Abstract
The evaluation of analytical methods for determining the level of residues and contaminants in food samples is a continuing need. To improve this evaluation, it is necessary to investigate different extraction procedures and conditions. A 23 factorial design was applied to establish an analytical method for determining pesticide residues in wheat by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Factors that influence the recovery of compounds, such as agitation and different processes of partition and cleanup, were investigated. Extracts were analyzed by LC-MS/MS with electrospray ionization in a triple quadrupole system. The use of ultrasonic agitation in the extraction step, deep freezing for the partition step, and C18 cleanup provided significantly better recoveries for most of the compounds evaluated. Assessment of each factor as well as interactions between factors allowed for a more effective evaluation of the parameters involved in the development of analytical methods. The validation results were satisfactory, since the method presented linearity (r 2) >0.99 for all compounds, the matrix effect ranged from 3 to 97 % and was corrected by matrix-matched standards, and recoveries ranged from 70 to 120 % with RSD ≤20 % for the spike levels of 10 and 100 μg kg−1. The method limit of detection and limit of quantification ranged from 3.3 to 6.7 μg kg−1 and from 10 to 20 μg kg−1, respectively, and the expanded uncertainty ranged from 15 to 32 %. The proposed method met the criteria for determination of 42 pesticides in wheat samples and was successfully tested in real samples.
Similar content being viewed by others
References
Alder L, Greulich K, Kempe G, Vieth B (2006) Residue analysis of 500 high priority pesticides: better by GC-MS or LC-MS/MS? Mass Spectrom Reviews 25:838–865
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 International 86:412–431
Andersson A, Pålsheden H (1991) Comparison of the efficiency of different GLC multi-residue methods on crops containing pesticide residues. Fresenius J Anal Chem 339:365–367
Cerqueira MBR, Caldas SS, Primel EG (2014) New sorbent in the dispersive solid phase extraction step of quick, easy, cheap, effective, rugged, and safe for the extraction of organic contaminants in drinking water treatment sludge. J Chromatogr A 1336:10–22
Chemat F, Huma Z, Khan MK (2011) Applications of ultrasound in food technology: processing, preservation and extraction. Ultrasonics Sonochem 18:813–835
Cho S, AM A e-a, Park KH, Park J, Assayed ME, Jeong YM, Park YS, Shim JH (2013) Simple multiresidue extraction method for the determination of fungicides and plant growth regulator in bean sprouts using low temperature partition and tandem mass spectrometry. Food Chem 136:1414–1420
Coscollà C, Yusà V, Beser MI, Pastor A (2009) Multi-residue analysis of 30 currently used pesticides in fine airborne particulate matter (PM 2.5) by microwave-assisted extraction and liquid chromatography–tandem mass spectrometry. J Chromatogr A 1216:8817–8827
El Atrache LL, Sghaier RB, Kefi BB, Haldys V, Dachraouia M, Tortajada J (2013) Factorial design optimization of experimental variables in preconcentration of carbamates pesticides in water samples using solid phase extraction and liquid chromatography–electrospray-mass spectrometry determination. Talanta 117:392–398
Facco JF, Martins ML, Bernardi G, Prestes OD, Adaime MB, Zanella R (2015) Optimization and validation of a multiresidue method for pesticide determination in maize using gas chromatography coupled to tandem mass spectrometry. Anal Methods 7:359–365
Farajzadeha MA, Bahram M, Mehr BG, Jönsson JA (2008) Optimization of dispersive liquid–liquid microextraction of copper (II) by atomic absorption spectrometry as its oxinate chelate: application to determination of copper in different water samples. Talanta 75:832–840
Ferreira SLC, Dos Santos WNL, Quintella CM, Neto BB, Bosque-Sandra JM (2004) Doehlert matrix: a chemometric tool for analytical chemistry—review. Talanta 63:1061–1067
Ferreira JA, Talamine V, Facco JF, Rizzetti TM, Ferreira JMS, Oliveira FA, Prestes OD, Zanella R, Martins ML, Adaime MB, Navickiene S, Bottoli CBG (2015) Determination of pesticide residues in coconut tree trunks by modified QuEChERS method and ultrahigh-performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry. Anal Methods 7:4237–4245
