Headspace analysis static methods

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... 

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. 

Headspace Extraction Headspace (HS) extraction is a well-known method of sample preparation and is frequently used in many laboratories, especially in industrial applications. It involves a partitioning equilibrium between the gas phase and a sample (liquid or solid). In this technique, an aliquot of gas phase is sampled into GC. There are two types of analysis, static and d3Uiamic. In the static version, when the equilibrium is reached, the gas phase is injected into GC. In dynamic analysis, the volatiles are exhaustively extracted by the stream of gas. However, matrix effects result in decreased sensitivity for certain substances, especially polar and hydrophilic samples. A comprehensive book describing HS techniques was presented by Kolb [31]. 

Soil spiked with trichloroethylene and toluene was analysed using a gas chromatograph equipped with a PT concentrator that was found to be replaceable by a headspace unit in order to simplify the overall assembly. The headspace analysis of soil samples was found to be restricted by incomplete desorption of the contaminants in soil-water mixtures this shortcoming, however, was effectively overcome by the addition of methanol. Henry s law constants for volatile organics in methanol must previously be determined if the method is to be applied to soils [142]. A comparison of the performance of static and dynamic (PT) headspace modes in the determination of nine VOCs in five different soils revealed poor PT recoveries in relation to those of static headspace (which ranged from 68 to 88%) the latter, however, required longer development times [143],... 

In combination with GC/IRMS, static headspace analysis for fuel containing compounds such as BTEX was apphed in different studies [73,74]. Headspace injection does not fractionate significantly for MTBE [74,75]. Method detection limits for 5 C static headspace-GC/IRMS applications are between 4000-5000 xg/L for MTBE [74,75]. 

Wasik and Brown (34) later modified McAuliffes static headspace method. They constructed a dynamic headspace analysis unit where... 

Various gas chromatographic (GC) methods, such as direct injection, dynamic headspace, and static headspace, have been used for the analysis of volatile products, resulting from the oxidative deterioration of vegetable oils. Though advantages and disadvantages are apparent with each GC method, for routine analyses, static headspace is the method of choice because it is rapid and requires no cleaning between samples. ... 

Table 3.2 Headspace analysis of oxidized soya bean oil (peroxide value 9.5) by three methods direct injection, dynamic headspace gas chromatography (HSGC) and static HSGC. OlOOH = oleic acid hydroperoxide LoOOH = linoleic acid hydroperoxide LnOOH = linolenic acid hydroperoxide.

There are many methods which enable determination of activity coefficients in infinite dilution. They are mostly based on differential ebulliometry or on gas chromatographic measurement of retention time, subsequently retention volume. The headspace chromatographic analysis is another popular technique which enables measurement of equilibrium compositions at given temperature. Some similarity with static methods may be found, however, degassing is not required since the pressure is not measured. The data may be obtained rather quickly, nevertheless their accuracy is not very high. Methods for measurement of activity coefficients in infinitely diluted solutions are not described here in detail because such data are not included in this volume. 

This constant is dependent on the analyte, the composition of the phases, pressure, and the temperature of the system. The distribution coefficient can be obtained experimentally by a method reported in Refs. [89,90]. Nevertheless, the pressure and gas-phase composition are parameters with no practical interest in the optimization of the static headspace analysis, as the sample is loaded in a sealed bottle/vial with ambient air filling the headspace, and the pressure in the system is generally a parameter that is fixed by the selected temperature. 

In static headspace analysis, the partition coefficient of the analytes is used to assess and plan the method (Kolb and Ettre, 2006). For the partition coefficient K of a volatile compound, the following equation is valid ... 

Gas chromatography Highly precise and (potentially) accurate method Applicable for homopolymers and copolymers Static-headspace analysis can be performed online... 

