Headspace Solid-phase Dynamic Extraction Research Articles

Preliminary Study of the Effect of Short Maceration with Cherry and Oak Wood Chips on the Volatile Composition of Different Craft Beers

In the last few years, the production and consumption of craft beers has increased notably. However, there is restricted knowledge about the potential impact of chips from different wood species on beer quality. Thus, this work aimed to evaluate the effect of the addition of wood chips from cherry and oak species—after the fermentation was completed and during a brief maceration time—on the volatile composition of three different beer groups (Ale, Lager, and Porter) through a headspace solid-phase dynamic extraction (HS-SPDE) and GC-MS analysis. Fifty-six volatile compounds from different chemical families (esters, alcohols, terpenes, acids, aldehydes, ketones, and pyrazines) were detected, identified, and considered in this study. In general, the volatile composition of the beers macerated with wood chips was very similar to that of the control beers. However, the control beers showed higher volatile compound levels. The results suggest potential interactions between beer volatile compounds and the wood chips during maceration. The outcomes of this research could be of practical interest to brewers since they could improve the knowledge of the impact of short-time contact and low wood chip concentration on the volatile composition of different craft beers.

Antimicrobial properties and volatile profile of bread and biscuits melanoidins

This work gives novel information about the antimicrobial effect and volatiles of melanoidins isolated from Maria biscuit, common and soft bread. Melanoidins were isolated from scraped and sieved crusts (1 mm), after gluten digestion, 10 kDa ultrafiltration, and diafiltration. Finally, they were freeze-dried. Headspace solid-phase dynamic extraction coupled with a gas chromatograph with a mass spectrometer was used to determine the volatile profiles. The antimicrobial effect was evaluated against isolated strains of the most relevant food spoilage and pathogen microorganisms, together with some molds and yeasts. Melanoidins from common bread exhibited the most extensive antimicrobial activities and showed the most composite volatile profile. No undesirable compounds, such as furfural and 5-hydroxy-methyl-furfural, were found in any of the melanoidins studied. The obtained data pointed out that bakery melanoidins can exert effective food technological properties as natural antimicrobials that can improve shelf-life and security of foodstuffs, together with a possible contribution to food aroma.

Screening of Volatile Compounds in Mate (Ilex paraguariensis) Tea—Brazilian Chimarrão Type—By HS-SPDE and Hydrodistillation Coupled to GC-MS

The volatile fraction of mate (Ilex paraguariensis) tea—specifically Brazilian chimarrão type, which has an odor profile comprising distinctive fresh, green, grass, and herbal notes—was investigated. Hydrodistillation in a Clevenger apparatus was employed in order to extract volatiles from the tea matrix. Headspace–solid-phase dynamic extraction (HS-SPDE) was employed to extract the volatiles from two types of infusions of this tea—a simple single infusion and a traditional preparation of consecutive infusions. Volatiles were analyzed by gas chromatography–flame ionization detection/mass spectrometry (GC-FID/MS). In total, 85 compounds were either identified or tentatively identified and semi-quantified. Semi-quantification comprised peak area integration of all the peaks (including the unidentified ones) in the chromatogram. Results obtained by hydrodistillation and by HS-SPDE were distinct, covering mostly different ranges of volatility and showing only 15 compounds in common. The identified compounds had their respective average and minimum odor thresholds and odor characteristics compiled from the literature. Several major compounds considered as key odorants in other mate tea products were not detected or only present at low levels in the samples of this research. Approximately half of the odorants identified in these samples were commonly reported in different mate tea types; the remaining 41 molecules—predominantly terpenoids (isoprenoids)—could be listed as specific to the Brazilian chimarrão type and are suggested to underlie its typical freshness.

