Headspace sampling techniques solid 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... 

Small solid seuaples can be analyzed directly by dynamic headspace sampling using a platinum coil and quartz crucible pyrolyzer and cold trap coupled to an open tubular column (341,369,379). This method has been used primarily for the analysis of mineral samples and of additives, catalysts and byproducts in finished polymers which yield unreliable results using conventional headspace techniques owing to the slow release of the volatiles to the headspace. At the higher temperatures (450-1000 C) available with the pyrolyzer the volatiles are more readily and completely removed from the sample providing for quantitative analysis. 

HS-GC methods have equally been used for chromatographic analysis of residual volatile substances in PS [219]. In particular, various methods have been described for the determination of styrene monomer in PS by solution headspace analysis [204,220]. Residual styrene monomer in PS granules can be determined in about 100 min in DMF solution using n-butylbenzene as an internal standard for this monomer solid headspace sampling is considerably less suitable as over 20 h are required to reach equilibrium [204]. Shanks [221] has determined residual styrene and butadiene in polymers with an analytical sensitivity of 0.05 to 5 ppm by SHS analysis of polymer solutions. The method development for determination of residual styrene monomer in PS samples and of residual solvent (toluene) in a printed laminated plastic film by HS-GC was illustrated [207], Less volatile monomers such as styrene (b.p. 145 °C) and 2-ethylhexyl acrylate (b.p. 214 °C) may not be determined using headspace techniques with the same sensitivities realised for more volatile monomers. Steichen [216] has reported a 600-fold increase in headspace sensitivity for the analysis of residual 2-ethylhexyl acrylate by adding water to the solution in dimethylacetamide. 

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). 

Control of the vapor pressure in the headspace over a solid can also be used to maintain a relative humidity over a solid. As shown in Eq. (4), the relative humidity is directly correlated to the partial pressure of water in the vapor phase. To utilize this technique for relative humidity control, the headspace above the sample must be completely evacuated prior to analysis. Pure water vapor can then be carefully admitted to the vapor phase. Because only water vapor is present, the pressure measured over the system is directly related to the relative humidity over the sample. ... 

The techniques discussed in this chapter vary in automatability and frequency of use. Thus, while automatic hydride and cold mercury vapour generation are implemented in laboratory-constructed or commercially available dynamic equipment that is straightforward, easy to operate and inexpensive, automating laboratory headspace modes and solid-phase microextraction is rather complicated and commercially available automated equipment for their implementation is sophisticated and expensive. Because of its fairly recent inception, analytical pervaporation lacks commercially available equipment for any type of sample however, its high potential and the interest it has aroused among manufacturers is bound to result in fast development of instrumentation for both solid and liquid samples. This technique, which is always applied under dynamic conditions, has invariably been implemented in a semi-automatic manner to date also, its complete automatization is very simple. 

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. 

A frequent use of GC with polymers is in the quantitative determination of residual monomer and solvent content, even at sub parts per million levels. This is especially important in food contact applications (e.g. printed packaging materials) where taint and odour issues are important. There are a range of sample preparation and injection techniques to deal with a vast range of samples including, for example, headspace sampling where a solid can be incubated for a period of time and then the vapours from above the solid are transferred into the GC capillary. 

Microwave-assisted desorption coupled to in situ headspace solid-phase microextraction (HS-SPME) was first proposed as a possible alternative pretreatment of samples collected from workplace monitoring. Therefore, pretreatment that takes a short time and uses little or no organic solvents has led to the recent development of a new extraction technique. Solid-phase micro-extraction (SPME) coupled with GC analysis has been used successfully to analyze pollutants in environmental matrices. MHS has been developed to achieve one-step, in situ headspace sampling of semivolatile organic compounds in aqueous samples, vegetables, and soil [7, 55-58]. 

The SPME sampling device can be immersed directly into an aqueous sample such as groundwater for a finite period of time, then withdrawn, the fiber and rod retracted back into the needle, brought to the hot-injection port of a gas chromatograph, and then inserted into the septum, the fiber and rod extended into the injection port for a finite period of time in which thermal desorption is accomplished. For analysis of aqueous samples for VOCs, the fiber is inserted into the headspace, sampled, retracted, and then injected directly into the injection port. For solids, wastewater, sludge, etc. this headspace technique is appropriate provided that analytes can partition... 

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. 

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