Research of the determination method of furfurals and furosine in milk and the application in the quality evaluation of milk

Main Article Content

Xiaomei Shi
Qiong Wu
Dandan Ren
Shuya Wang
Yunfeng Xie

Keywords

5-hydroxymethyl-2-furfural, furosine, GC-MS, milk, heat process, sterilization

Abstract

The heat treatment process usually affects the quality and safety of milk and could produce different compounds, including furosine and furfurals. To help evaluate the effect of different heating temperatures on furfurals, a method based on gas chromatography-mass spectrometry (GC-MS) combined with QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction technology was used to detect four furfural compounds, including furfural, 2-acetylfuran, 5-methyl-2-furfural, and 5-hydroxymethyl-2-furfural. A sample extraction was performed with acetonitrile, and the use of both octadecylsilyl (C18) and primary secondary amine (PSA) sorbents can provide satisfactory recoveries. The determination of furosine was performed by using a high performance of liquid chromatography method (HPLC), and the milk samples were hydrolyzed with HCl for 18 h at 110°C. Under the optimized conditions, good linearity was obtained with linear correlation coefficients (R2) above 0.99, and the recovery values from the spiked samples were 88.1–109.5%. The limits of detection were in the range of 0.005 mg/kg–0.015 mg/kg. The established GC-MS and HPLC methods were successfully applied to market milk samples and heat-treatment samples. The highest detection values for 5-hydroxymethyl-2-furfural and furosine were 0.051 mg/kg and 593.2 mg/100 g protein, respectively, in charcoal-flavored fermented milk. It showed a high correlation between the formation of 5-hydroxymethyl-2-furfural with the treatment temperature and time, and the maximum content was 0.886 mg/kg after heating for 180 min at 100°C. However, there was no noticeable linear increase of furosine concentrations when certain temperatures and heating times were reached; the maximum value was 55.0 mg/L after heating for 60 min at 100°C, and 55.4 mg/L after heating for 150 min at 80°C.

Abstract 913 | PDF Downloads 647 HTML Downloads 515 XML Downloads 142

References

Abraham, K., Gürtler, R., Berg, K., Heinemeyer, G., Lampen, A. and Appel, K.E., 2011. Toxicology and risk assessment of 5-Hydroxymethyl furfural in food. Molecular Nutrition & Food Research 55: 667–678. 10.1002/mnfr.201000564

Ahmadian-Kouchaksaraei, Z., Varidi, M., Javad Varidi, M. and Pourazarang, H., 2015. Study of stability characteristics of sesame milk: effect of pasteurization temperature, additives, and homogenisation pressure. Quality Assurance and Safety of Crops & Foods 7(5): 677–686. 10.3920/QAS2014.0465

Bignardi, C., Cavazza, A. and Corradini, C., 2012. Determination of furosine in food products by capillary zone electrophoresis-tandem mass spectrometry. Electrophoresis 33: 2382–2389. 10.1002/elps.201100582

Cattaneo, S., Masotti, F. and Pellegrino, L., 2008. Effects of overprocessing on heat damage of UHT milk. European Food Research and Technology 226: 1099–1106. 10.1007/s00217-007-0637-5

Chavez-Servin, J.L., Carbot, K., Garcia-Gasca, T., Castellote, A. and Lopez-Sabater, M.C., 2015. Content and evolution of potential furfural compounds in commercial milk-based infant formula powder after opening the packet. Food Chemistry 166: 486–491. 10.1016/j.foodchem.2014.06.050

Chávez-Servín, J.L., Castellote, A.I. and López-Sabater, M.C., 2006. Evolution of potential and free furfural compounds in milk-based infant formula during storage. Food Research International 39: 536–543. 10.1016/j.foodres.2005.10.012

Cho, Y.H., Hong, S.M. and Kim, C.H., 2012. Determination of lactulose and furosine formation in heated milk as a milk quality indicator. Food Science of Animal Resources 32: 540–544. 10.5851/kosfa.2012.32.5.540

Cortés Yáñez, D.A., Gagneten, M., Leiva, G.E. and Malec, L.S., 2018. Antioxidant activity developed at the different stages of Maillard reaction with milk proteins. LWT–Food Science and Technology 89: 344–349. 10.1016/j.lwt.2017.11.002

Cui, Y.Y., Shi, X.M., Tang, Y., Xie, Y.F. and Du, Z.X., 2020. The effects of heat treatment and fermentation processes on the formation of furfurals in milk-based dairy products using a QuEChERS technique followed by gas chromatography coupled with triple quadrupole mass spectrometry. Food Chemistry 313: 125930. 10.1016/j.foodchem.2019.125930

