Dispersive solid phase extraction in the determination of residues and contaminants in food

Cabrera, Liziara da Costa; Martins, Manoel Leonardo; Primel, Ednei Gilberto; Prestes, Osmar Damian; Adaime, Martha Bohrer; Zanella, Renato

Palavras-chave: Sample preparation, clean-up, sorbents.

ResumoThis paper provide an overview of the technique Dispersive Solid Phase Extraction (D-SPE) as an important step of the QuEChERS method that permit to obtain, in a easy and quick procedure, cleaned extracts for the multiresidue analysis. The D-SPE involves, in general, the use of one or more sorbent together with magnesium sulfate anhydrous in a centrifuge tube to remove the co-extractives from the organic extract. This technique is practical and efficient to clean-up extracts from different complex samples, like foods of vegetable or animal origin. Some practical details of different sorbents are presented with principal applications.

Referências Bibliográficas

1. Kinsella B, O’Mahony J, Malone E, Moloney M, Cantwell H, Furey A et al. Current trends in sample preparation for growth promoter and veterinary drug residue analysis. Journal of Chromatography A 2009; 1216(46):7977-8015. http://dx.doi. org/10.1016/j.chroma.2009.09.005
2. Prestes OD, Friggi CA, Adaime MB, Zanella R. QuEChERS – Um método moderno de preparo de amostra para determinação multirresíduo de pesticidas em alimentos por métodos cromatográficos acoplados à espectrometria de massas. Química Nova 2009; 32:1620-1634. S0100-40422009000600046
3. Picó Y, Blasco C, Font G. Environmental and food applications of LC-tandem mass spectrometry in pesticide-residue analysis: An overview. Mass Spectrometry Reviews 2004; 23:45-85. PMid:14625892.
4. Pinho GP, Neves AA, Queiroz MELR, Silverio FO. Efeito de matriz na quantificação de agrotóxicos por cromatografia gasosa. Química Nova 2009; 32:987-95.
5. Kruve A, Künnapas A, Herodes K, Leito I. Matrix effects in pesticide multi-residue analysis by liquid chromatography-mass spectrometry. Journal of Chromatography A 2008; 1187(1-2):58-66. http://
6. Saito Y, Kodama S, Matsunaga A, Yamamoto A. Multiresidue Determination of Pesticides in Agricultural Products by Gas Chromatography/ Mass Spectrometry with Large Volume Injection. Journal of AOAC International 2004; 87:1356-67. PMid:15675447.
7. Ueno E, Oshima H, Saito I, Matsumoto H, Yoshimura Y, Nakazawa H. Multiresidue Analysis of Pesticides in Vegetables and Fruits by Gas Chromatography/Mass Spectrometry after Gel Permeation Chromatography and Graphitized Carbon Column Cleanup. Journal of AOAC International 2004; 87(4):1003-15. PMid:15295897.
8. Hyötyläinen T. On-line coupling of extraction with gas chromatography. Journal of Chromatography A 2008; 1186(1-2):39-50. chroma.2007.11.066
9. Lambropoulou DA, Albanis TA. Methods of sample preparation for determination of pesticide residues in food matrices by chromatography-mass spectrometry-based techniques: a review. Analytical and Bioanalytical Chemistry 2007; 389(6):1663-83.
10. Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. Journal of AOAC International 2003; 86(2):412-31. PMid:12723926.
11. Lehotay SJ, Mastovská K, Lightfield AR. Use of Buffering and Other Means to Improve Results of Problematic Pesticides in a Fast and Easy Method for Residue Analysis of Fruits and Vegetables. Journal of AOAC International 2005; 88:615. PMid:15859090.
12. Prestes OD, Adaime MB, Zanella R. QuEChERS: possibilidades e tendências no preparo de amostra para determinação multirresíduo de pesticidas em alimentos. Scientia Chromatographica 2011; 3(1):51‑64. http://
13. Marazuela MD, Bogialli S. A review of novel strategies of sample preparation for the determination of antibacterial residues in foodstuffs using liquid chromatography-based analytical methods. Analytica Chimica Acta 2009; 645(1-2):5-17. PMid:19481624.
14. LeDoux M. Analytical methods applied to the determination of pesticide residues in foods of animal origin. A review of the past two decades. Journal of Chromatography A 2011; 1218:1021-36. http://dx.doi. org/10.1016/j.chroma.2010.12.097
15. Lehotay SJ, Son KA, Kwon H, Koesukwiwat U, Fu W, Mastovska K et al. Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. Journal of Chromatography A 2010; 1217(16):2548-60. PMid:20144460. chroma.2010.01.044
16. Ridgway K, Lalljie SPD, Smith RM. Sample preparation techniques for the determination of trace residues and contaminants in foods. Journal of Chromatography A 2007; 1153(1-2):36-53. chroma.2007.01.134
17. Barker SA, Long AR, Short CR. Isolation of drug residues from tissues by solid phase dispersion. Journal of Chromatography A 1989; 475(2):353-61.
