.0 μg m−3 for 1,3-butadiene were detected during the monitoring campaigns performed. Nevertheless, the average concentrations of these two compounds were always below the values set in the current air quality regulations, with maximum values of 1.3 μg m−3 for benzene and 1.5 μg m−3 for 1,3-butadiene near the North industrial park of Tarragona. Multivariate analysis results revealed four different patterns at the reference sites and discriminated between the sampling sites close to the petrochemical areas evaluated. The autumn-winter months, with thermal inversion phenomena and prevailing north and north-westerly winds, were the ones with the highest concentration levels of VOCs.

Identification of tropical wood species in paper: a new chemotaxonomic method based on extractives

Abstract The European Deforestation Regulation 2023/1115 (EUDR) prohibits trading of wood and wood products obtained from illegal logging on the EU market. While the identification of solid wood via anatomy, chemistry and genetics has already been established, there is a lack of identification methods for pulp and paper that complement anatomy. This publication presents a newly developed chemotaxonomic method for identifying mixed tropical hardwood (MTH) species in pulp and paper products based on their extractives analyzed with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). The measured data was processed and compared to identify marker substances and was then merged into a fingerprint database for identifying MTH species in paper of unknown composition. As database references, fully bleached kraft pulps were produced from 38 anatomically identified wood samples and then cryo-ball milled and extracted successively with n-hexane and acetone. The results show that the remaining wood extractives generated from bleached pulps are specific enough to find chemical relevant marker substances to detect MTH species. As chemical composition and anatomy are independent characteristics of wood, this paper makes a completely independent method available, which potentially improves the screening for Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES) protected species.

Catalytic oxidation of toluene over Co3O4-CeO2 bimetal oxides derived from Ce-based MOF

A series of Co–Ce oxide catalysts with different molar ratios were prepared by impregnation and pyrolysis using a Co-loaded Ce-based metal–organic framework as a precursor. Physicochemical properties of the catalysts were characterized by N2 adsorption–desorption measurements, X-ray diffraction, H2 temperature-programmed reduction, Raman analysis, X-ray photoelectron spectroscopy, transmission electron microscopy, thermal desorption-gas chromatography-mass spectrometry and scanning electron microscopy. Toluene was selected as a reference to evaluate catalytic performance. Results show that the catalyst prepared at a Co/(Ce+Co) molar ratio of 0.3 exhibits excellent catalytic activity in the catalytic oxidation of toluene. The temperature at 90 % conversion of toluene (T90) is 262 °C which is significantly lower than the catalyst prepared by the traditional preparation method. The specific surface area is not the main factor affecting the reaction. The high activity is due to the better low temperature reducibility, abundant lattice defects, more active oxygen species, higher surface Ce3+ species (oxygen vacancies). What's more, 30Co-Ce has superior stability at different conversion rates and tolerance in the presence of water vapor. The results stated above indicate that the surface properties of the Co-Ce catalysts significantly affected the toluene combustion reaction.