Rapid identification of volatile compounds in aromatic plants by automatic thermal desorption — GC-MS

Summary Thermal desorption is a valuable method for the fractionation of plant volatile components, which can be carried out on-line with GC analysis. The use of coupled GC-MS affords additional qualitative information, of special interest for plant species whose composition has not been previously studied. Some examples of the application of automatic thermal desorption, coupled to GC-MS to the identification and characterization of volatile components of plants of different families are given.     

Headspace methods for volatile components of grapefruit juice

Summary Static headspace, dynamic headspace (DHS) and strip/trap methods were evaluated with grapefruit juice volatiles and an aqueous model system of selected grapefruit volatile flavour components, to select the best method for the isolation of volatile components for subsequent GC analysis.Recoveries were calculated for these methods in the concentration range 0.01–10gml^–1 and compared. Analyte trapping followed by thermal desorption was performed with Tenax TA traps which gave good results in terms of very low blanks. DHS analysis gave the best results in terms of recovery efficiency and, if adequately combined with a simultaneous steam distillation/solvent extraction method, is the most suitable for the qualitative and quantitative investigation of grapefruit juice volatiles, and it might be extended to other fruit juices or liquid foods.     

Stability of workroom air volatile organic compounds on solid adsorbents for thermal desorption gas chromatography

The storage stability of the occupationally frequently occurring compounds, methylethylketone, methylisobutylketone, benzene, toluene, tetrachloroethylene, n-butylacetate, -pinene, β-pinene, limonene and n-decane, has been investigated on the adsorbents Tenax TA, Chromosorb 106 and Carbotrap using thermally desorbable tube type samplers, commonly utilized in ambient and workroom atmospheric measurements. Fifty and 500 ng of each compound were loaded on the various adsorbents tubes, stored at both ambient (20 °C) and refrigerated (4 °C) temperatures and analysed by means of thermal gas chromatography with mass spectrometric detection on days 0, 7, 14 and 28 after exposure. A 90% storage recovery was chosen as acceptance criteria for storage stability, and statistical testing by Student's t-test, analysis of variance and Bonferroni post hoc tests were employed to investigate the effect of the categorical variables storage time, storage temperature and analyte loading on the different adsorbents. Chromosorb 106 showed the overall best behaviour with recoveries of 90% or better for all analytes during the 28-day test period. Tenax TA and Carbotrap yielded lower recoveries and were more influenced by variations in storage time, storage temperature and analyte loading. Refrigerated temperatures were best avoided for storage on Tenax TA, but may increase the recovery of some compounds on Carbotrap (e.g. n-butylacetate). The blank build-up on the adsorbents was also investigated, and Carbotrap and Tenax TA showed no signs of artefact development over time. Chromosorb 106, however, contained inherently more artefacts that build up over time, which in spite of the excellent storage capability, may limit its use in field studies where long storage times are normal.     

Identification of volatile (micro) biological compounds from household waste and building materials by thermal desorption–capillary gas chromatography–mass spectroscopy

Volatile compounds from biodegradable household waste and infected building materials have been studied by dynamic or equilibrium headspace sampling and concentration on Tenax TA followed by thermal desorption and HRGC-MS. Equilibrium headspace sampling was also used to study vegetables stored for 14–18 days at ambient temperature. Over 200 compounds were tentatively identified. The concentration of organic sulfur compounds from garden waste was high enough to contribute to respiratory problems of waste handling personnel. Nitriles, alkyl nitro compounds, and alkyl nitrates were isolated from radish and carrot samples at low concentrations (10–50 ppb). Air monitoring in waste handling working environments may be required to ensure the safety of personnel. Branched aliphatic aldehydes, carboxylic acids, esters, and 2-alkanones were found in the headspace of the infected building materials, indicating that volatile compounds may be useful for detection of microbial growth in buildings.     