18. Barker SA. Applications of matrix solid-phase dispersion in food analysis. Journal of Chromatography A 2000; 880(1-2):63-8. S0021-9673(99)01290-X
19. Rodrigues SA, Caldas SS, Primel EG. A simple, efficient and environmentally friendly method for the extraction of pesticides from onion by matrix solidphase dispersion with liquid chromatography-tandem mass spectrometric detection. Analytica Chimica Acta 2010; 678(1):82-9. aca.2010.08.026
20. Rezić I, Horvat AJM, Babić S, Kaštelan-Macan M. Determination of pesticides in honey by ultrasonic solvent extraction and thin-layer chromatography. Ultrasonics Sonochemistry 2005; 12(6):477-81. http://
21. García-Valcárcel AI, Tadeo JL. A combination of ultrasonic assisted extraction with LC-MS/MS for the determination of organophosphorus pesticides in sludge. Analytica Chimica Acta 2009; 641:117-23. PMid:19393375.
22. Carabias-Martínez R, Rodríguez-Gonzalo E, Revilla-Ruiz P, Hernández-Méndez J. Pressurized liquid extraction in the analysis of food and biological samples. Journal of Chromatography A 2005; 1085(1-2):1-17. chroma.2005.06.072
23. Chuang JC, Hart K, Chang JS, Boman LE, Van Emon JM, Reed AW. Evaluation of analytical methods for determining pesticides in baby foods and adult duplicate-diet samples. Analytica Chimica Acta 2001; 444:87. 2670.(01)01164-3
24. Cho SK, El-Aty AMA, Jeon HR, Choi JH, Shin HC, Shim JH. Comparison of different extraction methods for the simultaneous determination of pesticide residues in kiwi fruit using gas chromatography-mass spectrometry. Biomedical Chromatography 2008; 22:727-35. http://dx.doi. org/10.1002/bmc.990
25. Ganzler K, Salgó A, Valkó K. Microwave extraction: A novel sample preparation method for chromatography. Journal of Chromatography A 1986; 371:299-306.
26. Satpathy G, Tyagi YK, Gupta RK. A novel optimised and validated method for analysis of multiresidues of pesticides in fruits and vegetables by microwave-assisted extraction (MAE)-dispersive solid-phase extraction (d-SPE)-retention time locked (RTL)-gas chromatography-mass spectrometry with Deconvolution reporting software (DRS). Food Chemistry 2011; 127:1300-08. http://dx.doi. org/10.1016/j.foodchem.2011.01.087
27. Zhao X, Xu X, Su R, Zhang H, Wang Z. An application of new microwave absorption tube in non-polar solvent microwave-assisted extraction of organophosphorus pesticides from fresh vegetable samples. Journal of Chromatography A 2012; 1229:6-12. http://dx.doi. org/10.1016/j.chroma.2012.01.018
28. Chen L, Ding L, Jin H, Song D, Zhang H, Li J et al. The determination of organochlorine pesticides based on dynamic microwave-assisted extraction coupled with on-line solid-phase extraction of high-performance liquid chromatography. Analytica Chimica Acta 2007; 589:239-46. aca.2007.03.003
29. Wardencki WM, Curylo J. A review of theoretical and practical aspects of solid-phase microextraction in food analysis. International Journal of Food Science and Technology 2004; 39:703-17. http://dx.doi. org/10.1111/j.1365-2621.2004.00839.x
30. Lehotay SJ, Hiemstra M, Bodegraven P, Kok A. Validation of a fast and easy method for the determination of residues from 229 pesticides in fruits and vegetables using gas and liquid chromatography and mass spectrometric detection. Journal of AOAC International 2005; 88:595-614. PMid:15859089.
31. Quick Easy Cheap Effective Rugged Safe. [cited 2012 Jun]. Available from:
32. Payá P, Anastassiades M, Mack D, Sigalova I, Tasdelen B, Oliva J et al. 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. Analytical and Bioanalytical Chemistry 2007; 389:1697-714. http://
33. Mastovska K, Dorweiler KJ, Lehotay SJ, Wegscheid JS, Szpylka KA. Pesticide Multiresidue Analysis in Cereal Grains Using Modified QuEChERS Method Combined with Automated Direct Sample Introduction GC-TOFMS and UPLC-MS/MS Techniques. Journal of Agricultural and Food Chemistry 2010; 58:5959-72. PMid:20028018.
34. Cunha SC, Lehotay SJ, Mastovska K, Fernandes JO, Oliveira BMPP. Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives. Journal of Separation Science 2007; 30:620-32. PMid:17444232.