Golge O, Kabak B (2015) Evaluation of QuEChERS sample preparation and liquid chromatography–triple-quadrupole mass spectrometry method for the determination of 109 pesticide residues in tomatoes. Food Chem 176:319–332
González-Curbelo MA, Hernández-Borges J, Borges-Miquel TM, Rodríguez-Delgado MA (2013) Determination of organophosphorus pesticides and metabolites in cereal-based baby foods and wheat flour by means of ultrasound-assisted extraction and hollow-fiber liquid-phase microextraction prior to gas chromatography with nitrogen phosphorus detection. J Chromatogr A 1313:166–174
González-Curbelo MÁ, Socas-Rodríguez B, Herrera-Herrera AV, González-Sálamo J, Hernández-Borges J, Rodríguez-Delgado MÁ (2015) Evolution and applications of the QuEChERS method. TrAC Trends Anal Chem 38:32–51
Granby K, Hinge Andersen J, Christensen HB (2004) Analysis of pesticides in fruit, vegetables and cereals using methanolic extraction and detection by liquid chromatography–tandem mass spectrometry. Anal Chim Acta 520:165–176
He Z, Wang L, Peng Y, Luo M, Wang W, Liu X (2015) Multiresidue analysis of over 200 pesticides in cereals using a QuEChERS and gas chromatography–tandem mass spectrometry-based method. Food Chem 169:372–380
Hercegova A, Domotorova M, Matisova M, Otrekala M, Kirchnera R, Stefuca V (2005) Fast gas chromatography with solid phase extraction clean-up for ultratrace analysis of pesticide residues in baby food. J Chromatogr A 1084:46–53
Hibbert DB (2012) Experimental design in chromatography: a tutorial review. J Chromatogr B 910:2–13
Horwitz W (1995) Protocol for the design, conduct and interpretation of method-performance studies. Pure and Applied Chem 67:331–343
Kaushik R, Saran S, Isar J, Saxena RK (2006) Statistical optimization of medium components and growth conditions by response surface methodology to enhance lipase production by Aspergillus carneus. J Mol Catal B Enzym 40:121–126
Kemmerich M, Rizzetti TM, Martins ML, Prestes OD, Adaime MB, Zanella R (2015) Optimization by central composite design of a modified QuEChERS method for extraction of pesticide multiresidue in sweet pepper and analysis by ultra-high-performance liquid chromatography-tandem mass spectrometry. Food Anal Methods 8:728–739
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 125:1436–1442
Kwon H, Lehotay SJ, Geis-Asteggiante L (2012) Variability of matrix effects in liquid and gas chromatography–mass spectrometry analysis of pesticide residues after QuEChERS sample preparation of different food crops. J Chromatogr A 1270:235–245
Leardi R (2009) Experimental design in chemistry: a tutorial. Anal Chim Acta 652:161–172
Li P, Yang X, Miaob H, Zhao Y, Liu W, Wu Y (2013) Simultaneous determination of 19 triazine pesticides and degradation products in processed cereal samples from Chinese total diet study by isotope dilution–high performance liquid chromatography–linear ion trap mass spectrometry. Anal Chim Acta 781:63–71
Liu S, Zheng Z, Wei F, Ren Y, Gui W, Wu G, Zhu G (2010) Simultaneous determination of seven neonicotinoid pesticide residues in food by ultraperformance liquid chromatography tandem mass spectrometry. J Agric Food Chem 58:3271–3278
Magnusson B, Örnemark U (eds.) (2014) Eurachem guide: the fitness for purpose of analytical methods—a laboratory guide to method validation and related topics. ISBN 978-91-87461-59-0
Muralidhar RV, Chirumamila RR, Marchant R, Nigam P (2001) A response surface approach for the comparison of lipase production by Candida cylindracea using two different carbon sources. Biochem Eng J 9:17–23
Ozcan S, Tor A, Aydin ME (2009) Application of miniaturized ultrasonic extraction to the analysis of organochlorine pesticides in soil. Anal Chim Acta 640:52–57
Pan J, Xia X, Liang J (2008) Analysis of pesticide multi-residues in leafy vegetables by ultrasonic solvent extraction and liquid chromatography-tandem mass spectrometry. Ultrasonics Sonochem 15:25–32
Pareja L, Fernandez-Alba AR, Cesio V, Heinzen H (2011) Analytical methods for pesticide residues in rice. TrAC: Trends Anal Chem 30:271–291
Pinho GP, Neves AA, Queiroz MELR, Silvério F (2010) Optimization of the liquid–liquid extraction method and low temperature purification (LLE–LTP) for pesticide residue analysis in honey samples by gas chromatography. Food Control 21:1307–1311
