Abstract
Interlaboratory validation procedures were proposed and performed to confirm the effectiveness of modified classical qualitative methods for the detection of adulterants in milk, including starch, chloride, and sucrose, which were previously validated by a single laboratory approach. Raw milk samples that were adulterated with 150 g L−1 of water and 0.0, 0.3, 0.8, and 1.2 g L−1 of starch, 0, 1.5, 2.0, and 2.5 g L−1 of chlorides, and 0.0, 2.4, 3.0, and 3.6 g L−1 of sucrose were sent to 10 collaborators in Brazil that represent the government, food control, food industry, and university affiliations. Reliability rates of 93 to 100, 98 to 100, and 99 to 100 % were obtained for the starch, chlorides, and sucrose methods, respectively. The prediction intervals for the probability of detection proved the sensitivity and selectivity of the methods. Concordance values were greater than 0.85 to starch, 0.98 to chlorides, and 0.99 to sucrose, indicating precision and that the procedures were properly standardized between the collaborators. The estimated detection limits and unreliability regions confirmed the fitness of the modified methods for their respective purposes.
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Interlaboratory validation of modified classical qualitative methods for detection of adulterants in milk
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References
Almeida MR, Oliveira KS, Stephani R, Oliveira LFC (2012) Application of FT-raman spectroscopy and chemometric analysis for determination of adulteration in milk powder. Anal Lett 45:2589–2602
AOAC (Association of Official Analytical Chemists) (2002) AOAC Official methods of analysis. Appendix D: guidelines for collaborative study procedures to validate characteristics of a method of analysis. Washington: AOAC, 2002
Botelho BG, Reis N, Oliveira LR, Sena MM (2015) Development and analytical validation of a screening method for simultaneous detection of five adulterants in raw milk using mid-infrared spectroscopy and PLS-DA. Food Chem 181:31–37
Brasil – Ministério da Agricultura, Pecuária e Abastecimento (2006) Instrução Normativa n° 68 de 12 de dezembro de 2006. Accessed on April 2015. Available in www.agricultura.gov.br
Brasil – Ministério da Agricultura, Pecuária e Abastecimento (2011) Instrução Normativa n° 62 de 29 de dezembro de 2011. Accessed on April 2015. Available in www.agricultura.gov.br
Capuano E, Boerrigter-Eenling R, Koot A, Ruth S (2015) Targeted and untargeted detection of skim milk powder adulteration by near-infrared spectroscopy. Food Anal Methods 8:2125–2134
Cardenas S, Valcarcel M (2005) Analytical features in qualitative analysis. Trends Anal Chem 24:477–87
Das S, Sivaramakrishnaa M, Biswasb K, Goswam B (2011) Performance study of a ‘constant phase angle based’ impedance sensor to detect milk adulteration. Sens Actuators A 167:273–278
Ellis DI, Brewster VL, Dunn WB, Allwood JW, Golovanov AP, Goodacre R (2012) Fingerprinting food: current technologies for the detection of food adulteration and contamination. Chem Soc Rev 41:5706–5727
Ellison SLR, Fearn T (2005) Characterising the performance of qualitative analytical methods: statistics and terminology. Trends Anal Chem 24:468–476
Ginn R, Wilson L, Souza SVC, Calle MB, Barbosa J, Berendsen B, Bockborn I, Brandtner M, Delahaut P, Doering T, Fuerst P, Griffin C, Gude T, Janosi A, Jaus A, Kennedy G, Mandix M, Hilla EM, Plonevez S, Posyniak A, Saari L, Bruijnsvoort M, Verdon E, Wohlfarth R (2006) Determination of semicarbazide in baby food by liquid chromatography/tandem mass spectrometry: interlaboratory validation study. J AOAC Int 89:728–734
