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.     

A universal temperature controlled membrane interface for the analysis of volatile and semi-volatile organic compounds

A universal temperature controlled membrane interface (TCMI) has been constructed for hollow-fibre membranes. The membrane temperature is controllable in the range -70 to 250 degrees C using an electric heater and a flow of cooled nitrogen or helium gas. Volatile and semi-volatile organic compounds may be detected either by continuous diffusion across the membrane or by in-membrane pre-concentration followed by thermal desorption into the detector. The TCMI interface is demonstrated in combination with mass spectrometry and GC-MS, for the determination of VOCs and SVOCs in aqueous and air samples and for the on-line monitoring of a bioreactor.     

Development of a sensitive thermal desorption method for the determination of trihalomethanes in humid ambient and alveolar air

A sensitive and reliable method has been developed for the determination of trihalomethanes (THMs) in air samples through adsorption in sorbent tubes and thermal desorption (TD) of the compounds, followed by gas chromatography (GC)–mass spectrometry (MS) analysis. Three commercial sorbent materials were compared in terms of adsorption efficiency and breakthrough volume, finding Chromosorb 102 to be the most appropriate adsorbent for air sampling. The method allows us to reach detection limits of 0.03 ng (0.01 μg m⁻³ for 3 l of air), linear ranges from 0.1 to 2000 ng and specific uncertainties of ca. 5.0 ± 0.2 ng for all THMs. Several salts were tested to reduce water retention (from the humid air of an indoor swimming pool) at the sampling stage, Na₂SO₄ being the one that provides optimum efficiency. The method was validated by a new recovery study in which several tubes with and without adsorbent were spiked with THMs and analyzed by TD-GC/MS, recoveries ranging from 92% to 97% for all the compounds. Finally, the performance of the method was evaluated through the analysis of ambient air samples from an indoor swimming pool and alveolar air samples from swimmers to assess their THM uptake. THMs were found to be stable in the sorbent tubes for at least 1 month when stored at 4 °C.     

Determination of methylmercury fluxes across the air–water and air–soil interfaces by gas chromatography with electron capture detection

A method for the determination of methylmercury (MeHg) fluxes across the air–water and air–soil interfaces was developed using an in situ chamber. The MeHg in the air coming out of the chamber was captured by a column containing sulfhydryl cotton fiber adsorbent. MeHg was then desorbed from the column by using 2 mol L^–1 HCl. The MeHg in the effluent was extracted with benzene, and determined by gas chromatography with electron capture detection. Finally, the MeHg flux was calculated using the chamber. The method was applied to simulated experiments, and the results showed that the MeHg fluxes in the air–water system were higher than those in the air–soil–water system. The method was also successfully applied to the field measurements of an environment polluted by a chemical factory, and the results showed that the MeHg fluxes across the air–soil and air–water interfaces were 0.21–3.09 and 0.14–0.79 ng m^–2 h^–1, respectively. The method will be a useful tool in the environmental study of MeHg.     

Hydroxyl radical at the air-water interface

Interaction of the hydroxyl radical with the liquid water surface was studied using classical molecular dynamics computer simulations. From a series of scattering trajectories, the thermal and mass accommodation coefficients of OH on liquid water at 300 K were determined to be 0.95 and 0.83, respectively. The calculated free energy profile for transfer of OH across the air-water interface at 300 K exhibits a minimum in the interfacial region, with the free energy of adsorbtion (DeltaGa) being about 1 kcal/mol more negative than the hydration free energy (DeltaGs). The propensity of the hydroxyl radical for the air-water interface manifests itself in partitioning of OH radicals between the bulk water and the surface. The enhancement of the surface concentration of OH relative to its concentration in the aqueous phase suggests that important OH chemistry may be occurring in the interfacial layer of water droplets, aqueous aerosol particles, and thin water films adsorbed on solid surfaces. This has profound consequences for modeling heterogeneous atmospheric chemical processes.     

TG Evolved Gas Analysis Using ATD Sample Tubes

A new variation of off-line TG evolved gas analysis is reported here. Gas collection is done by inserting sample tubes filled with a suitable adsorbent, into the exhaust from the TG instrument. The following gas analysis is carried out by placing the sample tubes into a commercial thermal desorption unit which is coupled to a GC/MS. In this way, both a chromatographic separation of components as well as a mass spectral identification are obtained. Two examples from the analysis of production chemicals demonstrate the usefulness of this approach. This revised version was published online in July 2006 with corrections to the Cover Date.     

