Gas Sampling Bags Research Articles

Performance of a Novel Electronic Nose for the Detection of Volatile Organic Compounds Relating to Starvation or Human Decomposition Post-Mass Disaster.

There has been a recent increase in the frequency of mass disaster events. Following these events, the rapid location of victims is paramount. Currently, the most reliable search method is scent detection dogs, which use their sense of smell to locate victims accurately and efficiently. Despite their efficacy, they have limited working times, can give false positive responses, and involve high costs. Therefore, alternative methods for detecting volatile compounds are needed, such as using electronic noses (e-noses). An e-nose named the 'NOS.E' was developed and has been used successfully to detect VOCs released from human remains in an open-air environment. However, the system's full capabilities are currently unknown, and therefore, this work aimed to evaluate the NOS.E to determine the efficacy of detection and expected sensor response. This was achieved using analytical standards representative of known human ante-mortem and decomposition VOCs. Standards were air diluted in Tedlar gas sampling bags and sampled using the NOS.E. This study concluded that the e-nose could detect and differentiate a range of VOCs prevalent in ante-mortem and decomposition VOC profiles, with an average LOD of 7.9 ppm, across a range of different chemical classes. The NOS.E was then utilized in a simulated mass disaster scenario using donated human cadavers, where the system showed a significant difference between the known human donor and control samples from day 3 post-mortem. Overall, the NOS.E was advantageous: the system had low detection limits while offering portability, shorter sampling times, and lower costs than dogs and benchtop analytical instruments.

Systematic study of polymer gas sampling bags for offline analysis of exhaled breath

Polymeric bags are a widely applied, simple, and cost-effective method for the storage and offline analysis of gaseous samples. Various materials have been used as sampling bags, all known to contain impurities and differing in their cost, durability, and storage capabilities. Herein, we present a comparative study of several well-known bag materials, Tedlar (PVF), Kynar (PVDF), Teflon (PTFE), and Nalophan (PET), as well as a new material, ethylene vinyl copolymer (EVOH), commonly used for storing food. We investigated the influences of storage conditions, humidity, bag cleaning, and light exposure on volatile organic compound concentration (acetone, acetic acid, isoprene, benzene, limonene, among others) in samples of exhaled human breath stored in bags for up to 48 h. Specifically, we show high losses of short-chain fatty acids (SCFAs) in bags of all materials (for most SCFAs, less than 50% after 8 h of storage). We found that samples in Tedlar, Nalophan, and EVOH bags undergo changes in composition when exposed to UV radiation over a period of 48 h. We report high initial impurity levels in all the bags and their doubling after a period of 48 h. We compare secondary electrospray ionization and proton transfer reaction mass spectrometry in the context of offline analysis after storage in sampling bags. We provide an analytical perspective on the temporal evolution of bag contents by presenting the intensity changes of all significantm/zfeatures. We also present a simple, automated, and cost-effective offline sample introduction system, which enables controlled delivery of collected gaseous samples from polymeric bags into the mass spectrometer. Overall, our findings suggest that sampling bags exhibit high levels of impurities, are sensitive to several environmental factors (e.g. light exposure), and provide low recoveries for some classes of compounds, e.g. SCFAs.

Odor-Cued Grab Air Sampling for Improved Investigative Odorant Prioritization Assessment of Transient Downwind Environmental Odor Events.

