Maomian Fan

Evaluation of Bio-VOC Sampler for Analysis of Volatile Organic Compounds in Exhaled Breath

Monitoring volatile organic compounds (VOCs) from exhaled breath has been used to determine exposures of humans to chemicals. Prior to analysis of VOCs, breath samples are often collected with canisters or bags and concentrated. The Bio-VOC breath sampler, a commercial sampling device, has been recently introduced to the market with growing use. The main advantage for this sampler is to collect the last portion of exhaled breath, which is more likely to represent the air deep in the lungs. However, information about the Bio-VOC sampler is somewhat limited. Therefore, we have thoroughly evaluated the sampler here. We determined the volume of the breath air collected in the sampler was approximately 88 mL. When sampling was repeated multiple times, with the succeeding exhalations applied to a single sorbent tube, we observed linear relationships between the normalized peak intensity and the number of repeated collections with the sampler in many of the breath VOCs detected. No moisture effect was observed on the Tenax sorbent tubes used. However, due to the limitation in the collection volume, the use of the Bio-VOC sampler is recommended only for detection of VOCs present at high concentrations unless repeated collections of breath samples on the sampler are conducted.

The identification of hypoxia biomarkers from exhaled breath under normobaric conditions

Pilots have reported experiencing in-flight hypoxic-like symptoms since the inception of high-altitude aviation. As a result, the need to monitor pilots, in-flight, for the onset of hypoxic conditions is of great interest to the aviation community. We propose that exhaled breath is an appropriate non-invasive medium for monitoring pilot hypoxic risk through volatile organic compound (VOC) analysis. To identify changes in the exhaled breath VOCs produced during periods of reduced O2 levels, volunteers were exposed to simulated flight profiles, i.e. sea level for 5 min, O2 levels found at elevated altitudes for 5 min or placebo and 5 min at 100% O2 recovery gas, using a modified flight mask interfaced with a reduced O2 breathing device. During the course of these test events, time series breath samples from the flight mask and pre/post bag samples were collected and analyzed by gas chromatography/mass spectrometry (GC/MS). Seven compounds (pentanal, 4-butyrolactone, 2-pentanone, 2-hexanone, 2-cyclopenten-1-one, 3-methylheptane and 2-heptanone) were found to significantly change in response to hypoxic conditions. Additionally, the isoprene, 2-methyl-1,3-butadiene, was found to increase following the overall exposure profile. This study establishes an experimental means for monitoring changes in VOCs in response to hypoxic conditions, a computational workflow for compound analysis via the Metabolite Differentiation and Discovery Lab and MatLab(©) software and identifies potential volatile organic compound biomarkers of hypoxia exposure.

The stability of Tenax TA thermal desorption tubes in simulated field conditions on the HAPSITE® ER

Due to the growing need to monitor aircraft cabin, cockpit and breathing-line air quality, functional assessment of sampling equipment for the specialised field conditions of flight need to be established for both in-flight and ground safety. In this article, we assess the reliability of Tenax TA thermal desorption tubes to perform under various relevant field sampling conditions, such as storage temperature, loading temperature, vibrational velocity, gravitational force (G Force) and altitude pressure with semi-real-time gas chromatograph-mass spectrometer (GC-MS) analysis on the field portable HAPSITE® ER (Hazardous Air Pollutants on Site Extended Range) instrument. First, we show that Tenax TA thermal desorption tubes can handle storage under extreme environmental conditions, 4–77°C, over numerous analytical test cycles. Next, we confirm that extreme loading temperature, both hot (77°C) and cold (4°C), does not affect the analytical reliability of Tenax TA thermal desorption tubes. Then, we illustrate that G Force may have a significant (p ≤ 0.0364) effect on Tenax TA performance while vibrational velocity (p ≤ 0.7265) and low ambient air pressure (p ≤ 0.1753), such as that found at high altitude, do not. Finally, several Tenax TA thermal desorption tubes were flight-tested, demonstrating that the durability of these tubes maybe insufficient for use on military cargo aircraft (p = 0.0107). The results presented here provide a rationale for additional testing of Tenax TA thermal desorption tubes for flight suitability.

