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Determination of Mycotoxins in Cereal-Based Porridge Destined for Infant Consumption by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

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Abstract

An analytical method applying ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) for the determination of aflatoxins M2, M1, G2, G1, B2, B1, deoxynivalenol, ochratoxin A, fumonisins B1 and B2, hydrolyzed fumonisins B1 and B2, zearalenone and sterigmatocystin in cereal-based porridge destined for infant consumption was developed and validated. The mycotoxins were extracted using an adequate solvent ratio (n-hexane/3% formic acid solution/acetonitrile) under rapid shaking and sonication, without any further cleanup steps. Recoveries ranged from 63.5 to 113.2% and were considered satisfactory, with relative standard deviations lower than 20%. The limits of quantification ranged from 0.14 to 6.73 μg kg−1. The validated method was then applied to the determination of mycotoxins in 84 samples of cereal-based porridge destined for infant consumption obtained in the metropolitan region of Rio de Janeiro, RJ. Aflatoxins B1 and G1, fumonisins B1 and B2, hydrolyzed fumonisins B1 and B2, deoxynivalenol, and zearalenone were found, respectively, in 7.1, 2.4, 47.6, 3.6, 65.5, and 60.7% of the analyzed samples. The maximum permissible limits set by the Brazilian legislation were exceeded for at least one mycotoxin in 21 (25%) of the analyzed samples.

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References

  • Alvito PC, Sizoo EA, Almeida CMM, van Egmond HP (2010) Occurrence of aflatoxins and ochratoxin A in baby foods in Portugal. Food Anal Methods 3:22–30

    Article  Google Scholar 

  • Araguás C, González-Peñas E, López de Cerain A (2005) Study on ochratoxin A in cereal-derived products from Spain. Food Chem 92:459–464

    Article  Google Scholar 

  • Baydar T, Erkekoglu P, Sipahi H, Sahin G (2007) Aflatoxin B1, M1 and ochratoxin A levels in infant formulae and baby foods marketed in Ankara, Turkey. J Food Drug Anal 15:89–92

    CAS  Google Scholar 

  • Belsley DA, Kuh E, Welsch RE (1980) Regression diagnostics: identifying influential data and sources of collinearity. Wiley, New York 292 p

    Book  Google Scholar 

  • Beltran E, Ibanez M, Sancho JV, Cortes MA, Yusa V, Hernandez F (2011) UHPLC–MS/MS highly sensitive determination of aflatoxins, the aflatoxin metabolite M1 and ochratoxin A in baby food and milk. Food Chem 126:737–744

    Article  CAS  Google Scholar 

  • Berthiller F, Brera C, Crews C, Iha MH, Krska R, Lattanzio VMT, MacDonald S, Malone RJ, Maragos C, Solfrizzo M, Stroka J, Whitaker TB (2016) Developments in mycotoxin analysis: an update for 2014-2015. World Mycotoxin J 9:5–30

    Article  CAS  Google Scholar 

  • Berthiller F, Brera C, Iha MH, Krska R, Lattanzio VMT, MacDonald S, Malone RJ, Maragos C, Solfrizzo M, Stranska-Zachariasova M, Stroka J, Tittlemier SA (2017) Developments in mycotoxin analysis: an update for 2015-2016. World Mycotoxin J 10:5–29

    Article  Google Scholar 

  • Bräse S, Encinas A, Keck J, Nising CF (2009) Chemistry and biology of mycotoxins and related fungal metabolites. Chem Rev 109:3903–3990

    Article  Google Scholar 

  • Brasil (2011) Ministério da Saúde. Agência Nacional de Vigilância Sanitária. Resolução RDC n° 7, de 18 do fevereiro de 2011. Dispõe sobre limites máximos tolerados (LMT) para micotoxinas em alimentos. Diário Oficial da República Federativa do Brasil, Brasília 46:66–67

    Google Scholar 

  • Brown BM, Forsythe AB (1974) Robust tests for the equality of variances. J Am Stat Assoc 69:364–367

    Article  Google Scholar 

  • Caldas ED, Silva ACS (2007) Mycotoxins in corn-based food products consumed in Brazil: an exposure assessment for fumonisins. J Agric Food Chem 55:7974–7980