A critical prelude to any community odor assessment should be the prioritization of specific chemical odorants that are most responsible for targeted downwind odors. Unfortunately, and historically, this is a step that has often been bypassed or overlooked. However, correct understanding of the specific impactful volatile organic compounds (VOCs) can inform the follow-on sampling, analytical, and remediation strategies that are most appropriate and efficient, based upon the chemistry behind the issue. With this understanding, the techniques and sampling strategies presented herein should be viewed as a qualitative prelude rather than an addendum to a follow-up routine, automated downwind odor monitoring. Downwind odor characteristics can vary depending upon the size of the upwind source, interim topography, and wind conditions. At one extreme, the downwind odor plume from a relatively large source located on a flat open plain and under stable, near-straight line wind conditions can be rather broad, sustained, and predictable. In contrast, the plume from a small point source (e.g., a roof vent stack) located on irregular topography and under rapidly shifting wind conditions can be intermittent and fleeting ("spikes" or "bursts"). These transient odor events can be surprisingly intense and offensive, despite their fleeting occurrence and perception. This work reports on improving and optimizing an environmental sampling strategy for odorant prioritization from such transient downwind odor conditions. This optimization addresses the challenges of (1) sampling of transient odor "spikes" and (2) prioritizing odors/odorants from multiple, closely colocated point sources under transient event conditions. Prioritizing is defined as identifying the key impactful odorants downwind. Grab air sampling protocol refinement has emerged from actual community environmental odor assessment projects. The challenge of assessing transient odor events has been mitigated by utilizing (a) rapid, odor-cued whole-air grab sampling (i.e., activated by and synchronous with the perceived sensory spikes) into metalized fluorinated ethylene polymer (m-FEP) gas sampling bags; (b) immediate transfer from bags onto solid-phase microextraction (SPME) fibers or sorbent tubes; and (c) maintaining refrigerated storage and shipment conditions between field collection and in-laboratory analysis. Results demonstrated approximately 11-fold increases in target odorant yields for 900 mL air sample capture on sorbent tube transfers from 2 to 3 s "burst" odor event bag captures compared to equivalent direct collections (with sorbent tubes) at the same downwind receptor location but during perceived (stable) odor "lull" periods. An application targeting general odor sampling and point-source differentiation utilizing tracer gases is also presented.

Tracing Low‐CO2 Fluxes in Soil Incubation and 13C Labeling Experiments: A Simplified Gas Sampling System for Respiration and Photosynthesis Measurements

AbstractQuantifying carbon dioxide (CO2) fluxes between soil and atmosphere is key in understanding net ecosystem C exchange and biogeochemical C cycling in plant‐soil systems. In ecosystems with low primary production and sparse vegetation, for example, dry lands or subpolar regions where C fluxes are small, measurement sensitivity is key—even so when measurements are combined with isotopic labeling. Here, we present a simplified gas sampling system developed to facilitate sampling and measurement of low soil CO2 fluxes as well as in situ 13CO2 labeling in the same setup. The capacity of the system was tested in a set of feature tests along with gas measurements of dryland soil‐biocrust systems. The system's sensitivity to capture minor changes in CO2 concentration was confirmed in respiration and photosynthesis measurements of soil‐biocrust systems, where fluxes down to 0.1 μmol CO2 m−2 s−1 were quantified. A balloon, implemented to counterbalance underpressure build‐up during gas withdrawal, mitigated 72% of pressure differences at sampling. The overall system volume was reduced to a minimum to limit contamination caused by residual air, and the design enabled one‐step flushing and evacuation of system compartments and gas sample bags, successfully ruling out cross‐contamination between samples. Ultimately, this system offers a flexible and accessible solution for CO2 measurements that can be applied not only on arid soils with low biological activity and turnover rates, but also on plant‐soil systems. The modifications enabled larger, and thereby more representative, sample volumes to be collected while limiting incubation, contamination, and pressure effects on the intact soil system.

Occupational exposure to nanomaterials and biomarkers in exhaled air and urine: Insights from the NanoExplore international cohort

The current evidence on nanomaterial toxicity is mostly derived from experimental studies making it challenging to translate it into human health risks. We established an international cohort (N = 141 workers) within the EU-LIFE project “NanoExplore” to address possible health effects from occupational exposures to nanomaterials. We used a handheld direct-reading optical particle counter to measure airborne nanoparticle number concentrations (PNC) and lung-deposited surface areas (LDSAs). Airborne particles were characterized by TEM and SEM-EDAX. We assessed oxidative/nitrosative stress with a panel of biomarkers in exhaled breath condensate (EBC) (8-isoprostane, malondialdehyde, nitrotyrosine), inflammation (high-sensitivity C reactive protein (hs-CRP), IL-1β, TNF-α, IL-10) and KL-6 (considered as biomarker of interstitial lung fibrosis) and urine (total antioxidant power (TAP), 8-isoprostane, and malondialdehyde). Exhaled breath sampled in gas-sampling bags were assessed for oxidative potential. These biomarkers were quantified pre-shift at the beginning of the workweek and post-shift the 4th day. Relationships between airborne nanoparticle concentration and biomarkers were assessed by multiple linear regression with log-transformed exposure and biomarker concentrations adjusted for potential confounders. We found a positive dose–response relationship for three inflammation biomarkers (IL-10, IL-1β and TNF-α) in EBC with both PNC and LDSA. A negative dose–response relationship was observed between PNC and TAP. This study suggests that occupational exposures to nanoparticles can affect the oxidative balance and the innate immunity in occupationally exposed workers. However, owing to the intrinsic variability of biomarkers, the observed changes along with their health significance should be assessed in a long-term perspective study.

