LC-GCxGC-FID; Mineral oil aromatic hydrocarbons (MOAH); deodorization; fats; refining; Health, Toxicology and Mutagenesis; Public Health, Environmental and Occupational Health; Toxicology; General Chemistry; General Medicine; Food Science
Abstract :
[en] The goal of this work was to investigate the impact of refining on coconut oil particularly on the most toxicologically relevant fraction of the mineral oil aromatic hydrocarbon (MOAH) contamination, namely the fraction composed by the three to seven aromatic rings. A fully integrated platform consisting of a liquid chromatography (LC), a comprehensive multidimensional gas chromatography (GC) (LC-GC × GC) and flame ionization detector (FID) was used to obtained a more detailed characterization of the MOAH sub-classes distribution. The revised EN pr 16995:2017-08 official method was used for preparing the samples, both with and without the auxiliary epoxidation step. Crude coconut oil was spiked with different MOAH standards, namely naphthalenes, alkylated naphthalenes, benzo(a)pyrene, and its alkylated homologues. Refining was modelled by deodorization at 230 °C, stripping with 10 kg/h of steam under 1 mbar vacuum for 3 h. Complete removal of the naphthalenes and reduction of more than 98.8% of the benzo(a)pyrenes was observed. Epoxidation had a significant impact on the MOAH fraction with more than three rings, but with a high dependency on the sample matrix, being significantly less evident in the refined samples than in the crude ones.
Disciplines :
Chemistry
Author, co-author :
Bauwens, Grégory ; Université de Liège - ULiège > TERRA Research Centre
Cavaco Soares, Alexandre; ITERG, Canejan, France
Lacoste, Florence; ITERG, Canejan, France
Ribera, Daniel; Cargill R&D Center, Vivoorde, Belgium
Blomsma, Coen; VERNOF, Association of the Dutch manufacturers of edible oils and fats, Zoetermeer, The Netherlands
Berg, Iekje; Sime Darby Oils, Zwijndrecht, The Netherlands
Albert C, Humpf HU, Brühl L. 2022. Determining mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) with high sensitivity in vegetable oil a new, reliable, and comparable approach using online LC-GC-FID evaluation of method precision data. J Agric Food Chem. 70 (33): 10337–10348. doi: 10.1021/acs.jafc.2c01189
Arcella D, Baert K, Binaglia M. 2019. Rapid risk assessment on the possible risk for public health due to the contamination of infant formula and follow‐on formula by mineral oil aromatic hydrocarbons (MOAH). European food Safety authority (EFSA) Support Publ. 16 (11):18. doi: 10.2903/sp.efsa.2019.en-1741
Barp L, Biedermann M, Grob K, Blas-Y-Estrada F, Nygaard UC, Alexander J, Cravedi JP. 2017a. Mineral oil saturated hydrocarbons (MOSH) in female Fischer 344 rats; accumulation of wax components; implications for risk assessment. Sci Total Environ. 583: 319–333. doi: 10.1016/j.scitotenv.2017.01.071
Barp L, Biedermann M, Grob K, Blas-Y-Estrada F, Nygaard UC, Alexander J, Cravedi JP. 2017b. Accumulation of mineral oil saturated hydrocarbons (MOSH) in female Fischer 344 rats: comparison with human data and consequences for risk assessment. Sci Total Environ. 575: 1263–1278. doi: 10.1016/j.scitotenv.2016.09.203
Barp L, Kornauth C, Wuerger T, Rudas M, Biedermann M, Reiner A, Concin N, Grob K. 2014. Mineral oil in human tissues, part I: concentrations and molecular mass distributions. Food Chem Toxicol. 72: 312–321. doi: 10.1016/j.fct.2014.04.029
Barp L, Purcaro G, Moret S, Conte LS. 2013. A high-sample-throughput LC-GC method for mineral oil determination. J Sep Sci. 36 (18): 3135–3139. doi: 10.1002/jssc.201300114
Bauwens G, Barp L, Purcaro G. 2023. Validation of the liquid chromatography-comprehensive multidimensional gas chromatography-time-of-flight mass spectrometer/flame ionization detector platform for mineral oil analysis exploiting interlaboratory comparison data. Green Anal Chem. 4 (2023): 100047. doi: 10.1016/j.greeac.2022.100047
Bauwens G, Conchione C, Sdrigotti N, Moret S, Purcaro G. 2022. Quantification and characterization of mineral oil in fish feed by liquid chromatography-gas chromatography-flame ionization detector and liquid chromatography-comprehensive multidimensional gas chromatography-time-of-flight mass spectrometer/flame ioni. J Chromatogr A. 1677: 463208. doi: 10.1016/j.chroma.2022.463208
Bauwens G, Pantó S, Purcaro G. 2021. Mineral oil saturated and aromatic hydrocarbons quantification: mono- and two-dimensional approaches. J Chromatogr A. 1643: 462044. doi: 10.1016/j.chroma.2021.462044
Biedermann M, Barp L, Kornauth C, Würger T, Rudas M, Reiner A, Concin N, Grob K. 2015. Mineral oil in human tissues, part II: characterization of the accumulated hydrocarbons by comprehensive two-dimensional gas chromatography. Sci Total Environ. 506–507: 644–655. doi: 10.1016/j.scitotenv.2014.07.038
Biedermann M, Fiselier K, Grob K. 2009. Aromatic hydrocarbons of mineral oil origin in foods: method for determining the total concentration and first result. J Agric Food Chem. 57 (19): 8711–8721. doi: 10.1021/jf901375e
Biedermann M, Grob K. 2010. Is recycled newspaper suitable for food contact materials? Technical grade mineral oils from printing inks. Eur Food Res Technol. 230 (5): 785–796. doi: 10.1007/s00217-010-1223-9
Biedermann M, Munoz C, Grob K. 2017. Update of on-line coupled liquid chromatography–gas chromatography for the analysis of mineral oil hydrocarbons in foods and cosmetics. J Chromatogr A. 1521: 140–149. doi: 10.1016/j.chroma.2017.09.028
Biedermann M, Munoz C, Grob K. 2020. Epoxidation for the analysis of the mineral oil aromatic hydrocarbons in food. An update. J Chromatogr A. 1624: 461236. doi: 10.1016/j.chroma.2020.461236
BLL- The German Federation of Food Law and Food Science. n.d. Toolbox for preventing the transfer of undesired mineral oil hydrocarbons into food. https://www.lebensmittelverband.de/de/lebensmittel/verpackung/mineraloeluebergaenge/toolbox-vermeidung-mosh-moah.
