Desorption Gas Chromatography Mass Spectrometry Research Articles

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.

Evaluation of highly adsorptive Guefoams (multifunctional guest-containing foams) as a potential sorbent for determination  of volatile organic compounds (VOCs) by means of thermal desorption

The present work delves into the feasibility of employing a novel structured sorbent referred to as GFAD (Guefoam Adsorption Device) for the determination of volatile organic compounds (VOCs) in liquid samples. The chosen method has been static headspace sorptive extraction-thermal desorption gas chromatography mass spectrometry (HSSE-TD-GC–MS). The GFAD comprises an aluminum cellular material with a distinct replication structure and a solid guest phase consisting of activated carbon particles dispersed within the cavities of the cellular aluminum. The extensive specific surface area, robustness, and exceptional thermal conductivity of this pioneering material offer distinct advantages over commercially available polydimethylsiloxane-based Twister® devices. Therefore, the trapping efficiency for volatile organic compounds is enhanced, and it is possible to perform the analysis of concentrated samples. According to computational simulations, it has been demonstrated that GFAD has a high heat conductivity. As a result, the desorption efficiency is improved, and minimal temperature gradients are generated throughout the GFAD during the heating process. Besides, the energy consumption is significantly lowered, thus aligning with environmentally conscientious and sustainable analytical practices.The experimental results give a proof of the suitability of the GFAD for determining gaseous compounds in liquid samples through HSSE-TD-GC–MS. For volatile species, the new material provides higher peak areas and lower limits of detection than a commercially available Twister® device. Furthermore, the GFAD is reusable, its adsorbing properties remaining unchanged during, at least, 100 consecutive analyses. In addition, unlike to the Twister®, no intense siloxane peaks are observed in the chromatograms obtained with the GFAD. The feasibility of qualitative and semi-quantitative analysis with the new accessory has been demonstrated with both standards and a cereal bioethanol real sample.Graphical abstract

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.

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.

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.

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.

Simultaneous screening of 33 restricted substances in polymer materials using pyrolysis/thermal desorption gas chromatography-mass spectrometry.

The purpose of this study was to offer a quick and efficient method to screen for multiple restricted additives in polymer materials. A solvent-free pyrolysis gas chromatography-mass spectrometry method was developed to simultaneously screen 33 restricted substances, comprising 7 phthalates, 15 bromine flame retardants, 4 phosphorus flame retardants, 4 ultraviolet stabilizers, and 3 bisphenols. The pyrolysis technique and temperatures affecting additive desorption were studied. Under optimized conditions, the instrument sensitivity was confirmed using in-house reference materials at concentrations of 100mg/kg and 300mg/kg. The linear range was between 100 and 1000mg/kg in 26 compounds, and in the other compounds it was between 300 and 1000mg/kg. In this study, in-house reference materials, certified reference materials, and proficiency testing samples were used for method verification. The relative standard deviation of this method was less than 15%, and recoveries ranged from 75.9 to 107.1% for most of the compounds, with a few exceeding 120%. Furthermore, the screening method was verified with 20 plastic products used in daily life and 170 recycled plastic particle samples from imports. The experimental results showed that phthalates were the main additives in plastic products, and among 170 recycled plastic particle samples, 14 samples were found to contain restricted additives. The main additives in recycled plastics were bis(2-ethylhexyl) phthalate, di-iso-nonyl phthalate, hexabromocyclododecane, and 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether at concentrations between 374 and 34785mg/kg, except for some results that exceeded the maximum measured value of the instrument. Compared with traditional methods, an important advantage is that this method simultaneously tests for 33 additives without sample pretreatment, covering a variety of additives limited by laws and regulations, and therefore can provide more comprehensive and thorough inspections.

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.

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.

Inoculation with black soldier fly larvae alters the microbiome and volatile organic compound profile of decomposing food waste

The black soldier fly (BSF; Hermetia illucens) is used in sustainable processing of many types of organic waste. However, organic waste being decomposed by BSF produces strong odors, hindering more widespread application. The odor components and how they are produced have yet to be characterized. We found that digestion of food waste by BSF significantly alters the microbial flora, based on metagenomic analyses, and the odor components generated, as shown by thermal desorption gas chromatography mass spectrometry analysis. Inoculation with BSF significantly decreased production of volatile organic sulfur compounds (dimethyl disulfide and dimethyl trisulfide), which are known to be released during methionine and cysteine metabolism by Lactobacillus and Enterococcus bacteria. BSF inoculation significantly changed the abundance of Lactobacillus and Enterococcus and decreased microbial diversity overall. These findings may help in optimizing use of BSF for deodorization of composting food waste.