Storage stability of exhaled breath on Tenax TA

Exhaled breath is coming to the forefront of non-invasive biomarker discovery efforts. Concentration of exhaled breath volatile organic compounds (VOCs) on thermal desorption (TD) tubes with subsequent analysis by gas chromatography-mass spectrometry (GC-MS) has dominated this field. As discovery experimentation increases in frequency, the need to evaluate the long-term storage stability of exhaled breath VOCs on thermal desorption adsorbent material is critical. To address this gap, exhaled breath was loaded on Tenax TA thermal desorption tubes and stored at various temperature conditions. 74 VOCs, 56 of which have been previously uncharacterized, were monitored using GC-MS over a period of 31 d. The results suggest that storage of exhaled breath at cold temperatures (4 °C) provides the most consistent retention of exhaled breath VOCs temporally. Samples were determined to be stable up to 14 d across storage conditions prior to gaining or losing 1-2 standard deviations in abundance. Through gene set enrichment analysis (GSEA), certain chemical classes were found to be positively (acids) or negatively (sulfur-containing) enriched temporally. By means of field sample collections, the effect of storage and shipping was found to be similar to those studies preformed in the laboratory at 4 °C. Collectively this study not only provides recommendations for proper storage conditions and storage length, but also illustrates the use of GSEA to exhaled breath based GC-MS data.

Detection of volatile organic compounds indicative of human presence in the air

Volatile organic compounds were collected and analyzed from a variety of indoor and outdoor air samples to test whether human-derived compounds can be readily detected in the air and if they can be associated with human occupancy or presence. Compounds were captured with thermal desorption tubes and then analyzed by gas chromatography with mass spectrometry. Isoprene, a major volatile organic compound in exhaled breath, was shown to be the best indicator of human presence. Acetone, another major breath-borne compound, was higher in unoccupied or minimally occupied areas than in human-occupied areas, indicating that its majority may be derived from exogenous sources. The association of endogenous skin-derived compounds with human occupancy was not significant. In contrast, numerous compounds that are found in foods and consumer products were detected at elevated levels in the occupied areas. Our results revealed that isoprene and many exogenous volatile organic compounds consumed by humans are emitted at levels sufficient for detection in the air, which may be indicative of human presence.

Field sampling demonstration of portable thermal desorption collection and analysis instrumentation

ABSTRACT The HAPSITE® (Hazardous Air Pollutants on Site) is a portable gas chromatography-mass spectrometry (GC–MS) unit designed to aid air sampling technicians by identifying and quantifying volatile organic compounds from occupational and environmental sampling. The main goal of the present study was to extend prior laboratory-based work with the portable HAPSITE® ER (extended range model) thermal desorption (TD) capability to real-world field samples from both indoor and outdoor environments using different types of active and passive sampling mechanisms. Understanding the performance of the HAPSITE® ER in a realistic field setting will allow air quality sampling technicians to make improved decisions related to sampling and analysis methods in the field. An important finding was that certain charcoal-based TD sorbents were contraindicated for the HAPSITE® ER because of a substantial hydrocarbon bleed which degraded system performance. A novel time series TD sampler (Logistically Enabled Sampling System-Portable [LESS-P]) was validated using Tenax TA TD tubes against standard active sampling across multiple field sampling sites, and the qualitative analytical trends and compound identities were similar between LESS-P replicates analysed via benchtop GC–MS and HAPSITE® ER. Once validated, the LESS-P was used to determine the reference concentrations for passive sampling calculations. The results confirmed the passive sampling methodology within the benchtop system, but highlighted some systemic sensitivity limitations that must be addressed in order for the HAPSITE® to be accurately applied to passive sampling. We propose that the LESS-P time-series sampler may help to alleviate the requirement for sampling technicians to be on-site during active sampling, allowing for automated sampling throughout the duration of a sampling event.