35. Koesukwiwat U, Lehotay SJ, Mastovska K, Dorweiler KJ, Leepipatpiboon N. Extension of the QuEChERS Method for Pesticide Residues in Cereals to Flaxseeds, Peanuts, and Doughs. Journal of Agricultural and Food Chemistry 2010; 58:5950-8. PMid:20025276.
36. Lehotay S. Determination of Pesticide Residues in Foods by Acetonitrile Extraction and Partitioning with Magnesium Sulfate: Collaborative Study. Journal of the Association of Official Analytical Chemists 2007; 90:485-520. PMid:17474521.
37. Anastassiades M, Scherbaum E, Tasdelen B, Stajnbaher D. Crop protection, public health, environmental safety. Weinheim, Germany: Wiley-VCH; 2007.
38. Hennion MC. Graphitized carbons for solidphase extraction. Journal of Chromatography A 2000; 885(1-2):73-95. S0021-9673(00)00085-6
39. Koesukwiwat U, Sanguankaew K, Leepipatpiboon N. Rapid determination of phenoxy acid residues in rice by modified QuEChERS extraction and liquid chromatography-tandem mass spectrometry. Analytica Chimica Acta 2008; 626:10-20. PMid:18761116.
40. Wilkowska A, Biziuk M. Determination of pesticide residues in food matrices using the QuEChERS methodology. Food Chemistry 2011; 125:803-12.
41. Nguyen TD, Lee MH, Lee GH. Rapid determination of 95 pesticides in soybean oil using liquid-liquid extraction followed by centrifugation, freezing and dispersive solid phase extraction as cleanup steps and gas chromatography with mass spectrometric detection. Microchemical Journal 2010; 95:113-9.
42. Cabrera L. Estudo do efeito matriz na determinação de agrotóxicos em diferentes tipos de arroz pelo método QuEChERS modificado e LC-MS/MS. [tese]. Santa Maria: Universidade Federal de Santa Maria; 2012.
43. Dotto GL, Vieira MLG, Gonçalves JO, Pinto LAdA. Remoção dos corantes azul brilhante, amarelo crepúsculo e amarelo tartrazina de soluções aquosas utilizando carvão ativado, terra ativada, terra diatomácea, quitina e quitosana: estudos de equilíbrio e termodinâmica. Química Nova 2011; 34:1193-9.
44. QuEChERS ChloroFiltr. [cited 2012 Jun]. Available from:
45. Zhao YG, Shen HY, Shi JW, Chen XH, Jin MC. Preparation and characterization of amino functionalized nano-composite material and its application for multi-residue analysis of pesticides in cabbage by gas chromatography-triple quadrupole mass spectrometry. Journal of Chromatography A 2011; 1218(33):5568-80. chroma.2011.06.090
46. Herbst MH, Macedo MIF, Rocco AM. Tecnologia dos nanotubos de carbono: tendências e perspectivas de uma área multidisciplinar. Química Nova 2004; 27:986-92. S0100-40422004000600025
47. Zhao P, Wang L, Zhou L, Zhang F, Kang S, Pan C. Multi-walled carbon nanotubes as alternative reverseddispersive solid phase extraction materials in pesticide multi-residue analysis with QuEChERS method. Journal of Chromatography A 2012; 1225:17‑25. http://
48. Díez C, Traag WA, Zommer P, Marinero P, Atienza J. Comparison of an acetonitrile extraction/partitioning and “dispersive solid-phase extraction” method with classical multi-residue methods for the extraction of herbicide residues in barley samples. Journal of Chromatography A 2006; 1131(1-2):11-23. http://
49. Lesueur C, Knittl P, Gartner M, Mentler A, Fuerhacker M. Analysis of 140 pesticides from conventional farming foodstuff samples after extraction with the modified QuECheRS method. Food Control 2008; 9:906-14. foodcont.2007.09.002
50. Nguyen TD, Yu JE, Lee DM, Lee G-H. A multiresidue method for the determination of 107 pesticides in cabbage and radish using QuEChERS sample preparation method and gas chromatography mass spectrometry. Food Chemistry 2008; 110:207-213.
51. Cieślik E, Sadowska-Rociek A, Ruiz JMM, Surma-Zadora M. Evaluation of QuEChERS method for the determination of organochlorine pesticide residues in selected groups of fruits. Food Chemistry 2011; 125:773-8. http://dx.doi. org/10.1016/j.foodchem.2010.09.019
52. Furlani RPZ, Marcilio KM, Leme FM, Tfouni SAV. Analysis of pesticide residues in sugarcane juice using QuEChERS sample preparation and gas chromatography with electron capture detection. Food Chemistry 2011; 126:1283-7. http://dx.doi. org/10.1016/j.foodchem.2010.11.074
53. Lopes RP, Reyes RC, Romero-González R, Frenich AG, Vidal JLM. Development and validation of a multiclass method for the determination of veterinary drug residues in chicken by ultra high performance liquid chromatography-tandem mass spectrometry. Talanta 2012; 89:201-8. talanta.2011.11.082
54. Kolberg DI, Prestes OD, Adaime MB, Zanella R. 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 Chemistry 2011; 125:1436‑42.