Urinary excretion of heptanones, heptanoles and 2,5-heptanedione after controlled acute exposure of volunteers to n-heptane

A lack of well-established parameters and assessment values currently impairs biomonitoring of n-heptane exposure. Using controlled inhalation experiments, we collected information on urinary n-heptane metabolite concentrations and the time course of metabolite excretion. Relationships between external and internal exposure were analysed to investigate the suitability of selected metabolites to reflect n-heptane uptake.Twenty healthy, non-smoking males (aged 19–38 years, median 25.5) were exposed for 3 h to 167, 333 and 500 ppm n-heptane, each. Spot urine samples of the volunteers, collected before exposure and during the following 24 h, were analysed for heptane-2-one, 3-one, 4-one, 2,5-dione, 1-ol, 2-ol, 3-ol, and 4-ol using headspace solid phase dynamic extraction gas chromatography/mass spectrometry (HS-SPDE-GC/MS).Starting from median pre-exposure concentrations between <0.5 (3-one) and 82.9 μg/L (4-one), exposure increased the concentrations for all parameters except for 4-one. Median post-exposure concentrations ranged up to 840.4 μg/L (2-ol) and decreased with half-lifes <3 h after exposure. Non-parametric correlation analyses (n = 47, p < 0.05) revealed weak to moderate associations of volume related metabolite excretion with external exposure for 2-one, 3-one and 2,5-dione (R = 0.332–0.753). Heptanol excretion was moderately associated with exposure (R ≥ 0.509) only after creatinine adjustment.Lacking association with external exposure impedes the use of 4-one as heptane biomarker, whereas 2-ol and 3-ol turned out to be sensitive indicators of exposure if creatinine correction is applied. By providing fundamental data on a panel of eight potential heptane metabolites, our study can help to promote biological monitoring of n-heptane exposure.

Optimization of a Solid Phase Dynamic Extraction (SPDE) Method for Beer Volatile Profiling

A headspace solid phase dynamic extraction coupled with gas chromatography-mass spectrometry (HS-SPDE-GC/MS) method for the analysis of the volatile fraction of beer was optimized using response surface methodology. A preliminary two-level full factorial design was performed, with extraction temperature, extraction strokes, and fill/eject speed as the main factors. The results showed that number of extraction strokes and temperature significantly affected the peak area response of the volatile compounds (p ≤ 0.05). To determine the ideal conditions for extraction, a second optimization of the significant factors was carried out using a Doehlert matrix design. The optimal conditions were identified as an extraction temperature of 60 °C and 55 extraction strokes. The optimized method was applied for the analysis of five commercial beers. A variety of compounds from different chemical classes were extracted from each sample, reflecting the effective application of the SPDE method for volatile compound extraction across different beers.

Pervaporation investigation of recovery of volatile compounds from brown crab boiling juice

Pervaporation has been used to obtain aroma concentrates from brown crab boiling juice. The boiling juice and the obtained permeate have been analysed by Headspace Solid Phase Dynamic Extraction Gas Chromatography/Mass Spectrometry. The effect of feed temperature on the pervaporation performance of the membrane has been analysed. The permeate aroma profile, at 25 ℃ and 40 ℃, was different from that of the boiling juice. Enrichment factors for some of the volatile compounds were much lower than those obtained in model aqueous dilute solutions. Pervaporation performance can be significantly improved by modifying the permeant circuit to include two condensation stages.

Comparison of the sensitivity of different aroma extraction techniques in combination with gas chromatography–mass spectrometry to detect minor aroma compounds in wine

MicroVinification platforms are used for screening purposes to study aroma development in wine. These high-throughput methodologies require flavor analysis techniques that allow fast detection of a high number of aroma compounds which often appear in very low concentrations (μg/l). In this work, a selection of aroma extraction techniques in combination with gas chromatography–mass spectrometry (GC–MS) were evaluated to detect minor wine aroma compounds in low sample volume. The techniques evaluated were headspace (HS), headspace solid-phase dynamic extraction (HS-SPDE), headspace solid-phase microextraction (HS-SPME), direct immersion solid-phase microextraction (DI-SPME), stir bar sorptive extraction (SBSE) and monolithic material sorptive extraction (MMSE). DI-SPME showed the highest sensitivity as expressed by detection of the highest percentage of total aroma compounds at concentrations around 0.1μg/l. SBSE and MMSE followed DI-SPME in terms of sensitivity. HS-SPME was less sensitive but considered sensitive enough for detection of most of the volatile compounds present in highly aromatic wines. Matrix effect was shown to strongly affect aroma extraction and therefore the sensitivity of the different extraction methods.

