SPE methods

Because perspiration and bathing are commonly associated with sun exposure, the need to determine the SPE after bathing or long after appHcation to the body site is important. In use, the quantity of screen appHed and its uniform distribution over the exposed area control the achieved SPE. Methods for assessing the water-resistant or waterproof qualities of sunscreen products have been estabflshed by the EDA. 

Supercritical fluid extraction (SFE) is a technique in which a supercritical fluid [formed when the critical temperature Tf) and critical pressure Pf) for the fluid are exceeded simultaneously] is used as an extraction solvent instead of an organic solvent. By far the most common choice of a supercritical fluid is carbon dioxide (CO2) because CO2 has a low critical temperature (re = 31.1 °C), is inexpensive, and is safe." SFE has the advantage of lower viscosity and improved diffusion coefficients relative to traditional organic solvents. Also, if supercritical CO2 is used as the extraction solvent, the solvent (CO2) can easily be removed by bringing the extract to atmospheric pressure. Supercritical CO2 itself is a very nonpolar solvent that may not have broad applicability as an extraction solvent. To overcome this problem, modifiers such as methanol can be used to increase the polarity of the SFE extraction solvent. Another problem associated with SFE using CO2 is the co-extraction of lipids and other nonpolar interferents. To overcome this problem, a combination of SFE with SPE can be used. Stolker et al." provided a review of several SFE/SPE methods described in the literature. 

An SPE method has been developed to replace the classical LLP method. Water sample is extracted with an SPE column such as Cig and styrene-divinylbenzene copolymer (PS-2) cartridges, which consist of a reversed bonded-phase silica sorbent, provided as an extraction tool. This is a simple and rapid method, and applied to the determination of residual amounts of naproanilide, propanil, mefenacet, etc. This system determines the residual amounts of most of the pesticides and has been successfully applied to determination of pesticides in water. 

Thus, organic solvent extraction methods for the extraction of pesticides from water samples can be replaced by the SPE method using Ci8 and PS-2. Ethobenzanid, clomeprop, naproanilide and their acidic metabolites are determined by a multi-residue analytical method using Cig or PS-2 cartridge extraction after acidification of the water samples with hydrochloric acid or other acidic media, followed by HPLC or LC/MS detection. 

Crescenzi et al. developed a multi-residue method for pesticides including propanil in drinking water, river water and groundwater based on SPE and LC/MS detection. The recoveries of the pesticides by this method were >80%. Santos etal. developed an on-line SPE method followed by LC/PAD and LC/MS detection in a simultaneous method for anilides and two degradation products (4-chloro-2-methylphenol and 2,4-dichlorophenol) of acidic herbicides in estuarine water samples. To determine the major degradation product of propanil, 3,4-dichloroaniline, the positive ion mode is needed for atmospheric pressure chemical ionization mass spectrometry (APCI/MS) detection. The LOD of 3,4-dichloroaniline by APCI/MS was 0.1-0.02 ng mL for 50-mL water samples. 

The use of SPE with porous materials such as alumina, diatomaceous earth, Horisil and silica for the cleanup of fat-soluble organochlorine pesticides in fatty foods such as meat, flsh, shellfish, milk and vegetable oils has been well documented. The choice of elution solvents is critical because relatively small amounts of lipid in the final extract can cause rapid deterioration of GC capillary columns and also contaminate the gas chromatograph. A number of workers have used a porous material in tandem with Cig to effect an improved cleanup.Di Mucchio employed a multicartridge system comprising Extrelut, silica and Cig to extract organophosphorus pesticides from oils and fatty extracts. Relatively few literature applications include the pyrethroids, but Ramesh and Balasubramanian reported a simple carbon-based SPE method for the analysis of pyrethroids in vegetable oil. 

Differentiation of SPE methods can be made according to the following criteria (i) the type of sorbent (ii) the mode of performing SPE (static or dynamic) (iii) (in case of dynamic SPE) off-line (cartridges) or on-line ... 

SPE offers many advantages over LLE, as shown in Table 3.44. The main disadvantage is the need for method development. There will never be a universal SPE method because the sample pretreatment depends strongly on the analytical demand. 

FIGURE 1.18 Phenomenex four-sorbent SPE method development plate. 

