Headspace sampling techniques liquid samples

Prom the experimental point of view the static headspace sampling technique is very simple. The sample, either solid or liquid, is placed in a glass vial of appropriate size and closed with a Teflon-lined silicone septum. The 1 is carefully... 

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... 

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). 

There are many techniques available for the preparation of volatile analytes prior to instrumental analysis. In this chapter the major techniques, leading primarily to gas chromatographic analysis, have been explored. It is seen that the classical techniques purge and trap, static headspace extraction, and liquid-liquid extraction still have important roles in chemical analysis of all sample types. New techniques, such as SPME and membrane extraction, offer promise as the needs for automation, field sampling, and solvent reduction increase. For whatever problems may confront the analyst, there is an appropriate technique available the main analytical difficulty may lie in choosing the most appropriate one. 

Headspace Sampling Technique. The method used a new gas chromatographic desorption - concentration - GC introduction device (D.C.I.) based on dynamic headspace analysis and available from Delsi Instruments (Paris, France). This apparatus made it possible to isolate volatiles from both solid and liquid samples (4). 

In the early 90s, a new technique called solid-phase-micro extraction (SPME), was developed (Arthur and Pawliszyn, 1990). The key-part component of the SPME device is a fused silica fiber coated with an adsorbent material such as polydimethylsiloxane (PDMS), polyacrylate (PA) and carbowax (CW), or mixed phases such as polydimethylsiloxane-divinylbenzene (PDMS-DVB), carboxen-polydimethylsiloxane (CAR-PDMS) and carboxen-polydimethyl-siloxane-divinylbenzene (CAR-PDMS-DVB). The sampling can be made either in the headspace (Vas et al., 1998) or in the liquid phase (De la Calle et al., 1996) of the samples. The headspace sampling in wine analyses is mainly useful for quantifying trace compounds with a particular affinity to the fiber phase, not easily measurable with other techniques. Exhaustive overviews on materials used for the extraction-concentration of aroma compounds were published by Ferreira et al. (1996), Eberler (2001), Cabredo-Pinillos et al. (2004) and Nongonierma et al. (2006). Analysis of the volatile compounds is usually performed by gas chromatography (GC) coupled with either a flame ionization (FID) or mass spectrometry (MS) detector. 

There is as yet no perfect extraction method for all types of samples. A minimum of a liquid extraction and a headspace sampling should lead to a fairly well rounded flavor or fragrance profile and analysis. The more techniques used to study a particular subject, the better the quality of the analytical results. However with experience the choice of extraction techniques will ensure more detailed analyses from fewer extracts. 

Another useful technique is solid phase microextraction. A fused silica fibre is attached to the base of a syringe with a fixed metal needle. The fibre is coated with a thin layer of stationary phase that is selective for the analytes of interest. The fibre is dipped into the liquid sample or into the headspace above the liquid for a period of time, allowing a fraction of the analyte to be extracted into the fibre. The fibre is then retracted into the syringe and the syringe injected into the injection port where the analyte is thermally desorbed from the fibre into the GC. 

Liquid-liquid extraction has a counterpart for the determination of VOCs in the technique known as static or equilibrium headspace sampling. The technique is most often combined with the determinative step and is often referred to as static headspace gas chromatography, abbreviated HS-GC. The principles that underlie this technique will be outlined in this section. The decision to measure VOCs in the environment by either HS or purge and trap (P T or dynamic headspace) represents one of the ongoing controversies in the field of TEQA. This author has worked in two different environmental laboratories in which one used P T as the predominant technique to determine VOCs in the environment and the other used HS-GC. 

Traditionally, products and adsorbates had to be volatile enough so that they could be carried from the cell into the mass spectrometer, either by headspace sampling, or, more commonly for near-simultaneous analysis (referred to as differential electrochemical mass spectrometry), across a nanoporous, gas-permeable membrane (e.g., Teflon) supported at the tip of a microcapillary placed close to the electrode. Alternatively, a Pt-coated membrane electrode can be used. But the advent of the so-called soft atmospheric pressure desorption/ionization techniques associated with liquid chromatography-mass spectrometry has allowed the sampling of the solvent and involatile solutes directly. The spectra are more... 

