Solid-phase microextraction capillary gas

De la Calle Garcia D, Reichenbacher M, Danzer K, Hurlbeck C, Bartzsch C, Feller K-H (1998) Use of solid-phase microextraction capillary gas chromatography (SPME-CGC) for the varietal characterization of wines by means of chemometrical methods. Fresenius J Anal Chem 360 784... 

Classification of wines according to the grape variety succeeds better, in general, because there are many more typical bouquet components (several hundreds) than mineral and trace elements being typical for the origin of wine. The organic compounds can be analyzed easily and reliably by Headspace Solid-Phase Microextraction Capillary Gas Chromatography and afterwards used for classification (De la Calle et al. [1998]). An example... 

S. Aguerre, C. Pecheyran, G. Lespes, E. Krupp, O. F. X. Donard and M. Potin-Gautier, Optimisation of the hyphenation between solid-phase microextraction, capillary gas chromatography and inductively coupled plasma atomic emission spectrometry for the routine speciation of organotin compounds in the environment, J. Anal. At. Spectrom., 16(12), 2001, 1429-1433. 

Moens, L., DeSmaele, T., Dams, R., VandenBroeck, R and Sandra, P. (1997) Sensitive, simultaneous determination of organomercury, -lead, and -tin compounds with headspace solid phase microextraction capillary gas chromatography combined with inductively coupled plasma mass spectrometry. Anal. Chem., 69, 1604—1611. 

Solid-phase microextraction capillary gas chromatography (SPME-GC) is also an interesting preconcentration method. After derivatization with tetraethylborate, tetrapropylborate, or tetraphenylborate, the ethylated compounds are extracted by SPME on a silica fiber coated with polydimeth-ylsiloxane (PDMS). SPME can be performed either in the aqueous phase or in the headspace. After SPME extraction, species are thermally desorbed, separated by GC, and analyzed.106... 

J. Vercauteren, A. De Meester, T. De Smaele, F. Vanhaecke, L. Moens., R. Dams, P. Sandra, Headspace solid-phase microextraction-capillary gas chromatography-ICP mass spectrometry for the determination of the organotin pesticide fentin in environmental samples, J. Anal. Atom. Spectrom., 15 (2000), 651D656. 

P. Grinberg, R. C. Campos, Z. Mester, R. E. Sturgeon, Solid phase microextraction capillary gas chromatography combined with furnace atomization plasma emission spectrometry for speciation of mercury in fish tissues, Spectrochim. Acta, 58B (2003), 427 -441. 

Demyttenaere, J.C.R., Dagher, C., Sandra, P., Kallithraka, S., Verhe, R., and De Kimpe, N. (2003). Flavour analysis of Greek white wine by solid-phase microextraction-capillary gas chromatography-mass spectrometry J. Chromatogr. A, 985,233-246. 

Tat, L. Comuzzo, P. Stolfo, 1. Battistutta, F. (2005). Optimization of wine headsp>ace analysis by solid-phase microextraction capillary gas chromatography with mass spectrometric and flame ionization detection. Food Chemistry 93, 361-369... 

Principles and Characteristics As mentioned already (Section 3.5.2) solid-phase microextraction involves the use of a micro-fibre which is exposed to the analyte(s) for a prespecified time. GC-MS is an ideal detector after SPME extraction/injection for both qualitative and quantitative analysis. For SPME-GC analysis, the fibre is forced into the chromatography capillary injector, where the entire extraction is desorbed. A high linear flow-rate of the carrier gas along the fibre is essential to ensure complete desorption of the analytes. Because no solvent is injected, and the analytes are rapidly desorbed on to the column, minimum detection limits are improved and resolution is maintained. Online coupling of conventional fibre-based SPME coupled with GC is now becoming routine. Automated SPME takes the sample directly from bottle to gas chromatograph. Split/splitless, on-column and PTV injection are compatible with SPME. SPME can also be used very effectively for sample introduction to fast GC systems, provided that a dedicated injector is used for this purpose [69,70],... 

Y. F. Sha, S. Chen, G. L. Duan, Rapid determination of tramadol in human plasma by headspace solid phase microextraction and capillary gas chromatography mass spectrometry, J. Pharrn. Biomed. Anal., 37, 143 147 (2005). 

Solid-phase microextraction (SPME). used as a sample introduction technique for high speed gc, utilizes small-diameter fused-silica fibers coated with polymeric stationary phase for sample extraction and concentration. SPME lias been utilized for determination of pollutants in aqueous solution by the adsorption of analyte onto stationary-phase coated fuscd-silica fibers, followed by thermal desorption in the injection system of a capillary gas chromatograph. Full automation can be achieved using an autosampler. 

S. Ulrich and J. Martens, Solid-phase microextraction with capillary gas-liquid chromatography and nitrogen-phosphorus selective detection for the assay of antidepressant drugs in human plasma , J. Chromatogr. B 696 217-234 (1997). 

M. Krogh, K. Johansen, F. Tonnesen and K. E. Rasmusen, Solid-phase microextraction for the determination of the free concentration of valproic acid in human plasma by capillary gas chromatography , J. Chromatogr. B 673 299-305 (1997). 

K. Takekawa, M. Oya, A. Kido and O. Suzuki, Analysis of cyanide in blood by headspace solid-phase microextraction (SPME) and capillary gas chromatography, Chromatographia, 47, 209-214 (1998). 

