Thermal Desorption-gas Chromatography-mass Spectrometry Research Articles

Analytical characterization of erucamide degradants by mass spectrometry

Polyolefins use erucamide as one of their primary slip agents. The degradation of erucamide can occur during polymer processing and long-term storage, leading to the formation of numerous oxidation products. Erucamide degradation produces compounds that adversely affect the odor and color properties of polyolefins. The article describes the comprehensive characterization of erucamide degradation products formed in three different lots of low-density polyethylene (LDPE) using thermal desorption-gas chromatography mass spectrometry (TD-GC/MS) and liquid chromatography-high resolution mass spectrometry (LCHRMS) techniques. More than 20 volatile and non-volatile degradation compounds of erucamide were identified in LDPE. The structures of non-volatile degradants were predicted using both the molecular formula generated and MS/MS fragmentation data obtained by LCHRMS. The non-volatile and volatile degradation compounds formed in odorous LDPE resins were compared with that of the reference sample of LDPE having no odor. Further, the plausible mechanism of formation of volatile and non-volatile degradation compounds of erucamide is proposed.

Real-Time Non-Invasive Monitoring of Short-Chain Fatty Acids in Exhaled Breath.

Short-chain fatty acids (SCFAs) are important metabolites produced by the gut microbiome as a result of the fermentation of non-digestible polysaccharides. The most abundant SCFAs are acetic acid, propionic acid, and butyric acid which make up 95% of this group of metabolites in the gut. Whilst conventional analysis SCFAs is done using either blood or fecal samples, SCFAs can also be detected in exhaled breath using proton transfer reaction-time-of-flight- mass spectrometry (PTR-ToF-MS) using H3O+ for ionization. However, no investigation has been performed to characterize the reactions of SCFAs with H3O+ and with other reagent ions, such as O2 + and NO+. Gas-phase samples of acetic acid, propionic acid, and butyric acid were analyzed with SRI/PTR-ToF-MS under dry and humid conditions. The ions generated and their distribution was determined for each reagent ion. It was found the humidity did not influence the product ion distribution for each SCFA. Using H3O+ as a reagent ion, SRI/PTR-ToF-MS analysis of an exhaled breath sample was performed in real-time to demonstrate the methodology. The presence of SCFAs in exhaled breath was confirmed by thermal desorption—gas chromatography—mass spectrometry (TD-GC-MS). Breath sampling repeatability was within acceptable limits (<15%) for an analytical methodology for each investigated SCFA. Nutritional intervention studies could potentially benefit from real-time monitoring of exhaled SCFAs as an alternative to measuring SCFAs invasively in blood or fecal samples since it is non-invasive, and requires minimal time investment from participants.

Secondary organic aerosol formation from cis-3-hexen-1-ol/NOx photo-oxidation: The roles of cis-3-hexen-1-ol concentration, illumination intensity, NOx and NH3

Cis-3-Hexen-1-ol (cis-HXO) is an important green leaf volatile (GLV), and its photochemical oxidation is an important pathway to generate secondary organic aerosol (SOA). In this study, smog chamber experiments were carried out to investigate the effects of cis-HXO concentration, illumination intensity, and nitrogen oxides (NOX) and ammonia (NH3) levels on the formation of cis-HXO photo-oxidation SOA in the presence of NOX. The number concentration, mass concentration and yield of SOA under different influencing factors were determined using a scanning mobility particle sizer (SMPS) and a single photon ionization time-of-flight mass spectrometer (SPIMS). The experimental results demonstrated that stronger illumination intensity and higher cis-HXO concentration promoted particles formation. The SOA yield showed a good positive correlation with NOX concentration, especially under high NOX conditions, due to the fragmentation of alkoxy radicals during the reaction to form more polymerizable products as well as the presence of dinitrate and trinitrate, thus promoting the production of SOA. To our surprise, although the addition of NH3 promoted the formation of particles, it inhibited the growth of particles, and thus reducing the particles geometric mean diameter. The chemical components of cis-HXO photo-oxidation SOAs were also analyzed by a thermal-desorption gas chromatography mass spectrometry (TD-GC-MS). Based on the detected products, a reaction mechanism for the cis-HXO photo-oxidation was proposed. The experimental results confirm that cis-HXO is a significant global source of SOA which has a great reference significance for regional air quality prediction and more accurate modelling of global SOA generation.

