Mass spectrometry pesticides

Microwave-Assisted Solvent Extraction Pressurized Fluid Extraction Supercritical Fluid Extraction Solid-Phase Extraction Solid-Phase Microextraction. Gas Chromatography Overview, Mass Spectrometry Environmental Applications. Immunoassays Overview. Liquid Chromatography Overview Reversed Phase Size-Exclusion Liquid Chromatography-Mass Spectrometry. Pesticides. Supercritical Fluid Chromatography Overview Applications. Thin-Layer Chromatography Overview. Water Analysis Organic Compounds. 

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). 

R. M. Marce, H. Prosen, C. Crespo, M. Calull, R Boirull and U. A. Th Brinkman, Online ti ace enrichment of polar pesticides in environmental waters by reversed-phase liquid cliromatography-diode array detection-particle beam mass spectrometry , J. Chromatogr. 696 63-74 (1995). 

C. Aguilar, R Bomtll and R. M. Marce, Determination of pesticides by on-line trace enrichment-reversed-phase liquid cliromatogr aphy-diode-array detection and confirmation by particle-beam mass spectrometry , Chromatographia 43 592-598 (1996). 

S. Lacorte and D. Barcelo, Determination of parts per trillion levels of organophospho-rus pesticides in groundwater by automated on-line liquid- solid extraction followed by liquid chr omatography/atmospheric pressure chemical ionization mass spectrometry using positive and negative ion modes of operation . Anal. Chem. 68 2464- 2470 (1996). 

If you frequently analyze pesticides, obtain the latest edition of Mass Spectrometry of Pesticides and Pollutants (Safe and Hutzinger. Boca Raton, FL, CRC Press). This book, combined with the list of most abundant ions (Table 25.1) and/or a computer library search, will be sufficient to identify most commercial pesticides. Also, see Chapters 17, 26, and 27. 

Figure 5.1 Pesticides included in the systematic investigations on APCI-MS signal response dependence on eluent flow rate the parameter IsTow represents the distribution coefficient of the pesticide between n-octanol and water. Reprinted from J. Chromatogr, A, 937, Asperger, A., Efer, 1., Koal, T. and Engewald, W., On the signal response of various pesticides in electrospray and atmospheric pressure chemical ionization depending on the flow rate of eluent applied in liquid chromatography-mass spectrometry , 65-72, Copyright (2001), with permission from Elsevier Science.

Figure 5.56 Structures of the three analytes pesticides used in an investigation of the matrix effects observed in LC-MS-MS. Reprinted from J. Chromatogr., A, 907, Choi, B. K., Hercnles, D. M. and Gnsev, A. I., Effect of liquid chromatography separation of complex matrices on liqnid chromatography-tandem mass spectrometry signal suppression , 337-342, Copyright (2001), with permission from Elsevier Science.

Barcelo D. 1988. Application of thermospray liquid chromatography/mass spectrometry for determination of organophosphoms pesticides and trialkyl and triaryl phosphates. Biomed Environ Mass Spectrom 17 363-369. 

Betowski LD, Jones TL. 1988. Analysis of organophosphoms pesticide samples by high-performance liquid chromatography/mass spectrometry and high-performance liquid chromatography/mass spectrometry/mass spectrometry. Environ Sci Technol 22 1430-1434. 

Roach JA, Andrzejewski D. 1987. Analysis for pesticide residues by collision-induced fragmentation. In Rosen JD, ed. Applications of new mass spectrometry techniques in pesticide chemistry. New York, NY Wiley Co., 187-210. 

Sheridan RS, Meola JR. 1999. Analysis of pesticide residues in fruits, vegetables, and milk by gas chromatography/tandem mass spectrometry. J AOAC Int 82(4) 982-990. 

Vol. 91. Applications of New Mass Spectrometry Techniques in Pesticide Chemistry. Edited by Joseph Rosen... 

Planas C, Caixach J, Santos FJ, et al. 1997. Occurrence of pesticides in Spanish surface waters. Analysis by high resolution gas chromatography coupled to mass spectrometry. Chemosphere 34(ll) 2393-2406. 