    Article  CAS  Google Scholar 

  • Cano-Sancho G, Gauchi JP, Sanchis V, Marín S, Ramos AJ (2011) Quantitative dietary exposure assessment of the Catalonian population (Spain) to the mycotoxin deoxynivalenol. Food Additives and Contaminants: Part A 28:1098–1109

    Article  CAS  Google Scholar 

  • Castro MF, Shephard GS, Sewram V, Vicente E, Mendonça TA, Jordan AC (2004) Fumonisins in Brazilian corn based foods for infant consumption. Food Addit Contam 21:693–699

    Article  Google Scholar 

  • Chu FS (1991) Mycotoxins: food contamination, mechanism, carcinogenic potential and preventive measures. Mutat Res 259:291–306

    Article  CAS  Google Scholar 

  • Cigić IK, Prosen H (2009) An overview of conventional and emerging analytical methods for the determination of mycotoxins. Int J Mol Sci 10:62–115

    Article  Google Scholar 

  • D’Arco G, Fernández Franzón M, Font G, Damiani P, Mañes J (2008) Analysis of fumonisins B1, B2 and B3 in corn-based baby food by pressurized liquid extraction and liquid chromatography/tandem mass spectrometry. J Chromatogr A 1209:188–194

    Article  Google Scholar 

  • Dall'Asta C, Galaverna G, Mangia M, Sforza S, Dossena A, Marchelli R (2009) Free and bound fumonisins in gluten-free food products. Molecular Nutrition and Food Research 53:492–499

    Article  Google Scholar 

  • Dombrink-Kurtzman MA, Dvorak TJ (1999) Fumonisin content in masa and tortillas from Mexico. J Agric Food Chem 47:622–627

    Article  CAS  Google Scholar 

  • Draper N, Smith H (1998) Applied regression analysis. Wiley, New York 706 p

    Book  Google Scholar 

  • Durbin J, Watson GS (1951) Testing for serial correlation in least squares regression ii. Biometrika 38:159–178

    Article  CAS  Google Scholar 

  • EC European Commission (2002) Commission decision 2002/657/EC of 12 August 2002. Implementing Council Directive 96/23/EC concerning performance of analytical methods and the interpretation of results. Official Journal of the European Communities, Brussels, 2002, L 221/8

  • EC European Commission (2006) Commission regulation (EC) no. 401/2006. Laying down the methods of sampling and analysis for the official control of the levels of mycotoxins in foodstuffs. Off J Eur Union L 70:12–34

    Google Scholar 

  • EC European Commission (2014) Guidance document on analytical quality control and validation procedures for pesticide residues analysis in food and feed. SANCO/12571/2013

  • Ezekiel CN, Sulyok M, Warth B, Odebode AC, Krska R (2012) Natural occurrence of mycotoxins in peanut cake from Nigeria. Food Control 27:338–342

    Article  CAS  Google Scholar 

  • Fang LX, Xiong AZ, Wang R, Ji S, Yang L, Wang ZT (2013) A strategy for screening and identifying mycotoxins in herbal medicine using ultra-performance liquid chromatography with tandem quadrupole time-of-flight mass spectrometry. J Sep Sci 36:3115–3122

    Article  CAS  Google Scholar 

  • FAO Food and Agriculture Organization of the United States (2004) Worldwide regulations for mycotoxins in food and feed in 2003. FAO Food and Nutrition Paper 81, Rome

  • Filazi A, Sireli UT (2013) Occurrence of aflatoxins in food, aflatoxins—recent advances and future prospects, Prof. Razzaghi-Abyaneh M. (Ed.), ISBN: 978-953-51-0904-4, InTech, 2013. http://www.intechopen.com/books/aflatoxins-recent-advances-and-future-prospects/occurrence-of-aflatoxins-in-food. Acessed 20 April 2017

  • Frenich AG, Vidal JLM, González RR, Luiz MMA (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 117:705–712

    Article  CAS  Google Scholar 

  • García-Campaña A, Cuadros-Rodríguez L, Aybar-Muñoz J, Alés-Barrero F (1997) Chemometric protocol to validate an analytical method in the presence of corrigible constant and proportional systematic errors. J AOAC Int 80:657–664

    Google Scholar 

  • Gottschalk C, Barthel J, Engelhardt G, Bauer J, Meyer K (2009) Simultaneous determination of type A, B and D trichothecenes and their occurrence in cereals and cereals products. Food Addit Contam 26:1273–1289