A recirculating system for concentrating volatile samples

Summary A recirculating system powered by a diaphragm pump which may be readily dismantled for cleaning, is described. The results of operating this system for dynamic headspace sampling in the closed or open mode to load volatiles onto a Tenax trap over a range of temperatures and loading volumes are shown. The system was designed to facilitate the analysis of volatiles in natural products and tested using an equimolar solution of 7 esters of boiling points ranging from 120°C to 299°C. The results showed that compounds in the boiling point range 120–200°C could be loaded onto the trap at 30°C by passing 1–21 of carrier gas through. In order to trap compounds of boiling points approaching 300°C, a temperature of 50–70°C and a loading volume of 2.5–3 1 was necessary. Using the apparatus, human sweat was analysed to show the degree of concentration possible with a natural sample and the variation in the chromatogram profiles of successive trapping from the same sample. Twelve chromatograms from the sweat of two pairs of identical twins were pattern matched to show the high degree of reproducibility possible using this apparatus to trap biological volatiles.     

Effects of electron beam irradiation on cork volatile compounds by gas chromatography-mass spectrometry

Summary The effects of electron beam irradiation on cork volatile compounds was studied at different doses (25, 100, 1000 kGy). Volatiles were isolated from cork using the dynamic headspace-sampling technique, then identified by gas chromatography-mass spectrometry (GC-MS). Similar gas chromatographic profiles were obtained for non-irradiated and irradiated corks. Quantitative differences induced by the three doses were evaluated by calculating peak areas for each compound identified. The quantitative differences between non-irradiated corks and those irradiated at 25 kGy were significant for only a few substances, whereas significant quantitative differences were found in samples irradiated at 100 and 1000 kGy. For these doses, the content of volatile compounds generally increased, especially that of aliphatic hydrocarbons and carbonyl compounds. The behaviour of radiolytic hydrocarbons indicates that the mechanisms proposed for their formation in irradiated foods could take place even in cork.     

Comparative study of solvent extraction and thermal desorption methods for determining a wide range of volatile organic compounds in ambient air

This paper compares two analytical methods for determining levels of 90 volatile organic compounds (VOCs) commonly found in industrial and urban atmospheres. Both methods are based on two official methods for determining benzene levels and involve collecting samples by active adsorptive enrichment on solid sorbents. The first method involves solvent extraction and uses activated charcoal as a sorbent. After sampling, the sorbent is extracted with 1 mL of carbon disulfide and then 1 μL of the extract is analysed in a GC-MS. The second method involves thermal desorption (TD) and uses Tenax TA and Carbograph 1TD as sorbents, which allows the whole sample to be analysed. In general, the thermal desorption method showed the best repetitivity and recovery and the lowest limit of detection and quantification for all target compounds. Because of its lower sensitivity, the solvent extraction method needs the preconcentration of large sample volumes of air (720 L vs. 2.64 L for the thermal desorption method) to yield similar limits of detection.The performance of both methods in real samples was tested in a location near to a petrochemical complex. The results of the 24-h samples for the solvent extraction method were compared with the average of 12 2-h samples for the TD method. In some cases, both methods found differences in the VOC concentrations, especially in those compounds whose concentrations fluctuate significantly during the day.     

Comparison of two methods based on dynamic head-space for GC-MS analysis of volatile components of cheeses

Summary Two methods based in dynamic headspace sampling have been compared for GC/MS analysis of volatile components in hard cheeses (Manchego and other ewe’s milk varieties). In the first approach a purge & trap concentrator allowed volatile on-line determination with reduced sample handling. The second method consisted of a manual device for trapping dinamically purged volatiles, which were then anaysed by using an automatic thermal desorption system, coupled on-line with a GC-MS. The influence of the most significant operating parameters (desorption times, flows and temperatures) on recovery and repeatability was studied for both methods. Automatic purge & trap gave the best sensitivity and repeatability for high valatility components, probably because its on-line operation mode, while the second procedure allowed the determination of a greater number of volatile components and gave better yields for fatty acids and other medium volatility components.     

Determination of volatile organic compounds in urban and industrial air from Tarragona by thermal desorption and gas chromatography-mass spectrometry

This study describes the optimisation of an analytical method to determine 54 volatile organic compounds (VOCs) in air samples by active collection on multisorbent tubes, followed by thermal desorption and gas chromatography-mass spectrometry. Two multisorbent beds, Carbograph 1/Carboxen 1000 and Tenax/Carbograph 1TD, were tested. The latter gave better results, mainly in terms of the peaks that appeared in blank chromatograms. Temperatures, times and flow desorption were optimised. Recoveries were higher than 98.9%, except methylene dichloride, for which the recovery was 74.9%. The method's detection limits were between 0.01 and 1.25 μg m⁻³ for a volume sample of 1200 ml, and the repeatability on analysis of 100 ng of VOCs, expressed as relative standard deviation for n = 3, was lower than 4% for all compounds. Urban and industrial air samples from the Tarragona region were analysed. Benzene, toluene, ethylbenzene and xylenes (BTEX) were found to be the most abundant VOCs in urban air. Total VOCs in urban samples ranged between 18 and 307 μg m⁻³. Methylene chloride, 1,4-dichlorobenzene, chloroform and styrene were the most abundant VOCs in industrial samples, and total VOCs ranged between 19 and 85 μg m⁻³.     

