Abstract
Ethyl carbamate, a by-product of fermentation and storage with widespread occurrence in fermented food and alcoholic beverages, is a compound potentially toxic to humans. In this work, a new approach for quantitative detection of ethyl carbamate in alcoholic beverages, based on surface-enhanced Raman scattering (SERS), is reported. Individual silver-coated gold nanoparticle colloids are used as SERS amplifiers, yielding high Raman enhancement of ethyl carbamate in three kinds of alcoholic beverages (vodka, Obstler, and white rum). The characteristic band at 1,003 cm-1, which is the strongest and best reproducible peak in the SERS spectra, was used for quantitative evaluation of ethyl carbamate. The limit of detection, which corresponds to a signal-to-noise ratio of 3, was 9.0 × 10-9 M (0.8 μg · L-1), 1.3 × 10-7 M (11.6 μg · L-1), and 7.8 × 10-8 M (6.9 μg · L-1), respectively. Surface-enhanced Raman spectroscopy offers great practical potential for the in situ assessment and identification of ethyl carbamate in the alcoholic beverage industry.
Similar content being viewed by others
References
Park SK, Kim CT, Lee JW, 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
Ubeda C, Balsera C, Troncoso AM, Callejón RM, Morales ML (2012) Validation of an analytical method for the determination of ethyl carbamate in vinegars. Talanta 89:178–182
Lee KG (2013) Analysis and risk assessment of ethyl carbamate in various fermented foods. Eur Food Res Technol 236:891–898
Hamlet CG, Jayaratne SM, Morrison C (2005) Application of positive ion chemical ionisation and tandem mass spectrometry combined with gas chromatography to the trace level analysis of ethyl carbamate in bread. Rapid Commun Mass Spectrom 19:2235–2243
Woo IS, Kim IH, Yun UJ, Chung SK, Rhee IK, Choi SW, Park HD (2001) An improved method for determination of ethyl carbamate in Korean traditional rice wine. J Ind Microbiol Biotechnol 26:363–368
Ha MS, Kwon KS, Kim M, Park HR, Hu SJ, Lee H, Kim KM, Ko EJ, Ha SD, Bae DH (2006) Exposure assessment of ethyl carbamate in alcoholic beverages. J Microbiol Biotechnol 16:480–483
Alcarde AR, de Souza LM, Bortoletto AM (2012) Ethyl carbamate kinetics in double distillation of sugar cane spirit. J Inst Brew 118:27–31
Wu P, Pan X, Wang L, Shen X, Yang D (2012) A survey of ethyl carbamate in fermented foods and beverages from Zhejiang, China. J Food Control 23:286–288
Haddow A, Sexton WA (1946) Influence of carbamic esters (Urethanes) on experimental animal tumours. Nature 157:500–503
International Agency for Cancer Research (2007) Alcohol consumption and ethyl carbamate. IARC monographs on the evaluation of carcinogenic risks to humans, vol 96. Lyon, France
Beland FA, Benson RW, Mellick PW, Kovatch RM, Roberts DW, Fang JL, Doerge DR (2005) Effect of ethanol on the tumorigenicity of urethane (ethyl carbamate) in B6C3F(1) mice. Food Chem Toxicol 43:1–19
Baan R, Straif K, Grosse Y, Secretan B, El Ghissassi F, Bouvard V, Altieri A, Cogliano V (2007) Carcinogenicity of alcoholic beverages. Lancet Oncol 8:292–293
Weber JV, Sharypov VI (2009) Ethyl Carbamate in Foods and Beverages - A Review. Environ Chem Lett 7:233–247
AOAC International (2009) Ethyl Carbamate (Urethane) in Distilled Spirits. Official methods of analysis 993.04
Baffa Junior JC, Santos Mendonca RC, Teixeira Kluge Pereira JMDA, Marques Pereira JA, Ferreira Soares NDF (2011) Ethyl-carbamate determination by gas chromatography-mass spectrometry at different stages of production of a traditional Brazilian spirit. Food Chem 129:1383–1387