Fingerprinting of red wine by headspace solid-phase dynamic extraction of volatile constituents

Headspace solid-phase dynamic extraction (HS-SPDE) was investigated for its applicability in quality control analysis of wine volatiles using gas chromatography-mass spectrometry. In total, 196 German red wines were analysed and 22 flavour-relevant alcohols and esters were quantified. The method detection limits were between 0.1 and 9.3 μg L(-1), allowing the dilution of the samples to decrease matrix and competition effects. Quantification resulted in a concentration range from about 1 μg L(-1) linalool up to 380 mg L(-1) 2-methyl-1-propanol. The measurement uncertainty budget was determined for all compounds in a "top-down" approach and was between 2.5 and 7.9%, with an average of 5.5%. A surveillance of the extraction performance of the HS-SPDE devices showed constant results for up to 400 extractions using one extraction needle tip. A chromatogram library for quality and authenticity control of wine samples was created using commercially available chromatogram comparison software.

Application of headspace solid phase dynamic extraction gas chromatography/mass spectrometry (HS-SPDE-GC/MS) for biomonitoring of n-heptane and its metabolites in blood

Solid phase dynamic extraction (SPDE) is an innovative sample preparation and enrichment technique in connection with gas chromatography (GC). Using SPDE, we developed a method for simultaneous determination of n-heptane and its mono-oxygenated metabolites heptane-4-one, 3-one, 2-one, 4-ol, 3-ol, 2-ol, and 1-ol in blood. After adjustment of various extraction and desorption parameters, method validation resulted in limits of detection (LOD) between 0.006 (heptane-4-one) and 0.021mg/L (heptane-1-ol). Intra-assay coefficients of variation ranged between 4.8% and 20.8% while relative recovery ranged between 100% and 117% (spiked concentration 0.128mg/L, n=8). The method was applied to blood samples, which have been collected from 20 volunteers after controlled inhalative exposure to 167, 333, and 500ppm n-heptane. After 3h of exposure, n-heptane and heptane-2-one were detectable in all samples in concentrations ranging up to 2.903 and 0.495mg/L, while the concentrations of the remaining analytes were closer to the respective LOD or even below. A significant linear relationship with ambient exposure (R2=0.701, p<0.001, n=55) was found for n-heptane in blood, which could be helpful for evaluation of biological exposure limits in future. Due to its high abundance in blood, 2-heptanone could be an interesting candidate as a biomarker also in alternative matrices such as urine or saliva.

Analysis of Volatile Profiles of Fermenting Grape Must by Headspace Solid-Phase Dynamic Extraction Coupled with Gas Chromatography−Mass Spectrometry (HS-SPDE GC-MS): Novel Application To Investigate Problem Fermentations

The occurrence of stuck and sluggish wine fermentations is a persisting problem in the wine industry worldwide. This study illustrates the suitability of headspace solid-phase dynamic extraction coupled with gas chromatography-mass spectrometry (HS-SPDE GC-MS) for wine analysis and the subsequent application to discriminate between control and problem fermentations using partial least-squares discriminant analysis (PLS-DA) models. The specific analytical technique is relatively new and has not yet to the authors' knowledge been evaluated for the analysis of wine within this context of problem fermentations. HS-SPDE GC-MS was used to determine 68 volatile compounds (higher alcohols, fatty acids, esters, and carbonyl compounds) in 94 monovarietal fermenting must samples consisting of 56 red and 38 white cultivars. PLS-DA models showed the potential to discriminate between control and problem fermentations using corrected peak area headspace data for the 68 analytes. This possibility to discriminate between problem and control fermentations with only the headspace data could possibly be applied for the prediction of problem fermentations in future studies and to better understand the chemical causes of problem fermentations.