Evaluation of VOCs from fungal strains, building insulation materials and indoor air by solid phase microextraction arrow, thermal desorption–gas chromatography-mass spectrometry and machine learning approaches

Solid phase microextraction Arrow and thermal desorption–gas chromatography–mass spectrometry allowed the collection and evaluation of volatile organic compounds (VOCs) emitted by fungal cultures from building insulation materials and in indoor air. Principal component analysis, linear discriminant analysis and supported vector machine were used for visualization and statistical assessment of differences between samples. In addition, a screening tool based on the soft independent modelling of class analogies (SIMCA) was developed for identification of fungal contamination of indoor air. Ten different fungal strains, incubated under ambient and microaerophilic conditions, were analyzed for time period ranging from 5 to 29 days after inoculation resulting in a total of 140 samples. In addition, the effect of additives on the fungal growing media was studied. The total number of compounds and concentration values were used for the evaluation of the results. Clear differences were observed for VOC profiles emitted by different fungal strains by exploiting long chain alcohols (3-octanol, 1-hexanol and 2-octen-1-ol) and sesquiterpenes (farnesene, cuprene). The analysis of glass-wool and cellulose based building insulation materials (3 samples) gave clear differences, mainly for oxygenated compounds (ethyl acetate and hexanal) and benzenoids (benzaldehyde). Moreover, the comparison of indoor air and insulation materials collected from a house with fungal indoor air problems indicated that 42% of the VOCs were found in both samples. The analysis of 52 indoor air samples demonstrated clear differences in their VOC profiles, especially for hydrocarbons, and between control (44 samples) and indoor air problem houses (8 samples). Finally, the SIMCA model enabled to recognize differences between control and fungi contaminated houses with a prediction capacity over 84%.

Neutral Per- and Polyfluoroalkyl Substances in In Situ Landfill Gas by Thermal Desorption–Gas Chromatography–Mass Spectrometry

Landfills receive over half of the municipal solid waste generated in the U.S. Wastes in landfills include consumer products, some of which are known to contain of per- and polyfluoroalkyl substances (PFAS). Although the occurrence of nonvolatile (ionic) PFAS in landfill leachate is established and volatile (neutral) PFAS are found in ambient air near landfills, the neutral PFAS composition of landfill gas (LFG) collected in situ from landfills is unknown. A thermal desorption–gas chromatography–mass spectrometry (TD-GC-MS) sampling and analysis approach was optimized for the quantification of 25 target neutral PFAS, including fluorotelomer alcohols (FTOHs) and five other PFAS classes, in landfill from a gas well or header pipe. Optimized LFG sampling parameters included the use of an explosion-proof pump, a 100 mL/min flow rate through a sorbent tube, and a LFG volume of 350 mL. The method was applied to LFG samples collected from southeastern U.S. landfills for method demonstration. Fluorotelomer alcohols were found at the highest levels, ranging from 830,000–4,900,000 pg/m3, which is approximately 2 orders of magnitude greater than FTOH levels reported in ambient air collected near landfills.

Multi-Analytical Approach to Characterize the Degradation of Different Types of Microplastics: Identification and Quantification of Released Organic Compounds.

Microplastics and nanoplastics represent one of the major environmental issues nowadays due to their ubiquitous presence on Earth, and their high potential danger for living systems, ecosystems, and human life. The formation of both microplastics and nanoplastics strongly depends on both the type of pristine materials and the degradation processes related to biological and/or abiotic conditions. The aim of this study is to investigate the effect of two of the most relevant abiotic parameters, namely temperature and light, taken under direct control by using a Solar box, on five types of reference polymers: high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET). A multi-analytical approach was adopted to investigate in detail the first steps of plastics degradation. Samples of plastic materials at different degradation times were analyzed by means of 1H NMR spectroscopy and thermal desorption gas chromatography mass spectrometry (TD-GC-MS) technique. Several minor molecular species released during degradation were consistently identified by both techniques thus providing a comprehensive view of the various degradation products of these five types of microplastics.

