Solid Phase Microextraction SPME

SPME is a very simple and efficient sample preparation method, requiring no solvent (at least for GC applications). Following its introduction (Belardi 1989 Arthur 1990), SPME has been widely used in different fields of analytical chemistry since its first applications to environmental and food analysis. A recent extensive review (Vas 2004) covers the principles and applications of the technique. Other reviews (Queiroz 2004 Hinshaw 2003 Wang 2004 O Reilly 2005 Ouyang 2006) describe special aspects. All conventional steps of extraction, concentration, possibly derivatization, and transfer to a GC are integrated into one step and one device, considerably simphf5dng the sample preparation procedure. (If HPLC is to be used, SPME more closely resembles conventional SPE in a special miniaturized format.) 

SPME uses a fused sihca fiber that is coated on the outside (occasionally internally if a capillary is used) with an appropriate stationary phase, typically an immobilized polymer, a solid adsorbent, or a combination of the two. A wide range of coatings is available, but probably the most widely used is polydimethylsiloxane (PDMS), weU known as a GC stationary phase that is thermally stable (can be used in a temperature range 20—320 ° C). The anal54es in the sample (liquid or gas) are directly extracted to the fibre coating, and are then thermally desorbed directly into the injection port of a GC or are extracted from the fiber using a suitable solvent for HPLC analysis this process provides high sensitivity because the complete extract can be analyzed. 

This expression for efficiency is the theoretical maximum, assuming that the extraction procedure is allowed to proceed to equilibrium (see above). If it is sought to increase Ep/ by increasing Vp, in general the equilibration rate will be slower. 

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An attractive approach to isolating analytes is a solid-phase microextraction (SPME). In one approach, which is illustrated in Figure 12.19, a fused silica fiber is placed inside a syringe needle. The fiber, which is coated with a thin organic film, such as polydimethyl siloxane, is lowered into the sample by depressing a plunger and is exposed to the sample for a predetermined time. The fiber is then withdrawn into the needle and transferred to the gas chromatograph for analysis. 

Solid-phase microextraction (SPME) was used for headspace sampling. The FFA were extracted from the headspace with PA, Car/PDMS, and CW/DVB fibers. It was examined whether addition of salt (NaCl) and decreasing the pH by addition of sulphuric acid (H SO ) increased the sensitivity. FFA were analyzed using gas chromatography coupled to mass spectrometry in selected ion monitoring. 

Although solid-phase microextraction (SPME) has only been introduced comparatively recently (134), it has already generated much interest and popularity. SPME is based on the equilibrium between an aqueous sample and a stationary phase coated on a fibre that is mounted in a syringe-like protective holder. Eor extraction, the fibre... 

A recent method, still in development, for determining total 4-nitrophenol in the urine of persons exposed to methyl parathion is based on solid phase microextraction (SPME) and GC/MS previously, the method... 

A recent method, still in development, for determining total 4-nitrophenol in the urine of persons exposed to methyl parathion is based on solid phase microextraction (SPME) and GC/MS previously, the method has been used in the analysis of food and environmental samples (Guidotti et al. 1999). The method uses a solid phase microextraction fiber, is inserted into the urine sample that has been hydrolyzed with HCl at 50° C prior to mixing with distilled water and NaCl and then stirred (1,000 rpm). The fiber is left in the liquid for 30 minutes until a partitioning equilibrium is achieved, and then placed into the GC injector port to desorb. The method shows promise for use in determining exposures at low doses, as it is very sensitive. There is a need for additional development of this method, as the measurement of acetylcholinesterase, the enzyme inhibited by exposure to organophosphates such as methyl parathion, is not an effective indicator of low-dose exposures. 

Pretreatment of hair samples also includes an extraction, usually with an alkaline sodium hydroxide solution, followed by cleaning up with LLE with n-hexane/ethyl acetate. Instead of LLE, the employment of SPE is also possible. Furthermore, the solid phase microextraction (SPME) in combination with head-space analysis is usable [104-106]. In the case of using hair samples, possible external contamination (e.g., by passive smoking of Cannabis) has to be considered as false positive result. False positive results can be avoided by washing of the hair samples previous to extraction [107]. Storage of collected samples is another important fact that can cause false results in their content of A9-THC and metabolites [108-110]. 

Several extraction methods for water samples are applicable, such as solvent extraction, SPE using a cartridge and disk and solid-phase microextraction (SPME). 

The most widely employed techniques for the extraction of water samples for triazine compounds include liquid-liquid extraction (LLE), solid-phase extraction (SPE), and liquid-solid extraction (LSE). Although most reports involving SPE are off-line procedures, there is increasing interest and subsequently increasing numbers of reports regarding on-line SPE, the goal of which is to improve overall productivity and safety. To a lesser extent, solid-phase microextraction (SPME), supercritical fluid extraction (SEE), semi-permeable membrane device (SPMD), and molecularly imprinted polymer (MIP) techniques have been reported. 

