Development and validation of an analytical method for quantification of formaldehyde content by HPLC in milk
DOI:
https://doi.org/10.18593/evid.32593Keywords:
Formaldehyde, CLAE-DAD, Milk, ANVISA, Analytical ValidationAbstract
Milk is a food constantly subject to fraud, the most frequent being the addition of water, restoratives and preservatives such as formaldehyde (FA), used to inhibit microbial growth, increasing the shelf life of the product. As new adulteration techniques emerge, new fraud detection methods must be developed in order to maintain the quality and authenticity of the milk. The present work aims to develop and validate a method with trace detection sensitivity and a good ability to resist small variations, in order to quantify FA in milk, using the liquid-liquid extraction technique, together with the liquid chromatography method high-efficiency detector with diode array detection (HPLC-DAD) at a wavelength of 360 nm. For method validation, the analytical parameters of linearity, selectivity, specificity, precision, accuracy, detection limit (LDM), method quantification (LQM) and robustness were applied. The method proved to be linear in the working range of 0.03 to 0.1 mg/L, LDM and LQM of 0.004 mg/kg and 0.01 mg/kg, respectively. The evaluated accuracy presented in the range of 88% to 110% of recovery. Precision showed a coefficient of variation (CV) in the range of 1% to 4%, demonstrating to be selective, precise and accurate. Traces of formaldehyde were found in only one sample with a value above the LQ where the concentration found for DNPH-FA was 0.028 mg/kg with a recovery of 93%. Thus, it can be concluded that the method was effective and could contribute to food security.
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References
Behmer MA. Tecnologia do leite. São Paulo: Nobel; 1999.
Universidade de São Paulo. Tabela Brasileira de Composição de Alimentos (TBCA). Food Research Center (FoRC). Versão 7.1. São Paulo; 2020 [citado em 2022 Ago 12]. Disponível em: http://www.fcf.usp.br/tbca
Instituto Brasileiro de Geografia e Estatísticas. Quantidade de leite cru adquirido e industrializado e variação, segundo os meses. Brasil; 2022 [citado em 2023 Maio 20]. Disponível em: https://www.ibge.gov.br/estatisticas/economicas/agricultura-e-pecuaria/9209-pesquisa-trimestral-do-leite.html?edicao=36443&t=resultados
Companhia Nacional de Abastecimento. Análise Mensal. Leite e Derivados. 2023 Mar [citado em 2023 Maio 23]. Disponível em: https://www.conab.gov.br/info-agro/analises-do-mercado-agropecuario-e-extrativista/analises-do-mercado/historico-mensal-de-leite
Nascimento CF, Santos PM, Pereira-Filho ER, Rocha FRP. Recent advances on determination of milk adulterants. Food chemistry. 2017;221:1232-44. DOI: https://doi.org/10.1016/j.foodchem.2016.11.034
Agência Nacional de Vigilância Sanitária. Relatório Estatístico. 2013 Abr [citado em 2023 Maio 23]. Disponível em: http://portal.anvisa.gov.br/documents/111522/2781944/Relat%C3%B3rio+Estat%C3%ADstico+Abril+2013/931ca621-8eb5-4819-b165-eb7a98766368
Instituto Nacional de Câncer. Formol. 2022 [citado em 2023 maio 1]. Disponível em: https://www.gov.br/inca/pt-br/assuntos/causas-e-prevencao-do-cancer/exposicao-no-trabalho-e-no-ambiente/solventes/formol
Costa ALR. Incidência de fraudes, alterações e adulterações em leite cru refrigerado comercializado clandestinamente no norte do Tocantins. [Trabalho de Conclusão de Curso]. Araguaína, TO: Universidade Federal do Norte do Tocantins; 2021 [citado em 2023 Maio 4]. Disponível em: http://repositorio.uft.edu.br/handle/11612/3066
Huaixiang T, Wu D, Chen B, Yuan H, Yu H, Lou X, et al. Rapid identification and quantification of vegetable oil adulteration in raw milk using a flash gas chromatography electronic nose combined with machine learning. Food Control. 2023;150:109758. DOI: https://doi.org/10.1016/j.foodcont.2023.109758
Guerreiro TM, Oliveira DN, Melo CFOR, Oliveira Lima E, Ribeiro MDS, Catharino RR. Evaluating the effects of the adulterants in milk using direct-infusion high-resolution mass spectrometry. Food Res Int. 2018;108:498-504. DOI: https://doi.org/10.1016/j.foodres.2018.03.079
Oliveira SRB, Moraes LDS, Coelho CP. Fraudes em alimentos industrializados. Pubsaúde. 2021;5:115. doi: https://dx.doi.org/10.31533/pubsaude5.a115 DOI: https://doi.org/10.31533/pubsaude5.a115
Balan B, Dhaulaniya AS, Jamwal R, Amit, Sodhi KK, Kelly S, et al. Application of Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy coupled with chemometrics for detection and quantification of formalin in cow milk. Vibrational Spectroscopy. 2020;107:103033. DOI: https://doi.org/10.1016/j.vibspec.2020.103033
European Food Safety Authority. Endogenous formaldehyde turnover in humans compared with exogenous contribution from food sources. EFSA Journal. 2014;12(2):3550. doi: https://doi.org/10.2903/j.efsa.2014.3550 DOI: https://doi.org/10.2903/j.efsa.2014.3550
Brasil. Ministério da Justiça, Ministério da Agricultura, Pecuária e Abastecimento, “Instrução Normativa nº 68, de 12 de dezembro de 2006”. Diário Oficial da República Federativa do Brasil. 2006 Dez 14;(seção 1):8-32.