Solid-phase microextraction (SPME) — is a procedure originally developed for sample preconcentration in gas chromatography (GC). In this procedure a small-diameter fused silica optical fiber, coated with a liquid polymer phase such as poly(dimethylsiloxane), is immersed in an aqueous sample solution. The -> analytes partition into the polymer phase and are then thermally desorbed in the GC injector on the column. The same polymer coating is used as a stationary phase of capillary GC columns. The extraction is a non-exhaustive liquid-liquid extraction with the convenience that the organic phase is attached to the fiber. This fiber is contained in a syringe, which protects it and simplifies introduction of the fiber into a GC injector. Both uncoated and coated fibers with films of different GC stationary phases can be used. SPME can be successfully applied to the analysis of volatile chlorinated organic compounds, such as chlorinated organic solvents and substituted benzenes as well as nonvolatile chlorinated biphenyls. 

Figure 1.20 Reconstructed ion chromatograms (RIC) of [M + H]+ species at m/z 240 (acetaldehyde-PFB-derivatives), m/z 266 ([M + H —18]+ ion of acetoin-PFB-derivatives), m/z 282 (diacetyl mono-PFB-derivatives), m/z 336 (IS-PFB-derivatives) and m/z 477 (diacetyl di-PFB-derivatives) of a Merlot wine at the first day of MLF (a), and after 5 days of MLF (b). Analytical conditions polyethylene glycol) (30m x 0.25 mm i.d. df 0.25 juim) fused silica capillary column programmed oven temperature 5 min at 60 °C, 3°C/min to 210 °C, 5 min at 210°C transfer line temperature 280 °C carrier gas He flow mode constant pressure 16psi. (Reprinted from Journal of Mass Spectrometry 40, Flamini et al., Monitoring of the principal carbonyl compounds involved in malolactic fermentation of wine by synthesis of 0-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine derivatives and solid-phase-microextraction positive-ion-chemical-ionization mass spectrometry analysis, p. 1563, Copyright 2005, with permission from John Wiley Sons Ltd)...

Several techniques have been used to overcome the problem of low column loadings on capillary columns. Capillary columns have been used after preconcentration of the alkylderivatives on a wide-bore fused-silica column or by solid-phase microextraction (SPME). " Large volume injection techniques have been applied on capillary columns coated with 0.25 /rm DB-5. Multicapillary GC (MCGC) (919 capillaries, 1 m X 40/rm i.d. coated with 0.2/rm SE 30 stationary phase (Alltech)) coupled to allows column loadings and carrier gas flow... 

Sha, Y., Deng, C., Liu, Z., Huang, T., Yung, B, and Duan, G. (2004). Headspace solid-phase microextraction and capillary gas chromaiographic-mass spectrometric deiermination of rivastigmine in canine plasma samples. J. Chromatogi B Anal, Technoi. Biomed. Life Sci. 806, 271-276. 

It has been coupled with enzyme immunoassay for efficient and fast polyaromatic hydrocarbon (PAH) screening in soil [21]. In a number of studies both static and dynamic superheated water extraction has been coupled to solid-phase microextraction [15, 25, 28, 30, 35, 38], sometimes with other analytical methods also coupled. It has been coupled with gas chromatography-mass spectrometry [31], capillary electrophoresis [31], liquid chromatography-mass spectrometry [32] and liquid chromatography-gas chromatography [41]. Sometimes other chemicals are added to the water used, such as acid [42] or phosphate buffer [43]. Different trapping methods for analytical extraction have been examined [44]. 

Present-day monodimensional (ID), open-tubular capillary column gas chromatography (GC) techniques can provide satisfactory analytical results for food samples of low complexity, but when challenged with moderate to highly complex matrices, these techniques often fail, as will be shown later in this chapter. As a typical example, the headspace solid-phase microextraction (HS-SPME) GC equipped with mass spectrometry (GC-MS) result for a sample of Arabica roasted coffee beans is shown in Figure 1 [1]. 

Solid-phase extraction (SPE) has been used in conjunction with separation techniques [gas chromatography (GC), liquid chromatography (LC), and capillary electrophoresis (CE)] for environmental analysis. Recent developments in both SPE and solid-phase microextraction (SPME) have been reviewed. Some of the solid phases investigated previously include graphitized carbon black, octadecylsilica, and Ci8 cartridges. Comparisons of the sorbent materials available for the extraction of phenols have been carried out in conjunction with chromatographic separations. A comparison of polycrystalline graphites and SPME fibers [poly (dimethyl... 

See also Capillary Electrochromatography. Capillary Electrophoresis Pharmaceutical Applications Low-Molecular-Weight Ions Food Chemistry Applications Clinical Applications. Extraction Solid-Phase Extraction Solid-Phase Microextraction. Gas Chromatography Mass Spectrometry. Liquid Chromatography Overview Liquid Chromatography-Mass Spectrometry. 

Solid-phase microextraction (SPME) SPME consists in the adsorption of the target compounds on a thin polymeric film deposed on the surface of a capillary fiber. The mass transfer can be achieved from liquid media in direct contact with the extracting coated fiber as well as from gaseous environments. Volatile or semivolatile herbicides existing in solid samples can be easily transferred in the gas phase on heating in closed vials, followed by trapping of the resulting vapors in the coated fiber (procedure is known as Headspace HD/SPME). 

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