Sampling bag-based emission chamber for measuring volatile organic compounds from household materials using solid-phase extraction-type collection device.

A simple screening analytical method for determining the emission of volatile organic compounds (VOCs) from household materials was developed using a solid-phase extraction (SPE)-type collection device and a gas sampling bag. The VOCs emitted from the sample material placed in the gas sampling bag with a volume of 20 L were extracted on the SPE-type collection device. In this study, complete sampling mode was developed in addition to a conventional flow sampling mode. The extracted VOCs were then eluted with 8mL of acetone and measured using gas chromatography-mass spectrometry. The proposed method does not require a stainless-steel chamber and a thermal desorption system; therefore, VOC emission from household materials could be easily evaluated with an affordable cost, suggesting that the method is suitable for the screening technique for evaluating VOC emission from solid materials.

Exhaled volatile fatty acids, ruminal methane emission, and their diurnal patterns in lactating dairy cows

To date, the commonly used methods to assess rumen fermentation are invasive. Exhaled breath contains hundreds of volatile organic compounds (VOC) that can reflect animal physiological processes. In the present study, for the first time, we aimed to use a noninvasive metabolomics approach based on high-resolution mass spectrometry to identify rumen fermentation parameters in dairy cows. Enteric methane (CH4) production from 7 lactating cows was measured 8 times over 3 consecutive days using the GreenFeed system (C-Lock Technology Inc.). Simultaneously, exhalome samples were collected in Tedlar gas sampling bags and analyzed offline using a secondary electrospray ionization high-resolution mass spectrometry system. In total, 1,298 features were detected, among them targeted exhaled volatile fatty acids (eVFA; i.e., acetate, propionate, butyrate), which were putatively annotated using their exact mass-to-charge ratio. The intensity of eVFA, in particular acetate, increased immediately after feeding and followed a similar pattern to that observed for ruminal CH4 production. The average total eVFA concentration was 35.5 count per second (CPS), and among the individual eVFA, acetate had the greatest concentration, averaging 21.3 CPS, followed by propionate at 11.5 CPS, and butyrate at 2.67 CPS. Further, exhaled acetate was on average the most abundant of the individual eVFA at around 59.3%, followed by 32.5 and 7.9% of the total eVFA for propionate and butyrate, respectively. This corresponds well with the previously reported proportions of these VFA in the rumen. The diurnal patterns of ruminal CH4 emission and individual eVFA were characterized using a linear mixed model with cosine function fit. The model characterized similar diurnal patterns for eVFA and ruminal CH4 and H2 production. Regarding the diurnal patterns of eVFA, the phase (time of peak) of butyrate occurred first, followed by that of acetate and propionate. Importantly, the phase of total eVFA occurred around 1 h before that of ruminal CH4. This corresponds well with existing data on the relationship between rumen VFA production and CH4 formation. Results from the present study revealed a great potential to assess the rumen fermentation of dairy cows using exhaled metabolites as a noninvasive proxy for rumen VFA. Further validation, with comparisons to rumen fluid, and establishment of the proposed method are required.

Novel field-portable high-pressure adsorbent tube sampler prototype for the direct in situ preconcentration of trace compounds in gases at their working pressures: application to biomethane.