More information on the comparative evaluation of protein precipitation methods may be obtained from Lei and coworkers.163 An interesting comparison of protein precipitation (PPT) and solid phase extraction (SPE) methods was presented in a technical library publication from Millipore164 that describes use of its Multi-SPE-MPC extraction plate and Multiscreen deep well Solvinert filter plate for SPE and PPT, respectively (Figure 1.45). A Biohit Proline multichannel pipette was used to add 400 /iL of acetonitrile to each well of the filter plate and then, using the pipette s double aspiration program, 100 /iL of spiked serum was aspirated and 100 /iL of acetonitrile from the filter plate was aspirated to initiate protein precipitation in the pipette tip. The mixture was deposited back in the filter plate and shaken vigorously for 2 min. 

Pre-concentration of bupivacaine from human plasma was performed with an MIP, followed by elution, and analysis via gas chromatography also demonstrated the high specificity of the SPE based on a MIP compared to a CP see Fig. 11. Compared to the MI-SPE method, SPE on a C18-column led to an extraction of not only the desired bupivacaine but also of many other ingredients of the plasma sample, thus complicating the subsequent analysis [43]. 

Gustavson et al. (2000) developed a convenient and novel solid phase extraction (SPE) method for the removal of methyl oleate from SPMD dialysates containing PAHs. A small SPE column (1 g or 0.5 g) containing a dual-zone silica (normal phase)-based restricted-access sorbent (Diazem, Midland, MI, USA) is used for the separation. The capacity of this sorbent to remove methyl oleate is about 1.8% (lipid/sorbent wt wt ). The PAHs are eluted with 19 mL of hexane and methylene chloride (97 3 VV ) and recoveries of all PAHs are typically >72%. 

Ogumi, Z., Takehara, Z. and Yoshizawa, S. 1984. Gas permeation in SPE method. 1. Oxygen permeation through Nation and Neosepta. JoHrMflZ of the Electrochemical Society 131 769-773. 

Analytical Methods Development. A solid-phase extraction (SPE) method that will isolate and fractionate metolachlor and its oxanilic acid (OXA) and ethanesulfonic acid (ESA) metabolites from soil and water will be developed. The SPE method will be used... 

IP LLE methods are generally employed for the extraction of LASs from river waters and the solvent sublation method of Wickbold is still used for their extraction from seawater [85]. SPE methods making use of C18 and C8 phases are largely employed [85]. The amount of sorbent is optimized as a function of the degree of pollution and the average composition of river waters [85]. The performances of C18 disks and C18 cartridges are compared [85]. 

SPE methods with different cartridge packings have been employed for the pre-concentration and clean up of sulfonated azo dyes from waters and soil extracts [110,111], The extraction of solid samples has been carried ont by sonication or Soxhlet extraction and the extracts treated like the water samples. C18 cartridges and columns [111] were used followed by the elution with aqueous organic solvents in the presence of TEA with recovery yields always greater than 65% [93,111], Higher recoveries have been obtained by using C18 columns, pre-conditioned with an ammonium acetate buffer and elnted with methanol [111], The use of styrene-divinylbenzene [93,112], as well as of cross-linked polymeric sorbents with sulfonate functions, was shown to be suitable in the SPE of the more polar componnds [111],... 

Several methods apply LEE followed by a direct injection [453,463,464] or by a simple purification step, like SPE [465,466]. Bonvehi [466] compares saponification to SPE method using a Shandon Hypersep Silica Sep-Pak (500 mg), and the results show a 20% higher recovery using the latter method. 

In summary, SPE methods, including extraction using both online and offline cartridges or more automated equipment such as the ASPEK, PROSPECT, or the OSP-2, are, without doubt, the preferred technique for the isolation and concentration of OPPs and OCPs from water samples prior to HPLC determination. 

Kuiken J, Mitchell T, Mann T, Burke M. SPE method improves drug analysis. Drug Discov Dev 2000 Nov/Dec 75-78. 

For the determination of CCA in biological samples, methods not based on LC-MS/MS technology [39, 41-43] and methods that used LC-MS/MS [40, 52] have been reported. Most of the sample extraction methods used liquid-liquid extraction (LLE) technology, since this extraction method is simpler and able to minimize matrix effects. Consequently, LLE methods are considered to provide cleaner samples as compared to solid phase extraction (SPE) methods. Since LC-MS/MS methodology uses nonvolatile solvents or a combination of nonvolatile and volatile solvents, difficulties in the evaporation process and associated interferences when samples are injected onto the system can arise [51]. However, Bahrami as well as Souri [42,43] applied a combination of nonvolatile and volatile solvents in which the nonvolatile solvents were acidic buffers (pH 5 or less). Analytes eluted from SPE prepared samples did not undergo evaporation as applied commonly encountered in extraction procedures [37, 45]. 

---