Headspace analysis purge-and-trap

Separation of carbon tetrachloride from biological samples may achieved by headspace analysis, purge-and-trap collection from aqueous solution or slurry samples, solvent extraction, or direct collection on resins. Headspace analysis offers speed, simplicity, and good reproducibility, but partitioning of the analyte between the headspace and the sample matrix is dependent upon the nature of the matrix and must be determined separately for each different kind of matrix (Walters 1986). 

Headspace analysis, purge and trap analysis and gas chromatography coupled to mass spectrometry have all been employed in determinations of gasoline hydrocarbons in soil, yielding detection limits as low as 5 xg/g [24,25]. 

See also Air Analysis Sampling. Chromatography Overview Principles. Clinical Analysis Sample Handling. Drug Metabolism Metabolite Isolation and Identification. Extraction Solid-Phase Extraction. Food and Nutritional Analysis Sample Preparation. Forensic Sciences Volatile Substances. Headspace Analysis Purge and Trap. Perfumes. Sample Handling Sample Preservation Automated Sample Preparation. Sampling Theory. 

In addition to headspace analysis, purge-and-trap procedures can be employed that drive volatile anal 4 es from a sample and collect them on an adsorbent colunm for subsequent analysis. Distillation techniques, including azeotropic distillation and vacuum distillation are also used to isolate volatile analjdes. 

V lie PL. 1988. Comparing headspace with purge and trap for analysis of volatile priority pollutants. American Water Works Association 80 65-72. 

There are numerous textbooks on and guides to chromatography, it is not intended to discuss the details of this technique in this chapter. The use of capillary columns, particularly in conjunction with headspace or purge and trap analysis, and modem bench-top mass spectrometers with large desk-top computing capacity, has produced a powerful technique for the analysis of VOCs. Typically, the separation, identification and quantification of up to about one hundred compounds in a single analysis are possible and routinely carried out. 

Wylie, P.L. (1987) Comparison of headspace with purge and trap techniques for the analysis of volatile priority pollutants, in 8tii International Symposium on Capillary Chromatography Riva del Garda, May 19th-21st 1987 (ed. P. Sandra), Huethig, pp. 482 -499. 

Purge-and-trap methods have also been used to analyze biological fluids for the presence of trichloroethylene. Breast milk and blood were analyzed for trichloroethylene by purging onto a Tenax gas chromatograph to concentrate the volatiles, followed by thermal desorption and analysis by GC/MS (Antoine et al. 1986 Pellizzari et al. 1982). However, the breast milk analysis was only qualitative, and recoveries appeared to be low for those chemicals analyzed (Pellizzari et al. 1982). Precision (Antoine et al. 1986) and sensitivity (Pellizzari et al. 1982) were comparable to headspace analysis. 

Analysis of environmental samples is similar to that of biological samples. The most common methods of analyses are GC coupled to MS, ECD, a Hall s electrolytic conductivity detector (HECD), or a flame-ionization detector (FID). Preconcentration of samples is usually done by sorption on a solid sorbent for air and by the purge-and-trap method for liquid and solid matrices. Alternatively, headspace above liquid and... 

Analysis of soils and sediments is typically performed with aqueous extraction followed by headspace analysis or the purge-and-trap methods described above. Comparison of these two methods has found them equally suited for on-site analysis of soils (Hewitt et al. 1992). The major limitation of headspace analysis has been incomplete desorption of trichloroethylene from the soil matrix, although this was shown to be alleviated by methanol extraction (Pavlostathis and Mathavan 1992). 

Gas phase stripping (purge-and-trap) techniques can iaq>rove the yield of organic volatiles from water or biological fluids by facilitating the transfer of volatiles from the liquid to the gas phase it is also more suitable than dynamic headspace sampling when the sample volume is restricted (320 23,347-351). Tbe technique is used routinely in many laboratorl B for the analysis... 

Figure 8.27 A, apparatus for dynaaic headspace analysis of urine with sorbent trapping. B, gas phase stripping apparatus (purge-and-trap).

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. 

Headspace analysis (EPA 3810, 5021) also works well for analyzing volatile petroleum constituents in soil. In the test method, the soil is placed in a headspace vial and heated to drive out the volatiles from the sample into the headspace of the sample container. Salts can be added for more efficient release of the volatile compounds into the headspace. Similar to water headspace analysis, the soil headspace technique is useful when heavy oils and high analyte concentrations are present, which can severely contaminate purge-and-trap instrumentation. Detection limits are generally higher for headspace analysis than for purge-and-trap analysis. 

The analysis involves gas chromatographic methods such as purge and trap, vacuum distillation, and headspace (Askari et al., 1996). On the other hand, samples for the determination of semi- and nonvolatile hydrocarbons need not be collected in such a rigorous manner. On arrival at the laboratory, they require extraction by techniques such as solvent or supercritical fiuid. Some cleanup of... 

Sample collection and preparation for the analysis of 1,2-dibromoethane in foods includes the purge-and-trap method, headspace gas analysis, liquid-liquid extraction, and steam distillation (Alleman et al. 1986 Anderson et al. 1985 Bielorai and Alumot 1965, 1966 Cairns et al. 1984 Clower et al. 1985 Pranoto-Soetardhi et al. 1986 Scudamore 1985). GC equipped with either ECD or HECD is the technique used for measuring 1,2-dibromoethane in foodstuffs at ppt levels (Clower et al. 1985 Entz and Hollifield 1982 Heikes and Hopper 1986 Page et al. 1987 Van Rillaer and Beernaert 1985). 

The key advantage of this headspace method, compared to static headspace analysis, is the sensitivity obtained. While static headspace shows the status at equilibrium and can measure thermodynamic constants, purge-and-trap or dynamic headspace can measure the kinetics of... 

In flavor analysis, the most frequent use of volatile traps is in analyzing the flavor compounds in foods using purge-and-trap or dynamic headspace, followed by GC-MS or GCO. Additionally, the traps can be used to measure static headspace and air-matrix partition coefficients where air is pushed out of an equilibrated cell containing the sample onto a volatile trap (Chaintreau et al., 1995). Volatile traps have been also used for flavor release measurements during eating (Linforth and Taylor, 1993) or simulated eating (Roberts and Acree, 1995). 

For a compound to contribute to the aroma of a food, the compound must have odor activity and volatilize from the food into the head-space at a concentration above its detection threshold. Since aroma compounds are usually present in a headspace at levels too low to be detected by GC, headspace extraction also requires concentration. SPME headspace extraction lends itself to aroma analysis, since it selectively extracts and concentrates compounds in the headspace. Some other methods used for sample preparation for aroma analysis include purge-and-trap or porous polymer extraction, static headspace extraction, and solvent extraction. A comparison of these methods is summarized in Table Gl.6.2. 

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