Effect of calcination temperature on the structure and performance of rod-like MnCeOx derived from MOFs catalysts

In our work, metal organic framework (MOFs)-derived MnCeOx catalysts were synthesized by different calcination temperatures. Effect of calcination temperature was characterized by thermogravimetric (TG), X-ray diffraction (XRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), N2 adsorption-desorption (BET), X-ray photoelectron spectroscopy (XPS) and temperature programmed H2 reduction (H2-TPR). Performance testing of toluene found that 1Mn1Ce-300 showed the best performance (T90 = 244 °C), good durability and reliable water resistance in catalyzing toluene. The better catalytic performance of 1Mn1Ce-300 was attributed to the higher molar ratios of Ce3+/Ce4+, Mn3+/Mn4+ and Oads/Olatt, more adsorbed oxygen, surface oxygen vacancy and better low-temperature reduction. In situ diffuse reflectance, infrared Fourier transform spectroscopy (in-situ DRIFTS) and thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) proved that benzoic acid and benzene were the main intermediates. This work was instructive for the preparation of metal oxide catalysts by pyrolysis of MOFs.

Aroma characterization of raw and electrochemically treated goat whey wastewater

Whey wastewater is considered to be the main polluting product of the dairy industry. Electrocoagulation (EC) and electrooxidation (EO) processes using aluminum electrodes and inactive boron-doped diamond (BDD), respectively, were applied to reduce the chemical oxygen demand (COD), total nitrogen (TN), phosphate (PO4-3), nitrate (NO3-), chloride (Cl-), total phenolic compounds (TPCs), and optical density. In parallel, thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) with HiSorb passive sorption extraction probe was employed to monitor the emitted volatile organic compounds (VOCs) from the electrochemical treatments. A total of 35 VOCs were extracted and identified in the raw whey wastewater, while 27 and 53 VOCs were identified in the EC and EO treated whey wastewater, respectively. EO-treatment was more concerning as chlorinated VOCs were detected showing a total presence of 50%. Two trichloromethanes (THMs), methane bromodichloro and trichloromethane, as well as ethane 1,2-dichloro, and propane 1,2-dichloro were quantified and their mean concentrations were 5.0, 125.2, 15.1, and 6.4 ppbv, respectively. Overall, the aroma profile remained mostly unaffected by the EC-treatment. Also, COD, TN, Cl-, NO3-, PO4-3, TPCs, and optical density presented a reduction of 7.4, 52.5, 11.9, 27, 16.8, 54.8, and 17.3% with EC. On the contrary, EO was only effective for COD and optical density, with removal of 14.3, and 23.5%, respectively, while all the other concentrations of pollutants increased (TN, Cl-, NO3-, PO4-3, TPCs).

Sea Buckthorn Hippophae rhamnoides and Fruit Flies Rhagoletis batava: Search for Volatile Semiochemicals Involved in Pest Attraction

Rhagoletis batava (Diptera: Tephritidae), is the most important pest of Hippophae rhamnoides fruits. For detection and monitoring of R. batava, traps supplied with nonspecific attractants are used. Thus, new, more specific attractants for environment-friendly pest control are needed. Such attractants could be fruit-related semiochemicals that are involved in the host location by flies. Behavioural Y-olfactometer tests revealed that R. batava males were attracted to ripe fruit odour, while females preferred unripe and semi-ripe fruits. Thermal desorption gas chromatography-mass spectrometry (GC-MS) analysis revealed substantial quantitative and qualitative changes in volatiles between unripe and ripe fruits. In the unripe fruit emission, 41 volatile compounds were isolated, whereas 64 compounds were sampled from the ripe fruits. The total amount of volatiles increased five times during the fruit ripening. Gas chromatography-electroantennogram detection (GC-EAD) and GC-MS analyses of the fruit headspace volatiles revealed at least 26 compounds in unripe and 27 compounds in ripe fruits eliciting antennal responses of R. batava for both sexes. The fruits of these two ripening stages differed qualitatively in the single EAD-active compound only, i.e., 3-methylbutyl 2-methylpropionate. Esters were the most abundant volatiles, composing 84% and 93% of EAD-active compounds in the emissions of unripe and ripe fruits, respectively. Based on the persistent EAG responses, 17 compounds were selected as the most promising candidates for kairomone attractants of the sea buckthorn pest R. batava.

