Electronic Nose Functionality for Breath Gas Analysis during Parabolic Flight

The presence of humans in space represents a constant threat for their health and safety. Environmental factors such as living in a closed confinement, as well as exposure to microgravity and radiation, are associated with significant changes in bone metabolism, muscular atrophy, and altered immune response, which has impacts on human performance and possibly results in severe illness. Thus, maintaining and monitoring of crew health status has the highest priority to ensure whole mission success. With manned deep space missions to moon or mars appearing at the horizon where short-term repatriation back to earth is impossible the availability of appropriate diagnostic platforms for crew health status is urgently needed. In response to this need, the present experiment evaluated the functionality and practicability of a metal oxide based sensor system (eNose) together with a newly developed breath gas collecting device under the condition of altering acceleration. Parabolic flights were performed with an Airbus A300 ZeroG at Bordeaux, France. Ambient air and exhaled breath of five healthy volunteers was analyzed during steady state flight and parabolic flight maneuvres. All volunteers completed the study, the breath gas collecting device valves worked appropriately, and breathing through the collecting device was easy and did not induce discomfort. During breath gas measurements, significant changes in metal oxide sensors, mainly sensitive to aromatic and sulphur containing compounds, were observed with alternating conditions of acceleration. Similarly, metal oxide sensors showed significant changes in all sensors during ambient air measurements. The eNose as well as the newly developed breath gas collecting device, showed appropriate functionality and practicability during alternating conditions of acceleration which is a prerequisite for the intended use of the eNose aboard the International Space Station (ISS) for breath gas analysis and crew health status monitoring. The observed changes in breath gas composition are most likely associated with changes in ambient air volatile organic and inorganic compound composition and require further evaluation.     

Development of a multibed sorption trap, comprehensive two-dimensional gas chromatography, and time-of-flight mass spectrometry system for the analysis of volatile organic compounds in human breath

A method for the determination of volatile organic compounds (VOCs) at sub-trace levels in breath samples based on a multibed sorption trap for the collection and concentration of VOCs, a comprehensive multidimensional gas chromatograph (GCxGC) for the separation of complex mixtures, and a time-of-flight mass spectrometer detector is designed and developed. The good performance of the trap tube device developed for the concentration together with the high sensitivity and separation power of the GCxGC results in a powerful system. In the analysis of samples, more than 100 different compounds are detected of which between 65 and 85 are clearly identified. A total of approximately 250 different compounds are observed in all the samples evaluated of which 142 are identified. A preliminary study to evaluate breath biomarkers for active smoking is performed. The levels of previously described biomarkers are found to be strongly time-dependent with amounts found approximately 1 h after smoking returning to the levels found in nonsmoking volunteers. However, 2,5-dimethylfuran, 2-methylfuran, and furan are found to be effective biomarkers given that they were only found in samples taken from smokers and could still be detected more than 2 h after smoking.     

卷烟商标残留成份SPME-GC/MS分析

本文建立了一种研究卷烟商标残留挥发性有机物(VOCs)的快速分析方法。利用顶空固相微萃取(HS-SPME)技术对样品进行前处理,与GC-MS联用对卷烟商标残留有机挥发性成份进行分析。并对纤维头类型、平衡时间、萃取温度等参数进行了优化,着重对SMPE重复性进行了讨论。确定SPME条件为65μmCW/DVB纤维头、平衡时间为20min、萃取温度为100℃。结果表明该方法可有效地分析羟基环已基苯甲酮、二苯甲酮、酯类化合物以及苯系物,为卷烟商标质量控制与有害成份监控提供依据。     

Atmospheric pressure air direct current glow discharge ionization source for ion mobility spectrometry

A new atmospheric pressure air direct current glow discharge (DCGD) ionization source has been developed for ion mobility spectrometry (IMS) to overcome the regularity problems associated with the conventional (63)Ni source and the instability of the negative corona discharge. Its general electrical characteristics were experimentally investigated. By equipping it to IMS, a higher sensitivity was obtained compared to that of a (63)Ni source and corona discharge, and a linear dynamic range from 20 ppb to 20 ppm was obtained for m-xylene. Primary investigations showed that alkanes, such as pentane, which are nondetectable or insensitively detectable with (63)Ni-IMS, can be efficiently detected by DCGD-IMS and the detection limit of 10 ppb can be reached. The preliminary results have shown that the new DCGD ionization source has great potential applications in IMS, such as online monitoring of environment pollutants and halogenated compounds.     