Solid-phase microextraction (SPME) consists of dipping a fiber into an aqueous sample to adsorb the analytes followed by thermal desorption into the carrier stream for GC, or, if the analytes are thermally labile, they can be desorbed into the mobile phase for LC. Examples of commercially available fibers include 100-qm PDMS, 65-qm Carbowax-divinylbenzene (CW-DVB), 75-qm Carboxen-polydimethylsiloxane (CX-PDMS), and 85-qm polyacrylate, the last being more suitable for the determination of triazines. The LCDs can be as low as 0.1 qgL Since the quantity of analyte adsorbed on the fiber is based on equilibrium rather than extraction, procedural recovery cannot be assessed on the basis of percentage extraction. The robustness and sensitivity of the technique were demonstrated in an inter-laboratory validation study for several parent triazines and DEA and DIA. A 65-qm CW-DVB fiber was employed for analyte adsorption followed by desorption into the injection port (split/splitless) of a gas chromatograph. The sample was adjusted to neutral pH, and sodium chloride was added to obtain a concentration of 0.3 g During continuous... 

The need to understand the fate of pesticides in the environment has necessitated the development of analytical methods for the determination of residues in environmental media. Adoption of methods utilizing instrumentation such as gas chro-matography/mass spectrometry (GC/MS), liquid chromatography/mass spectrometry (LC/MS), liquid chromatography/tandem mass spectrometry (LC/MS/MS), or enzyme-linked immunosorbent assay (ELISA) has allowed the detection of minute amounts of pesticides and their degradation products in environmental samples. Sample preparation techniques such as solid-phase extraction (SPE), accelerated solvent extraction (ASE), or solid-phase microextraction (SPME) have also been important in the development of more reliable and sensitive analytical methods. 

During the last few years, miniaturization has become a dominant trend in the analysis of low-level contaminants in food and environmental samples. This has resulted in a significant reduction in the volume of hazardous and expensive solvents. Typical examples of miniaturization in sample preparation techniques are micro liquid/liquid extractions (in-vial) and solvent-free techniques such as solid-phase microextraction (SPME). Combined with state-of-the-art analytical instrumentation, this trend has resulted in faster analyses, higher sample throughputs and lower solvent consumption, whilst maintaining or even increasing assay sensitivity. 

Principles and Characteristics Solid-phase microextraction (SPME) is a patented microscale adsorp-tion/desorption technique developed by Pawliszyn et al. [525-531], which represents a recent development in sample preparation and sample concentration. In SPME analytes partition from a sample into a polymeric stationary phase that is thin-coated on a fused-silica rod (typically 1 cm x 100 p,m). Several configurations of SPME have been proposed including fibre, tubing, stirrer/fan, etc. SPME was introduced as a solvent-free sample preparation technique for GC. 

Diffusive sampler Membrane extraction (MESI) Liquid-liquid extraction (LLE) Solid-phase extraction (SPE) SPE-PTV-GC Solid-phase microextraction (SPME) Headspace GC (SHS, DHS) Large-volume injection (LVI) Coupled HPLC-GC Membrane extraction (MESI) Difficult matrix introduction (DMI) Conventional solvent extraction methods 1 Pressurised solvent extraction methods Headspace GC (SHS, DHS) Thermal desorption (TD, DTD) Pyrolysis (Py) Photolysis Photon extraction (LD) Difficult matrix introduction (DMI)... 

Solid-phase microextraction (SPME) is compatible with high-speed separations. SPME-IR has been applied to VOCs in soil [156]. G6recki and Pawliszyn [69] reported separation of 28 volatile organic compounds listed in EPA method 624, with ITMS detection, in less than 150 s. 

Miniaturisation of scientific instruments, following on from size reduction of electronic devices, has recently been hyped up in analytical chemistry (Tables 10.19 and 10.20). Typical examples of miniaturisation in sample preparation techniques are micro liquid-liquid extraction (in-vial extraction), ambient static headspace and disc cartridge SPE, solid-phase microextraction (SPME) and stir bar sorptive extraction (SBSE). A main driving force for miniaturisation is the possibility to use MS detection. Also, standard laboratory instrumentation such as GC, HPLC [88] and MS is being miniaturised. Miniaturisation of the LC system is compulsory, because the pressure to decrease solvent usage continues. Quite obviously, compact detectors, such as ECD, LIF, UV (and preferably also MS), are welcome. 

Treves, K., Shragina, L., Rudich, Y. (2001) Measurement of octanol-air partition coefficients using solid-phase microextraction (SPME) - application to hydroxy alkyl nitrates. Atmos. Environ. 35, 5843-5854. 

Figure 4.10 from Solid Phase Microextraction (SPME), (Feb/Mar 1999) by permission of Rose Ward Publishing, Guildford, U.K. 

Solid Phase Microextraction (SPME) as Sample Preparation Technique.53... 

Among the techniques listed in Section 1.2.1, the two most documented approaches in addition to SPE, LLE, and PPT are solid phase microextraction (SPME) and affinity capture of analytes based on molecularly imprinted polymers (MIPs). Recent developments in these areas are briefly discussed below. 

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