Boogaard PJ, Goyak KO, Biles RW, van Stee LLP, Miller MS, Miller MJ. 2012. Comparative toxicokinetics of low-viscosity mineral oil in Fischer 344 rats, Sprague-Dawley rats, and humans - Implications for an Acceptable Daily Intake (ADI). Regul Toxicol Pharmacol. 63 (1): 69–77. doi: 10.1016/j.yrtph.2012.02.014
Bratinova S, Hoekstra E. 2019. Guidance on sampling, analysis and data reporting for the monitoring of mineral oil hydrocarbons in food and food contact materials. Luxembourg: Publications Office of the European Union. doi: 10.2760/208879
Cravedi J, Grob K, Nygaard UC, Alexander J. 2017. Bioaccumulation and toxicity of mineral oil hydrocarbons in rats ‐ specificity of different subclasses of a broad mixture relevant for human dietary exposures. European Food Safety Authority (EFSA) Support Publ. 14 (2): 1090E. doi: 10.2903/sp.efsa.2017.en-1090
DG SANTE. 2022. Mineral oil hydrocarbons in food: follow-up to the December 2021 Foodwatch report. https://ec.europa.eu/info/strategy/priorities-2019-2024/stronger-europe-world/eu-solidarity-ukraine/eu-sanctions-against-russia-following-invasion-ukraine_ru#relatedlinks
[EC] European Commission. 2011. Commission Regulation (EU) No 835/2011 of 19 August 2011. Off J Eur Union. L 215 (835): 4–8.
[EC] European Commission. 2017. Commission Recommendation (EU) 2017/84 of 16 January 2017 on the monitoring of mineral oil hydrocarbons in food and in materials and articles intended to come into contact with food. Off J Eur Union. L12 (84): 95–96.
[EFSA] European Food Safety Authorithy. 2012. Scientific opinion on mineral oil hydrocarbons in food. EFSA J. 10: 1–185. doi: 10.2903/j.efsa.2012.2704
Griffis LC, Twerdok LE, Francke-Carroll S, Biles RW, Schroeder RE, Bolte H, Faust H, Hall WC, Rojko J. 2010. Comparative 90-day dietary study of paraffin wax in Fischer-344 and Sprague-Dawley rats. Food Chem Toxicol. 48 (1): 363–372. doi: 10.1016/j.fct.2009.10.024
Grob K. 2008. Could the Ukrainian sunflower oil contaminated with mineral oil wake up sleeping dogs? Eur J Lipid Sci Technol. 110 (11): 979–981. doi: 10.1002/ejlt.200800234
Grob K, Artho A, Biedermann M, Egli J. 1991. Food Contamination by hydrocarbons from lubricating oils and release agents: determination by coupled LC-GC. Food Addit Contam. 8 (4): 437–446. doi: 10.1080/02652039109373993
Hochegger A, Moret S, Geurts L, Gude T, Leitner E, Mertens B, O'Hagan S, Poças F, Simat TJ, Purcaro G. 2021. Mineral oil risk assessment: knowledge gaps and roadmap. Outcome of a multi-stakeholders workshop. Trends Food Sci Technol. 113: 151–166. doi: 10.1016/j.tifs.2021.03.021
[IARC] International Agency for Research on Cancer. 2012. Mineral oils, untreated or mildly treated. IARC monographs on the evaluation of carcinogenic risks to humans. Vol. 100. Lyon (France): World Health Organization.
Miller MJ, Lonardo EC, Greer RD, Bevan C, Edwards DA, Smith JH, Freeman JJ. 1996. Variable responses of species and strains to white mineral oils and paraffin waxes. Regul Toxicol Pharmacol. 23 (1 Pt 1): 55–68. doi: 10.1006/rtph.1996.0009
Nestola M, Schmidt TC. 2017. Determination of mineral oil aromatic hydrocarbons in edible oils and fats by online liquid chromatography–gas chromatography–flame ionization detection–evaluation of automated removal strategies for biogenic olefins. J Chromatogr A. 1505: 69–76. doi: 10.1016/j.chroma.2017.05.035
Purcaro G, Moret S, Conte LS. 2013. Overview on polycyclic aromatic hydrocarbons: occurrence, legislation and innovative determination in foods. Talanta. 105: 292–305. doi: 10.1016/j.talanta.2012.10.041
Stauff A, Schnapka J, Heckel F, Matissek R. 2020. Mineral oil hydrocarbons (MOSH/MOAH) in edible oils and possible minimization by deodorization through the example of cocoa butter. Eur J Lipid Sci Technol. 122 (7): 1900383–12. doi: 10.1002/ejlt.201900383
Trimmer GW, Freeman JJ, Priston RAJ, Urbanus J. 2004. Results of chronic dietary toxicity studies of high viscosity (P70H and P100H) white mineral oils in Fischer 344 rats. Toxicol Pathol. 32 (4): 439–447. doi: 10.1080/01926230490465865