Determination of gamma-hydroxybutyric acid in serum and urine by headspace solid-phase dynamic extraction combined with gas chromatography–positive chemical ionization mass spectrometry

Gamma-hydroxybutyric acid is an emerging drug of abuse. Beside relaxation and euphoria it causes hypnosis and unconsciousness. Therefore the substance is misused as recreational drug and at drug-facilitated sexual assaults. An automated and effortless method for quantitation of gamma-hydroxybutyric acid in serum and urine was optimized and validated. Five hundred microliters sample volume are used for both matrices. The acid catalyzed conversion of gamma-hydroxybutyric acid to the corresponding gamma-butyrolactone is applied. Furthermore the method is based on headspace solid-phase dynamic extraction coupled with gas chromatography–mass spectrometry. The extraction process is performed by repeated aspiration and ejection of the headspace through a steel cannula which is coated on the inside with a polydimethylsiloxane sorbent. Thus absorption of analyte molecules by the sorbent is achieved. The influence of parameters as sorbent type, incubation temperature, number of extraction strokes, injection port temperature and injection flow speed on extraction recovery was investigated. The validation revealed good accuracy with a bias less than ±5%. Intra- and interday precision determined at 10, 50 and 150 μg/ml for each matrix were in following ranges: 1.96–3.49% (intraday, serum), 2.38–4.31% (intraday, urine), 2.33–5.13% (interday, serum) and 2.53–5.64% (interday, urine). The method provided good linearity between 2 and 200 μg/ml yielding coefficients of determination R 2 ≥ 0.9985. Limit of detection were determined at 0.16 μg/ml for serum and 0.17 μg/ml for urine, respectively. This method exhibits a fast, solvent-free and widely automated extraction process. It has been applied to toxicological routine analysis and therapeutic drug monitoring successfully.

Analysis of Unmetabolized VOCs in Urine by Headspace Solid‐Phase Microcolumn Extraction

Exposure to high concentrations of volatile organic compounds (VOCs) can lead to adverse health effects. Among VOCs, benzene is a haematotoxic substance that can induce acute myleoid leukaemia in occupational exposure, and has been classified as a carcinogen in humans by the International Agency for Research on Cancer. Other VOCs, trihalomethanes (chloroform, bromodichloromethane and dibromochloromethane) were detected in the urine of all persons attending a swimming pool, where the water was treated with chlorine. Tetrachloroethylene in urine of drycleaners has been used as biologic index of low-level exposure. A significant correlation was found between the environmental t r ich loroe thylene concent ra t ion and ur inary trichloroethylene concentration. BTEX (benzene, toluene, ethylbenzene and isomeric xylenes) have attained great relevance as ubiquitous pollutants of outdoor human environments and analysis of urine has been used for the evaluation of environmental exposures to these compounds. Similarly, styrene analysis in urine is a useful biological indicator of exposed workers. Generally, VOCs analyses involve either static or dynamic headspace (HS) sampling, followed by gas chromatographic separation and flame ionization (GCFID) or mass spectrometric detection (GC-MS). In the majority of the newly developed HS sample preparation techniques, the recovery of volatiles is based on sorption in a solid phase . Among them, equilibrium sampling techniques such as HS solid-phase microextraction, HS sorptive extraction , and a non-equilibrium sampling technique, HS solid-phase dynamic extraction, are available. In this study we have used the recently developed sampling technique, solid-phase microcolumn extraction (SPMCE), for the analysis of BTEX, styrene, chloroform, trichloroethylene and tetrachloroethylene in urine using GC-FID.