Delgado-Andrade, C., Rufian-Henares, J.A. and Morales, F.J., 2005. Fast method to determine furosine in breakfast cereals by capillary zone electrophoresis. European Food Research and Technology 221: 707–711. 10.1007/s00217-005-0030-1

Ferrer, E., Alegria, A., Farre, R., Abellán, P. and Romero, F., 2005. High-performance liquid chromatographic determination of furfural compounds in infant formulas during full shelf-life. Food Chemistry 89: 639–645. 10.1016/j.foodchem.2004.05.040

Ferrer, E., Alegria, A., Farre, R., Abellán, P., Romero, F. and Clemente, G., 2003. Evolution of available lysine and furosine contents in milk-based infant formulas throughout the shelf-life storage period. Journal of the Science of Food and Agriculture 83: 465–472. 10.1002/jsfa.1402

Gaspar, E.M.S.M. and Lopes, J.F., 2009. Simple gas chromatographic method for furfural analysis. Journal of Chromatography A 1216: 2762–2767. 10.1016/j.chroma.2008.10.049

Giovanelli, G. and Cappa, C., 2021. 5-Hydroxymethyl furfural formation in bread as a function of heat treatment intensity: correlations with browning indices. Foods 10: 417. 10.3390/foods10020417

Gokmen, V. and Senyuva, H.Z., 2006. Improved method for the determination of hydroxymethyl furfural in baby foods using liquid chromatography-mass spectrometry. Journal of Agricultural and Food Chemistry 54: 2845–2849. 10.1021/jf053091y

Gómez-Narváez, F., Medina-Pineda, Y. and Contreras-Calderón, J., 2017. Evaluation of the heat damage of whey and whey proteins using multivariate analysis. Food Research International 102: 768–775. 10.1016/j.foodres.2017.09.074

Kalal, H.S., Mahani, M.K., Maragheh, M.G. and Chaloosi, M., 2007. HPLC determination of furfural after preliminary extraction to aqueous phase. Journal of Liquid Chromatography & Related Technologies 30: 2081–2093. 10.1080/10826070701435087

Lan, X.Y., Wang, J.Q., Bu, D.P., Shen, J.S., Zheng, N. and Sun, P., 2010. Effects of heating temperatures and addition of reconstituted milk on the heat indicators in milk. Journal of Food Science 75: 653–658. 10.1111/j.1750-3841.2010.01802.x

Li, Y., Wu, Y.R., Quan, W., Jia, X.D., He, Z.Y., Wang, Z.J., Adhikari, B., Chen, J. and Zeng, M.M., 2021. Quantitation of furosine, furfurals, and advanced glycation end products in milk treated with pasteurization and sterilization methods applicable in China. Food Research International 140(10): 110088. 10.1016/j.foodres.2020.110088

Liu, H.T., Huang, R.M., Zeng, G.F., Xu, Z.L., Sun, Y.M., Lei, H.T., Sheng, Y.D., Wang, H.M., Xu, B.J. and Wei, X.Q., 2020. Discrimination of reconstituted milk in China market using the content ratio of lactulose to furosine as a marker determined by LC-MS/MS. LWT 117: 108648. 10.1016/j.lwt.2019.108648

Masoumeh, M.T., Marzieh, K. and Abdorreza, M., 2015. Determination of furfural and hydroxymethyl furfural from baby formula using dispersive liquid–liquid microextraction coupled with high performance liquid chromatography and method optimization by response surface methodology. Journal of Food Composition and Analysis 40: 1–7. 10.1016/j.jfca.2014.12.004

Mayer, H.K., Raba, B., Meier, J. and Schmid, A., 2010. RP-HPLC analysis of furosine and acid-soluble beta-lactoglobulin to assess the heat load of extended shelf life milk samples in Austria. Dairy Science & Technology 90: 413–428. 10.1051/dst/2009058

Mesías-García, M., Guerra-Hernandez, E. and García-Villanova, B., 2010. Determination of furan precursors and some thermal damage markers in baby foods: ascorbic acid, dehydroascorbic acid, hydroxyl methyl furfural and furfural. Journal of Agricultural and Food Chemistry 58: 6027–6032. 10.1021/jf100649z

Pérez-Burillo, S., Jiménez-Zamora, A., Párragab, J., Rufián-Henares, J.A. and Pastoriza, S., 2019. Furosine and 5-hydroxymethyl furfural as chemical markers of tea processing and storage. Food Control 99: 73–78. 10.1016/j.foodcont.2018.12.029