Xu X, Gao Y, Cao X, Wang X, Song G, Zhao J, Hu Y (2012) Derivatization followed by gas chromatography-mass spectrometry for quantification of ethyl carbamate in alcoholic beverages. J Sep Sci 35:804–810
Brumley WC, Canas BJ, Perfetti GA, Mossoba MM, Sphon JA, Corneliussen PE (1988) Quantitation of ethyl carbamate in whiskey, sherry, port, and wine by gas-chromatography tandem mass-spectrometry using a triple quadrupole mass-spectrometer. Anal Chem 60:975–978
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
Chung SWC, Kwong KP, Chen BLS (2010) Determination of ethyl carbamate in fermented foods by GC-HRMS. Chromatographia 72:571–575
Fu M, Liu J, Chen Q, Liu X, He G, Chen J (2010) Determination of ethyl carbamate in Chinese yellow rice wine using high-performance liquid chromatography with fluorescence detection. Int J Food Sci Technol 45:1297–1302
Ajtony Z, Szoboszlai N, Bencs L, Viszket E, Mihucz VG (2013) Determination of ethyl carbamate in wine by high performance liquid chromatography. Food Chem 141:1301–1305
Madrera RR, Valles BS (2013) Determination of ethyl carbamate in cider spirits by HPLC-FLD. Food Control 20:139–143
de Resende Machado AM, Cardoso MDG, Saczk AA, dos Anjos JP, Zacaroni LM, Dorea HS, Nelson DL (2013) Determination of ethyl carbamate in cachaca produced from copper stills by HPLC. Food Chem 138:1233–1238
Deak E, Gyepes A, Stefanovits-Banyai E, Dernovics M (2010) Determination of ethyl carbamate in palinka spirits by liquid chromatography-electrospray tandem mass spectrometry after derivatization. Food Res Int 43:2452–2455
Yaffe NR, Blanch EW (2008) Effects and anomalies that can occur in SERS spectra of biological molecules when using a wide range of aggregating agents for hydroxylamine-reduced and citrate-reduced silver colloids. Vib Spectrosc 48:196–201
Xie Y, Li Y, Niu L, Wang H, Qian H, Yao W (2012) A novel surface-enhanced Raman scattering sensor to detect prohibited colorants in food by graphene/silver nanocomposite. Talanta 100:32–37
Zhang Z, Liu R, Xu D, Liu J (2012) In situ detection of acid orange II in food based on shell-isolated Au@SiO2 nanoparticle-enhanced Raman spectroscopy. Acta Chim Sin 70:1686–1689
Wang Y, Yan B, Chen L (2013) SERS Tags: Novel Optical Nanoprobes for Bioanalysis. Chem Rev 113:1391–1428
Frens G (1973) Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions. Nat Phys Sci 241:20–22
Liu B, Han G, Zhang Z, Liu R, Jiang C, Wang S, Han M (2011) Shell thickness-dependent Raman enhancement for rapid identification and detection of pesticide residues at fruit peels. Anal Chem 84:255–261
Constantino CJL, Lemma T, Antunes PA, Aroca R (2001) Single-molecule detection using surface-enhanced resonance Raman scattering and Langmuir-Blodgett monolayers. Anal Chem 73:3674–3678
Yang D, Mircescu NE, Zhou H, Leopold N, Chiş V, Oltean M, Ying Y, Haisch C (2013) DFT study and quantitative detection by surface-enhanced Raman scattering (SERS) of ethyl carbamate. J Raman Spectrosc. doi:10.1002/jrs.4375
Acknowledgments
This work was supported by the Research Fund for the Doctoral Program of Higher Education (no. 20120101130009) and the China Scholarship Council. Natalia P. Ivleva is thanked for instruction on how to use the Raman instrument, and M. Hanzlik is thanked for TEM measurements.
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(PDF 1995 kb)
Rights and permissions
About this article
Cite this article
Yang, D., Zhou, H., Ying, Y. et al. Surface-enhanced Raman scattering for quantitative detection of ethyl carbamate in alcoholic beverages. Anal Bioanal Chem 405, 9419–9425 (2013). https://doi.org/10.1007/s00216-013-7396-x
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-013-7396-x