Headspace sampling is probably the simplest and easiest technique. A brief introduction to the topic has been published by Hinshaw [16], and a complete coverage of the theory and practice has just appeared [17]. The sample (liquid or solid) is placed in a sealed vial and heated to a predetermined temperature for a fixed period of time. Volatile components of the sample partition between the gas and sample phases, usually reaching equilibrium. Residual monomers diffuse only slowly from some highly cross-linked polymers, so sufficient time must be allowed for the vaporization from these samples. 

A new technique, which is applicable for sampling in air and liquids or in the headspace above a liquid or a solid sample, is solid-phase micro-extraction (SPME). The mechanism of SPME, which has been developed by Pawliszyn et al. 1225], [226], is based on the partition equilibrium of the analytes between the sample or the head-space above the sample, respectively, and a fused silica fiber coated with a suitable stationary phase. The amount of analyte extracted by the fiber is proportional to the initial analyte concentration in the sample and depends on the type of fiber. After sampling, the fiber can be thermally desorbed directly into the injector of a gas chromatograph. SPME combines sampling, analyte enrichment, matrix separation, and sample introduction within one step [226]. Since its development, this innovative technique has found widespread use in environmental analysis. It has, for example, been applied in the determination of volatile organic compounds [227], 228]. phenols [229],... 

This is a simplified representation where n is the amount of analyte extracted, Kfs is the distribution coefficient of the analyte between stationary phase and sample, Vf is the volume of the stationary phase, and Q is the start concentration of the analyte in the sample. The sample volume is not of importance in SPME, since it relies on the equilibrium (nonexhaustive) and the fact that the volume of the stationary phase is very small compared to the sample volume. This makes SPME a good sample preparation technique for in the field sampling. Note that the equilibrium is obtained much faster when performing headspace sampling compared to immersion sampling. This is due to the faster movement of the analytes in the gas phase compared to that in the liquid phase. 

Dynamic headspace sampling (DHS) is a nonequilibrium process in which air or an inert gas such as nitrogen is passed over the sample (in the case of a solid) or through the sample (in case of a liquid). In the case of a liquid sample, this is more commonly referred to as the purge-and-trap technique, which is used widely in the environmental field. 

The SPME device not only combines extraction and concentration but also directly transfers the absorbed compounds into a GC injector. These features of HS-SPME provide major advantages over previous headspace techniques. Coupling to GC, GC-MS (including ion-trap), split/splitless and on-column injection or desorption of the analytes in an SPME-HPLC interface have been described. A significant difference in sensitivity between direct and headspace sampling can occur only for very volatile analytes. HS-SPME introduces some selectivity into the extraction technique as only analytes with sufficient vapour pressure at room temperature are detected. An obvious drawback of HS-SPME is that semi- and non-volatiles will not be present in detectable amounts in the headspace. In combination with GC this is actually advantageous and enables faster equilibration than sampling from liquid [992]. 

Because liquid and headspace sampUng methods differ in kinetics, the two approaches are complementary. Equilibrium is attained more rapidly in headspace SPME than in direct-immersion SPME, because there is no liquid to hinder diffusion of the analyte onto the stationary phase. For a given sampling time, immersion SPME is more sensitive than HS-SPME for analytes predominantly present in the liquid. The reverse is true for analytes that are primarily in the headspace. Several additional factors can affect SPME and do influence the choice between immersion and headspace sampling [997]. Overall extraction with HS-SPME is apt to be lower than in direct-immersion because transfer of analytes from the sample to the gas phase seldom is quantitative. HS-SPME was compared with PT [998] and HS-GC-MS [954,999]. Application of HS-SPME eliminates many problems of other headspace techniques and extends headspace sampling to less volatile compounds due to the concentration effect at the fibre coating. Thermal desorption... 

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