Solid phase extraction pesticides

Two examples from the analysis of water samples illustrate how a separation and preconcentration can be accomplished simultaneously. In the gas chromatographic analysis for organophosphorous pesticides in environmental waters, the analytes in a 1000-mL sample may be separated from their aqueous matrix by a solid-phase extraction using 15 mb of ethyl acetate. After the extraction, the analytes are present in the ethyl acetate at a concentration that is 67 times greater than that in... 

This publication provides several examples of the use of solid-phase extractions for separating analytes from their matrices. Some of the examples included are caffeine from coffee, polyaromatic hydrocarbons from water, parabens from cosmetics, chlorinated pesticides from water, and steroids from hydrocortisone creams. Extracted analytes maybe determined quantitatively by gas (GC) or liquid chromatography (LG). 

A method which uses supercritical fluid/solid phase extraction/supercritical fluid chromatography (SE/SPE/SEC) has been developed for the analysis of trace constituents in complex matrices (67). By using this technique, extraction and clean-up are accomplished in one step using unmodified SC CO2. This step is monitored by a photodiode-array detector which allows fractionation. Eigure 10.14 shows a schematic representation of the SE/SPE/SEC set-up. This system allowed selective retention of the sample matrices while eluting and depositing the analytes of interest in the cryogenic trap. Application to the analysis of pesticides from lipid sample matrices have been reported. In this case, the lipids were completely separated from the pesticides. 

Figure 13.15 Chromatograms obtained by on-line ti ace enrichment of 50 ml of Ebro river water with and without the addition of different volumes of 10% Na2S03 solution for every 100 ml of sample (a) blank with the addition of 1000 p.1 of sulfite (b) spiked with 4 p.g 1 of the analytes and 1000 p.1 of sulfite (c) spiked with 4 p.g 1 of the analytes and 500 p.1 of sulfite (d) spiked with 4 p.g 1 of the analytes without sulfite. Peak identification is as follows 1, oxamyl 2, methomyl 3, phenol 4, 4-niti ophenol 5, 2,4-dinitrophenol 6, 2-chlorophenol 7, bentazone 8, simazine 9, MCPA 10, atrazine. Reprinted from Journal of Chromatography, A 803, N. Masque et ai, New chemically modified polymeric resin for solid-phase extraction of pesticides and phenolic compounds from water , pp. 147-155, copyright 1998, with permission from Elsevier Science.

C. Aguilar, P. BottuII and R. M. Marce, On-line and off-line solid-phase extraction with styrene-divinylbenzene-membrane extr action disks for determining pesticides in... 

C. Aguilar, I. Feirer, R Bonnll, R. M. Marce and D. Barcelo, Monitoring of pesticides in river water based on samples previously stored in polymeric cartridges followed by on-line solid-phase extraction-liquid cliromatography-diode array detection and confirmation by atmospheric pressure chemical ionization mass spectrometry . Anal. Chim. Acta 386 237-248 (1999). 

J. Slobodnik, O. Ostezkizan, H. Lingeman and U. A. Th Brinkman, Solid-phase extraction of polar pesticides from environmental water samples on grapliitised carbon and Empore-activated carbon disks and on-line coupling to octadecyl-bonded silica analytical columns , J. Chromatogr. 750 227-238 (1996). 

S. Lacorte, J. J. Vreuls, J. S. Salau, R Ventura and D. Barcelo, Monitoring of pesticides in river water using fully automated on-line solid-phase extraction and liquid cliro-matography with diode array detection with a novel filrtation device , J. Chromatogr. 795 71-82(1998). 

Table 3 Summary of solid-phase extraction techniques applied to the preparation of water samples for the determination of triazine pesticides...

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. 

The development of solid-phase extraction (SPE) absorbents such as silica gel, alumina and Florisil tremendously aided in the purification or cleanup of pesticide residues from water. 

Palma P, Kuster M, Alvarenga P, Palma VL, Fernandes RM, Soares AMVM, Lopez de Alda MJ, Barcelo D, Barbosa IR (2009) Risk assessment of representative and priority pesticides, in surface water of the Alqueva reservoir (South of Portugal) using on-line solid phase extraction-liquid chromatography-tandem mass spectrometry. Environ Int 35 545-551... 