In Europe, renewable energy gases such as biomethane are aimed at substituting natural gas provided their stringent compliance to natural gas quality standards stipulating maximal levels of several chemical trace compounds (TC). Preconcentration is generally required to detect TC and inasmuch as biomethane is compressed for injection in the natural gas grid, preconcentration is commonly either done by collecting the bulk pressurized gas in a high-pressure cylinder or by first depressurizing it to collect a bulk volume in e.g. a gas sampling bag. Such whole gas samples are then transported to the lab and transferred to a preconcentration unit, entailing contamination and TC loss risks. Therefore, here a novel handy field-portable device for the direct in situ high-pressure preconcentration of TC is presented, enabling to sample gases at pressures up to 200 bara through a self-assembled Tenax®TA + Carbopack™X multibed adsorbent tube. The effect of the gas sampling pressure on the preconcentration of TC on adsorbent tubes was evaluated using a synthetic gas mixture containing 41 halogenated volatile organic compounds each at 1 ppmmol in N2. At given normalized sampled volumes and in the pressure range 5–100 bara handled in French gas transport grids, the pressure had no influence on the preconcentration when the gas circulates through the adsorbent tubes and as long as the adsorbents are not saturated. Next, for the first time, a real biomethane stream was sampled using the novel direct high-pressure preconcentration method on Tenax®TA + Carbopack™X multibed adsorbent tubes, allowing to preconcentrate, in a single sampling run, a wide range of volatile organic TC. More than 26 distinct TC were detected, belonging to seven chemical families: alkenes, aromatics, alkanes (linear, cyclic and polycyclic), sulphur-compounds and terpenes, with linear alkanes (pentane, heptane, octane) and terpenes predominating. Semi-quantification indicated pentane, dimethylcyclopropane, hexane, heptane, octane, α-pinene and camphene are present at a ≤1 ppmmol concentration threshold in the biomethane.

Development of a Non-invasive Diagnostic Method for Esophageal Squamous Cell Carcinoma by Gas Chromatographic Analysis of Exhaled Breath.

Since esophageal carcinoma progresses asymptomatically, for many patients the disease is already advanced at the time of diagnosis. The main methods that are currently used to diagnose esophageal carcinoma are upper gastrointestinal radiographic contrast examinations and upper gastrointestinal endoscopy, but early discovery of this disease remains difficult. There is a need to develop a diagnostic method using biomarkers that is non-invasive while both highly sensitive and specific. Exhaled breath was collected from 17 patients with esophageal squamous cell carcinoma (ESCC), as well as 9 control subjects without history of any cancer. For each fasting subject, 1L of exhaled breath was collected in a gas sampling bag. Volatile organic compounds (VOCs) were then extracted from each sample using Solid phase micro-extraction (SPME) fibers and analyzed by gas chromatography-mass spectrometry (GC-MS). Levels of acetonitrile, acetic acid, acetone, and 2-butanone in exhaled breath were significantly higher in the patient group than in the control group (p = 0.0037, 0.0024, 0.0024 and 0.0037, respectively). ROC curves were drawn for these 4 VOCs, and the results for the area-under-the-curve (AUC) indicated that ESCC patients can be identified with a high probability of 0.93. We found distinctive VOCs in exhaled breath of ESCC patients. These VOCs have a potential as new clinical biomarkers for ESCC. The measurement of VOCs in exhaled breath may be a useful, non-invasive method for diagnosis of ESCC.

Quantification of volatile organic compounds by secondary electrospray ionization-high resolution mass spectrometry

Secondary electrospray ionization coupled with high resolution mass spectrometry (SESI-HRMS) is a direct mass spectrometry technique, which can identify trace volatile organic compounds (VOCs) in real time without sample pretreatment and chromatographic separation. SESI-HRMS has been successfully applied in multiple applications, including breath analysis, animals and plants VOCs emissions, analysis of headspace of cell cultures and indoor and outdoor air. The range of areas where the technique can potentially have a substantial impact is very broad. However, one critical aspect that requires further development to consolidate the technique is absolute quantification. Therefore, in this study we aim to develop a quantitative method for eight representative VOCs, including ketones (acetone, 2-butanone and 2-pentanone), alkenes (isoprene and α-terpinene) and aromatics (toluene, styrene and mesitylene). The mass spectrometric platform includes a commercial SESI source hyphenated with a Q-Exactive hybrid quadrupole Orbitrap high resolution mass spectrometer. Within the concentration range of 0–100 ppbv studied, the optimal coefficient of determination for linear regression (R2 = 0.993–0.999) between signal intensity and concentration is obtained in the range of 0–10 ppbv for all eight VOCs. The detection limits range between 3 (2-Pentanone) and 15 (Acetone) pptv. The intra-day (n = 10) and inter-day (n = 30) coefficients of variation (CV) are ≤ 6% and ≤10%, respectively. Finally the method is applied for the fast evaluation (<5 min) of different materials widely used for the collection, storage or pretreatment of gas sample. Better recovery of trace levels of eight VOCs is observed for PTFE gas sampling bag as compared to Nalophan and Tedlar bags; when Nafion tube is used to pretreat the gas sample, recovery of ≤50% are obtained for 2-pentanone, α-terpinene and all three aromatics.

