New method for the discovery of adulterated cognacs and brandies based on solid-phase microextraction and gas chromatography - mass spectrometry
The article represents new method for discovery of adulterated cognacs and brandies based on solidphase microextraction (SPME) in combination with gas chromatography – mass spectrometry (GC-MS). The work comprised optimization of SPME parameters (extraction temperature and time, concentration of added salt) with subsequent analysis of authentic samples and comparison of the obtained chromatograms using principal component analysis (PCA). According to the obtained results, increase of extraction temperature resulted in an increase of response of the most volatile brandy constituents. To avoid chemical transformations and/or degradation of the samples, the extraction temperature must be limited to 30!C. Increase of the extraction time lead to higher total peak area, but longer extraction times (>10 min for 100 µm polydimethylsiloxane and >2 min for divinylbenzene/Carboxen/polydimethylsiloxane fibers) caused displacement of analytes. Salt addition increased total response of analytes, but caused problems with reproducibility. The developed method was successfully applied for discovery of adulterated samples of brandy, cognac, whisky and whiskey sold in Kazakhstan. The obtained data was analyzed applying principal component analysis (PCA). Five adulterated brandy and whisky samples were discovered and confirmed. The developed method is recommended for application in forensic laboratories.
1 Yoki.ru News (2013) Czech police confiscated more than one million liters of illegal alcohol [Cheshskaya policiya konfiskovala bolle milliona litrov nelegalnogo alkogolya]. http://www.yoki.ru/news/news/24-05-2013/403018-illegal-0/ (Accessed 05/05/2014, In Russian)
2 BBC News (2012) Czechs partially lift spirits ban after mass poisoning. http://www.bbc.com/news/world-europe-19738765 (Accessed 05/05/2014)
3 (2001) GOST R 51786-2001. Vodka and ethanol originated from food raw material. Gas chromatographic method for determination of authenticity [Vodka i spirt etilovyiy iz pischevogo syrya. Gazohromatograficheskiy metod opredeleniya podlinnosti]. Izdatelstvo Standartov, Moscow, Russia. (In Russian)
4 (2001) GOST R 51698-2000. Vodka and ethanol originated from food raw material. Express gas chromatographic method for determination of toxic microimpurities [Vodka i spirt etilovyiy iz pischevogo syrya. Gazohromatograficheskiy ekspress-metod opredeleniya soderzhaniya toksichnyih mikroprimesey]. Izdatelstvo Standartov, Moscow, Russia. (In Russian)
5 García-Falcón MS, Simal-Gándara J (2005) Food Addit Contam 22:791-797. http://dx.doi.org/10.1080/02652030500198498
6 Schwarz M, Rodríguez MC, Guillén DA, Barroso CG (2009) J Sep Sci 32:1782-1790. http://dx.doi.org/10.1002/jssc.200800706
7 Lachenmeier DW (2007) Food Chem 101:825–832. http://dx.doi.org/10.1016/j.foodchem.2005.12.032
8 Pontes MJC, Santos SRB, Araujo MCU, Almeida LF, Lima RAC, Gaiao EN, Souto UTCP (2006) Food Res Int 39:182–189. http://dx.doi.org/10.1016/j.foodres.2005.07.005
9 Ogrinc N, Kosir IJ, Spangenberg JE, Kidric J (2003) Anal Bioanal Chem 376:424-430. http://dx.doi.org/10.1007/s00216-003-1804-6
10 Savchuk SA, Kolesov GM (2005) J Anal Chem+ 60:752–771. http://dx.doi.org/10.1007/s10809-005-0176-9
11 Dall'Asta C, Cirlini M, Morini E, Galaverna G (2011) J Chromatogr A 42:7557-7565. http://dx.doi.org/10.1016/j.chroma.2011.08.042
12 Fitzgerald G, James KJ, MacNamara K, Stack MA (2000) J Chromatogr A 896:351–359. http://dx.doi.org/10.1016/S0021-9673(00)00737-8
13 Pino JA (2007) Food Chem 104:421–428. http://dx.doi.org/10.1016/j.foodchem.2006.09.031
14 Camara JS, Marques JC, Perestrelo RM, Rodrigues F, Oliveira L, Andrade P, Caldeira M (2007) J Chromatogr A 1150:198–207. http://dx.doi.org/10.1016/j.chroma.2006.09.014
15 Cardeal ZL, Marriott PJ (2009) Food Chem 112:747–755. http://dx.doi.org/10.1016/j.foodchem.2008.06.057
16 Rodrigues F, Caldeira M, Camara JS (2008) Anal Chim Acta 609:82–104. http://dx.doi.org/10.1016/j.aca.2007.12.041
17 Plutowska B, Wardencki W (2008) Anal Chim Acta 613:64–73. http://dx.doi.org/10.1016/j.aca.2007.12.041
18 Bacchus OJSC (2014) Three-stars ordinary cognac “Kazakhstan”. http://bacchus.kz/en/catalog/cognac/ordinary/58-konyak-tri-zvezdochki.html (Accessed on 05/05/2014, In Russian)
19 Cognac.fr (2014) Cognac. Controlled appellation of origin. http://www.cognac.fr/cognac/_en/2_cognac/index.aspx?page=appellation (Accessed on 15/05/2014)
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License (CC BY-NC-ND 4.0) that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.