Gondim CS, Coelho OAM, Alvarenga RL, Junqueira RG, Souza SVC (2014) An appropriate and systematized procedure for validating qualitative methods: Its application in the detection of sulfonamide residues in raw milk. Anal Chim Acta 830:11–22
Gondim CS, Souza RCS, Palhares MPP, Junqueira RG, Souza SVC (2015) Performance improvement and single laboratory validation of classical qualitative methods for the detection of adulterants in milk: starch, chlorides and sucrose. Anal Methods 7:9692–9701
India - Ministry of Health and Family Welfare of India (2005) Manual of Methods of Analysis of Foods - Milk and Milk Products
Jawaid S, Talpur FN, Afridi HI, Nizamani SM, Khaskheli AA, Naz S (2014) Quick determination of melamine in infant powder and liquid milk by Fourier transform infrared spectroscopy. Anal Methods 6:5269–5273
Karoui R, De Baerdemaeker J (2007) A review of the analytical methods coupled with chemometric tools for the determination of the quality and identity of dairy products. Food Chem 102:621–640
Kartheek M, Smith AA, Muthu AK, Manavalan R (2011) Determination of adulterants in food: a review. J Chem Pharm Res 3:629–636
Langton SD, Chevennement R, Nagelkeke N, Lombard B (2002) Analysing collaborative trials for qualitative microbiological methods: accordance and concordance. Int J Food Microbiol 79:171–181
Liu J, Ren J, Liu ZM, Guo BH (2015) A new comprehensive index for discriminating adulteration in bovine raw milk. Food Chem 172:251–256
Lima RMJ, Fernandes SMV, Rangel AOSS (2004) Enzymatic determination of urea in milk by sequential injection with spectrophotometric and conductometric detection. J Agric Food Chem 52:6887–6890
López MI, Colomer N, Ruisánchez I, Callao MP (2014) Validation of multivariate screening methodology. Case study: detection of food fraud. Anal Chim Acta 827:28–33
López MI, Callao MP, Ruisánchez I (2015) A tutorial on the validation of qualitative methods: from the univariate to the multivariate approach. Anal Chim Acta 891:62–72
Macarthur R, Holst C (2012) A protocol for the validation of qualitative methods of detection. Anal Methods 4:2744–2754
NATA (National Association of Testing Authorities – Australia) (2013) Technical Note 17 – October 2013 - Guidelines for the validation and verification of quantitative and qualitative test methods. Accessed on January 2016. Available in http://www.nata.com.au/nata/phocadownload/publications/Guidance_information/tech-notes-information-papers/technical_note_17.pdf
Nigam A, Ayyagari A (2007) Laboratory manual in biochemistry: immunology and biotechnology. Tata McGraw-Hill, New Delhi
Rani R, Medhe S, Raj KR, Srivastava MM (2012) High performance thin layer chromatography for routine monitoring of adulterants in milk. Natl Acad Sci Lett 35:309–313
Renny EF, Daniel DK, Krastanov AI, Zachariah CA, Elizabeth R (2005) Enzyme based sensor for detection of urea in milk. Biotechnol Biotechnol Equip 19:198–201
Santos PM, Wentzell PD, Pereira-Filho ER (2012) Scanner digital images combined with color parameters: a case study to detect adulterations in liquid cow’s milk. Food Anal Method 5:89–95
Santos PM, Pereira-Filho ER (2013) Digital image analysis—an alternative tool for monitoring milk authenticity. Anal Methods 5:3669–3674
Scampicchio M, Eisenstecken D, De Benedictis L, Capici C, Ballabio D, Mimmo T, Robatscher P, Kerschbaumer L, Oberhuber M, Kaser A, Huck C, Cesco S (2015) Multimethod approach to trace the geographical origin of alpine milk: a case study of Tyrol region. Food Anal Chem. doi:10.1007/s12161-015-0308-2
Silva RAB, Montes RHO, Richter EM, Munoz RAA (2012) Rapid and selective determination of hydrogen peroxide residues in milk by batch injection analysis with amperometric detection. Food Chem 133:200–204