Comparison of Sampling Probe and Thermal Desorber in HAPSITE ER for Analysis of TO-15 Compounds

The Hazardous Air Pollutants on Site (HAPSITE), a portable Gas Chromatograph-Mass Spectrometer (GCMS), has been used to detect, identify, and quantify Volatile Organic Compounds (VOCs) from environmental samples, providing on-site analysis to aid in operational risk management. HAPSITE is equipped with a hand-held sampling probe in which an air sample is delivered into a concentrator, and the VOCs collected in the concentrator are transferred, separated, and identified in the GC-MS. An upgraded version, HAPSITE ER, has recently been introduced with additional sampling capability for solid phase micro extraction and Thermal Desorption (TD). To our knowledge, however, no study has yet evaluated the performance of the thermal desorber accommodated in HAPSITE ER. In this study, therefore, we analyzed EPA Method TO-15 compounds with two different sampling methods (probe and thermal desorber for TD tubes) in a HAPSITE ER, and compared their results against each other. A major finding was that the peak intensities of the TO-15 compounds, particularly those with high Boiling Point (BP), were substantially higher in the results obtained with the thermal desorber than in those with the sampling probe. The lower peak intensities of the compounds observed in the probe analysis are likely due to the condensation of the VOCs in the probe (transfer) line that is 6 feet long and maintained at 40°C as they are delivered from the probe to the concentrator, whereas the thermal desorber is directly connected to the HAPSITE (no transfer line is used), thereby eliminating the condensation of VOCs. In conclusion, our study suggests that for the analysis of VOCs with high up to 220°C, the use of TD tubes followed by desorption in the thermal desorber offered by the newer version of HAPSITE is recommended.

Evaluation of thermal desorption analysis on a portable GC–MS system

ABSTRACT The HAPSITE-ER-TD (Hazardous Air Pollutants on Site Extended Range HAPSITE-ER) portable gas chromatograph–mass spectrometer (GC–MS) combines the sensitivity of a thermal desorption (TD) GC–MS with the advantages of field-portable instrumentation. Though previous iterations of the HAPSITE have been extensively evaluated in the literature, performance assessment of the TD-equipped instrument is lacking. In this manuscript, the variability in the HAPSITE-ER-TD response was established for both internal standards and test compounds across three instruments over a 5-week time course. These data show poor normalised internal standard reproducibility with %RSD values from 17.84% to 49.97% on the HAPSITE-ER-TD when compared to a bench-top instrument (%RSD < 11.6%), suggesting that use of TD tubes preloaded with an internal standard may be valuable for normalisation purposes. Though our determined method detection limit (MDL) values reveal that substantial variabilities exist between separate HAPSITE-ER-TD systems, MDL values comparable to the standard bench-top equipment can be achieved. Additionally, data generated with the TO-15/TO-17 65 component target compound mix and JP-8 jet fuel show statistically significant (p value = 0.0014) compound-dependent system carryover on the HAPSITE-ER-TD, indicating that procedural modifications to eliminate instrumental carryover may be necessary. This study establishes several limitations associated with the use of the HAPSITE-ER TD accessory with suggestions for addressing the shortcomings to allow for reliable field use.

Dimerization Products of Chloroprene are Background Contaminants Emitted from ALTEF (Polyvinylidene Difluoride) Gas Sampling Bags

Gas sampling bags have been used for collecting air samples. Tedlar bags are most commonly used, but bleed background chemicals such as N,N-dimethylacetamide and phenol. It is often necessary to remove the contaminant by flushing the bags with pure nitrogen or air. In this study, we identified four chloroprene dimerization products as background contaminants emitted from ALTEF bags that are made of a proprietary polyvinylidene difluoride (PVDF). No monomer chloroprene was detected in the bags analyzed. All of the dimers gradually increased once bags were filled with nitrogen due to diffusion from the bag surface. Flushing the bags with nitrogen reduced their concentrations, but was not effective for removing the contaminants. When the bags that had been flushed with nitrogen 5 times were left for 24 h, they increased again, indicating that the dimers were constantly emitted from the ALTEF bag surface. To our knowledge, these compounds have never been demonstrated in ALTEF or other PVDF bags. Our finding indicates that ALTEF might be incorporated with Neoprene (chloroprene-based polymer) during its manufacturing process.