A novel quantitation method for phthalates in air using a combined thermal desorption/gas chromatography/mass spectrometry application

In this study, a novel quantitation method was developed to facilitate the simple and effective sampling and analysis of phthalates in air based on a sorbent tube-thermal desorption-gas chromatography-mass spectrometry system combination. The performance of the thermal desorption-based analysis was assessed using three different sorbent combinations [1]: quartz wool (QW) [2], glass wool (GW), and [3] quartz wool plus Tenax TA (QWTN) in terms of relative recovery in reference to a direct injection method. There was no significant difference in the average recovery rate for seven target phthalates based on sorbent tube type (QW, 70.2 ± 4.28; GW, 73.2 ± 8.8; and QWTN, 72.5 ± 5.02%). However, the recovery rate of phthalates in each sorbent tube type was distingusihed by physicochemical properties of the target compound (e.g., molecular weight and boiling point). The recovery rate of the QW tube was high for dimethyl phthalate and diethyl phthalate compared to other sorbent tubes, while that of the GW tube exhibited greater values for dibutyl phthalate, benzyl butyl phthalate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) phthalate, and di-n-octyl phthalate. The simple sorbent tube-thermal desorption approach is feasible for the quantitation of seven phthalates present at 0.45–24.5 ng m⁻³ levels in actual air samples (20 L).     

Development of a novel solid-phase extraction element for thermal desorption gas chromatography analysis

A novel solid-phase extraction element is developed for sorptive enrichment of dilute analytes from liquid samples with high extraction efficiencies due to its larger amounts of polydimethylsiloxane (PDMS) absorbent than the conventional syringe type of solid-phase microextraction (SPME). The extraction element is made of titanium (Ti) open tubular tube (30 mm x 1.2 mm i.d. x 1.6 mm o.d.) coated with a chemically bonded layer of PDMS (500 microm in thickness). The extraction element combined with thermal desorption-gas chromatography-mass spectrometry using a pyrolysis-gas chromatography-mass spectrometry system was used to extract and analyze a typical herbicide, bethrodine in water samples over a concentration range from 2.5 to 2.5 x 10(4) ng/l. Thus obtained calibration curve showed good linearity for the tested whole concentration range with regression coefficient of 0.992. Detection limit of 0.5 ng/l level was achieved and the reproducibility of the measurements for bethrodine at 10 ng/l level was found to be fairly good with relative standard deviation below 7.5%.     

Advances in the determination of volatile organic solvents and other organic pollutants by gas chromatography with thermal desorption sampling and injection

Summary The problem of the separation of 34 volatile organic chlorinated compounds is solved by using three different GC columns selected according to the needs of the particular separation required. The effect of water vapor contained as moisture in the trapped air on the retention of some characteristic compounds is studied. The influence of dead volumes on trap injection is also studied.Dedicated to Prof. Dr. A. Liberti on the occasion of his 70th birthday.     

Comparison of different calibration approaches in the application of thermal desorption technique: A test on gaseous reduced sulfur compounds

In this study, the reliability of thermal desorbing technique was investigated using the gaseous standards of five reduced sulfur compounds (RSCs: hydrogen sulfide, methane thiol, dimethyl sulfide, carbon disulfide, and dimethyl disulfide). A series of calibration experiments for RSCs were performed using gas chromatography (GC) with pulsed flame photometric detector (PFPD) that is interfaced with a thermal desorber (TD) unit. These calibration data were evaluated by means of two contrasting concepts: fixed standard concentration method (FSC: variable volumetric injection of standard gases prepared at a given concentration) and fixed standard volume method (FSV: injection of multiple standards with varying concentrations at a given volume). When the results of both methods were compared, RSCs generally showed enhanced sensitivity with increasing concentration (FSC) and sample loading volume (FSV). This study highlights that TD-based calibration properties are practically undistinguishable between different sample transfer approaches (e.g., FSV and FSC). As a result, the calibration properties of RSCs derived by thermal desorption technique are greatly distinguished from those of direct injection into GC.     