Chemical characterization of Brazilian propolis using automated direct thermal desorption-gas chromatography-mass spectrometry.

Propolis, produced by honey bees, is used around the world, displaying several corroborated biological activities. Brazil is one of the leading producers of propolis, with a great diversity of types, each with a characteristically chemical fingerprint influenced by the flora of the local region. The secondary metabolite's composition of propolis strongly impacts its biological properties, and its chemical characterization is of great importance for its quality control. Several chromatographic techniques have been applied to characterize propolis, highlighting the extraction of its volatiles and its analysis through gas chromatography. Fourteen Brazilian propolis samples collected in four states, including brown, green and red propolis types, were chemically characterized using the automated direct thermal desorption-gas chromatography-mass spectrometry (DTD-GC-MS). Red propolis type was characterized by acyclic saturated hydrocarbons, fatty alcohols, terpenes, and phenylpropanoids as nonacosane, α-copaene, β-amyrin acetate, anethole, and 7-O-methylvestitol. Brown propolis presented hydrocarbons, monoterpenes, and sesquiterpenes, as α-pinene and α-bisabolol. Brazilian green propolis presented polycyclic aromatic hydrocarbons and sesquiterpenes, including 1-methyl-octahydroanthracene, 2,5-dimethyl-γ-oxo-benzenebutanoic acid, nerolidol, and spathulenol. Principal component analysis (PCA) was performed, allowing for clustering brown and red propolis types, indicating a divergence with the chemical composition of the green propolis samples. The hierarchical cluster analysis (HCA) allowed the chemical fingerprint of each propolis type to be differentiated. Red propolis was characterized by sesquiterpenes, pterocarpans, and isoflavans; brown propolis was characterized by hydrocarbons, aldehydes, and monoterpenes, while green propolis samples were characterized by the presence of polycyclic aromatic hydrocarbons, sesquiterpenes, and naphthalene derivatives. © 2022 Society of Chemical Industry.

Effects of long-term vegan diet on breath composition

The composition of exhaled breath derives from an intricate combination of normal and abnormal physiological processes that are modified by the consumption of food and beverages, circadian rhythms, bacterial infections, and genetics as well as exposure to xenobiotics. This complexity, which results wide intra- and inter-individual variability and is further influenced by sampling conditions, hinders the identification of specific biomarkers and makes it difficult to differentiate between pathological and nominally healthy subjects. The identification of a ‘normal’ breath composition and the relative influence of the aforementioned parameters would make breath analyses much faster for diagnostic applications. We thus compared, for the first time, the breath composition of age-matched volunteers following a vegan and a Mediterranean omnivorous diet in order to evaluate the impact of diet on breath composition. Mixed breath was collected from 38 nominally healthy volunteers who were asked to breathe into a 2 l handmade Nalophan bag. Exhalation flow rate and carbon dioxide values were monitored during breath sampling. An aliquot (100 ml) of breath was loaded into a sorbent tube (250 mg of Tenax GR, 60/80 mesh) before being analyzed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Breath profiling using TD-GC-MS analysis identified five compounds (methanol, 1-propanol, pentane, hexane, and hexanal), thus enabling differentiation between samples collected from the different group members. Principal component analysis showed a clear separation between groups, suggesting that breath analysis could be used to study the influence of dietary habits in the fields of nutrition and metabolism. Surprisingly, one Italian woman and her brother showed extremely low breath isoprene levels (about 5 pbv), despite their normal lipidic profile and respiratory data, such as flow rate and pCO2. Further investigations to reveal the reasons behind low isoprene levels in breath would help reveal the origin of isoprene in breath.