Silva LCCD (2013) Capacidade de detecção de adulterantes e suficiência das provas oficiais para assegurar a qualidade do leite pasteurizado. PhD Thesis, Universidade Estadual de Londrina. Accessed on January 2016. Available in https://www.lume.ufrgs.br/bitstream/handle/10183/81561/000905445.pdf?sequence=1
Souza SS, Cruz AG, Walter EHM, Faria JJF, Celeghini RMS, Ferreira MMC, Granato D, Santana AS (2011) Monitoring the authenticity of Brazilian UHT milk: a chemometric approach. Food Chem 124:692–695
Thompson M, Ellison SLR, Wood R (2006) The international harmonized protocol for the proficiency testing of analytical chemistry laboratories. Pure Appl Chem 78:145–196
Tronco VM (2010) Manual para inspeção da qualidade do leite. Editora da UFSM, Santa Maria
Trullols E, Ruisánchez I, Rius FX (2004) Validation of qualitative methods of analysis that use control samples. Trend Anal Chem 23:137–145
Van der Voet H, Van Rhijn JA, Van de Wiel HJ (1999) Inter-laboratory, time, and fitness-for-purpose aspects of effective validation. Anal Chim Acta 391:159–171
Veloso ACA, Teixeira N, Ferreira IMPLVO, Ferreira MA (2002) Detecção de adulterações em produtos alimentares contendo leite e/ou proteínas lácteas. Quim Nov. 25:609–615
Ward JH (1963) Hierarchical grouping to optimize an objective function. J Am Stat Assoc 58:236–244
Zang LG, Zang X, Ni LJ, Xue ZB, Gu X, Huang SX (2014) Rapid identification of adulterated cow milk by non-linear pattern recognition methods based on near infrared spectroscopy. Food Chem 145:342–348
Acknowledgments
The authors acknowledge the experimental farm of “Professor Hélio Barbosa” of the Veterinary School/Federal University of Minas Gerais State (EV/UFMG) for allowing the use of their facilities and animals during this project and for providing the raw cow milk samples. We acknowledge Pedro Paulo Borges Santos for his analytical assistance and the Brazilian agency “Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)” for financial support. The authors also express their appreciation to the collaborators for their participation in the study: GMO Centro de Pesquisas e Controle de Qualidade Ltda.; Hidrocepe Servicos de Qualidade Ltda. Epp; Ita Alimentos—Laticínios Ita Indústria e Comércio de Alimentos Ltda.; Itambé Alimentos S.A.; Laboratório de Análise Físico-Química em Alimentos do Laboratório de Química Agropecuária do Instituto Mineiro de Agropecuária (LAFQ/LQA/IMA); Laboratório de Química Bromatológica da Fundação Ezequiel Dias (FUNED); Laboratório Nacional Agropecuário de Minas Gerais do Ministério da Agricultura, Pecuária e Abastecimento (LANAGRO-MG/MAPA); Laboratório de Bromatologia—Unidade de Pesquisa Análise de Alimentos da Faculdade de Farmácia da Universidade Federal de Minas Gerais (BRO-UPAA/FAFAR/UFMG); NUGAP—Núcleo Global de Análise e Pesquisa Ltda.; and Trevo Alimentos—Nogueira e Rezende Indústria de Laticínio Ltda.
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Carina de Souza Gondim declares that she has no conflict of interest. Roberto Gonçalves Junqueira declares that he has no conflict of interest. Scheilla Vitorino Carvalho de Souza declares that she has no conflict of interest.
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de Souza Gondim, C., Gonçalves Junqueira, R. & Vitorino Carvalho de Souza, S. Interlaboratory Validation of Modified Classical Qualitative Methods for Detection of Adulterants in Milk: Starch, Chloride, and Sucrose. Food Anal. Methods 9, 2509–2520 (2016). https://doi.org/10.1007/s12161-016-0432-7
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DOI: https://doi.org/10.1007/s12161-016-0432-7