Food Analytical Methods

, Volume 7, Issue 4, pp 935–945 | Cite as

Multi-mycotoxins Analysis in Dried Fruit by LC/MS/MS and a Modified QuEChERS Procedure

  • Ines Azaiez
  • Federica Giusti
  • Gianni Sagratini
  • Jordi Mañes
  • Mónica Fernández-Franzón


A sensitive and reliable multi-mycotoxin method was developed for the simultaneous determination of 16 toxicological important mycotoxins, such as aflatoxins B1, B2, G1, and G2; enniatins A, A1, B, and B1; beauvericin; ochratoxin A; fumonisin B1, B2, and B3; diacetoxyscirprenol; HT-2; and T-2 toxin in dried fruits using liquid chromatography combined with electrospray ionization-triple quadrupole tandem-mass spectrometry. Mycotoxins have been extracted from the samples using a modified quick, easy, cheap, effective, rugged, and safe procedure. The method was based on a single extraction with acidified acetonitrile, followed by partitioning with salts, avoiding any further clean-up step. Limits of detections ranged from 0.08 to 15 μg kg−1 and limits of quantification ranged from 0.2 to 45 μg kg−1, which were below the legal limit set by the European Union for the legislated mycotoxines. The recoveries in spiked samples ranged from 60 to 135 % except for beauvericin using matrix-matched calibration curves for quantification, with good inter- and intraday repeatability (respective relative standard deviation ≤20 and 9 %). The developed method was applied to 15 commercial dried fruits: raisins, figs, apricots, plums, and dates purchased in local markets from Spain. Among the mycotoxins studied, enniantins and aflatoxins were the most predominant mycotoxins.


Mycotoxins QuEChERS Dried fruits LC/MS/MS 



This work was supported by the Spanish Ministry of Science and Innovation (AGL2010-17024/ALI).

Conflict of Interest

Ines Azaiez has no conflict of interest. Federica Giusti has no conflict of interest. Gianni Sagratini has no conflict of interest. Jordi Mañes has no conflict of interest. Mónica Fernández has no conflict of interest. This article does not contain any studies with human or animal subjects.