    Article  CAS  Google Scholar 

  • Horwitz W, Latimer GW (2005) Official methods of analysis of AOAC International, 18th edn. AOAC International, Gaithersburg

    Google Scholar 

  • Huang B, Han Z, Cai Z, Wu Y, Ren Y (2010) Simultaneous determination of aflatoxins B1, B2, G1, G2, M1 and M2 in peanuts and their derivative products by ultra-high-performance liquid chromatography-tandem mass spectrometry. Anal Chim Acta 662:62–68

    Article  CAS  Google Scholar 

  • IARC International Agency for Research on Cancer (1993) Evaluation of carcinogen risks to humans. Some naturally occurring substances: foods items and constituents, heterocyclic aromatic amines and mycotoxins

  • IARC International Agency for Research on Cancer (2002) Monographs 56: 489–521. IARC monographs on the evaluation of carcinogenic risks to humans. Volume 82: 301–366. Some traditional herbal medicines, some mycotoxins, naphthalene and styrene. IARC, Lyon

    Google Scholar 

  • Jia W, Chu X, Ling Y, Huang J, Chang J (2014) Multi-mycotoxin analysis in dairy products by liquid chromatography coupled to quadrupole orbitrap mass spectrometry. J Chromatogr A 1345:107–114

    Article  CAS  Google Scholar 

  • Juan C, Raiola A, Manes J, Ritieni A (2014) Presence of mycotoxin in commercial infant formulas and baby foods from Italian market. Food Control 39:227–236

    Article  CAS  Google Scholar 

  • Kabak B (2009) Ochratoxin A in cereal-derived products in Turkey: occurrence and exposure assessment. Food Chem Toxicol 47:348–352

    Article  CAS  Google Scholar 

  • Köppen R, Koch M, Siegel D, Merkel S, Maul R, Nehls I (2010) Applied microbiology and biotechnology determination of mycotoxins in foods: current state of analytical methods and limitations. Appl Microbiol Biotechnol 86:1595–1612

    Article  Google Scholar 

  • Kostelanská M, Sosnovcová I, Ondrej L, Hajslová J (2010) Determination of mycotoxins in infant and baby food using UPLC-MS/MS analytical method. Proceedings of 6 th ISC Modern Analytical Chemistry. Prague

  • Krska R, Schubert-Ullrich P, Molinelli A, Sulyok M, Macdonald S, Crews C (2008) Mycotoxin analysis: an update. Food Addit Contam 25:152–163

    Article  CAS  Google Scholar 

  • Lacina O, Zachariasova M, Urbanova J, Vaclavikova M, Cajka T, Hajslova J (2012) Critical assessment of extraction methods for the simultaneous determination of pesticide residues and mycotoxins in fruits, cereals, spices and oil seeds employing ultra-high performance liquid chromatography-tandem mass spectrometry. J Chromatogr A 1262:8–18

    Article  CAS  Google Scholar 

  • Lee HJ, Ryu D (2017) Worldwide occurrence of mycotoxins in cereals and cereal-derived food products: public health perspectives of their co-occurrence. Journal of Agricultural and Food Chemistry

  • Lombaert GA, Pellaers P, Roscoe V, Mankotia M, Neil R, Scott PM (2003) Mycotoxins in infant cereal foods from the Canadian retail market. Food Addit Contam 20:494–504

    Article  CAS  Google Scholar 

  • Mahnine N, Meca G, Fernández-Franzón M, Mañes J, Zinedine A (2012) Occurrence of fumonisins B1, B2 and B3 in breakfast and infant cereals from Morocco. Phytopathol Mediterr 51:193–197

    CAS  Google Scholar 

  • Mavungu DDJ, Monbaliu S, Scippo ML, Maghuin-Rogister G, Schneider YJ, Larondelle Y, Callebaut A, Robbens J, Van Peteghem C, De Saeger S (2009) LC-MS/MS multi-analyte method for mycotoxin determination in food supplements. Food additives and contaminants. Part A Chem Anal Control Expo Risk Assess 26:885–895

    Article  Google Scholar 

  • Maziero MT, Bersot LS (2010) Micotoxinas em alimentos produzidos no Brasil. Revista Brasileira de Produtos Agroindustriais 12:89–99