An interior needle electropolymerized pyrrole-based coating for headspace solid-phase dynamic extraction

A headspace solid-phase dynamic extraction (HS-SPDE) technique was developed by the use of polypyrrole (PPy) sorbent, electropolymerized inside the surface of a needle, as a possible alternative to solid-phase microextraction (SPME). Thermal desorption was subsequently, employed to transfer the extracted analytes into the injection port of a gas chromatography–mass spectrometry (GC–MS). The PPy sorbent including polypyrrole-dodecyl sulfate (PPy-DS) was deposited on the interior surface of a stainless steel needle from the corresponding aqueous electrolyte by applying a constant deposition potential. The homogeneity and the porous surface structure of the coating were examined using the scanning electron microscopy (SEM). The developed method was applied to the trace level extraction of some polycyclic aromatic hydrocarbons (PAHs) from aqueous sample. In order to enhance the extraction efficiency and increase the partition coefficient of analytes, the stainless steel needle was cooled at 5 °C, while the sample solution was kept at 80 °C. Optimization of influential experimental conditions including the voltage of power supply, the time of PPy electrodeposition, the extraction temperature, the ionic strength and the extraction time were also investigated. The detection limits of the method under optimized conditions were in the range of 0.002–0.01 ng mL −1. The relative standard deviations (R.S.D.) at a concentration level of 0.1 ng mL −1 were obtained between 7.54 and 11.4% ( n = 6). The calibration curves of PAHs showed linearity in the range of 0.01–10 ng mL −1. The proposed method was successfully applied to the extraction of some selected PAHs from real-life water samples and the relative recoveries were higher than 90% for all the analytes.

Benzene, alkylated benzenes, chlorinated hydrocarbons and monoterpenes in snow/ice at Jungfraujoch (46.6°N, 8.0°E) during CLACE 4 and 5

Benzene, alkylated benzenes, chlorinated hydrocarbons and monoterpenes were measured in snow/ice collected directly in-cloud at Jungfraujoch (3580 m asl) in February and March 2005 and 2006 during the CLoud and Aerosol Characterization Experiments CLACE 4 and CLACE 5. Melted snow/ice samples were analyzed by headspace-solid-phase-dynamic-extraction (HS-SPDE) followed by gas chromatography/mass spectrometry (GC/MS). Generally, there was a tendency in the results that higher concentrations were found after longer precipitation-free periods, suggesting that higher concentrations in snow/ice may be caused by the washout effect of precipitation. High concentration variations in snow/ice samples taken at the same time at the same place highlight the heterogeneous nature of snow/ice. Air concentrations calculated by scavenging ratios and measured snow/ice values markedly exceed the typically reported concentrations of benzene and alkylbenzenes in air (Li Y, Campana M, Reimann S, Schaub KS, Staehlin J, Peter T. Hydrocarbon concentrations at the alpine mountain sites Jungfraujoch and Arosa. Atmos Environ 2005;39:1113–27). This argues for an efficient snow/ice scavenging of those compounds from the atmosphere during precipitation formation.

Analysis of benzene, toluene, ethylbenzene, xylenes and n-aldehydes in melted snow water via solid-phase dynamic extraction combined with gas chromatography/mass spectrometry

