Headspace extraction

Welch, W. G. Greco, T. G. An Experiment in Manual Multiple Headspace Extraction for Gas Ghromatography, ... 

Bianchi, F., Careri, M., and Musci, M. (2005). Volatile norisoprenoids as markers of botanical origin of Sardinian strawberry-tree (Arbutus unedo L.) honey Characterisation of aroma compounds by dynamic headspace extraction and gas chromatography-mass spectrometry. Food Chem. 89,527-532. 

The principles behind MAP liquid-phase and gas-phase extractions are fundamentally similar and rely on the use of microwaves to selectively apply energy to a matrix rather than to the environment surrounding it. MAP gas-phase extractions (MAP-HS) give better sensitivity than the conventional static headspace extraction method. MAP-HS may also be applied in dynamic applications. This allows the application of a prolonged, low-power irradiation, or of a multi-pulse irradiation of the sample, thus providing a means to extract all of the volatile analytes from the matrix [477]. 

Hcxanc can be determined in biological fluids and tissues and breath using a variety of analytical methods. Representative methods are summarized in Table 6-1. Most methods utilize gas chromatographic (GC) techniques for determination of -hexane. The three methods used for preparation of biological fluids and tissues for analysis are solvent extraction, direct aqueous injection, and headspace extraction. Breath samples are usually collected on adsorbent traps or in sampling bags or canisters prior to analysis by GC. 

Few well characterized, validated methods are available for the determination of w-hexane in blood. A purge-and-trap method for volatiles has been developed and validated by researchers at the Centers for Disease Control and Prevention (CDC) (Ashley et al. 1992, 1994). Extension of the method to include /7-hexane should be possible. Current analytical methods utilize capillary GC columns and MS detection to provide the sensitivity and selectivity required for the analysis. Detection limits are in the low ppb range (Brugnone et al. 1991 Schuberth 1994). Headspace extraction followed by GC analysis has also been utilized for the determination of /7-hexanc in blood (Brugnone et al. 1991 Michael et al. 1980 Schuberth 1994) however, very little performance data are available. 

Some methods are available for determining -hexane in urine and tissues. A modified dynamic headspace extraction method for urine, mother s milk, and adipose tissue has been reported (Michael et al. 1980). Volatiles swept from the sample are analyzed by capillary GC/FID. Acceptable recovery was reported for model compounds detection limits were not reported (Michael et al. 1980). A solvent extraction procedure utilizing isotope dilution followed by GC/MS analysis has been reported for tissues (White et al. 1979). Recovery was good (104%) and detection limits are approximately 100 ng/mL (White etal. 1979). 

Dynamic headspace-extraction stripping and purge-and-trap methodology are used most often for determination of M-hcxanc in water and hazardous wastes. Dynamic headspace extraction techniques have been applied to water samples (Roberts and Burton 1994) and sediment (Bianchi et al. 1991). Detection limits of 0.5 g/L were reported for lake water (Roberts and Burton 1994) and 20 ng/kg (ppt) for sediment (Bianchi et al. 1991). Supercritical fluid extraction (SFE) is a relatively new technique that has been applied to -hcxane in soil (Yang et al. 1995). Membrane extraction of M-hexane from water samples has been developed to provide online, continuous monitoring (Wong et al. 1995 Xu and Mitra... 

The pheromone of Leptocorisa chinensis illustrates the critical importance of the interplay between attractive and inhibitory chemicals [21]. Headspace extracts from males and females were qualitatively similar. From the eight compounds in headspace extracts that elicited strong antennal responses from males, four were discounted as being defensive chemicals or alarm pheromones. The remaining group of four chemicals, consisting of octanol,... 

Brachet, A. and Chaintreau, A. Determination of air-to-water partition coefficients using automated multiple headspace extractions. Anal Chem., 77(10) 3045-3052, 2005. 

Chai, X.S. and Zhu, J.Y. Simultaneous measurements of solute concentration and Hetrry s constant trsing mrrltiple headspace extraction gas chromatography, Anal. Chem., 70(16) 3481-3487, 1998a. 

Schoenmakers et al. [72] analyzed two representative commercial rubbers by gas chromatography-mass spectrometry (GC-MS) and detected more than 100 different compounds. The rubbers, mixtures of isobutylene and isoprene, were analyzed after being cryogenically grinded and submitted to two different extraction procedures a Sohxlet extraction with a series of solvents and a static-headspace extraction, which entailed placing the sample in a 20-mL sealed vial in an oven at 110°C for 5,20, or 50 min. Although these are not the conditions to which pharmaceutical products are submitted, the results may give an idea of which compounds could be expected from these materials. Residual monomers, isobutylene in the dimeric or tetrameric form, and compounds derived from the scission of the polymeric chain were found in the extracts. Table 32 presents an overview of the nature of the compounds identified in the headspace and Soxhlet extracts of the polymers. While the liquid-phase extraction was able to extract less volatile compounds, the headspace technique was able to show the presence of compounds with low molecular mass... 

Delaunay-Bertoncini, N., van der Wielen, F. W. M., De Voogt, P., Erlandsson, B., and Schoenmakers, P. J. (2004), Analysis of low-molar-mass materials in commercial rubber samples by Soxhlet and headspace extractions followed by GC-MS analysis, /. Pharm. Biomed. Anal, 35,1059-1073. 

To determine the chemical composition of drinking water, concentration by headspace, extraction, and XAD-2 adsorption were applied to acquire concentrates. Sensory-directed fractionation of these concentrates has led to the identification of odor-intensive compounds of industrial origin. 

Headspace extraction, see also Dilution analysis Solid-phase microextraction Hemoglobin... 

As an alternative to headspace extraction, analytes can be extracted by submersion of an SPME fiber in a liquid sample such as a beverage. While the ratio of analytes in the liquid phase is different from that which would be observed in the corresponding headspace gases, the concentration of most analytes is much higher in the liquid phase. Submersion SPME is most applicable when the basic composition in the food is desired. It is often used as a replacement for solvent extraction. 

Exposure time can be arbitrarily chosen or the time to equilibrium can be used. Time to equilibrium can be determined by extracting for incremental time periods until a stable extracted concentration is achieved. Equilibration time is much greater for submersion extraction than for headspace extraction. It is imperative that the selected exposure time be used exactly and consistently for any measurements that are to be compared. 

Because SPME extracts compounds selectively, the response to each compound must be calibrated for quantification. A specific compound can be quantified by using three GC peak area values from solvent injection, static headspace (gas-tight syringe), and SPME. The solvent injection is used to quantify the GC peak area response of a compound. This is used to quantify the amount of the compound in the headspace. The SPME response is then compared to the quantified static headspace extraction. These three stages are necessary because a known gas-phase concentration of most aroma compounds at low levels is not readily produced. A headspace of unknown concentration is thus produced and quantified with the solvent injection. Calibration must be conducted independently for each fiber and must include each compound to be quantified. 

Figure G1.6.2 Apparatus for quantification of headspace extraction in Support Protocol 1.

SPME is a sample-preparation technique based on absorption that is useful for extraction and concentration of analytes either by submersion in a liquid phase or exposure to a gaseous phase (Belardi and Pawliszyn, 1989 Arthur et al., 1992). Following exposure of the fiber to the sample, absorbed analytes can be thermally desorbed in a conventional GC injection port. The fiber behaves as a liquid solvent that selectively extracts analytes, with more polar fibers having a greater affinity for polar analytes. Headspace extraction from equilibrium is based on partition coefficients of individual compounds between the food and headspace and between the headspace and the fiber coat-... 

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