Optimization of dynamic headspace sampling for the analysis of trace volatile components of grape juice: Use of a PTV injector for intermediate trapping

The use of a programmed temperature vaporizing (PTV) injector has been evaluated for the on-line concentration and injection of trace organic compounds either sampled from the head-space above grape juices or purged from solution. The Simplex method was used to improve the sensitivity of the method by optimization of the experimental conditions.     

Gas-phase cleanup method for analysis of trace atmospheric semivolatile organic compounds by thermal desorption from diffusion denuders

A novel gas-phase cleanup method was developed for use with a thermal desorption method for analysis of trace semivolatile organic compounds (SOCs) in the atmosphere using diffusion denuder samplers to separate gas-phase from particle-associated fractions. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds that is present in ambient air samples. Abraham solvation parameters were found to be useful predictors of recovery of compounds through the cleanup method; most compounds with A + B < 0.3 and L ≤ 12.3 were fully recovered through the cleanup method. Addition of the cleanup method successfully produced baseline resolution in air samples and improved method precision. The utility of the method was demonstrated in an investigation of the built environment as a continuing source of semivolatile persistent, bioaccumulative, and toxic chemicals (PBTs) to the atmosphere.     

A dynamic dilution system-based evaluation of the procedure adopted for determining ozone precursor volatile compounds

A dynamic dilution system was created to evaluate the performance and the reliability of ozone precursor volatile organic compound (VOC) sampling (TO-Can canisters) and analysis (thermal desorption/gas chromatography/flame ionisation detection) techniques used by the Laboratoire Interrégional de Chimie du Grand Est (LIC). Different atmospheres of VOCs were generated at concentrations between 0.8 and 25 ppb, with temperatures of 0, 10, 20 and 30 °C, and with relative humidities of 0, 30, 50, 70 and 90%. These conditions are generally representative of those commonly observed in ambient air in the eastern France. This dynamic dilution allows the simulation of a wide range of scenarios (concentrations, temperatures and relative humidities). After assessing the capacity and performance of the system, it was applied in order to evaluate the recoveries and stabilities of VOCs from canisters used for the collection and analysis of two mixtures of VOCs. The first mixture contained six alkanes (ethane, propane, butane, pentane, hexane and heptane), and the second contained five alkenes (ethene, propene, butene, 1-pentene and 1-hexene), five aromatics (benzene, toluene, ethylbenzene, m-xylene and o-xylene), acetylene, and 1,3-butadiene. No significant losses of alkanes from the canisters were observed after 21 days of storage, and good recoveries of alkanes from the canisters (>80%) were obtained regardless of the concentration, the temperature and the relative humidity. However, losses of certain aromatics were noted at low relative humidity.     

Quantitative analysis of poly- and perfluoroalkyl compounds in water matrices using high resolution mass spectrometry: Optimization for a laser diode thermal desorption method

An alternative analysis technique for the quantitation of 15 poly- and perfluoroalkyl substances (PFASs) in water matrices is reported. Analysis time between each sample was reduced to less than 20 s, all target molecules being analyzed in a single run with the use of laser diode thermal desorption atmospheric pressure chemical ionization (LDTD/APCI) coupled with high resolution accurate mass (HRMS) orbitrap mass spectrometry. LDTD optimal settings were investigated using either one-factor-at-a-time or experimental design methodologies, while orbitrap parameters were optimized simultaneously by means of a Box–Behnken design. Following selection of an adequate sample concentration and purification procedure based on solid-phase extraction and graphite clean-up, the method was validated in an influent wastewater matrix. Environmentally significant limits of detection were reported (0.3–4 ng L⁻¹ in wastewater and 0.03–0.2 ng L⁻¹ in surface water) and out of the 15 target analytes, 11 showed excellent accuracies (±20% of the target values) and recovery rates (75–125%). The method was successfully applied to a selection of environmental samples, including wastewater samples in 7 locations across Canada, as well as surface and tap water samples from the Montreal region, providing insights into the degree of PFAS contamination in this area.