Kuster M, de Alda MJL, Barata C, Raldua D, Barcelo D (2008) Analysis of 17 polar to semi-polar pesticides in the Ebro river delta during the main growing season of rice by automated on-line solid-phase extraction-liquid chromatography-tandem mass spectrometry. Talanta 75(2) 390-401... 

Aguilar C, Borrull F, Marce RM (1997) Determination of pesticides in environmental waters by solid-phase extraction and gas chromatography with electron-capture and mass spectrometry detection. J Chromatogr A 771(1-2) 221-231... 

Analysis of pesticides in water was performed by fully automated online solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/ MS) [25, 31]. These pesticides (a total of 22 belonging to the classes of triazines, OP, chloroacetanilides, phenylureas, thiocarbamates, acid herbicides, and anilides) were selected on the basis of previously published studies [20, 25], information gathered from the water authorities, and known use in rice crops. 

Kampioti AA, da Cunha ACB, de Alda ML et al (2005) Fully automated multianalyte determination of different classes of pesticides, at picogram per litre levels in water, by online solid-phase extraction-liquid chromatography-electrospray-tandem mass spectrometry. Anal Bioanal Chem 382 1815-1825... 

Asperger A. et al., 2002. Trace determination of priority pesticide in water by means of high-speed online solid-phase extraction-liquid chromatography-tandem mass spectrometry using turbulent-flow chromatography columns for enrichment and a short monolithic column for fast liquid chromatographic separation. J Chromatogr A 960 109. 

Hogenboom A.C., Niessen W.M.A., and Brinkman U.A., 1999a. Online solid-phase extraction-short-column liquid chromatography combined with various tandem mass spectrometric scanning strategies for the rapid study of transformation of pesticides in surface water. J Chromatogr A 841 33. 

Lacorte S. and Barceld D., 1995. Determination of organophosphorus pesticides and their transformation products in river waters by automated online solid-phase extraction followed by thermospray liquid chromatography. J Chromatogr A 712 103. 

L6pez-Roldan P., de Alda M.J.L., and Barcelo D., 2004. Simultaneous determination of selected endocrine disrupters (pesticides, phenols and phthalates) in water by in-field solid-phase extraction (SPE) using the prototype PROFEXS followed by online SPE (PROSPEKT) and analysis by liquid chromatography-atomspheric pressure chemical ionization-mass spectrometry. Anal Bioanal Chem 378 599. 

Due to the predicted and previously detected low concentrations of pesticides in environmental samples (usually around the nanogram per liter level), a preconcentration step of the water samples is necessary prior to measurement. In this way, a preconcentration factor of several orders of magnitude (200-1,000-fold) is mandatory to reach the low detection limits necessary for the identification of pesticides, especially in complex wastewater samples. Also, the use of surrogate standards (e.g., triphenyl phosphate) added before the extraction step is a common practice in order to account for possible errors during the extraction process and for quantitative purposes. The commonly used extraction methods for polar compounds from water matrices involve isolation using liquid-liquid extraction (LLE) and solid-phase extraction (SPE), which are commented on below. Other methods such as semipermeable membrane devices (SPMD) are also mentioned. 

Manes J, Font G, Pico Y. 1993. Evaluation of a solid-phase extraction system for determining pesticide residues in milk. J Chromatog 642 195-204. 

Solid phase extraction Herbicides, pesticides Atrazine [39-41]... 

J.M. Pozzebon, S.C.N. Queiroz, L.F.C. Melo, M.A.Kapor and I.C.S.F. Jardim, Application of new high-performance liquid chromatography and solid-phase extraction materials to the analysis of pesticides in human urine. J. Chromatogr.A 987 (2003) 381-387. 

Postigo C, de Alda MIL, Barcelo D et al (2010) Analysis and occurrence of selected medium to highly polar pesticides in groundwater of Catalonia (NE Spain) an approach based on on-line solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry detection. J Hydrol 383 83-92... 

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