The present study describes a method based on headspace-solid-phase dynamic extraction (HS-SPDE) followed by GC/MS for the qualitative and quantitative analysis of benzene, toluene, ethylbenzene, o-, m- and p-xylene (BTEX), and n-aldehydes (C 6–C 10) in water. To enhance the extraction capability of the HS-SPDE a new cooling device was tested that controls the temperature of the SPDE needle during extraction. Extraction and desorption parameters such as the number of extraction cycles, extraction temperature, desorption volume and desorption flow rate have been optimized. Detection limits for BTEX ranged from 19 ng/L (benzene) to 30 ng/L ( m/ p-xylene), while those for n-aldehydes ranged from 21 ng/L ( n-heptanal) to 63 ng/L ( n-hexanal). At a concentration level of 2 μg/L, the relative standard deviations (RSDs) for BTEX ranged from 3.9% (benzene) to 15.3% (ethylbenzene), while RSDs for n-aldehydes were between 6.1% ( n-octanal) and 16.5% ( n-hexanal) ( n = 7). Best results were obtained when the analyzed water samples were heated to 50 °C. At a water temperature of 70 °C GC responses decreased for all analyzed compounds. At a defined water temperature, a significant improvement of the GC response was achieved by cooling of the SPDE fiber during water extraction in comparison to an extraction keeping the fiber at room temperature. Evaluating the extraction cycles, for BTEX, the sensitivity was almost similar using 20, 40 and 60 extraction cycles. In contrast, the highest GC responses for n-aldehydes were achieved by the use of 60 extraction cycles. Optimizing the desorption parameters, best results were achieved using the smallest technical available desorption volume of 500 μL and the highest technical desorption flow rate of 50 μL/s. The method was applied to the analysis of melted snow samples taken from the Jungfraujoch, Switzerland (3580 m asl), revealing the presence of BTEX and aldehydes in snow.

Use of in-tube sorptive extraction techniques for determination of benzene, toluene, ethylbenzene and xylenes in soft drinks

A comparison is made between static headspace analysis and headspace solid-phase dynamic extraction (HS-SPDE) for the quantitative determination of trace level BTEX solvents (benzene, toluene, ethylbenzene and o-, m-, and p-xylene) in soft drinks. Two non-polar extraction phases were investigated for SPDE using an automated sampler with a gas-tight syringe equipped with a special needle coated on the inside with the extraction phase. Following adsorption onto the phase, the analytes were thermally desorbed directly into a GC–MS. The techniques were optimised and evaluated by analysis of spiked soft drink samples. The use of the SPDE device gave comparable results to the static headspace method, with lower detection limits for some compounds, and also offers advantages for applications where lower temperatures are preferred.

Determination of volatile organic hydrocarbons in water samples by solid-phase dynamic extraction

In the present study a headspace solid-phase dynamic extraction method coupled to gas chromatography-mass spectrometry (HS-SPDE-GC/MS) for the trace determination of volatile halogenated hydrocarbons and benzene from groundwater samples was developed and evaluated. As target compounds, benzene as well as 11 chlorinated and brominated hydrocarbons (vinyl chloride, dichloromethane, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, carbon tetrachloride, chloroform, trichloroethylene, tetrachloroethylene, bromoform) of environmental and toxicological concern were included in this study. The analytes were extracted using a SPDE needle device, coated with a poly(dimethylsiloxane) with 10% embedded activated carbon phase (50-microm film thickness and 56-mm film length) and were analyzed by GC/MS in full-scan mode. Parameters that affect the extraction yield such as extraction and desorption temperature, salting-out, extraction and desorption flow rate, extraction volume and desorption volume, the number of extraction cycles, and the pre-desorption time have been evaluated and optimized. The linearity of the HS-SPDE-GC/MS method was established over several orders of magnitude. Method detection limits (MDLs) for the compounds investigated ranged between 12 ng/L for cis-dichloroethylene and trans-dichloroethylene and 870 ng/L for vinyl chloride. The method was thoroughly validated, and the precision at two concentration levels (0.1 mg/L and a concentration 5 times above the MDL) was between 3.1 and 16% for the analytes investigated. SPDE provides high sensitivity, short sample preparation and extraction times and a high sample throughput because of full automation. Finally, the applicability to real environmental samples is shown exemplarily for various groundwater samples from a former waste-oil recycling facility. Groundwater from the site showed a complex contamination with chlorinated volatile organic compounds and aromatic hydrocarbons.