Association of Official Analytical Chemists. AOAC. Official Method 931.08 Formaldehyde in Food.
Khalil SR, Awad A, Ali SA. Melamine and/or formaldehyde exposures affect steroidogenesis via alteration of StAR protein and testosterone synthetic enzyme expression in male mice. Environmental toxicology and pharmacology. 2017;50:36-144. DOI: https://doi.org/10.1016/j.etap.2017.01.018
Wanderley CH, Silva ACO, Silva FER, Mársico ETM, Conte Junior CA. Avaliação da sensibilidade de métodos analíticos para verificar fraude em leite fluido. Revista de Ciências da Vida. 2013;33(1/2):54-63.
Faria IDL, Gouvêa MM, Netto ADP, Marques FFC. Determination of formaldehyde in bovine milk by micellar electrokinetic chromatography with diode array detection. LWT – Food Science and Technology. 2022:163:113473. DOI: https://doi.org/10.1016/j.lwt.2022.113473
Kochetkova M, Timofeeva I, Bulatov A. A derivatization and microextraction procedure with organic phase solidification on a paper template:Spectrofluorometric determination of formaldehyde in milk. Spectrochimica Acta, Part A:Molecular and Biomolecular Spectroscopy (SAA). 2021;263:120160. DOI: https://doi.org/10.1016/j.saa.2021.120160
Giokas DL, Tsogas GZ, Vlessidis AG. On-line derivatization coupled to flow injection permanganate chemiluminescence detection of total carbonyl compounds in natural waters and drinking water. Analytica Chimica Acta. 2009;651(2):188-95. DOI: https://doi.org/10.1016/j.aca.2009.08.028
Pillai AKKV, Gautam K, Jain A, Verma KK. Headspace in-drop derivatization of carbonyl compounds for their analysis by high-performance liquid chromatography-diode array detection. Analytica Chimica Acta. 2009;632:208-15. doi: http://doi.org/10.1016/j.aca.2008.11.021 DOI: https://doi.org/10.1016/j.aca.2008.11.021
Vairavamurthy A, Roberts JM, Newman L. Methods for determination of low molecular weight carbonyl compounds in the atmosphere:a review. Atmos. Environ. Part A, Gen. Top. 1992;26(11):1965-93. DOI: https://doi.org/10.1016/0960-1686(92)90083-W
Instituto Nacional de Metrologia. DOQ-CGCRE-008:2016 Orientação sobre Validação de Métodos Analíticos. Revisão 05; 2011.
Agência Nacional de Vigilância Sanitária. 2017 [citado em 2023 Maio 23]. Disponível em: http://portal.anvisa.gov.br/documents/10181/2721567/RDC166_2017_COMP.pdf/d5fb92b3-6c6b-4130-8670-4e3263763401
Kaminski J, Atwal AS, Mahadevan S. High Performance Liquid Chromatographic Determination of Formaldehyde in Milk. Journal of Liquid Chromatography. 1993;16 (2):521-26, doi: https://dor.org/10.1080/10826079308020929 DOI: https://doi.org/10.1080/10826079308020929
Rezende FBF, Cheibub AMSS, Netto ADP, Marques FFC. Determination of formaldehyde in bovine milk using a high sensitivity HPLC-UV method. Microchemical Journal. 2017;134:383-89. DOI: https://doi.org/10.1016/j.microc.2017.07.003
National Association of Testing Authorities. Guidelines for the validation and verification of quantitative and qualitative test methods. Technical Note 17. Australia; 2013.
Codex Alimentarius Comission. Guidelines for the design and implementation 75 of national regulatory food safety assurance programme associated with the use of veterinary drugs in food producing animals. GL, 2009;71:16. (Revised in 2012).
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