Volatile Organic Compounds in Mainstream Smoke of Sixty Domestic Little Cigar Products.

The mainstream smoke yields of five volatile organic compounds (VOCs) were determined from 60 commercial U.S. little cigar products under ISO 3308 and Canadian Intense (CI) smoking regimens on linear smoking machines using a gas sampling bag collection. The five VOCs, 1,3-butadiene, acrylonitrile, benzene, isoprene, and toluene were analyzed using an automated GC/MS analytical method validated for measuring various VOCs in mainstream smoke. The VOCs range in amounts from micrograms to milligrams per little cigar. VOC deliveries vary considerably among the little cigar products under the ISO smoking regimen primarily due to varying filter ventilation. Under the CI smoking regimen where filter ventilation is blocked, the delivery range narrows, although individual and total VOC yields are approximately 2 fold higher than those under the ISO smoking regimen. Correlation analysis reveals strong associations between acrylonitrile and 1,3-butadiene or toluene under the ISO smoking regimen. Compared to cigarettes, little cigars delivered substantially higher VOC mainstream smoke yields under both ISO and CI smoking regimens. Moreover, little cigar smoke also contains higher VOCs than cigarette smoke when adjusted for mass of tobacco.

Enhance Ocean Carbon Observations: Successful Implementation of a Novel Autonomous Total Alkalinity Analyzer on a Ship of Opportunity

Over recent decades, observations based on merchant vessels (Ships of Opportunity—SOOP) equipped with sensors measuring the CO2 partial pressure (pCO2) in the surface seawater formed the backbone of the global ocean carbon observation system. However, the restriction to pCO2 measurements alone is one severe shortcoming of the current SOOP observatory. Full insight into the marine inorganic carbon system requires the measurement of at least two of the four measurable variables which are pCO2, total alkalinity (TA), dissolved inorganic carbon (DIC), and pH. One workaround is to estimate TA values based on established temperature-salinity parameterizations, but this leads to higher uncertainties and the possibility of regional and/or seasonal biases. Therefore, autonomous SOOP-based TA measurements are of great interest. Our study describes the implementation of a novel autonomous analyzer for seawater TA, the CONTROS HydroFIAⓇ TA system (-4H-JENA engineering GmbH, Germany) for unattended routine TA measurements on a SOOP line operating in the North Atlantic. We present the installation in detail and address major issues encountered with autonomous measurements using this analyzer, e.g., automated cleaning and stabilization routines, and waste handling. Another issue during long-term deployments is the provision of reference seawater in large-volume containers for quality assurance measurements and drift correction. Hence, a stable large-volume seawater storage had to be found. We tested several container types with respect to their suitability to store seawater over a time period of 30 days without significant changes in TA. Only one gas sampling bag made of polyvinylidene fluoride (PVDF) satisfied the high stability requirement. In order to prove the performance of the entire setup, we compared the autonomous TA measurements with TA from discrete samples taken during the first two trans-Atlantic crossings. Although the measurement accuracy in unattended mode (about ± 5 μmol kg^-1) slightly deteriorated compared to our previous system characterization, its overall uncertainty fulfilled requirements for autonomous TA measurements on SOOP lines. A comparison with predicted TA values based on an established and often used parameterization pointed at regional and seasonal limitations of such TA predictions. Consequently, TA observations with better coverage of spatiotemporal variability are needed, which is now possible with the method described here.