Determination of tire wear markers in soil samples and their distribution in a roadside soil

Tire wear (TW) constitutes a significant source of microplastic in terrestrial ecosystems. It is known that particles emitted by roads can have an effect up to 100 m into adjacent areas. Here, we apply for the first-time thermal extraction desorption gas chromatography-mass spectrometry (TED-GC/MS) to determine TW in soil samples by detection of thermal decomposition products of styrene-butadiene rubber (SBR), without additional enrichment. Additionally, zinc contents were determined as an elemental marker for TW. Mixed soil samples were taken along three transects along a German motorway in 0.3, 2.0, and 5.0 m distance from the road. Sampling depths were 0–2, 2–5, 5–10, and 10–20 cm. Four fine fractions, 1 000–500, 500–100, 100–50, and <50 μm, were analyzed.TW contents based on SBR ranged from 155 to 15 898 mg kg−1. TW contents based on zinc were between 413 and 44 812 mg kg−1. Comparison of individual values of SBR and zinc reveals SBR as a more specific marker. Results confirm that most TW ends up in the topsoil within a 2 m distance.The sampling strategy resulted in representative data for a larger area. Standard deviations of quadruple TED-GC/MS determination of SBR were <10% for all grain size fractions. TED-GC/MS is a suitable analytical tool for determining TW in soil samples without the use of toxic chemicals, enrichment, or special sample preparation.

The Impact of a Graded Maximal Exercise Protocol on Exhaled Volatile Organic Compounds: A Pilot Study.

Exhaled volatile organic compounds (VOCs) are of interest due to their minimally invasive sampling procedure. Previous studies have investigated the impact of exercise, with evidence suggesting that breath VOCs reflect exercise-induced metabolic activity. However, these studies have yet to investigate the impact of maximal exercise to exhaustion on breath VOCs, which was the main aim of this study. Two-litre breath samples were collected onto thermal desorption tubes using a portable breath collection unit. Samples were collected pre-exercise, and at 10 and 60 min following a maximal exercise test (VO2MAX). Breath VOCs were analysed by thermal desorption-gas chromatography-mass spectrometry using a non-targeted approach. Data showed a tendency for reduced isoprene in samples at 10 min post-exercise, with a return to baseline by 60 min. However, inter-individual variation meant differences between baseline and 10 min could not be confirmed, although the 10 and 60 min timepoints were different (p = 0.041). In addition, baseline samples showed a tendency for both acetone and isoprene to be reduced in those with higher absolute VO2MAX scores (mL(O2)/min), although with restricted statistical power. Baseline samples could not differentiate between relative VO2MAX scores (mL(O2)/kg/min). In conclusion, these data support that isoprene levels are dynamic in response to exercise.

On-Line Trace Monitoring of Volatile Halogenated Compounds in Air by Improved Thermal Desorption-Gas Chromatography-Mass Spectrometry

On-Line Trace Monitoring of Volatile Halogenated Compounds in Air by Improved Thermal Desorption-Gas Chromatography-Mass Spectrometry

UiO-66 Selective Enrichment Integrated with Thermal Desorption GC-MS for Detection of Benzene Homologues in Ambient Air.

In this study, UiO-66 was selected as sorbent media packed in the tube to selectively enrich trace levels of benzene homologues such as benzene, toluene, and xylene (BTX) in ambient air prior to thermal desorption (TD)-GC-MS determination. A series of experiments were conducted to obtain the optimal TD conditions. The results indicated that the optimal TD parameters were as follows: desorption temperature of 180°C, desorption flow rate of 50 mL min−1, and desorption time of 30 min. Furthermore, the method based on UiO-66 enrichment integrated with TD-GC-MS for trace levels of BTX was successfully developed. It exhibited a good linearity (R2 > 0.99) in the range of 50–1000 ng, except for p, m-xylene in the range of 100–2000 ng, and achieved the recovery of 69.4–101.3%, and the relative standard deviation of 3.8–6.4%. The detection limits of BTX were 1.6–4.0 ng; according to 10 L of sampling volume, the method detection limits would be in the range of 0.16–0.40 µg m−3. Additionally, the method was successfully applied to determine BTX in indoor air and showed good selectivity and sensitivity. In summary, the findings in this work revealed that UiO-66 was an attractive adsorbent for selective enrichment trace levels of BTX compounds in ambient air, which was favorable for the subsequent detection by TD-GC-MS.

