Abstract
In this work, we describe a 2-min direct injection electrospray tandem quadrupolar mass spectrometric method for ethyl carbamate (EC) detection in Brazilian sugar cane spirit (SCS). Analyses were carried out with 18-crown-6/trifluoracetic acid (30 ppm/0.1%) additives to sequester metal cations by eliminating unwanted [EC + Na]+ and [EC + K]+ ions, favoring analyte detection as sole [EC + H]+ ions. Standard addition of EC was carried out with 18-crown-6/trifluoracetic acid (30 ppm/0.1%), resulting in spiked SCS samples (0, 75, 150, 300, 450, 600, 750, and 900 μg L−1). A carrier solution of methanol:18-crown-6:trifluoroacetic acid (99.9:30 ppm:0.10, v/v/v) was pumped to the mass spectrometer using positive ion mode and multiple reaction monitoring of 90 > 62 for EC. The limits of detection and quantification were 7.5 and 75.0 μg L−1, respectively, and the dynamic range used was 75–900 μg L−1. The validation results and application of the method to the analysis of real samples and certified SCS demonstrate its applicability to quality control and regulatory analysis.
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References
Abreu SM, Alves A, Oliveira B, Herbert P (2005) Determination of ethyl carbamate in alcoholic beverages: an interlaboratory study to compare HPLC-FLD with GC-MS methods. Anal Bioanal Chem 382:498–503
Agencia Nacional de Vigilância Sanitária - ANVISA (2003) GUIA PARA VALIDAÇÃO DE MÉTODOS ANALÍTICOS E BIOANALÍTICOS MÉTODOS-RE no 899, 1–12
Aresta M, Boscolo M, Franco DW (2001) Copper(II) catalysis in cyanide conversion into ethyl carbamate in spirits and relevant reactions. J Agric Food Chem 49:2819–2824
Baffa Júnior JC, Mendona RCS, Pereira JMATK, Pereira JAM, Soares NFF (2011) Ethyl-carbamate determination by gas chromatography-mass spectrometry at different stages of production of a traditional Brazilian spirit. Food Chem 129:1383–1387
Bruno SNF, Vaitsman DS, Kunigami CN (2007) Influence of the distillation processes from Rio de Janeiro in the ethyl carbamate formation in Brazilian sugar cane spirits. Food Chem 104:1345–1352
Chen D, Ren Y, Zhong Q, Shao Y, Zhao Y, Wu Y (2017) Ethyl carbamate in alcoholic beverages from China: levels, dietary intake, and risk assessment. Food Chem 72:283–288
FAO (1997) Food and Agriculture Organization of the United Nations, Validation of analytical methods for food control. http://www.fao.org/3/a-w8420e.pdf. Accessed 10 Aug 2018
FDA (2013) Food and Drug Administration, Guide for Industry, Bioanalytical Method Validation. Available on < https://www.fda.gov/downloads/drugs/guidances/ucm368107.pdf > Accessed on April 9th 2018
Fenn JB, Mann M, Meng CK, Wong SF, Whitehouse CM (1989) Electrospray ionization for mass spectrometry of large biomolecules. Science 246:64–71
INMETRO (2016) National institute of metrology, quality and technology. Certificate of Reference Material. Available on:<http://www.inmetro.gov.br/metcientifica/mrc.asp> Accessed March 2, 2017
Kostiainen R, Kauppila TJ (2009) Effect of eluent on the ionization process in liquid chromatography-mass spectrometry. J Chrom A 1216:685–699
Lachenmeier DW, Frank W, Kuballa T (2005) Application of tandem mass spectrometry combined with gas chromatography to the routine analysis of ethyl carbamate in stone-fruit spirits. Rapid Commun Mass Spectrom 19:108–112
Leça M, Pereira V, Pereira AC, Marques JC (2014) Rapid and sensitive methodology for determination of ethyl carbamate in fortified wines using microextraction by packed sorbent and gas chromatography with mass spectrometric detection. Anal Chim Acta 811:29–35
Li G, Zhong Q, Wang D, Zhang X, Gao H, Shen S (2015) Determination and formation of ethyl carbamate in Chinese spirits. Food Control 56:169–176
Machado AMDR, Cardoso MDG, Saczk AA, Anjos JP, Emídio ES, Zacaroni LM, Dorea HS, Nelson DL (2013) Determination of ethyl carbamate in cachaça produced from copper stills by HPLC. Food Chem 138:1233–1238
MAPA (2014) Ministry of agriculture, livestock and food supply. Normative Instruction No 28, of August 8, 2014. Available on:< http://www.lex.com.br/legis_25819224_INSTRUCAO_NORMATIVA_N_28_DE_8_DE_AGOSTO_DE_2014.aspx>. Accessed 2 Mar 2017
Nanita SC, Kaldon LG (2016) Emerging flow injection mass spectrometry methods for high-throughput quantitative analysis. Anal Bioanal Chem 408(1):23–33. https://doi.org/10.1007/s00216-015-9193-1
Park S-K, Kim CT, Lee J-W, Jhee OH, Om AS, Kang JS, Moon TW (2007) Analysis of ethyl carbamate in Korean soy sauce using high-performance liquid chromatography with fluorescence detection or tandem mass spectrometry and gas chromatography with mass spectrometry. Food Control 18:975–982
Ryu D, Choi B, Kim N, Koh E (2016) Validation of analytical methods for ethyl carbamate in nine food matrices. Food Chem 211:770–775
Tonin APP, Ribeiro M, Silva VM, Oliveira CC, Saragiotto MH, Eberlin MN, Meurer EC (2017) 18-Crown-6 spiking in direct infusion ESI–MS analysis of complex mixtures: “one ion per analyte” relationship facilitating ion assignments and eliminating isobaric interferences. Int J Mass Spectrom 418:37–40
Zimmerli B, Schlatter J (1991) Ethyl carbamate: analytical methodology, occurrence, formation, biological activity and risk assessment. Mutat Res 259:325–350
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This study received financial support from the Waters Company, Forquimica Company, Jamel Company and UFPR.
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Marcos Alessandro Ribeiro declares that he has no conflict of interest. Angelica Parussolo Tonin declares that she has no conflict of interest. Camila Burihan Poliseli declares that she has no conflict of interest. Jesui Vergilio Visentainer declares that he has no conflict of interest. Claudio Celestino de Oliveira declares that he has no conflict of interest. Valquiria de Moraes Silva declares that she has no conflict of interest. Eduardo Cesar Meurer declares that he has no conflict of interest.
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Ribeiro, M.A., Tonin, A.P.P., Poliseli, C.B. et al. Determination of Ethyl Carbamate in Sugar Cane Spirit by Direct Injection Electrospray Ionization Tandem Mass Spectrometry Using 18-Crown-6/Trifluoroacetic Acid Spiking Additives. Food Anal. Methods 12, 69–75 (2019). https://doi.org/10.1007/s12161-018-1339-2
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DOI: https://doi.org/10.1007/s12161-018-1339-2