Piñeiro-García, A., González-Alatorre, G., Tristan, F., Fierro-Gonzalez, J.C. and Vega-Díaz, S.M., 2018. Simple preparation of reduced graphene oxide coatings for solid phase micro-extraction (SPME) of furfural to be detected by gas chromatography/mass spectrometry. Materials Chemistry and Physics 213: 556–561. 10.1016/j.matchemphys.2018.04.057

Poojary, M.M., Zhang, W., Greco, I., Gobba, C.D., Olsen, K. and Lund, M.N., 2019. Liquid chromatography quadrupole-Orbitrap mass spectrometry for the simultaneous analysis of advanced glycation end products and protein-derived cross-links in food and biological matrices. Journal of Chromatography A 1615: 460767. 10.1016/j.chroma.2019.460767

Rada-Mendoza, M., Sanz, M.L., Olano, A. and Villamiel, M., 2004. Formation of hydroxymethyl furfural and furosine during the storage of jams and fruit-based infant foods. Food Chemistry 85: 605–609. 10.1016/j.foodchem.2003.07.002

Sabater, C., Montilla, A., Ovejero, A., Prodanov, M., Olano, A. and Corzo, N., 2018. Furosine and HMF determination in prebiotic-supplemented infant formula from Spanish market. Journal of Food Composition and Analysis 66: 65–73. 10.1016/j.jfca.2017.12.004

Sakkas, L., Moutafi, A., Moschopoulou, E. and Moatsou, G., 2014. Assessment of heat treatment of various types of milk. Food Chemistry 159: 293–301. 10.1016/j.foodchem.2014.03.020

Sun, Y., Guan, Z.B., Cai, H.W., Huang, Y.Y., Lin, Y.W. and Hu, X.S., 2017. Highly sensitive method for aldehydes detection: application to furfurals analysis in raisin and bovine milk powder. Analytica Chimica Acta 987: 47–55. 10.1016/j.aca.2017.08.032

Sunds, A.V., Rauh, V.M., Sørensen, J. and Larsen, L.B., 2018. Maillard reaction progress in UHT milk during storage at different temperature levels and cycles. International Dairy Journal 77: 56–64. 10.1016/j.idairyj.2017.08.008

Teixidó, E., Santos, F.J., Puignou, L. and Galceran, M.T., 2006. Analysis of 5-hydroxymethyl furfural in foods by gas chromatography-mass spectrometry. Journal of chromatography A 1135: 85–90. 10.1016/j.chroma.2006.09.023

Tokusoglu, O., Akalin, A.S. and Unal, K., 2006. Rapid high performance liquid chromatographic detection of furosine (ε-N-2-furoylmethyl L-lysine) in yogurt and cheese marketed in turkey. Journal of food quality 29: 38–46. 10.1111/j.1745-4557.2006.00054.x

Truzzi, C., Annibaldi, A., Illuminati, S., Finale, C., Rossetti, M. and Scarponi, G., 2012. Determination of very low levels of 5-(Hydroxymethyl)-2-furaldehyde (HMF) in natural honey: comparison between the HPLC technique and the spectrophotometric white method. Journal of Food Science 77: C784–C790. 10.1111/j.1750-3841.2012.02782.x

Wang, H., Yang, J., Yang, M. and Ji, W., 2019. Antioxidant activity of Maillard reaction products from a Yak casein-glucose model system. International Dairy Journal 91: 55–63. 10.1016/j.idairyj.2018.12.010

Wherry, B.M., Jo, Y. and Drake, M.A., 2019. Concentration of furfuryl alcohol in fluid milk, dried dairy ingredients, and cultured dairy products. Journal of Dairy Science 102: 3868–3878. 10.3168/jds.2018-15714

Xing, Q.Q., Fu, X.F., Liu, Z.M., Cao, Q. and You, C.P., 2021. Contents and evolution of potential furfural compounds in milk-based formula, ultra-high temperature milk and pasteurised yoghurt. International Dairy Journal 120: 105086. 10.1016/j.idairyj

Yang, L., Liu, Y.H. and Ruan, R.S., 2012. Rapid determination of 5-hydroxymethyl furfural by ultraviolet spectrophotometry in glucose diphasic hydrolysate. Advanced Materials Research 361–363: 1713–1717. 10.4028/www.scientific.net/AMR.361-363.1713

Zhang, Y.M., Yi, S.N., Lu, J., Pang, X.Y., Xu, X.X., Lv, J.P. and Zhang, S.W., 2021. Effect of different heat treatments on the Maillard reaction products, volatile compounds and glycation level of milk. International Dairy Journal 123: 105182. 10.1016/j.idairyj.2021.105182