Volatile Components and Preliminary Antibacterial Activity of Tamarillo (Solanum betaceum Cav.).

Tamarillo is a nutrient-dense fruit with a unique aroma from its volatile compounds (VCs). In this study, we aimed to compare the volatile profiles: (i) of fresh and freeze-dried tamarillo; (ii) detected using Thermal Desorption–Gas Chromatography–Mass Spectrometry (TD–GC–MS) and Solid-Phase MicroExtraction–Gas Chromatography-Mass Spectrometry (SPME–GC–MS); (iii) of freeze-dried pulp and peel of New Zealand grown tamarillo. The possible antibacterial activity of freeze-dried tamarillo extracts was also investigated. We show that freeze-drying maintained most of the VCs, with some being more concentrated with the loss of water. The most abundant VC in both fresh and freeze-dried tamarillo was hexanoic acid methyl ester for pulp (30% and 37%, respectively), and (E)-3-Hexen-1-ol for peel (36% and 29%, respectively). With the use of TD–GC–MS, 82 VCs were detected for the first time, when compared to SPME–GC–MS. Methional was the main contributor to the overall aroma in both peel (15.4 ± 4.2 μg/g DW) and pulp (118 ± 8.1 μg/g DW). Compared to water as the control, tamarillo extracts prepared by water and methanol extraction showed significant antibacterial activity against E. coli, P. aeruginosa, and S. aureus with zone of inhibition of at least 13.5 mm. These results suggest that freeze-dried tamarillo has a potential for use as a natural preservative to enhance aroma and shelf life of food products.

Uptake and Release of Aroma Compounds by an Ethylene Propylene Diene Monomer Rubber Sealing Polymer: Investigating Aroma Carryover in a Model Wine System.

Aromatized wines and regular table wines are often filled on the same bottling line. Sealing polymers in the filling line absorb volatiles from aromatized wines and may migrate due to insufficient cleaning into the subsequently bottled regular wine. Unintentional carryover of volatiles may lead to accusation of illegal aromatization of wine. Absorption, cleaning efficacy, and migration of volatiles into ethylene propylene diene monomer rubber were investigated in a model system. Direct thermal desorption-gas chromatography-mass spectrometry analysis of seven aroma compounds monitored variation in the polymer (μg/g). Absorption of volatiles was mostly driven by their octanol/water partition coefficients. Cleaning of polymers removed 11 to 62% of the absorbed volatiles. Subsequent immersion of cleaned polymers into model wine revealed migration of 20 to 57% of the remaining volatiles. Sensory tests suggested the impact of transferred volatiles into subsequent model wine. For α-ionone, an odor activity value of 1.03 indicated a potential sensory impact.

Development, Optimization and Validation of a Sustainable and Quantifiable Methodology for the Determination of 2,4,6-Trichloroanisole, 2,3,4,6-Tetrachloroanisole, 2,4,6-Tribromoanisole, Pentachloroanisole, 2-Methylisoborneole and Geosmin in Air

Compounds 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), 2,4,6-tribromoanisole (TBA) and pentachloroanisole (PCA), 2-methylisoborneol (2MIB) and geosmin (GSM) have been reported as being responsible for cork and wine taint. A sustainable method based on thermal desorption-gas chromatography–mass spectrometry (TD-GC/MS) has been developed and optimized, taking into account desorption parameters and chromatographic and mass spectrometric conditions. The combination of parameters that jointly maximized the compound detection was as follows: desorption temperature at 300 °C, desorption time at 30 min, cryo-temperature at 20 °C and trap high temperature at 305 °C. The proposed methodology showed a good linearity (R ≤ 0.994) within the tested range (from 0.1 to 2 ng) for all target compounds. The precision expressed as repeatability and reproducibility was RSD &lt; 10% in both. The limits of quantification ranged from 0.05 to 0.1 ng. The developed methodology and the sampling rates (R-values) of all targeted compounds (from 0.013 to 0.071 m3 h−1) were applied to the air analysis of two wineries. The results showed that the developed methodology is a sustainable and useful tool for the determination of these compounds in air.

