Food Analytical Methods

, Volume 6, Issue 4, pp 1099–1112 | Cite as

Development of Specific LC-ESI-MS/MS Methods to Determine Bifenthrin, Lufenuron, and Iprodione Residue Levels in Green Beans, Peas, and Chili Peppers Under Egyptian Field Conditions

  • Anna A. Bletsou
  • Ahmad H. Hanafi
  • Marilena E. Dasenaki
  • Nikolaos S. Thomaidis


The dissipation of bifenthrin, lufenuron, and iprodione was studied in green beans, peas, and chilli peppers under Egyptian field conditions. For this purpose, three specific and one multi-analyte liquid chromatography-electrospray ionization-tandem mass spectrometry methods were developed and validated according to SANCO guidelines for the determination of bifenthrin, iprodione, and lufenuron residues in the selected commodities. Sample preparation was carried out by the QuEChERs approach, and determination was performed in positive ionization mode for iprodione and bifenthrin and in negative mode for lufenuron. Optimization of the ionization parameters and the chromatographic conditions was performed for each method developed. All methods showed satisfactory performance criteria. Linear dynamic range, limits of detection (LOD) and quantification (LOQ), precision, recovery, and matrix effects were estimated, and the calculated LODs were in the micrograms-per-kilogram range, namely 0.14, 0.61, and 1.4 μg/kg for bifenthrin, lufenuron, and iprodione, respectively. Field trials were carried out in one of the biggest farms in Egypt (Blue Nile) that exports significant quantities of vegetables to the European Union (EU) countries. All the examined pesticides showed high degradation rates. The t 1/2 values for bifenthrin were 3.3, 2.1, and 9.6 days in green beans, peas, and chili peppers, respectively. For iprodione, they reached 2.4 and 14.4 days in green beans and peppers. Furthermore, the calculated pre-harvest interval (PHI) values, according to the maximum residue limits set by EU, were 0, 4, and 0 days for bifenthrin in green beans, peas, and peppers, respectively, and for iprodione, 2 days in green beans and 0 days in peppers. In case of lufenuron, no t 1/2 and PHI were estimated as no residues were found in all pea samples.


Pesticides Vegetables LC-MS/MS Degradation rate Pre-harvest intervals (PHI) 



The authors are grateful to the general manager of Blue Nile Egypt for funding the field trials.

Supplementary material

12161_2012_9515_MOESM1_ESM.doc (166 kb)
ESM 1 (DOC 166 kb)