Stability of reactive low boiling hydrocarbons on carbon based adsorbents typically used for adsorptive enrichment and thermal desorption

In the context of evaluating air sampling methods, laboratory experiments were performed to investigate the stability of eleven selected low boiling hydrocarbons (e.g. 1,3-butadiene, isoprene) adsorbed on four different carbon based adsorbents. The carbon molecular sieves Carboxen 569, Carboxen 1003, Carbosieve SIII and the graphitized carbon black Carbotrap X were tested. The influence of storage duration on the recovery of the analytes was examined by loading the adsorbent tubes with the test compounds via a sample loop under inert gas. Furthermore, the influence of sampling the hydrocarbons continuously from air on the recovery of the analytes was investigated using a simple experimental set-up providing a flow of synthetic air spiked with the hydrocarbons. Analysis of the loaded adsorbent tubes was performed by thermal desorption and capillary gas chromatography. Losses up to 80% of 1,3-butadiene and isoprene were observed for the carbon molecular sieves, occurring even immediately after the sampling step. In contrast, no significant losses of these reactive constituents were detected for Carbotrap X over a storage time of seven days. The laboratory investigations were confirmed in a field experiment.     

Determination of Airborne Nicotine by Automatic Two-Stage Thermal Desorption Gas Chromatography

Abstract

An automated two-stage thermal desorption technique has been developed for the determination of airborne nicotine. Pumped samples are collected on adsorbent tubes and analysed by capillary gas chromatography using flame ionisation detection. The preconcentration effect of the adsorbent compared to solvent trapping or solvent desorption methods permits shorter sampling times and precludes the need for a selective detector.

By use of a basic program all exposure volumes and component details are entered into a method run table and after analysis exposure levels are automatically calculated and printed in report form by the data handling system. Consequently a large throughput samples may be analysed automatically and efficiently with minimal analyst involvement or sample preparation.

The technique described was originally developed to sample airborne nicotine in workplace environments where tobacco is processed. Comparison between this technique and the standard NIOSH method for airborne nicotine is discussed.     

Sorbent-Based Method for the Analysis of Ambient Air Using Supercritical Fluid Desorption/Gas Chromatography

Abstract

The work described in this paper shows how we have investigated the utility of polar polyimide sorbents for the collection of polar and non-polar volatile organic compounds in ambient air. The results indicate that supercritical carbon dioxide can be used to recover a variety of compounds with a wide range of volatilities from polyimide sorbents and that these compounds can be effectively collected onto an adsorbent micro-trap after the expansion of the fluid prior to thermal desorption gas chromatographic analysis. Molecular sieve 3A was used and found to have a very high capacity for removal of water from the supercritical fluid extract stream. The sieve tended to adsorb polar compounds in the absence of water; the presence of water sometimes reduced analyte adsorption. The method was used to collect, recover, and analyze volatile organic compounds from the air of a laboratory building and was shown to be quite sensitive for appropriate compounds.     

A simple and easily fabricated device for desorbing volatiles from porous polymers and other adsorbents

A device has been developed for the rapid desorption of organic compounds from adsorbent traps. Some advantages over previous devices include its ease of fabrication from inexpensive and readily obtainable materials, and its high portability between instruments. No major modification of the gas chromatograph (GC) inlet system is necessary and in a matter of seconds the desorber can be removed from the injection port for normal syringe injections. The adsorbent tubes can be transported into the field for sampling and returned to the laboratory for desorption and analysis by GC or GC-MS. Additionally, the device is useful for head space analysis, volatile organics analysis in aqueous solutions, and impurities in gaseous feed streams.     