The requirements regarding commodities which are difficult to analyze are also not very clear. The listed crops do not cause difficulties in each kind of determination [e.g., brassica or bulb vegetables in gas chromatography/mass spectrometry (GC/MS)]. On the other hand, different species of the same crop may have different interference peaks, which may or may not affect quantitation. Presumably, the easiest approach is to perform additional validations, even if the final extracts are not difficult to analyze. In the author s experience, validations should generally include hops and tobacco, if the pesticide is used in these crops. 

A multi-residue method based on SPE cleanup and gas chromatography/ion trap mass spectrometry (GC/ITMS) was developed for the determination of 120 pesticides and related metabolites in two soils with organic matter contents of 4.0-5.2%. 

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 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 new fiber coatings in the near future should further improve the specificity of SPME and overcome some of the observed matrix effects. Quantification by stable isotope dilution gas chromatography/mass spectrometry (GC/MS) may assist in improving analytical performance. Along with the possible application of micro LC and capillary LC columns to in-tube SPME, the development of novel derivatization methods and the potential for the analysis of fumigant pesticides, SPME appears to be a technique with a future in the analysis of pesticide residues in food. 

Mass spectrometry (MS) has proven to be far superior to other forms of detection for the determination and confirmation of pesticide residues in food, because its... 

The development of a robust analytical method is a complex issue. The residue analyst has available a vast array of techniques to assist in this task, but there are a number of basic rules that should be followed to produce a reliable method. The intention of this article is to provide the analyst with ideas from which a method can be constructed by considering each major component of the analytical method (sample preparation, extraction, sample cleanup, and the determinative step), and to suggest modern techniques that can be used to develop an effective and efficient overall approach. The latter portion emphasizes mass spectrometry (MS) since the current trend for pesticide residue methods is leading to MS becoming the method of choice for simultaneous quantitation and confirmation. This article also serves to update previous publications on similar topics by the authors. ... 

The most widely regarded approach to accomplish the determination of as many pesticides as possible in as few steps as possible is to use MS detection. MS is considered a universally selective detection method because MS detects all compounds independently of elemental composition and further separates the signal into mass spectral scans to provide a high degree of selectivity. Unlike GC with selective detectors, or even atomic emission detection (AED), GC/MS may provide acceptable confirmation of the identity of analytes without the need for further information. This reduces the need to re-inject a sample into a separate GC system (usually GC/MS) for pesticide confirmation. Through the use of selected ion monitoring (SIM), efficient ion-trap or quadrupole devices, and/or tandem mass spectrometry (MS/MS), modern GC/MS instruments provide LODs similar to or lower than those of selective detectors, depending on the analytes, methods, and detectors. 

MS detection does not necessarily require as highly resolved GC separations as in the case of selective detectors because the likelihood of an overlapping mass spectral peak among pesticides with the same retention time is less than the likelihood of an overlapping peak from the same element. Unfortunately, this advantage cannot always be optimized because SIM and current gas chromatography/tandem mass spectrometry (GC/MS/MS) methods, it is difficult to devise sequential SIM or MS/MS retention time windows to achieve fast GC separations for approximately > 50 analytes in a single method. 

E.M. Thurman, 1. Ferrer, and D. Barcelo, The ionization-continuum diagram a concept for selection of APCl and ESI conditions for HPLC/MS of pesticides , in 17th Montreux Symposium on Liquid Chromatography/Mass Spectrometry, Montreux, Switzerland, November 8-10, 2000 , p. 31 (2000). 

Pastorelli, R., Allevi, R., Romagnano, S., Meli, G., Fanelli, R., and Airoldi, R. (1995) Gas chromatography-mass spectrometry determination of ethylenthiourea hemoglobin adducts a possible indicator of exposure to ethylene-fczs-dithiocarbam-ate pesticides, Archives of Toxicology, 69(5) 306-311. 

Rodriguez, R., Manes, J., Pico, Y. (2003). Off-line solid-phase microextraction and capillary electrophoresis mass spectrometry to determine acidic pesticides in fruits. Anal. Chem. 75, 452 159. 

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