    Article  Google Scholar 

  • Mol HG, Plaza-Bolaños P, Zomer P, de Rijk TC, Stolker AA, Mulder PP (2008) Toward a generic extraction method for simultaneous determination of pesticides, mycotoxins, plant toxins, and veterinary drugs in feed and food matrixes. Anal Chem 80:9450–9459

    Article  CAS  Google Scholar 

  • Mol HGJ, MacDonald SJ, Anagnostopoulos C, Spanjer M, Bertuzzi T, Pietri A (2016) European survey on sterigmatocystin in cereals, cereals-based products, beer and nuts. World Mycotoxin J 9:633–642

    Article  Google Scholar 

  • Murphy PA, Hendrich S, Landgren C, Bryant CM (2006) Food mycotoxins: an update. J Food Sci 71:51–65

    Article  Google Scholar 

  • Ozden S, Akdeniz AS, Alpertunga B (2012) Occurrence of ochratoxin A in cereal-derived food products commonly consumed in Turkey. Food Control 25:69–74

    Article  CAS  Google Scholar 

  • Peraica M, Radic B, Lucic A, Pavlovic M (1999) Toxic effects of mycotoxins in humans. Bull World Health Organ 77:754–766

    CAS  Google Scholar 

  • Plattner RD (1999) HPLC/MS analysis of fusarium mycotoxins, fumonisins and deoxynivalenol. Nat Toxins 7:365–370

    Article  CAS  Google Scholar 

  • Prandini A, Tansini G, Sigolo S, Filippi L, Laporta M, Piva G (2009) On the occurrence of aflatoxin M1 in milk and dairy products. Food Chem Toxicol 47:984

    Article  CAS  Google Scholar 

  • Ren Y, Zhang Y, Shao S, Cai Z, Feng L, Pan H, Wang Z (2007) Simultaneous determination of multi-component mycotoxin contaminants in foods and feeds by ultra-performance liquid chromatography tandem mass spectrometry. J Chromatogr A 1143:48–64

    Article  CAS  Google Scholar 

  • Righetti L, Paglia G, Galaverna G, Dall’Asta C (2016) Recent advances and future challenges in modified mycotoxin analysis: why HRMS has become a key instrument in food contaminant research. Toxins 8:361

    Article  Google Scholar 

  • Rocha MEB, Freire FCO, Maia FEF, Guedes MIF, Rondina D (2014) Mycotoxins and their effects on human and animal health. Food Control 36:159–165

    Article  Google Scholar 

  • Romagnoli B, Ferrari M, Bergamini C (2010) Simultaneous determination of deoxynivalenol, zearalenone, T-2 and HT-2 toxins in breakfast cereals and baby food by high-performance liquid chromatography and tandem mass spectrometry. J Mass Spectrom 45:1075–1080

    Article  CAS  Google Scholar 

  • Rubert J, Dzuman Z, Vaclavikova M, Zachariasova M, Soler C, Hajslova J (2012a) Analysis of mycotoxins in barley using ultra high liquid chromatography high resolution mass spectrometry: comparison of efficiency and efficacy of different extraction procedures. Talanta 99:712–719

    Article  CAS  Google Scholar 

  • Rubert J, Soler C, Mañes J (2012b) Application of an HPLC–MS/MS method for mycotoxin analysis in commercial baby foods. Food Chem 33:176–183

    Article  Google Scholar 

  • Ryan TA, Joiner BL (1976) Normal probability plots and tests for normality. Pennsylvania State University, The State College

    Google Scholar 

  • Saeger S (2011) Determining mycotoxins and mycotoxigenic fungi in food and feed. Woodhead publishing series in food science, technology and nutrition: number 203. Woodhead Publishing Limited, Cambridge

    Book  Google Scholar 

  • Sartori AV, Mattos JS, Moraes MHP, Nóbrega AW (2015a) Determination of aflatoxins M1, M2, B1, B2, G1, G2 and ochratoxin A in UHT and powdered milk by modified QuEChERS method and ultra-high performance liquid chromatography-tandem mass spectrometry. Food Anal Methods 8:2321–2330

    Article  Google Scholar 

  • Sartori AV, Mattos JS, Souza YP, Santos RP, Moraes MHP, Nóbrega AW (2015b) Determination of aflatoxins M1, M2, B1, B2, G1 and G2 in peanut by modified QuEChERS method and ultra-high performance liquid chromatography-tandem mass spectrometry. Revista Visa em Debate 3:115–121