Thermal desorption gas chromatography-mass spectrometric analysis of polycyclic aromatic hydrocarbons in atmospheric fine particulate matter

Thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) is used to analyze polycyclic aromatic hydrocarbons (PAHs) in atmospheric fine particulate matter. However, despite the high sensitivity of TD-GC-MS, the recovery rate of PAHs is greatly influenced by active sites in the equipment. PAHs are decomposed or adsorbed at active sites, decreasing quantitative accuracy. Also, the thermal extraction of PAHs is easily affected by the matrix in PM2.5 samples, decreasing the thermal extraction efficiency. Herein, the analytical sensitivities of PAHs were improved by adding analyte protectant (AP) and thermal desorption aid (TDA) as an auxiliary agent. The combination of 2 µL of 0.5 w/v% D-sorbitol (as AP) and 2 µL of 10 w/v% Tween®20 (as TDA) was found to be most effective in improving the analytical sensitivity of PAHs. The sensitivities of 5–6-ring PAHs with high boiling points increased most when analyzing blank filter papers added with PAHs standard sample or real samples of PM2.5 compared with the samples without the auxiliary agent. When analyzing real samples of PM2.5, the peak areas of 5-ring and 6-ring PAHs in the PM2.5 sample added with the optimized auxiliary agent were 1.40 and 1.96 times that without the auxiliary agent. It is considered that AP in the auxiliary agent covered active sites and protected PAHs undergoing decomposition or adsorption. TDA improved the thermal extraction rate of high boiling point PAHs. When using alternative heat sampling equipment to analyze low concentrations of high boiling point components, the auxiliary agent proposed herein can increase the analytical sensitivity toward the target compounds.

Diffusive uptake rates for passive air sampling: Application to volatile organic compound exposure during FIREX-AQ campaign

Passive (diffusive) sampling using sorbents is an economical and versatile method of measuring pollutants in air, including volatile organic compounds (VOCs). Diffusive uptake rates (UTRs) are needed for each analyte to obtain average concentrations during a specific passive sampling time duration. Here, a simultaneous active/diffusive ambient air sampling technique on Tenax®TA was employed to measure 24-hours, 7, 14 and 28-days UTRs of up to 27 VOCs, including benzene, toluene, ethylbenzene, xylenes (BTEX), C6–C12 hydrocarbons, benzenes derivatives, tetrachloroethylene, pinenes and limonene. Samples were analyzed via thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) for desired analytes. Seven-day UTR values ranged from 0.17 to 0.59 mL/min and many compounds exhibited a linear relationship with UTR and time duration up to 14 or 28 days. This may be the most comprehensive UTR tabulation of VOCs on Tenax®TA for time periods of 24 hours –28 days available. These rates were applied to VOC data measured during the 2019 NASA/NOAA Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign, with goals to determine the chemical composition of western US wildfire smoke and to assess human exposure to air toxics. Summer 2019 exposure levels of BTEX at five Northwestern cities were low and the cancer risk due to benzene was assessed during FIREX-AQ to be background or 1 × 10−6. The UTRs derived here can be useful in applications of diffusive sampling, including estimation of sub-chronic to chronic human exposure risk of air toxics and wildfire smoke.