  1. Agüera A, López S, Fernández-Alba AR, Contreras M, Crespo J, Piedra L (2006) One-year routine application of a new method based on liquid chromatography–tandem mass spectrometry to the analysis of 16 multiclass pesticides in vegetable samples. J Chromatogr A 1045:125–135Google Scholar
  2. Anastassiades M, Lehotay S, Štajnbaher D, Schenk JF (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. J AOAC Int 86:412–431Google Scholar
  3. Balinova A, Mladenova R, Shtereva D (2007) Solid-phase extraction on sorbents of different retention mechanisms followed by determination by gas chromatography–mass spectrometric and gas chromatography–electron capture detection of pesticide residues in crops. J Chromatogr A 1150:136–144CrossRefGoogle Scholar
  4. Bester K, Bordin G, Rodriguez A, Schimmel H, Pauwels J, Van Vyncht G (2001) How to overcome matrix effects in the determination of pesticides in fruit by HPLC-ESI-MS-MS. Anal Bioanal Chem 371:550–555Google Scholar
  5. Botitsi HV, Garbis SD, Economou A, Tsipi DF (2011) Current mass spectrometry strategies for the analysis of pesticides and their metabolites in food and water matrices. Mass Spectrom Rev 30:907–939Google Scholar
  6. Chen T, Chen G (2007) Identification and quantitation of pyrethroid pesticide residues in vegetables by solid-phase extraction and liquid chromatography/electrospray ionization ion trap mass spectrometry. Rapid Commun Mass Spectrom 21:1848–1854CrossRefGoogle Scholar
  7. Chen L, Shang Guan L, Wu Y, Xu L, Fu F (2012) Study on the residue and degradation of fluorine-containing pesticides in Oolong tea by using gas chromatography-mass spectrometry. Food Control 25:433–440CrossRefGoogle Scholar
  8. De Koning S, Lach G, Linkerhagner M, Loscher R, Tablack PH, Brinkman UAT (2003) Trace-level determination of pesticides in food using difficult matrix introduction–gas chromatography–time-of-flight mass spectrometry. J Chromatogr A 1008:247–252CrossRefGoogle Scholar
  9. Esteve-Turrillas FA, Pastor A, De la Guardia M (2005) Determination of pyrethroid insecticide residues in vegetable oils by using combined solid-phases extraction and tandem mass spectrometry detection. Anal Chim Acta 553:50–57CrossRefGoogle Scholar
  10. European Union (2005) Commission Regulation (EC) No. 396/2005 of the European Parliament and of the Council of 23 February 2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EECText with EEA relevance. L70:1–16Google Scholar
  11. FAO Statistics (2009) (last access: 10/08/2012)
  12. Filho AM, dos Santos FN, de Paula PPA (2010) Development, validation and application of a methodology based on solid-phase micro extraction followed by gas chromatography coupled to mass spectrometry (SPME/GC–MS) for the determination of pesticide residues in mangoes. Talanta 81:346–354CrossRefGoogle Scholar
  13. Hanafi A, Garau VL, Caboni P, Sarais G, Cabras P (2010) Minor crops for export: a case study of boscalid, pyraclostrobin, lufenuron and lambda-cyhalothrin residue levels on green beans and spring onions in Egypt. J Environ Sci Health Part B 45:493–500CrossRefGoogle Scholar
  14. Hengel MJ, Miller M (2009) Analysis of pesticides in dried hops by liquid chromatography-tandem mass spectrometry. J Agric Food Chem 56:6851–6856CrossRefGoogle Scholar
  15. Hernandez F, Pozo OJ, Sancho JV, Bijlsma L, Barreda M, Pitarch E (2006) Multiresidue liquid chromatography tandem mass spectrometry determination of 52 non gas chromatography-amenable pesticides and metabolites in different food commodities. J Chromatogr A 1109:242–252CrossRefGoogle Scholar
  16. Jansson C, Pihlstroem T, Ostedahl BG, Markides KE (2004) A new multi-residue method for analysis of pesticide residues in fruit and vegetables using liquid chromatography with tandem mass spectrometric detection. J Chromatogr A 1023:93–104CrossRefGoogle Scholar
  17. Kolberg DI, Prestes OD, Adaime MB, Zanella R (2011) Development of a fast multiresidue method for the determination of pesticides in dry samples (wheat grains, flour and bran) using QuEChERS based method and GC–MS. Food Chem 125:1436–1442CrossRefGoogle Scholar
  18. Leandro CC, Hancock P, Fussell RJ, Keely BJ (2007) Ultra-performance liquid chromatography for the determination of pesticide residues in foods by tandem quadrupole mass spectrometry with polarity switching. J Chromatogr A 1144:161–169CrossRefGoogle Scholar
  19. Li HP, Lin CH, Jen JF (2009) Analysis of aqueous pyrethroid residuals by one-step microwave-assisted headspace solid-phase microextraction and gas chromatography with electron capture detection. Talanta 79:466–471CrossRefGoogle Scholar