Stability of reactive low boiling hydrocarbons on carbon based adsorbents typically used for adsorptive enrichment and thermal desorption

In the context of evaluating air sampling methods, laboratory experiments were performed to investigate the stability of eleven selected low boiling hydrocarbons (e.g. 1,3-butadiene, isoprene) adsorbed on four different carbon based adsorbents. The carbon molecular sieves Carboxen 569, Carboxen 1003, Carbosieve SIII and the graphitized carbon black Carbotrap X were tested. The influence of storage duration on the recovery of the analytes was examined by loading the adsorbent tubes with the test compounds via a sample loop under inert gas. Furthermore, the influence of sampling the hydrocarbons continuously from air on the recovery of the analytes was investigated using a simple experimental set-up providing a flow of synthetic air spiked with the hydrocarbons. Analysis of the loaded adsorbent tubes was performed by thermal desorption and capillary gas chromatography. Losses up to 80% of 1,3-butadiene and isoprene were observed for the carbon molecular sieves, occurring even immediately after the sampling step. In contrast, no significant losses of these reactive constituents were detected for Carbotrap X over a storage time of seven days. The laboratory investigations were confirmed in a field experiment. Received: 28 June 1999 / Revised: 18 August 1999 / Accepted: 23 August 1999     

Application of thermal desorption to the development of a gas chromatographic/mass spectrometric method for the determination of toluene,chlorinated aromatic hydrocarbons,and 2,3,7,8-tetrachlorodibenzo-p-dioxin in combustion emissions

A fast and accurate analytical method, which uses commercially available adsorbents (Tenax TA, Carbotrap B and C, and Carbosieve S-III), was developed for the sampling and determination of aromatic hydrocarbons, chloroaromatic compounds, and 2,3,7,8-tetrachlorodibenzo-p-dioxin. The breakthrough volume data show that Carbotrap C has a good capacity for compounds of high molecular weight, whereas Carbosieve S-III and Tenax TA are efficient for volatile compounds. The organic components are thermally desorbed and transferred to a gas chromatograph/mass spectrometer. Importantly, thermal desorption avoids conventional solvent extraction procedures and also allows reuse of adsorbent tubes. Preliminary results for recovery of analytes from tubes packed with single adsorbent prove that a single-adsorbent bed is not capable of sampling a wide range of compounds. The best method to obtain the desired collection and desorption properties is to use adsorbent tubes containing several different materials. The results of optimization studies are summarized.     

磁性多壁碳纳米管固相萃取-气相色谱-质谱法检测水样中的13种邻苯二甲酸酯类化合物

建立了磁性多壁碳纳米管(MWCNTs)固相萃取结合气相色谱-质谱检测水样中13种邻苯二甲酸酯类化合物(PAEs)的方法。优化了萃取时间、水样pH值、解吸溶剂的种类和用量、解吸时间等影响萃取效率的主要条件。最终确定萃取时间为10 min,水样pH 5～7,解吸溶剂为2 mL丙酮,解吸时间为5 min。在优化的条件下,各组分的萃取回收率为89.7%～100.5%。方法具有较高的灵敏度,检出限(信噪比(S/N)为3)为0.08～0.47 μg/L。3种实际样品的加标回收率为84.5%～107.5%,相对标准偏差为1.9%～12.8%。该方法操作简便、省时,准确、灵敏、环保,可用于水样中PAEs的检测,并成功地应用于自来水、瓶装饮用水和湖水样品的分析,13种PAEs均未检出。     

Flux of gases across the air-water interface studied by reversed-flow gas chromatography.

In the present work the reversed-flow gas chromatographic technique was applied for the study of flux of gases across the air-water interface. The model system was vinyl chloride-water, which is of great significance in food and environmental chemistry. Using suitable mathematical analysis, equations were derived by means of which the following physicochemical quantities were calculated: diffusion coefficient of vinyl chloride (VC) into water, partition coefficient of VC between the water (at the interface and the bulk) and the carrier gas nitrogen, overall mass transfer coefficients of VC in the gas (nitrogen) and the liquid (water), gas and liquid film transfer coefficients of VC, gas and liquid phase resistances for the transfer of VC into the water, and finally the thickness of the stagnant film in the liquid phase, according to the two-film theory of Whitman. From the variation of the above parameters with temperature, as well as the volume and the free surface area of the water, useful conclusions concerning the mechanism for the transfer of VC into water were extracted. These are discussed in comparison with the same parameters calculated from empirical equations or determined experimentally by other techniques.     