Solid-phase dynamic extraction for the enrichment of polar volatile organic compounds from water

Headspace solid-phase dynamic extraction coupled to gas chromatography–mass spectrometry (HS-SPDE-GC/MS) was evaluated for the trace determination of polar volatile organic compounds (PVOC) from aqueous matrices. The target compounds included 3 ethers and 12 alcohols. Four SPDE needle coatings with different phase polarities and sorption properties (WAX, 1701, PDMS, PDMS/AC) were tested. The effects of extraction temperature, number of extraction cycles, and ionic strength on partitioning of the target compounds have been investigated in detail, including the determination of salting-out constants for the investigated compounds. Lowest method detection limits (MDLs) were obtained with the WAX and the PDMS/AC phase. The WAX phase showed MDLs for ethers in the range of 0.06 μg/L (MTBE) to 0.8 μg/L (1,4-dioxane) and for alcohols between 0.02 μg/L (3-methyl-1-pentanol) and 3.5 μg/L (1-propanol). The evaluated MDLs for ethers with the PDMS/AC were in the range 0.06 μg/L (MTBE) to 1.2 μg/L (1,4-dioxane) and for alcohols between 0.004 μg/L (1-hexanol) and 4.9 μg/L (ethanol). Using either of these two phases, SPDE provides comparable or better sensitivities for the investigated compounds than other enrichment techniques, high sample throughput because of full automation, and short extraction times as well as a high robustness of the extraction phase because of its protection inside the steel needle. SPDE applicability has been demonstrated for the determination of fusel oils in different alcoholic beverages.

A Survey on High-Concentration-Capability Headspace Sampling Techniques in the Analysis of Flavors and Fragrances

This survey critically discusses high-concentration-capacity (HCC) headspace (HS) techniques applied to sample the volatile fraction of matrices of interest in the flavors and fragrance fields. In particular, the advantages, limits, and fields of application of HS solid-phase microextraction (SPME), high-capacity HS sorptive extraction (HSSE) and HS solid-phase dynamic extraction (SPDE) are evaluated. These techniques are discussed in view of the peculiar characteristic of HCC-HS techniques, from the standpoint that these techniques are a bridge between static (S-HS) and dynamic HS (D-HS) because they are as simple, fast, easy to automate, and reliable as S-HS, yet afford analyte concentration factors comparable to those of D-HS. Moreover, the different degree of their development is a consequence of the different times in which they were introduced into the market, because the potential of HS-SPME is now well known, having been introduced approximately 12 years ago, but that of HSSE has still to be fully explored, and HS-SPDE still has to be investigated because it is very recent.

Automated headspace solid-phase dynamic extraction to analyse the volatile fraction of food matrices.

High concentration capacity headspace techniques (headspace solid-phase microextraction (HS-SPME) and headspace sorptive extraction (HSSE)) are a bridge between static and dynamic headspace, since they give high concentration factors as does dynamic headspace (D-HS), and are as easy to apply and as reproducible as static headspace (S-HS). In 2000, Chromtech (Idstein, Germany) introduced an inside-needle technique for vapour and liquid sampling, solid-phase dynamic extraction (SPDE), also known as "the magic needle". In SPDE, analytes are concentrated on a 50 microm film of polydimethylsiloxane (PDMS) and activated carbon (10%) coated onto the inside wall of the stainless steel needle (5 cm) of a 2.5 ml gas tight syringe. When SPDE is used for headspace sampling (HS-SPDE), a fixed volume of the headspace of the sample under investigation is sucked up an appropriate number of times with the gas tight syringe and an analyte amount suitable for a reliable GC or GC-MS analysis accumulates in the polymer coating the needle wall. This article describes the preliminary results of both a study on the optimisation of sampling parameters conditioning HS-SPDE recovery, through the analysis of a standard mixture of highly volatile compounds (beta-pinene, isoamyl acetate and linalool) and of the HS-SPDE-GC-MS analyses of aromatic plants and food matrices. This study shows that HS-SPDE is a successful technique for HS-sampling with high concentration capability, good repeatability and intermediate precision, also when it is compared to HS-SPME.