  20. MacLachlan DJ, Hamilton D (2010) Estimation methods for maximum residue limits for pesticides. Reg Toxicol Pharmacol 58:208–218CrossRefGoogle Scholar
  21. Markoglou AN, Bempelou ED, Liapis KS, Ziogas BN (2007) Determination of benzoylurea insecticide residues in tomatoes by high-performance liquid chromatography with ultraviolet-diode array and atmospheric pressure chemical ionization-mass spectrometry detection. J AOAC Int 90:1395–1401Google Scholar
  22. Martınez DB, Vazquez PP, Galera MM, Gil Garcıa MD (2006) Determination of pyrethroid insecticides in vegetables with liquid chromatography using detection by electrospray mass spectrometry. Chromatographia 63:487–491CrossRefGoogle Scholar
  23. Martins J, Esteves C, Limpo-Faria A, Barros P, Ribeiro N, Simυes T, Correia M, Delerue-Matos C (2012) Analysis of six fungicides and one acaricide in still and fortified wines using solid-phase microextraction-gas chromatography/tandem mass spectrometry. Food Chem 132:630–636CrossRefGoogle Scholar
  24. Miliadis GE, Tsiropoulos NG, Aplada-Sarlis PG (1999) High-performance liquid chromatographic determination of benzoylurea insecticides residues in grapes and wine using liquid and solid-phase extraction. J Chromatogr A 835:113–120CrossRefGoogle Scholar
  25. Miller JN, Miller JC (2005) Statistics and chemometrics for analytical chemistry, 5th edn. Pearson Education Limited, Essex, EnglandGoogle Scholar
  26. Omirou M, Vryzas Z, Papadopoulou-Mourkidou E, Economou A (2009) Dissipation rates of iprodione and thiacloprid during tomato production in greenhouse. Food Chem 116:499–504CrossRefGoogle Scholar
  27. Payá P, Anastassiades M, Mack D, Sigalova I, Tasdelen B, Oliva J, Barba A (2007) Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection. Anal Bioanal Chem 389:1697–1714CrossRefGoogle Scholar
  28. SANCO Document No. SANCO/10684/2009 Method validation and quality control procedures for pesticide residues analysis in food and feed (last access: 10/08/2012)
  29. Santos LFS, Souza NRS, Ferreira JA, Navickiene S (2012) A reversed-phase high-performance liquid chromatography method combined with matrix solid-phase dispersion extraction for the determination of teflubenzuron, lufenuron and bifenthrin residues in lyophilized coconut water. J Food Compos Anal (in press), 10.1016/j.jfca.2012.03.007
  30. Silva MGD, Aquino A, Dorea HS, Navickiene S (2008) Simultaneous determination of eight pesticide residues in coconut using MSPD and GC/MS. Talanta 76:680–684CrossRefGoogle Scholar
  31. Soler C, Manes J, Pico Y (2004) Liquid chromatography–electrospray quadrupole ion-trap mass spectrometry of nine pesticides in fruits. J Chromatogr A 1048:41–49Google Scholar
  32. Štajnbaher D, Zupancic-Kralj L (2003) Multiresidue method for determination of 90 pesticides in fresh fruits and vegetables using solid-phase extraction and gas chromatography–mass spectrometry. J Chromatogr A 1015:185–198CrossRefGoogle Scholar
  33. Tewary DK, Kumar V, Ravindranath SD, Shanker A (2005) Dissipation behavior of bifenthrin residues in tea and its brew. Food Control 16:231–237CrossRefGoogle Scholar
  34. Thurman EM, Ferrer I, Barcelo D (2001) Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides. Anal Chem 73:5441–5449CrossRefGoogle Scholar
  35. Thurman EM, Ferrer I, Malato O, Fernández-Alba AR (2006) Feasibility of LC/TOFMS and elemental database searching as a spectral library for pesticides in food. Food Addit Contam A 23:1169–1178CrossRefGoogle Scholar
  36. Trufelli H, Palma P, Famiglini G, Cappiello A (2011) An overview of matrix effects in liquid chromatography–mass spectrometry. Mass Spectrom Rev 30:491–509CrossRefGoogle Scholar
  37. Vanni A, Gamberini R, Calabria A, Nappi P (2000) Determination and identification of metabolites of the ungicides iprodione and procymidone in compost. Chemosphere 41:1431–1439CrossRefGoogle Scholar
  38. Walorczyk S, Gnusowski B (2006) Fast and sensitive determination of pesticide residues in vegetables using low-pressure gas chromatography with a triple quadrupole mass spectrometer. J Chromatogr A 1128:236–243CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2012

Authors and Affiliations

  • Anna A. Bletsou
    • 1
  • Ahmad H. Hanafi
    • 2
  • Marilena E. Dasenaki
    • 1
  • Nikolaos S. Thomaidis
    • 1
  1. 1.Laboratory of Analytical Chemistry, Department of Chemistry, Faculty of ScienceUniversity of AthensAthensGreece
  2. 2.Plant Protection Department, Faculty of AgricultureAin Shams UniversityCairoEgypt

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