Odor-active volatile organic compounds along the seafront of Thessaloniki, Greece. Implications for sources of nuisance odor

Volatile organic compounds (VOCs) have long been associated with odor nuisance at urban sites close to emission sources. Sulfur containing volatile organic compounds (VOSCs) in particular, constitute a major category of malodorous compounds since some of them are characterized by intense odor and low odor thresholds. VOSCs have both, anthropogenic and biogenic sources. The purpose of this study was to assess the concentration levels of a variety of VOCs (mercaptans, sulfides, thiophenes, aromatics and aldehydes) along the seafront of the city of Thessaloniki, northern Greece, a city with frequent citizen complaints for nuisance odor. 1-Hour sampling on adsorption tubes was carried out concurrently at 3 sites along the seafront of the city (EAST, CENTER and WEST) three times during the day in winter and summer 2020. VOCs analysis, performed on a Thermal Desorption - Gas Chromatography/Mass Spectroscopy (TD-GC/MS) system. Diurnal and seasonal variations, and correlations with prevailing meteorological conditions were investigated. Concentrations found along the seafront were compared to previous data from inner-city sites affected by urban and/or industrial activities. Most VOCs were found at lower concentrations at the seafront in comparison to inner-city sites demonstrating better air quality. Typical biogenically-deriving VOSCs such as carbonyl sulfide and dimethyl sulfide were found at the seafront either at higher or at similar levels with inner city thus suggesting negligible contribution from biogenic sources. Odor activity values were further calculated and assessed. Odor nuisance at all seafront sites was significantly higher in winter, being in both seasons maximum at the WEST seafront that is closer to port activities, polluted creek estuaries and industrial facilities. Mercaptans were identified as the major contributors to odor pollution followed by aldehydes. The new findings described in this study might contribute to the better understanding of the odor pollution from VOCs at coastal urban sites.

Anchoring the quantification of VX and Russian VX using portable gas chromatography-mass spectrometry and focusing agents

Field portable gas chromatography-mass spectrometry, GC-MS, have been established as the ‘gold standard’ of chemical identification and quantification for chemical threats however several chemical warfare agents have been shown to evade required detection limits. This work demonstrates the derivatization of O-ethyl S-(2-diisopropylaminoethyl) methylphosphonothioate (VX) and N,N-diethyl-2-[methyl(2-methylpropoxy)phosphoryl]sulfanylethanamine (Russian VX, RVX) into VX-G (O-ethyl methylphosphonofluoridate) and RVX-G (O-isobutyl methylphosphonofluoridate) through V-to-G conversion. The G-analogues of VX and RVX are collected on Tenax® TA thermal desorption tubes and are then analyzed by thermal desorption GC-MS. Each thermal desorption tube is loaded with a target-based standard called a focusing agent. Here, we provide relative response factors for the focusing agent diethyl malonate as well as diethyl ethylthiophosphonate that is derivatized into the G-analogue. Our results provide a more reliable and reproducible quantification method for VX (10.4% RSD) and RVX (10.9% RSD) than the bromopentafluorobenzene internal standard (32.9% RSD).

Assessment of outdoor odor emissions from polluted sites using simultaneous thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS), electronic nose in conjunction with advanced multivariate statistical approaches

Poor air quality, particularly in urban areas, causes various diseases and degrades living standards. Air quality could be affected by emissions of odor, Volatile Organic Compounds (VOCs), and other gases. Therefore, assessment and monitoring of odorous air quality using sensitive, simple, rapid, accurate and portable tools is very important for public health. This study aimed to characterize odor emissions to detect malfunctions in facilities and to prevent air pollution and olfactory nuisance in the environment. A gas chromatographic method, in conjunction with sensorial analysis were performed for odorous air samples analysis collected from neighborhood of Meknes city (Morocco). Advanced multivariate statistical approaches, such as Principal Components Analysis (PCA), Discriminant Function Analysis (DFA), Support Vector Machines (SVMs), and Hierarchical Cluster Analysis (HCA), were used to describe samples similarities. The electronic nose (e-nose) data processing exhibits a satisfactory discrimination between the odorous air samples. Twenty-four VOCs with known molecular formulas were identified with Thermal Desorption-Gas Chromatography-Mass Spectrometry (TD-GC-MS). A validated Partial Least Square (PLS) model foresees good calibration between e-nose measurement and TD-GC-MS analysis. The finding indicates that TD-GC–MS approach in conjunction with e-nose unit could be suitable tool for environmental measurement-based odor emissions.