Application of low-temperature glassy carbon-coated macrofibers for solid-phase microextraction analysis of simulated breath volatiles

With increasing interest in the detection of disease-related volatile organic compounds (VOCs) found in human breath, breath analysis could prove to be a very useful diagnostic tool, especially for the early detection of lung cancer. Solid-phase microextraction (SPME) is a technique well suited for breath analysis and has been applied to studying VOCs in the nanomolar concentration range. However, many compounds of interest in human breath are excreted at picomolar concentrations and may be unsuitable for analysis using conventional SPME sorbent phases. To extend the concentration range of conventional SPME, a novel 4-cm-long, low-temperature glassy carbon (LTGC) macrofiber was developed. The LTGC SPME macrofibers were used to extract five lung cancer-related VOCs (2-methylheptane, styrene, propylbenzene, decane, undecane) at conditions simulating human breath, and they were analyzed via gas chromatography/mass spectrometry. Results show that detection limits are lower using the SPME macrofibers compared to a conventional SPME fiber, in the low- to sub-picomolar range for the compounds of interest, which should be adequate for the analysis of these compounds in human breath. Also, the LTGC SPME macrofibers demonstrate significantly greater extraction efficiencies, sensitivity, and peak identification accuracy compared to that of commercial PDMS/DVB fibers without excessive chromatographic peak broadening. The use of SPME macrofibers broadens the potential range of application of SPME where the rapid extraction of very low levels of volatile compounds is required.     

A field-portable plasma source monitor for real-time air particulate monitoring

In this research, a novel portable instrument for on-site, real-time air particulate monitoring was developed. It is highly desirable to use microwave plasmas for on-site, real-time environmental and occupational hazard monitoring because they can be sustained with various gases at relatively low power and possess excellent detection capabilities for both metal and nonmetal air pollutants. In the new instrument design, a microwave plasma was selected as an excitation source and was used in conjunction with atomic emission spectrometry. A small, integrated spectrometer with a charge-coupled detector (CCD) was used for optical signal detection. An efficient, in situ air-sampling system was developed for direct sampling of air particles into the plasma. Characterization and calibration of the new instrument were achieved with an in-house-fabricated high-efficiency nebulization-desolvation system. Tolerance of the microwave argon plasma source to air introduction was tested, and the operational parameters were optimized. Analytical performance and the feasibility of the newly developed portable instrument for aerosol particle analysis were evaluated. Some advantages and possible applications of the new instrument are discussed. The instrument provides an innovative tool for rapid environmental and occupational hazard monitoring.     

Ion mobility spectrometry of gas-phase ions from laser ablation of solids in air at ambient pressure

A mobility spectrometer was used to characterize gas-phase ions produced from laser ablation of solids in air at 100 degrees C and at ambient pressure with a beam focused to a diameter of 相似文献   

Exhaust air heat recovery in buildings

The technique of heat recovery from ventilation air in dwellings started in Sweden in late 1979. This was due to an energy crisis and new building codes. The competing heat recovery system, air to air heat exchangers, had a firm grip on the market. Today the situation is on the contrary. Almost all new single family houses are equipped with exhaust air heat pumps. This paper describes the development of the market in Sweden and Germany and also the different techniques of supplementary heating due to national differences in electricity prices. Germany has a situation very similar to Sweden concerning new building codes concerning the allowable energy use for space heating. Starting in 1976 and continued from 1982 to 1995, the building code has prescribed tighter and more insulated houses. The new building code for the year 2000 contains requirements for well insulated and tight buildings so the energy demand for heating from ventilation air tends to reach about 60% of the total annual energy demand for the building. Under these circumstances new buildings must have ventilation systems with heat recovery. Different means of heat recovery from the ventilation system, and the benefit for the environment, by using heat pumps are described. The German market for heat recovery systems is approx. 5–10.000 units/year. Most important for the efficiency of a ventilation system is to maintain the quality criterias concerning:equipmentplanning, installation, taking into operationoperation.VEW ENERGIE AG has accomplished a field survey of 60 units from 1994 to 1996. As the result was not statistically sufficient, the field survey is followed by an investigation into air quality and reliability.     

Electrochemical oxidation by square-wave potential pulses in the imitation of oxidative drug metabolism

Electrochemistry combined with mass spectrometry (EC-MS) is an emerging analytical technique in the imitation of oxidative drug metabolism at the early stages of new drug development. Here, we present the benefits of electrochemical oxidation by square-wave potential pulses for the oxidation of lidocaine, a test drug compound, on a platinum electrode. Lidocaine was oxidized at constant potential and by square-wave potential pulses with different cycle times, and the reaction products were analyzed by liquid chromatography-mass spectrometry [LC-MS(/MS)]. Application of constant potentials of up to +5.0 V resulted in relatively low yields of N-dealkylation and 4-hydroxylation products, while oxidation by square-wave potential pulses generated up to 50 times more of the 4-hydroxylation product at cycle times between 0.2 and 12 s (estimated yield of 10%). The highest yield of the N-dealkylation product was obtained at cycle times shorter than 0.2 s. Tuning of the cycle time is thus an important parameter to modulate the selectivity of electrochemical oxidation reactions. The N-oxidation product was only obtained by electrochemical oxidation under air atmosphere due to reaction with electrogenerated hydrogen peroxide. Square-wave potential pulses may also be applicable to modulate the selectivity of electrochemical reactions with other drug compounds in order to generate oxidation products with greater selectivity and higher yield based on the optimization of cycle times and potentials. This considerably widens the scope of direct electrochemistry-based oxidation reactions for the imitation of in vivo oxidative drug metabolism.     