Evaluation of Reductions in Fume Emissions (VOCs and SVOCs) from Warm Mix Asphalt Incorporating Natural Zeolite and Reclaimed Asphalt Pavement for Sustainable Pavements

Conventional asphalt mixtures used for road paving require high manufacturing temperatures and therefore high energy expenditure, which has a negative environmental impact and creates risk in the workplace owing to high emissions of pollutants, greenhouse gases, and toxic fumes. Reducing energy consumption and emissions is a continuous challenge for the asphalt industry. Previous studies have focused on the reduction of emissions without characterizing their composition, and detailed characterization of volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) in asphalt fumes is scarce. This communication describes the characterization and evaluation of VOCs and SVOCs from asphalt mixtures prepared at lower production temperatures using natural zeolite; in some cases, reclaimed asphalt pavement (RAP) was used. Fumes were extracted from different asphalt mix preparations using a gas syringe and then injected into hermetic gas sample bags. The compounds present in the fumes were sampled with a fiber and analyzed by gas-liquid chromatography coupled to mass spectrometry (GC/MS). In general, the preparation of warm mix asphalts (WMA) using RAP and natural zeolite as aggregates showed beneficial effects, reducing VOCs and SVOCs compared to hot mix asphalts (HMA). The fumes captured presented a similar composition to those from HMA, consisting principally of saturated and unsaturated aliphatic hydrocarbons and aromatic compounds but with few halogenated compounds and no polycyclic aromatic hydrocarbons. Thus, the paving mixtures described here are a friendlier alternative for the environment and for the health of road workers, in addition to permitting the re-use of RAP.

Gas Chromatography-Tandem Mass Spectrometry Method for Selective Detection of 2-Nitropropane in Mainstream Cigarette Smoke.

Although 2-nitropropane is a potentially harmful compound present in cigarette smoke, there are few fully-validated, modern methods to quantitate it in mainstream cigarette smoke. We developed an isotope dilution gas chromatography-tandem mass spectrometry (ID-GC-MS/MS) method for the detection of 2-nitropropane in mainstream cigarette smoke. The vapor fraction of mainstream cigarette smoke was collected in inert polyvinyl fluoride gas sampling bags and extracted with hexanes containing isotopically labeled internal standard, then purified and concentrated via solid-phase extraction using a normal phase silica adsorbent and a 100% dichloromethane eluant. This method is sensitive enough to measure vapor phase 2-nitropropane concentrations in the nanogram range, with a 19 ng per cigarette method limit of detection. Product variability estimated from the analysis of 15 cigarette products yielded relative standard deviations ranging from 5.4% to 15.7%, and estimates of precision from two quality control products yielded relative standard deviations of 9.49% and 14.9%. Under the Health Canada Intense smoking regimen, 2-nitropropane in machine-generated mainstream smoke from 15 cigarette products ranged from 98.3 to 363 ng per cigarette.

Improved accuracy and precision of water stable isotope measurements using the direct vapour equilibration method

A method to measure the δ2 H and δ18 O composition of pore water in soil samples using direct vapour equilibration and laser spectrometry was first described in 2008, and was rapidly adopted. Here, we describe an improved setup to measure pore water δ2 H and δ18 O values through direct vapour equilibration with a laser spectrometer, combining a liquid and a vapour mode for water isotope analyses, and resulting in improved accuracy. We first tested new gas sampling bags as part of the equilibration protocol. Then, to assess measurement accuracy, vapour samples from equilibrated liquid waters of known isotope composition were measured in the liquid mode of the analyser using the new setup as well as the manufacturer's vapour mode. Various modes of preparing liquid water standards, namely equilibration, nebulisation, and vapourisation, were tested to determine the best calibration in terms of accuracy. Finally, the proposed modified liquid setup was validated by analysing water vapour equilibrated from soil pore water of a known composition. The δ2 H and δ18 O measurements were found to be more accurate by the modified liquid mode than by the factory-setup vapour mode. The strong and non-linear dependence of measured δ2 H and δ18 O values on H2 O concentration in vapour mode, especially at concentrations equal to the vapour pressure saturation typically found in laboratories, is problematic for corrections. Regarding calibration and standards, the use of two equilibrated liquid water standards was found to best calibrate measurements in the modified liquid setup. Finally, the modified liquid mode setup and its calibration, as described here, were shown to be appropriate for soil pore water analysis. The proposed modified setup results in more precise δ2 H and δ18 O soil pore water values than the usual protocols. An average standard deviation of 0.04‰ for δ18 O values and 0.3‰ for δ2 H values, based on 228 soil sample analyses, was obtained.

