Pesticide multiresidue analysis

The QuEChERS method was invented and described for the first time in 2003 by Anastassiades et al. [98] as a fast, simple, inexpensive, and convenient preparation procedure for fruit and vegetable samples used for pesticide multiresidue analysis. Currently, this methodology is used for determinations of pesticides, pesticide residues, and other compounds of environmental concern such as phenol derivatives, perfluorinated compounds, and chlorinated hydrocarbons pharmaceutical compounds in food and agricultural matrices and environmental samples such as soil, sediments, and water (see for example [99-102]). 

Recent Developments in QuEChERS Methodology for Pesticide Multiresidue Analysis... 

QuEChERS, which stands for Quick, Easy, Cheap, Effective, Rugged, and Safe, is one of those new-generation sample preparation methods for pesticide multiresidue analysis [1]. Although very recently introduced (development between 2000-2002, publication in 2003), the method has been widely embraced by the international pesticide residue analysts community and is already being used in numerous laboratories worldwide [2-6]. Aiming to deliver an economical and... 

QuEChERS, Dispersive SPE, D-SPE, Pesticides, Multiresidue Analysis, LC-MS/MS, PSA, GCB, Ereeze-Out... 

Rissato, S. R., Galhiane, M. S., KnoU, F. R. N., and Apon, B. M. 2004. Supercritical fluid extraction for pesticide multiresidue analysis in honey Determination by gas chromatography with electron-capture and mass spectrometry detection. J. Chromatogr. A 1048 153-159. 

Anastassiades, M., Scherbaum, E., Tasdelen, B., and Stajnbaher, D., (2007) Recent developments in QuEChERS methodology for pesticide multiresidue analysis, ini Pesticide Chemistry, Crop Protection, Public Health, Environmental Safety (eds Hideo Ohkawa, Hisashi Miyagawa, and Philip W. Lee) Wiley-VCH Verlag GmbH Co. KGaA. 

Multiresidue analysis of 72 pesticides including three diphenyl ethers was carried out by GC/NPD under the following conditions column, 5% DB-5 (30 m x 0.53-mm i.d., 0.53- xm film thickness) temperature, column 100°C(1 min) increased at 5 °Cmin to 280°C (lOmin), inlet and detector 280°C gas flow rates. He 11.2mLmin H2 3.5mLmin air llOuiLmin" injection volume, 2 rL. The retention times... 

Okumura et al reported State regulatory programs for pesticide residues in food crops analyzed by the CDFA. In the multiresidue analysis of several organochlorine pesticides including diphenyl ether herbicides, bifenox, nitrofen and oxyfluorfen, HPLC has also been used. 

For detection, MS is rapidly becoming the method of choice for multiclass, multiresidue analysis owing to its many advantages, recent improvements in technology, and availability of cost-effective commercial instrumentation. Detection systems in general are continually being improved, and in combination with the improvements in chromatographic instruments and techniques, an exceptionally low limit of detection (LOD) is possible for pesticide residues. 

Nakamura Y, Tonogai Y, Sekiguchi Y, et al. 1994. Multiresidue analysis of 48 pesticides in agricultural products by capillary gas chromatography. J Agric Food Chem 42(11) 2508-2518. 

Kadenczki L, Arpad Z, Gardi I, et al. 1992. Column extraction of residues of several pesticides from fruits and vegetables A simple multiresidue analysis method. J AOAC International 75(1) 53-61. 

Pichon, V., L. Chen, N. Durand, F. Le Groffic, and M.C. Hennion (1996). Selective trace enrichment on immunosorbents for the multiresidue analysis of phenylurea and triazine pesticides. J. Chromatogr. A, 725 107-119. 

Pichon, V., M. Charpak, and M.C. Hennion (1998). Multiresidue analysis of pesticides using new laminar extraction disks and hquid chromatography and application to the French priority list. /. Chromatogr. A, 795 83-92. 

Barnes and coworkers pioneered in this area. They reported the analysis of diflubenzuron in mushrooms [39], and of diflubenzuron and clofentezine in various fmit drinks [73], and the development of a multiresidue study for ten pesticides in fmit, involving ionization polarity switching in LC-APCI-MS [123]. In these studies, significant attention is paid to matrix-dependent ion suppression or enhancement effects (Ch. 6.7), which is observed even in APCI. Matrix effects in food analysis must be studied in detail for each fmit or vegetable. Obviously, optimization of the sample pretreatment procedures plays an important role in method development for pesticide residue analysis in food. 

Thurman and Ferrer [109, 135-137] recently promoted the use of oa-TOF-MS in the multiresidue analysis and identification of pesticides and their metabolites and degradation products in fraits and vegetables. 

D. Ortelli, P. Edder, C. Corvi, Multiresidue analysis of 74 pesticides in fruits and vegetables by LC-ESI-MS-MS, Anal. Chim. Acta, 520 (2004) 33. 

One of the most important analytical techniques used today is high-resolution gas chromatography (HRGC). The pesticide residues can be analyzed by specihe or multiresidue methods. When crops are treated with several pesticides, the use of a multiresidue method is preferable due the reduced cost and time of analysis. The methods of pesticides residue analysis usually present an initial step of extraction with a solvent which is not miscible with water, followed by a cleanup step and the analyte determination by gas chromatography. 

Increasing demand for screening our environment for pesticide residues has generated a need for more efficient residue methods. Multiresidue methods, or those which measure several compounds at once, are generally more efficient than single residue methods in satisfying these needs. A mass spectrometer can be used as a universal selective detector for multiresidue analysis in different sample matrices, since it is generally blind to interferences present in the sample. In addition to selectivity, use of a mass spectrometer offers structure confirmation, and in many cases, can eliminate sample cleanup steps. 

Previously, pesticide extraction procedures from grapes and wine in the multiresidue analysis were carried out with polar solvents such as methanol and acetone (Holland and Malcolm, 1992). To increase the recovery of more polar analytes, the extracts were salted out with NaCl, Na2S04 or MgS04, and then partitioned with non-polar solvents such as CH2C12, petroleum ether, etc (Holland and Malcolm, 1992). 

Figure 6.2 GC and electron-capture-detector (GC-ECD) analysis of a chloroor-ganic and pyrethroids pesticides standard solution. (From Holland, P.T. and Malcolm, C.P. (1992) Multiresidue analysis in fruits and vegetables , in T. Cairns and J. Sherma (Eds) Emerging Strategies for Pesticide Analysis, Modern Methods for Pesticide Analysis Series, CRC Press, Boca Raton)...

Table 6.8 LC-MS conditions for multiresidue analysis of pesticides in grape.

Table 6.11 GC-MS conditions used in the multiresidue analysis of pesticides in wines.

Pichon, V. and Hennion, M. C. 1996. Selective trace enrichment using immunosorbents for multiresidue analysis of pesticides, J. Chromatog., US. 107-119. 

Wong, J.W. and Halverson, C.A. (1999). Multiresidue analysis of pesticides in wines using C-18 solid-phase extraction and gas chromatography-mass spectrometry, Am. J. Enol. Vide., 50(4), 435-442. 

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