55. Georgakopoulos P, Zachari R, Mataragas M, Athanasopoulos P, Drosinos EH, Skandamis PN. Optimisation of octadecyl (C18) sorbent amount in QuEChERS analytical method for the accurate organophosphorus pesticide residues determination in low-fatty baby foods with response surface methodology. Food Chemistry 2011; 128:536-42.
56. Lombardo-Agüí M, García-Campaña AM, Gámiz- Gracia L, Cruces-Blanco C. Determination of quinolones of veterinary use in bee products by ultrahigh performance liquid chromatography-tandem mass spectrometry using a QuEChERS extraction procedure. Talanta 2012; 93:193-9. http://dx.doi. org/10.1016/j.talanta.2012.02.011
57. García-Reyes JF, Ferrer C, Gómez-Ramos MJ, Fernández-Alba AR, Molina-Díaz A. Determination of pesticide residues in olive oil and olives. Trends in Analytical Chemistry 2007; 26:239-51. http://dx.doi. org/10.1016/j.trac.2007.01.004
58. Xu R, Wu J, Liu Y, Zhao R, Chen B, Yang M et al. Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection. Chemosphere 2011; 84:908-12.
59. Usui K, Hayashizaki Y, Hashiyada M, Funayama M. Rapid drug extraction from human whole blood using a modified QuEChERS extraction method. Legal Medicine 2012. legalmed.2012.04.008
60. Hiemstra M, De Kok A. Comprehensive multiresidue method for the target analysis of pesticides in crops using liquid chromatography-tandem mass spectrometry. Journal of Chromatography A 2007; 1154:3-25. chroma.2007.03.123
61. Melo A, Mansilha C, Pinho O, Ferreira IMPLVO. Analysis of Pesticides in Tomato Combining QuEChERS and Dispersive Liquid-Liquid Microextraction Followed by High-Performance Liquid Chromatography. Food Analytical Methods 2012. In press. s12161-012-9469-4
62. Wang P, Yang X, Wang J, Cui J, Dong AJ, Zhao HT et al. Multi-residue method for determination of seven neonicotinoid insecticides in grains using dispersive solid-phase extraction and dispersive liquid-liquid micro-extraction by high performance liquid chromatography. Food Chemistry 2012, 134:1691-8.
63. Mao X, Wan Y, Yan A, Shen M, Wei Y. Simultaneous determination of organophosphorus, organochlorine, pyrethriod and carbamate pesticides in Radix astragali by microwave-assisted extraction/dispersivesolid phase extraction coupled with GC-MS. Talanta 2012, 97:131-41. talanta.2012.04.007
64. Lentza-Rizos C, Avramides EJ, Kokkinaki K. Residues of azoxystrobin from grapes to raisins. Journal of Agricultural and Food Chemistry 2006; 54:138-41. PMid:16390190.
65. Rübensam G, Barreto F, Hoff RB, Pizzolato TM. Determination of avermectin and milbemycin residues in bovine muscle by liquid chromatography-tandem mass spectrometry and fluorescence detection using solvent extraction and low temperature cleanup. Food Control 2013; 29:55-60. foodcont.2012.05.075
66. Goulart SM, Alves RD, Neves AA, De Queiroz JH, De Assis TC, De Queiroz M. Optimization and validation of liquid-liquid extraction with low temperature partitioning for determination of carbamates in water. Analytica Chimica Acta 2010; 671:41-7. http://dx.doi. org/10.1016/j.aca.2010.05.003
67. Goulart S, Dequeiroz M, Neves A, Dequeiroz J. Low-temperature clean-up method for the determination of pyrethroids in milk using gas chromatography with electron capture detection. Talanta 2008; 75:1320-23. talanta.2008.01.058
68. Chen S, Yu X, He X, Xie D, Fan Y, Peng J. Simplified pesticide multiresidues analysis in fish by low-temperature cleanup and solid-phase extraction coupled with gas chromatography/mass spectrometry. Food Chemistry 2009; 113:1297-300. http://dx.doi. org/10.1016/j.foodchem.2008.08.045
69. Hong J, Kim HY, Kim DG, Seo J, Kim KJ. Rapid determination of chlorinated pesticides in fish by freezing-lipid filtration, solid-phase extraction and gas chromatography-mass spectrometry. Journal of Chromatography A 2004; 1038:27-35. http://dx.doi. org/10.1016/j.chroma.2004.03.003.