    Google Scholar 

  • Shotwell OL, Goulden ML, Hesseltine CW (1976) Aflatoxin M1. Occurrence in stored and freshly harvested corn. J Agric Food Chem 24:683–684

    Article  CAS  Google Scholar 

  • Souza SVC, Junqueira RG (2005) A procedure to assess linearity by ordinary least squares method. Anal Chim Acta 552:25–35

    Article  Google Scholar 

  • Sulyok M, Krska R, Schuhmacher RA (2007) Liquid chromatography/tandem mass spectrometric multi-mycotoxin method for the quantification of 87 analytes and its application to semi-quantitative screening of moldy food samples. Anal Bioanal Chem 389:1505–1523

    Article  CAS  Google Scholar 

  • Tam J, Mankotia M, Mably M, Pantazopoulos P, Neil RJ, Calway P, Scott PM (2006) Survey of breakfast and infant cereals for aflatoxins B1, B2, G1 and G2. Food Addit Contam 23:693–699

    Article  CAS  Google Scholar 

  • Tamura 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 27:629–635

    Article  CAS  Google Scholar 

  • Tamura M, Matsumoto K, Watanabe J, Lida J, Nagatomi Y, Mochizuki N (2012) High throughput quantitative analysis of multi-mycotoxin in beer-based drinks using UHPLC-MS/MS. Shimadzu corporation, First edition

  • Tamura M, Matsumoto K, Watanabe J, Iida J, Nagatomi Y, Mochizuki N (2014) Minimization of carryover for high-throughput liquid chromatography with tandem mass spectrometry analysis of 14 mycotoxins in corn grits. J Sep Sci 37:1552–1560

    Article  CAS  Google Scholar 

  • Turner NW, Subrahmanyam S, Piletsky SA (2009) Analytical methods for determination of mycotoxins: a review. Anal Chim Acta 632:168–180

    Article  CAS  Google Scholar 

  • Turner NW, Bramhmbhatt H, Szabo-Vezse M, Poma A, Coker R, Piletsky SA (2015) Analytical methods for determination of mycotoxins: an update (2009-2014). Anal Chim Acta 901:12–33

    Article  CAS  Google Scholar 

  • Vesonder R, Haliburton J, Stubblefield R, Gilmore W, Peterson S (1991) Aspergillus flavus and aflatoxins B1, B2, and M1 in corn associated with equine death. Arch Environ Contam Toxicol 20:151–153

    Article  CAS  Google Scholar 

  • Zachariasova M, Cajka T, Godula M, Malachova A, Veprikova Z, Hajslova J (2010) Analysis of multiple mycotoxins in beer employing (ultra)-high-resolution mass spectrometry. Rapid Commun Mass Spectrom 24:3357–3367

    Article  CAS  Google Scholar 

  • Zain ME (2011) Impact of mycotoxins on humans and animals. J Saudi Chem Soc 15:129–144

    Article  CAS  Google Scholar 

  • Zhang K, Wong JW, Krynitsky AJ, Trucksess MW (2014) Determining mycotoxins in baby foods and animal feeds using stable isotope dilution and liquid chromatography tandem mass spectrometry. J Agric Food Chem 62(36):8935–8943

    Article  CAS  Google Scholar 

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  1. Department of Chemistry, National Institute for Quality Control in Health, Oswaldo Cruz Foundation (INCQS, FIOCRUZ), Av. Brasil 4.365, Manguinhos, Rio de Janeiro, 21.040-900, Brazil

    André Victor Sartori, Maria Heloísa Paulino de Moraes, Rosana Pereira dos Santos, Yuri Pereira Souza & Armi Wanderley da Nóbrega

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  2. Maria Heloísa Paulino de Moraes
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Correspondence to André Victor Sartori.

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André Victor Sartori declares that he has no conflict of interest. Maria Heloísa Paulino de Moraes declares that she has no conflict of interest. Rosana Pereira dos Santos declares that she has no conflict of interest. Yuri Pereira Souza declares that he has no conflict of interest. Armi Wanderley da Nóbrega declares that he has no conflict of interest.

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Sartori, A.V., de Moraes, M.H.P., dos Santos, R.P. et al. Determination of Mycotoxins in Cereal-Based Porridge Destined for Infant Consumption by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry. Food Anal. Methods 10, 4049–4061 (2017). https://doi.org/10.1007/s12161-017-0965-4

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