Investigation of an individual with background levels of exhaled isoprene: a case study

Isoprene is one of the most abundant and most frequently evaluated volatile organic compounds in exhaled breath. Recently, several individuals with background levels of exhaled isoprene have been identified. Here, case study data are provided for an individual, identified from a previous study, with this low prevalence phenotype. It is hypothesized that the individual will illustrate low levels of exhaled isoprene at rest and during exercise. At rest, the subject (7.1 ppb) shows background (μ = 14.2 ± 7.0 ppb) levels of exhaled isoprene while the control group illustrates significantly higher quantities (μ = 266.2 ± 72.3 ppb) via proton transfer reaction mass spectrometry (PTR-MS). The result, background levels of isoprene at rest, is verified by thermal desorption gas chromatography mass spectrometry (TD-GC-MS) collections with the individual showing −3.6 ppb exhaled isoprene while the room background contained μ= −4.1 ± 0.1 ppb isoprene. As isoprene has been shown previously to increase at the initiation of exercise, exercise bike experiments were performed with the individual identified with low isoprene, yielding low and invariant levels of exhaled isoprene (μ = 6.6 ± 0.1 ppb) during the exercise while control subjects illustrated an approximate 2.5-fold increase (pre μ = 286.3 ± 43.8 ppb, exercise μ = 573.0 ± 147.8 ppb) in exhaled isoprene upon exercise start. Additionally, exhaled breath bag data showed a significant decrease in isoprene (delta post/pre, p = 0.0078) of the control group following the exercise regimen. Finally, TD-GC-MS results for exhaled isoprene from the individual’s family (mother, father, sister and maternal grandmother) illustrated that the mother and father exhibited isoprene values (28.5 ppb, 77.2 ppb) below control samples 95% confidence interval (μ = 166.8 ± 43.3 ppb) while the individual’s sister (182.0 ppb) was within the control range. These data provide evidence for a large dynamic range in exhaled isoprene in this family. Collectively, these results provide additional data surrounding the existence of a small population of individuals with background levels of exhaled isoprene.

Circular economy without chemicals controls? Evidence of recirculated toxic plasticizers in flexible PVC products

The global push towards a circular economy (CE) has led to increasing efforts to improve resource utilization efficiency, including plastics recycling. However, the presence of additives, especially those that are toxic, complicates plastics recycling in several ways. Without sufficient controls, the spread of hazardous additives via recycling activities represents a significant public health challenge, particularly among developing nations. This study demonstrates evidence of such uncontrolled recycling, based on an investigation of four household flexible PVC product groups available in Thailand. A versatile pyrolysis/thermal desorption gas chromatography-mass spectrometry (Py/TD-GC-MS) method was employed to simultaneously screen 18 target plasticizers in these products. Di-(2-ethylhexyl) phthalate (DEHP) and diisononyl phthalate (DINP) are the most frequently detected primary plasticizers. DEHP is dominant in vinyl boots, flooring sheets, and hoses, while DINP is dominant in cable sheaths, likely due to a spill-over effect from the EU Restriction of Hazardous Substances (RoHS) directive. Chlorinated paraffins (CPs) are secondary plasticizers that are also detected in most samples, except for boots. The other plasticizers detected include other ortho-phthalates and non-phthalates. These results provide insight into combinatory patterns of plasticizer ‘cocktails’, that comprise restricted, as-yet-unrestricted, and non-restricted plasticizers, embedded in the same individual samples, with a maximum of seven plasticizers found in a single cable sheath. These findings indicate the existence of potentially risky recycling practices that target embedded plasticizers to save cost, without due consideration of their inherent toxicity. Proper interventions are necessary to ensure that CE and chemical safety can be synergized.