Profiling Volatile Constituents of Homemade Preserved Foods Prepared in Early 1950s South Dakota (USA) Using Solid-Phase Microextraction (SPME) with Gas Chromatography⁻Mass Spectrometry (GC-MS) Determination.

An essential dimension of food tasting (i.e., flavor) is olfactory stimulation by volatile organic compounds (VOCs) emitted therefrom. Here, we developed a novel analytical method based on solid-phase microextraction (SPME) sampling in argon-filled gas sampling bags with direct gas chromatography–mass spectrometry (GC-MS) determination to profile the volatile constituents of 31 homemade preserves prepared in South Dakota (USA) during the period 1950–1953. Volatile profiles varied considerably, but generally decreased in detected compounds, complexity, and intensity over three successive 2-h SPME sampling periods. Volatile profiles were generally predominated by aldehydes, alcohols, esters, ketones, and organic acids, with terpenoids constituting much of the pickled cucumber volatiles. Bisphenol-A (BPA) was also serendipitously detected and then quantified in 29 samples, at levels ranging from 3.4 to 19.2 μg/kg, within the range of levels known to induce endocrine disruption effects. Absence of BPA in two samples was attributed to their lids lacking plastic liners. As the timing of their preparation coincides with the beginning of BPA incorporation into consumer products, these jars may be some of the first BPA-containing products in the USA. To the best of our knowledge, this is the first effort to characterize BPA in and volatile profiles of rare historical foods with SPME.

Direct injection mass spectrometry technique for the odorant losses at ppb(v) level from nalophan™ sampling bags

Trace compound stability is crucial for real time gas analysis and for high efficiency energy generators, where part per billion concentrations have a high impact. In this context, the container type chosen for the gas analysis becomes important. Several types of containers, such as stainless-steel canisters, glass bulbs, gas tight syringes and sampling bags can be adopted for sampling and storing such samples. Sampling bags are cheap and easy to manage, for these reasons other solutions are rarely used. Literature studies have showed how nalophan™ bags represent the best choice for the collection of samples due to the extremely low cost, the good sample stability and the low background interaction. No studies have considered the biogas trace constituents, especially at an ultra-low concentration level. Most of the studies relating to trace compound detection, use a GC–MS instrument and focus on few compounds of interest. In this paper, one of the most rapid and reliable direct injection mass spectrometry techniques was used. PTR-QMS was adopted to investigate the real biogas mixture stability. The concentration losses were studied continuously during 24 h from the sampling. These losses may be related to the wall adsorption and/or through the wall diffusion phenomena. The most stable compounds detected were acetone, methanol and formaldehyde with a concentration loss below 5%. Terpenes and sulphur compounds had a concentration loss of around 50%, while hydrocarbons and aromatic compounds showed concentration losses around 60%. The stability of the compounds monitored with acceptable losses (below 5%), was achieved within the first 3 h after the sampling was carried out.

Activated carbon fiber filters could reduce the risk of surgical smoke exposure during laparoscopic surgery: application of volatile organic compounds.