Prestes OD, Friggi CA, Adaime MB, Zanella R (2009) QuEChERS—a modern sample preparation method for pesticide multiresidue determination in food by chromatographic methods coupled to mass spectrometry. Quim Nov. 32:1620–1634
Raschea C, Fournes B, Dirks U, Speer K (2015) Multi-residue pesticide analysis (gas chromatography–tandem mass spectrometry detection)—improvement of the quick, easy, cheap, effective, rugged, and safe method for dried fruits and fat-rich cereals—benefit and limit of a standardized apple purée calibration (screening). J Chromatogr A 1403:21–31
Rizzetti TM, Kemmerich M, Martins ML, Prestes OD, Adaime MB, Zanella R (2016) Optimization of a QuEChERS based method by means of central composite design for pesticide multiresidue determination in Orange juice by UHPLC–MS/MS. Food Chem 196:25–33
Romero-Gonzalez R, Garrido Frenich A, Martinez Vidal JL, Prestes OD, Grio SL (2011) Simultaneous determination of pesticides, biopesticides and mycotoxins in organic products applying a quick, easy, cheap, effective, rugged and safe extraction procedure and ultra-high performance liquid chromatography–tandem mass spectrometry. J Chromatogr A 1218:1477–1485
Sahoo SK, Battu RS, Singh B (2011) Development and validation of QuEChERS method for estimation of propamocarb residues in tomato (Lycopersicon esculentum Mill) and soil. Am J Anal Chem 2:26–31
SANCO (2013). Method validation and quality control procedures for pesticide residues analysis in food and feed. Commission of the European communities. SANCO/12571/2013.
Silvério FO, Silva JGS, Aguiar MCS, Cacique AP, Pinho GP (2012) Analysis of pesticides in water using liquid-liquid extraction at low temperature and high performance liquid chromatography. Quim Nov. 35:2052–2056
Šramková Z, Gregová E, Šturdík E (2009) Chemical composition and nutritional quality of wheat grain. Acta Chim Slovaca 2:115–138
Teng Y, Xu Y (2008) Culture condition improvement for whole-cell lipase production in submerged fermentation by Rhizopus chinensis using statistical method. Bioresour Technol 99:3900–3907
Teófilo RF, Ferreira MM (2006) Chemometrics II: spreadsheets for experimental design calculations, a tutorial. Quim Nov. 29:338–350
Tor A, Aydin ME, Ozcan S (2006) Ultrasonic solvent extraction of organochlorine pesticides from soil. Anal Chim Acta 559:73–180
Walorczyk S, Drozdzynski D (2012) Improvement and extension to new analytes of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography–tandem quadrupole mass spectrometry revisited. J Chromatogr A 1251:219–231
Wilkowska A, Biziuk M (2011) Determination of pesticide residues in food matrices using the QuEChERS methodology. Food Chem 125:803–812
Wu CFJ (2000) Experiments—planning, analysis and parameter design optimization. Wiley-Interscience Publication, New York
Zhang K, Wong JW, Yang P, Tech K, Dibenedetto AL, Lee NS, Hayward DG, Makovi CM, Krynitsky AJ, Banerjee K, Jao L, Dasgupta S, Smoker MS, Simonds R, Schreiber A (2011) Multiresidue pesticide analysis of agricultural commodities using acetonitrile salt-out extraction, dispersive solid-phase sample clean-up, and high-performance liquid chromatography tandem mass spectrometry. J Agric Food Chem 59:7636–7646
Acknowledgments
The authors are grateful to the financial support and fellowship grants from the Brazilian agencies CNPq and CAPES. This study was funded by the National Council of Scientific and Technological Development (CNPq), Brazil.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of Interest
Maria T. Friedrich, Manoel L. Martins, Osmar D. Prestes, and Renato Zanella declare that they have no conflict of interest.
Ethical Approval
This article does not contain any studies with human participants or animals performed by any of the authors.
Rights and permissions
About this article
Cite this article
Friedrich, M.T., Martins, M.L., Prestes, O.D. et al. Use of Factorial Design in the Development of Multiresidue Method for Determination of Pesticide Residues in Wheat by Liquid Chromatography-Tandem Mass Spectrometry. Food Anal. Methods 9, 2541–2551 (2016). https://doi.org/10.1007/s12161-016-0447-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12161-016-0447-0