Detection of the chemical warfare agents bis-(2-chloroethyl)ethylamine (HN-1) and tris-(2-chloroethyl)amine (HN-3) in air.

This paper describes the method development and validation for detection of the chemical warfare agents HN-1 and HN-3 in air using C8 solid-phase extraction disks followed by liquid desorption and analysis by gas chromatography. The method is contrasted to the standard approach which uses solid sorbent tubes followed by thermal desorption and analysis by gas chromatography.     

Sensitive indoor air monitoring of monoterpenes using different adsorbents and thermal desorption gas chromatography with mass-selective detection

A simple method using active trapping on adsorbents and thermal desorption followed by GC-MS analysis was developed for the indoor air monitoring of monoterpenes. The study was carried out using a dynamically generated atmosphere consisting of 11 monoterpenes: camphene, camphor, delta 3-carene, 1,8-cineol, limonene, linalool, alpha-pinene, beta-pinene, alpha-terpinene, gamma-terpinene, fenchyl alcohol. The influence of the different adsorbents Tenax TA, Tenax GR, Carbosieve SIII, Chromosorb 106 on the yield of six selected monoterpenes at indoor air concentrations was studied. The adsorbent Tenax GR gave relatively the best yields followed by Tenax TA. Detection limits of approximately 1 microgram m3 were determined with Tenax GR for most of the monoterpenes.     

Dual Adsorber-Capillary Column System for Gas Chromatographic Analysis of Air Samples

Abstract

An interface which allows thermal desorption and subsequent capillary gas chromatographic analysis of air samples is described. A small solid-sorbent trap is positioned between the sampling tube and capillary column. A sample thermally released from the sampling tube is transferred by a carrier gas at high flow rate to the trap and retained. From there it is again thermally released and transferred to the capillary column by carrier gas at a low flow rate, as required by capillary GC. The transfer and injection steps are effected by means of externally placed solenoid valves. The performance of the system depends on the desorption temperature and time allowed for transfer of the sample between the two adsorbers and the column. These parameters are programmable and can be changed to suit the requirements of a particular analysis. The system allows the analysis of sub-parts-per-billion concentrations of organic compounds in a comparatively simple and reproducible manner. Operation of the system does not require cryogenic cooling of either the trap or the GC oven. Chromatograms of a variety of air samples are presented and discussed.     

富勒烯烟炱的吸附性及其在大气挥发性有机物分析中的应用

研究了富勒烯烟炱对挥发性有机物(VOCs)的吸附作用.17种VOCs气体在烟炱上的比保留体积V_g²⁰为17.4～2634L/g.富勒烯烟炱充填的吸附管对VOCs气体的吸附-热脱附回收率在40.8%～117%之间,大部分为(100±20)%.结果表明,富勒烯烟炱能够用于吸收和富集大气中痕量的VOCs     

Graphitized carbon black in quartz tubes for the sampling of indoor air nicotine and analysis by microwave thermal desorption-capillary gas chromatography

Nicotine in a smoky indoor air environment can be determined using graphitized carbon black as a solid sorbent in quartz tubes. The temperature stability, high purity, and heat absorption characteristics of the sorbent, as well as the permeability of the quartz tubes to microwaves, enable the thermal desorption by means of microwaves after active sampling. Permeation and dynamic dilution procedures for the generation of nicotine in the vapor phase at low and high concentrations are used to evaluate the performances of the sampler. Tube preparation is described and the microwave desorption temperature is measured. Breakthrough volume is determined to allow sampling at 0.1-1 L/min for definite periods of time. The procedure is tested for the determination of gas and paticulate phase nicotine in sidestream smoke produced in an experimental chamber.     

Behavior of pH-sensitive core shell particles at the air-water interface

In this article, the adsorption of latex core-responsive polymer-shell nanoparticles at the air-water interface is investigated using a Langmuir trough. Phase transition isotherms are used to explore their responsive behavior at the interface as a function of changes in the pH of the subphase. By adjusting the pH of the water prior to particle deposition, we probe the effect of the stabilizing polymer wetting by the water subphase on the stability of these particles at the air-water interface. In addition, by initially compressing a stable film of adsorbed particles and then subsequently changing the pH of the subphase we study desorption of these particles into the water phase.