A sensitive method for the quantification of acrolein and other volatile carbonyls in ambient air

Acrolein, an unsaturated aldehyde found in both indoor and outdoor air, is considered one of the greatest noncancer health risks of all organic air pollutants. Current methods for determining acrolein often employ sorbent-filled cartridges containing a carbonyl derivatizing agent (e.g., dinitrophenylhydrazine). These methods are of limited use for unsaturated compounds due to the formation of unstable derivatives, coelution of similar compounds, long sample collection times, and ozone interferences that result in poor sensitivity, selectivity, and reproducibility. The goal of this research was to develop an analytical method for determining ppt concentrations of acrolein and other carbonyls in air with short sampling times (10 min). The method uses a mist chamber to collect carbonyls by forming water-soluble carbonyl-bisulfite adducts. The carbonyls are then liberated from the bisulfite, derivatized, and quantified by gas chromatography/electron capture negative ionization mass spectrometry. The method was applied to determine atmospheric acrolein concentrations at three sites in northern California reflecting hemispheric background concentrations, biogenic-dominated regions, and urban environments. The resulting acrolein concentrations were 0.056, 0.089, and 0.29 microg/m3, respectively, which are all above the EPA Reference Concentration of 0.02 microg/m3. The minimum detection limit of 0.012 microg/m3 is below that of other published methods. Methacrolein, methyl vinyl ketone, crotonaldehyde, glyoxal, methyl glyoxal, and benzaldehyde were also quantified.     

Bioconcentration factors for volatile organic compounds in vegetation

Samples of air and leaves were taken at the University of Nevada [Formula: see text] Las Vegas campus and analyzed for volatile organic compounds using vacuum distillation coupled with gas chromatography/mass spectrometry. The data were used to estimate the bioconcentration of volatile organic compounds (VOCs) and to characterize the equilibration of VOCs between the leaves and air. The bioconcentration of volatiles in the leaves of some species can be predicted using the partition coefficients between air and octanol (K(oa)) and only considering VOC absorption in the lipid fraction of leaves. For these leaves, the bioconcentration factors agreed with existing models. Leaves of some species displayed a bioconcentration of volatiles that greatly exceeded theory. These hyperbioconcentration leaves also contain appreciable concentrations of monoterpenes, suggesting that a terpenoid compartment should be considered for the bioconcentration of organic compounds in leaves. Adding an additional "terpenoid" compartment should improve the characterization of volatile organic compounds in the environment. The uptake of VOCs from air by leaves is rapid, and the equilibration rates are seen to be quicker for compounds that have higher vapor pressures. The release of VOCs from the leaves of plants is slower for hyperbioconcentration leaves.     

Experimental upgrades of membrane introduction mass spectrometry for water and air analysis

Some improvements to the membrane introduction mass spectrometry (MIMS) technique, resulting in low-ppt detection limits for volatile organohalogen compounds (CX) in water (namely, chloroform, bromoform, bromodichloromethane, chlorodibromomethane, tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane, and carbon tetrachloride) and low-microgram per cubic meter detection limits for benzene, toluene, ethylbenzene, and xylenes (BTEX) in gaseous samples, are shown. A static MIMS configuration was compared to a dynamic one, the former requiring longer time to obtain the analytical response. A cryotrapping preconcentration step is introduced and linearity of response, mixture effects, and detection limits are presented. The instrumental setup consists of a hollow fiber silicone membrane, a water or air container, a cryofocusing trap based on Tenax adsorbent, a Peltier cell, and a Varian ion trap benchtop mass spectrometer is described. This instrumental setup, which we named membrane extraction trap focusing mass spectrometry, allowed the detection of CX in water at a concentration as low as 8 ppt and of benzene in air at 0.1 microg/m3. The whole assembly shows great potential for on-site routine monitoring of drinking water resources and urban and indoor air under current EU and Italian regulations.     