Generation of smoke is inevitable during surgical procedures. Some volatile organic compounds (VOCs) in surgical smoke are known to be strong carcinogens. We used a prototype of a multi-layered complex filter in an attempt to eliminate VOCs. From June 2015 to July 2015, 20 patients underwent transperitoneal laparoscopic nephrectomy for renal cell carcinoma. Smoke (pre-filter) was collected 20min after the electrocautery device was first used during the surgery, by the direct collection method, with a 5-L Tedlar® gas-sampling bag. Twenty and 120min after the filter was applied, smoke (post-filter) was again collected using the same method. The sample was analyzed by gas chromatography and mass spectrography. The cancer risk and hazard quotient were analyzed based on US Environmental Protection Agency guidelines. Twenty patients with a median age of 54.5 (30-80) years were enrolled in the study. Eighteen VOCs were detected using the Japanese indoor air standards mix analysis. The total elimination rate of the VOCs was 86.49 ± 2.83%. The post-filter (120min) cancer risk (mean ± standard deviation) reduced to a negligible level for benzene, ethylbenzene, and styrene except 1,2-dichloroethane. The post-filter (120min) hazard quotient for each compound decreased to levels posing a negligible risk for acetone, hexane, benzene, toluene, p-xylene, o-xylene, and styrene. Strong carcinogens, such as 1,2-dichloroethane, benzene, and ethylbenzene, were eliminated by more than 85% by using this activated carbon fiber filter and the risks from these compounds decreased to an almost negligible level. We suggest using every measure, including these filters, to protect the health of operating room personnel.

Thermal desorption comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry for vapour phase mainstream tobacco smoke analysis

A thermal desorption comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (TD-GC×GC-TOFMS) method has been developed for the analysis of mainstream tobacco smoke (MTS) vapour phase (VP). The selection process of the sample introduction approach involved comparing the results obtained from three different approaches: a) use of gas sampling bag followed by SPME (Tedlar®-SPME), b) gas sampling bag followed by TD (Tedlar®-TD), and c) sampling directly on TD sorbents (Direct-TD). Six different SPME fibers and six different TD sorbent beds were evaluated for the extraction capacities in terms of total number of peaks and related intensities or peak areas. The best results were obtained for the Direct-TD approach using Tenax TA/Carbograph1TD/Carboxen1003 sorbent tubes. The optimisation of TD tube desorption parameters was carried out using a face-centered central composite experimental design and resulted in the use of the Tenax TA/Carbograph 1TD/Carboxen 1003 sorbent with a 7.5min desorption time, a 60mL/min tube desorption flow, and a 250°C tube desorption temperature. The optimised method was applied to the separation of MTS-VP constituents, with 665 analytes detected. The method precision ranged from 1% to 15% for over 99% of identified peak areas and from 0% to 3% and 0% to 1% for both first (1tR) and second (2tR) dimension retention times, respectively. The method was applied to the analyses of two cigarette types differing in their filter construction. Principal component analysis (PCA) allowed a clear differentiation of the studied cigarette types (PC1 describing 94% of the explained variance). Supervised Fisher ratio analysis permitted the identification of compounds responsible for the chemical differences between the two sample types. A set of 91 most relevant compounds was selected by applying a Fisher ratio cut-off approach and most of them were selectively removed by one of the cigarette filter types.

A study of CO/syngas bioconversion by Clostridium autoethanogenum with a flexible gas-cultivation system.

Bioconversion of CO/syngas to produce ethanol is a novel route in bioethanol production, which can be accomplished by some acetogens. Specific culture vessels and techniques are needed to cultivate these microorganisms since they are anaerobic and substrates are gaseous. In this work, gas-sampling bag was applied as a gas-cultivation system to study CO/syngas bioconversion by Clostridium autoethanogenum and was demonstrated to be efficient because of its flexibility and excellent ability to maintain the headspace atmosphere. C. autoethanogenum can use CO as the sole carbon and energy source to produce ethanol, acetate as well as CO2. In the experimental range, higher ethanol production was favored by higher yeast extract concentrations, and the maximum ethanol concentration of 3.45g/L was obtained at 1.0g/L of yeast extract. Study with various bottled gases showed that C. autoethanogenum preferred to use CO other than CO2 and produced the highest level of ethanol with 100% CO as the substrate. C. autoethanogenum can also utilize biomass-generated syngas (36.2% CO, 23.0% H2, 15.4% CO2, 11.3% N2), but the process proceeded slowly and insufficiently due to the presence of O2 and C2H2. In our study, C. autoethanogenum showed a better performance in the bioconversion of CO to ethanol than Clostridium ljungdahlii, a strain which has been most studied, and for both strains, ethanol production was promoted by supplementing 0.5g/L of acetate.