Headspace methods provide an indirect method of sample analysis suitable for the determination of organic volatiles [11,318-323]. The gas diase in contact with the sample and not the sample matrix itself is taken for analysis. If the sample is in thermodynamic equilibrium with the gas phase in a closed thermostated vessel, then this method of analysis is referred to as static headspace. If a carrier gas is passed over the sample and the sample volatiles accumulated in a cryogenic or sorbent trap, then the method is generally referred to as dynamic headspace. If the carrier gas is introduced below the surface of... 

Applications The potential of a variety of direct solid sampling methods for in-polymer additive analysis by GC has been reviewed and critically evaluated, in particular, static and dynamic headspace, solid-phase microextraction and thermal desorption [33]. It has been reported that many more products were identified after SPME-GC-MS than after DHS-GC-MS [35], Off-line use of an amino SPE cartridge for sample cleanup and enrichment, followed by TLC, has allowed detection of 11 synthetic colours in beverage products at sub-ppm level [36], SFE-TLC was also used for the analysis of a vitamin oil mixture [16]. 

In static headspace sampling [301,302] the polymer is heated in a septum-capped vial for a time sufficient for the solid and vapour phases to reach equilibrium (typically 2 hours). The headspace is then sampled (either manually or automatically) for GC analysis, often followed by FID or NPD detection. Headspace sampling is a very effective method for maintaining a clean chromatographic system. Changing equilibrium temperature and time, and the volumes present in the headspace vial can influence the sensitivity of the static headspace system. SHS-GC-MS is capable of analysing volatile compounds in full scan with ppb level... 

Rancidity measurements are taken by determining the concentration of either the intermediate compounds, or the more stable end products. Peroxide values (PV), thiobarbituric acid (TBA) test, fatty acid analysis, GC volatile analysis, active oxygen method (AOM), and sensory analysis are just some of the methods currently used for this purpose. Peroxide values and TBA tests are two very common rancidity tests however, the actual point of rancidity is discretionary. Determinations based on intermediate compounds (PV) are limited because the same value can represent two different points on the rancidity curve, thus making interpretations difficult. For example, a low PV can represent a sample just starting to become rancid, as well as a sample that has developed an extreme rancid characteristic. The TBA test has similar limitations, in that TBA values are typically quadratic with increasing oxidation. Due to the stability of some of the end-products, headspace GC is a fast and reliable method for oxidation measurement. Headspace techniques include static, dynamic and solid-phase microextraction (SPME) methods. Hexanal, which is the end-product formed from the oxidation of Q-6 unsaturated fatty acids (linoleate), is often found to be a major compound in the volatile profile of food products, and is often chosen as an indicator of oxidation in meals, especially during the early oxidative changes (Shahidi, 1994). 

Stuart et al. [ 184] studied the analysis of volatile organic compounds in soil using an automated static headspace method. Recoveries increased in the or-... 

Static headspace extraction is also known as equilibrium headspace extraction or simply as headspace. It is one of the most common techniques for the quantitative and qualitative analysis of volatile organic compounds from a variety of matrices. This technique has been available for over 30 years [9], so the instrumentation is both mature and reliable. With the current availability of computer-controlled instrumentation, automated analysis with accurate control of all instrument parameters has become routine. The method of extraction is straightforward A sample, either solid or liquid, is placed in a headspace autosampler (HSAS) vial, typically 10 or 20 mL, and the volatile analytes diffuse into the headspace of the vial as shown in Figure 4.1. Once the concentration of the analyte in the headspace of the vial reaches equilibrium with the concentration in the sample matrix, a portion of the headspace is swept into a gas chromatograph for analysis. This can be done by either manual injection as shown in Figure 4.1 or by use of an autosampler. 

A static headspace is frequently used for the determination of VOCs in complex matrices such as food [32, 33], urine [34], blood [35], and swimming pool water [36]. This method is also routinely used in the analysis of residual solvents in the pharmaceutical industry [37]. Currently, there are various types of automatic HS systems (Fig. 14.5) [38]. 

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