A Study on the Adsorption Capture-Thermal Desorption Gas Chromatography Mass Spectrometry Analysis of Biogenic Volatile Organic Compounds in Forests

Phytoncide, a forest healing indicator, is known to help suppress depression, anxiety, and stress of human. Furthermore, it has positive effects on blood pressures, pulses, and mood fluctuations. Previous studies mostly focused on phytoncide emission trends and its concentration prediction in forest. Moreover, a direct comparison of phytoncide concentrations between existing studies is often challenging owing to the use of differingunits, target analytes, analysis conditions, as well as unreported concentrations per type of the compound. Therefore, this study evaluated the overall performance of adsorption sampling and thermal desorption coupled with gas chromatography to evaluatethe phytoncide concentration in a forest atmosphere. To this end, the analysis quality management and analysis accuracy were evaluated for on-site samples in two different laboratories. The phytoncide analysis results obtained from each laboratory can serve as reference data for the adsorption capture-thermal desorption method applied to biogenic volatile organic compounds.

Real-world emission characteristics of semivolatile/intermediate-volatility organic compounds originating from nonroad construction machinery in the working process

Detailed emission characterization of semivolatile/intermediate-volatility organic compounds (S/IVOCs) originating from nonroad construction machines (NRCMs) remains lacking in China. Twenty-one NRCMs were evaluated with a portable emission measurement system in the working process. Gas phase S/IVOCs were collected by Tenax TA tubes and analyzed via thermal desorption-gas chromatography–mass spectrometry (TD–GC–MS). Particle phase S/IVOCs were collected by quartz filters and analyzed via GC–MS. The average emission factors (EFs) for fuel-based total (gas + particle phase) IVOCs and SVOCs of the assessed NRCMs were 221.45 ± 194.60 and 11.68 ± 10.67 mg/kg fuel, respectively. Compared to excavators, the average IVOC and SVOC EFs of loaders were 1.32 and 1.55 times higher, respectively. Compared to the working mode, the average IVOC EFs under the moving mode (only moving forward or backward) were 1.28 times higher. The IVOC and SVOC EFs for excavators decreased by 69.06% and 38.37%, respectively, from China II to China III. These results demonstrate the effectiveness of emission control regulations. In regard to individual NRCMs, excavators and loaders were affected differently by emission standards. The volatility distribution demonstrated that IVOCs and SVOCs were dominated by gas- and particle-phase compounds, respectively. The mode of operation also affected S/IVOC gas-particle partitioning. Combined with previous studies, the mechanical type significantly affected the volatility distribution of IVOCs. IVOCs from higher volatile fuels are more distributed in the high-volatility interval. The total secondary organic aerosol (SOA) production potential was 104.36 ± 79.67 mg/kg fuel, which originated from VOCs (19.98%), IVOCs (73.87%), and SVOCs (6.15%). IVOCs were a larger SOA precursor than VOCs and SVOCs. In addition, normal (n-) alkanes were suitably correlated with IVOCs, which may represent a backup solution to quantify IVOC EFs. This work provides experimental data support for the refinement of the emission characteristics and emission inventories of S/IVOCs originating from NRCMs.

Evaluation of the effectiveness of a high-speed method of screening phthalate esters in polymers using pyrolyzer/thermal desorption–gas chromatography-mass spectrometry

The international analytical standard IEC62321–8 specifies a pyrolyzer/thermal desorption-gas chromatography-mass spectrometry (Py/TD-GC/MS) method of screening seven phthalate esters in polymers that requires an analysis time of 30 min. This article describes a new, high-speed method that dramatically reduces this analysis time to about 12 min with a method detection limit (MDL) under 30 mg/kg for all phthalate esters. When this high-speed method was used to analyze phthalate ester-containing reference materials of various base polymers, the phthalate ester recovery rates ranged from 92 to 115%. The conventional method described in IEC62321–8 and this high-speed method were also used to analyze real samples and reference materials (24 samples in total) to evaluate equivalence between the two methods. Linear approximation of a scatter plot of quantitative results obtained by both methods produced a regression line that showed good correlation between the methods with a slope of 1.0326 and a coefficient of determination (R2) of 0.9699. A Bland-Altman plot was also used to analyze the concentration range under 2000 mg/kg, which is near the phthalate ester level restricted by the RoHS (Restriction of the use of certain Hazardous Substances in electrical and electronic equipment) Directive (1000 mg/kg) and important for screening outcomes. As a result, the bias in the difference between the two methods was +20 mg/kg, the 95% confidence interval limits of agreement were -134 mg/kg and +175 mg/kg, and no fixed bias or proportional bias was observed. These findings indicate that the high-speed method is equivalent to the conventional method and can be used to screen for phthalate esters.