  1. Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ (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
  2. Capriotti AL, Caruso G, Cavaliere C, Foglia P, Samperi R, Laganà A (2012) Multiclass mycotoxin analysis in food, environmental and biological matrices with chromatography/mass spectrometry. Mass Spectrom Rev 31:466–503CrossRefGoogle Scholar
  3. Commission of the European Communities (2006) Commission Regulation (EC) No 1881/2006 of 19 December 2006 setting maximum levels for certain contaminants in foodstuffs. Off J Eur Union L364:5–24Google Scholar
  4. Commission of the European Communities (2010) Commission Regulation (EU) No 1058/2012 of 12 November 2012 amending Regulation (EC) No 1881/2006 as regards maximum levels for aflatoxins in dried figs. Off J Eur Union L313:14–15Google Scholar
  5. Cunha SC, Fernandes JO (2010) Development and validation of a method based on a QuEChERS procedure and heartcutting GC-MS for determination of five mycotoxins in cereal products. J Sep Sci 33:600–611CrossRefGoogle Scholar
  6. Desmarchelier A, Oberson JM, Tella P, Gremaud E, Seefelder W, Mottier P (2010) Development and comparison of two multiresidue methods for the analysis of 17 mycotoxins in cereals by liquid chromatography electrospray ionization tandem mass spectrometry multi-mycotoxin analysis in complex biological matrices using LC-ESI/MS: experimental study. J Agric Food Chem 13:7510–7519CrossRefGoogle Scholar
  7. Document SANCO/12495/2011 Method validation and quality control procedures for pesticide residues analysis in food and feed. Available from Accessed on 28 Mar 12)
  8. Ediage EN, Di Mavungu JD, Monbaliu S, Peteghem VC, De Saeger S (2011) A validated multianalyte LC-MS\MS method for quantification of 25 mycotoxins in casava flour, peanut cake and maize samples. J Agric Food Chem 59:5173–5180CrossRefGoogle Scholar
  9. Fernández-Cruz ML, Mansilla ML, Tadeo JL (2010) Mycotoxins in fruits and their processed products: analysis, occurrence and health implications. JAR 1(2):113–122CrossRefGoogle Scholar
  10. Ferreira I, Fernandes JO, Cunha SC (2012) Optimization and validation of a method based in a QuEChERS procedure and gas chromatography–mass spectrometry for the determination of multi-mycotoxins in popcorn. Food Control 27(1):188–193CrossRefGoogle Scholar
  11. Garrido Frenich A, Vidal Martínez JL, Romero-González R, Aguilera-Luiz M (2009) Simple and high-throughput method for the multimycotoxin analysis in cereals and related foods by ultra-high performance liquid chromatography/tandem mass spectrometry. Food Chem 117:705–712CrossRefGoogle Scholar
  12. Garrido Frenich AG, Romero-González R, Gómez-Pérez ML, Vidal JL (2011) Multi-mycotoxin analysis in eggs using a QuEChERS-based extraction procedure and ultra-high-pressure liquid chromatography coupled to triple quadrupole mass spectrometry. J Chromatogr A 1218(28):4349–4356CrossRefGoogle Scholar
  13. Heperkan D, Karbancioglu Güüler F, Oktay HI (2012) Mycoflora and natural occurrence of aflatoxin, cyclopiazonic acid, fumonisin and ochratoxin A in dried figs. Food Addit Contam A 29:277–286CrossRefGoogle Scholar
  14. Karbancıoglu-Guler F, Heperkan D (2008) Natural occurrence of ochratoxin A in dried figs. Anal Chim Acta 617:32–36CrossRefGoogle Scholar
  15. Knudsen PB, Mogensen JM, Larsen TO, Nielsen KF (2011) Occurrence of fumonisins B(2) and B(4) in retail raisins. J Agric Food Chem 59(2):772–776CrossRefGoogle Scholar
  16. Köppen R, Koch M, Siegel D, Merkel S, Maul R, Nehls I (2010) Determination of mycotoxins in foods: current state of analytical methods and limitations. Appl Microbiol Biotechnol 86:1595–1612CrossRefGoogle Scholar
  17. Moretti A, Ferracane L, Somma S, Ricci V, Mulèè G, Susca A, Ritieni A, Logrieco AF (2010) Identification, mycotoxin risk and pathogenicity of Fusarium species associated with fig endosepsis in Apulia, Italy. Food Addit Contam A 27:718–728CrossRefGoogle Scholar
  18. Reinhold L, Reinhardt K (2011) Mycotoxins in foods in Lower Saxony (Germany): results of official control analyses performed in 2009. Mycotoxin Res 27:137–143CrossRefGoogle Scholar
  19. Rodríguez-Carrasco Y, Berrada H, Font G, Mañes J (2012) Multi-mycotoxin analysis in wheat semolina using an acetonitrile-based extraction procedure and gas chromatography-tandem mass spectrometry. J Chromatogr A 1270:28–40CrossRefGoogle Scholar
  20. Rodríguez-Carrasco Y, Font G, Mañes J, Berrada H (2013) Determination of mycotoxins in bee pollen by gas chromatography-tandem mass spectrometry. J Agric Food Chem 61(8):1999–2005CrossRefGoogle Scholar
  21. Rubert J, James KJ, Mañes J, Soler C (2012) Applicability of hybrid linear ion trap-high resolution mass spectrometry and quadrupole-linear ion trap-mass spectrometry for mycotoxin analysis in baby food. J Chromatogr A 1223:84–92CrossRefGoogle Scholar
  22. Sospedra I, Blesa J, Soriano JM, Mañes J (2010) Use of the modified quick easy cheap effective rugged and safe sample preparation approach for the simultaneous analysis of type A- and B-trichothecenes in wheat flour. J Chromatogr A 1217:1437–1440CrossRefGoogle Scholar
  23. Sulyok M, Berthiller F, Krska R, Schuhmacher R (2006) Development and validation of a liquid chromatography/tandem mass spectrometric method for the determination of 39 mycotoxins in wheat and maize. Rapid Commun Mass Spectrom 20:2649–2659CrossRefGoogle Scholar
  24. Sulyok M, Krska R, Schuhmacher R (2010) Application of an LC-MS/MS based multi-mycotoxin method for the semi-quantitative determination of mycotoxins occurring in different types of food infected by moulds. Food Chem 119:408–416CrossRefGoogle Scholar
  25. Tamzura M, Uyama A, Mochizuki N (2011) Development of a multi-mycotoxin analysis in beer-based drinks by a modified QuEChERS method and ultra-high-performance liquid chromatography coupled with tandem mass spectrometry. Anal Sci 27:629–635CrossRefGoogle Scholar
  26. Tang YY, Lin HY, Chen YC, Su WT, Wang SC, Chiueh LC, Shin YC (2013) Development of a quantitative multi-mycotoxin method in rice, maize, wheat and peanut using UPLC-MS/MS. Food Anal Methods 6(3):727–736CrossRefGoogle Scholar
  27. Tolosa J, Font G, Mañes J, Ferrer E (2013) Nuts and dried fruits: natural occurrence of emerging Fusarium mycotoxins. Food Control 33(1):215–220CrossRefGoogle Scholar
  28. Trucksess MW, Scott PM (2008) Mycotoxins in botanicals and dried fruits: a review. Food Addit Contam A 25:181–192CrossRefGoogle Scholar
  29. Yogendrarajah P, Van Poucke C, De Meulenaer B, De Saeger S (2013) Development and validation of a QuEChERS based liquid chromatography tandem mass spectrometry method for the determination of multiple mycotoxins in spices. J Chromatogr A 1297:1–11CrossRefGoogle Scholar
  30. Zinedine A, Soriano JM, Juan C, Mojemmi B, Moltó JC, Bouklouze A, Cherrah Y, Idrissi L, El Aouad R, Mañes J (2007) Incidence of ochratoxin A in rice and dried fruits from Rabat and Saléé area, Morocco. Food Addit Contam A 24:285–291CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • Ines Azaiez
    • 1
  • Federica Giusti
    • 2
  • Gianni Sagratini
    • 2
  • Jordi Mañes
    • 1
  • Mónica Fernández-Franzón
    • 1
  1. 1.Laboratory of Food Chemistry and Toxicology, Faculty of PharmacyUniversity of ValenciaBurjassotSpain
  2. 2.Scuola di Scienze del Farmaco e dei Prodotti della SaluteUniversità di CamerinoCamerinoItaly

Personalised recommendations