Breath analysis and monitoring by membrane extraction with sorbent interface

An analytical system consisting of a sampling chamber, membrane extraction module, sorbent trap and gas chromatograph with flame ionization or ion mobility detector was used for on-line monitoring of the composition of the last 250 mL portion of human expired breath. The sampling chamber consisted of a tube fitted with check valves on both ends to allow the air to pass through during expiration, but not to return or allow mixing with ambient air. The last portion of breath was held in the chamber at the end of breath expiration. The organic components in the trapped breath were transferred to the carrier gas by permeation through the membrane in the extraction module and were concentrated in the sorbent trap before introduction as a sharp plug on the front of chromatographic column. Moisture in the breath did not penetrate the membrane to a substantial degree. This system was used to investigate presence of acetone as a biologically important marker of human health as well as exposure to volatile compounds.     

Real-time, on-line characterization of diesel generator air toxic emissions by resonance-enhanced multiphoton ionization time-of-flight mass spectrometry

The laser-based resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) technique has been applied to the exhaust gas stream of a diesel generator to measure, in real time, concentration levels of aromatic air toxics. Volatile organic compounds, as well as several polycyclic aromatic hydrocarbons were detected in the concentration range of 10-200 ppb in the steady-state diesel generator exhaust. The results were verified and compared with conventional extractive sampling and analytical techniques using gas chromatography/mass spectrometry (GC/MS). The high isomer selectivity of the REMPI-TOFMS instrument provided data for individual xylene isomers that are otherwise (partially) coeluting in standard GC/MS analyses. Good agreement was observed between results for volatile and semivolatile organic compounds obtained with REMPI-TOFMS and conventional extractive sampling. Transient events, such as cold start-ups of the diesel generator, resulted in sharp (less than 15 s) peak emissions that were, for benzene, up to a factor of 90 higher than the predominately constant concentrations observed during steady-state operation; warm restarts resulted in lower peak concentrations by a factor of 2.5. These fast transient emissions are only detectable using a real-time approach (1-s resolution) as demonstrated here using REMPI-TOFMS.     

Cobalt modified solid superacid assisted electrochemical reaction of toluene with methanol

The electrochemical catalytic reaction of toluene with methanol, assisted with a pair of porous graphite plate electrodes, catalyzed by solid superacid of cobalt modification catalyst with chemical conversion higher than 81%, was described and investigated by UV-vis spectrum, scan electron microscopy (SEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and gas chromatography-mass spectrometry (GC-MS). A possible free radical reaction mechanism was proposed. It may be concluded that a simply and feasible electrochemical catalytic coupling oxidation reaction at room temperature and air pressure may be possible.     

High-throughput data analysis for detecting and identifying differences between samples in GC/MS-based metabolomic analyses

In metabolomics, the objective is to identify differences in metabolite profiles between samples. A widely used tool in metabolomics investigations is gas chromatography-mass spectrometry (GC/MS). More than 400 compounds can be detected in a single analysis, if overlapping GC/MS peaks are deconvoluted. However, the deconvolution process is time-consuming and difficult to automate, and additional processing is needed in order to compare samples. Therefore, there is a need to improve and automate the data processing strategy for data generated in GC/MS-based metabolomics; if not, the processing step will be a major bottleneck for high-throughput analyses. Here we describe a new semiautomated strategy using a hierarchical multivariate curve resolution approach that processes all samples simultaneously. The presented strategy generates (after appropriate treatment, e.g., multivariate analysis) tables of all the detected metabolites that differ in relative concentrations between samples. The processing of 70 samples took similar time to that of the GC/TOFMS analyses of the samples. The strategy has been validated using two different sets of samples: a complex mixture of standard compounds and Arabidopsis samples.     

Study of double bond equivalents and the numbers of carbon and oxygen atom distribution of dissolved organic matter with negative-mode FT-ICR MS

A strong linear relationship was observed between the average double bond equivalence (DBE) and the ratio of carbon to oxygen atoms in oxygenated compounds of dissolved organic matter (DOM). Data were acquired by a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS), equipped with a negative-mode electrospray ionization source. The slope and y-intercepts extracted from the linear relationship can be used to compare DOM samples originating from different locations. Significant differences in these parameters were observed between inland riverine and offshore coastal DOM samples. Offshore coastal DOM molecules underwent a change of one DBE for each removal or addition of two oxygen atoms. This suggested the existence of multiple carboxyl groups, each of which contains a double bond and two oxygen atoms. Inland riverine samples exhibited a change of ~1.5 DBE following the addition or removal of two oxygen atoms. This extra change in DBE was attributed to cyclic structures or unsaturated chemical bonds. The DBE value with maximum relative abundance and the minimum DBE value for each class of oxygenated compounds showed that approximately two oxygen atoms contributed to a unity change in DBE. The qualitative analyses given here are in a good agreement with results obtained from analyses using orthogonal analytical techniques. This study demonstrates that DBE and the carbon number distribution, observed by high resolution mass spectrometry, can be valuable in elucidating and comparing structural features of oxygenated molecules of DOM.