Express determination of croton aldehyde in alcoholic beverages by gas chromatography-mass spectrometry
Abstract
The article presents an express method for determining croton aldehyde in alcoholic beverages using gas chromatography-mass spectrometry (GC-MS). The development is aimed at solving the problem of improving the analytical quality control and safety of alcoholic beverages. Comparison of the results of the determination of the volume fraction of croton aldehyde in model solutions obtained by GC-MS and gas chromatography with flame ionization detection (GC-FID) showed the identity of the definitions within acceptable errors, which allows us to conclude that it is advisable to use a combination of these two analytical tools for reliable identification of alcohol-containing products. Currently, GC-MS is becoming a priority instrumental method used in accredited analytical laboratories in the identification of contaminants in alcoholic beverages. Croton aldehyde is contained in quantities higher than MPC in alcohol surrogates, in denatured ethanol. The development of express methods for identification and quantitative determination of croton aldehyde on chromato-mass spectrometric equipment is an urgent problem. The analysis was performed on an Agilent 8890 gas chromatograph equipped with a Model 5977B mass-selective detector and a 50 m long HP-FFAP high-polarity capillary column. As a result of the experiments carried out, optimal modes for the determination of croton aldehyde were selected. The developed method for determining croton aldehyde in alcoholic beverages using GC-MS can be recommended for use in quality control and safety of alcoholic beverages, as well as in forensic medical examination as a reference technique to confirm the reliability of identification of croton aldehyde. The most effective in such identification are parallel definitions using GC-MS and a certified methodology using GC-FID (GOST 31811-2012).
Downloads
References
Rudakov O.B., Shelekhova N.V., Polyanskij K.K., Selemenev V.F. Opre-delenie furfurola v etilovom spirte i vodkah metodom gazovoj hromato-mass-spektrometrii. Sorbtsionnye i khromato-graficheskie protsessy. 2021; 21(6): 812-818. https://doi.org/10.17308/soipchrom.2021.21/3826 (In Russ.)
Rudakov O.B., Shelekhova N.V., Rudakov YA.O. et al. Ekspressnoe opre-delenie metanola v spirtnyh napitkah metodom gazovoj hromato-mass-spektrometrii. Sorbtsionnye i khromato-graficheskie protsessy. 2022; 22(2): 116-125. https://doi.org/10.17308/sorpchrom.2022.22/9214 (In Russ.)
Nikitina S.Yu., Rudakov O.B., Grigor'ev A.M. Primenenie hromato-mass-spektrometrii dlya identifikacii mikro-primesej v pobochnyh frakciyah rektifiko-vannogo spirta iz melassy. Proizvodstvo spirta i likyoro-vodochnyh izdelij. 2013; 4: 38-41. (In Russ.)
Nikitina S.Yu. Sovremennoe sos-toyanie i osnovnye napravleniya razvitiya tekhnologii rektifikacionnoj ochistki pishchevogo etanola v Rossii. Pr-vo spirta i likyoro-vodochnyh izdelij. 2011; 3: 4-7. (In Russ.)
Nikitina S.Yu. Skhemotekhnika i metodiki raschyotov bragorektifikacionnyh ustanovok. Voronezhskij GASU. Voronezh; 2013. 208 р.
Gryaznov V.P. Prakticheskoe rukovodstvo po rektifikacii spirta. M.: Pishchevaya promyshlennost'; 1968. 195 р.
Wyganowski, C. Spectrophotomet-ric determination of crotonaldehyde. Mikrochim Acta. 1978; 69: 229-232. https://doi.org/10.1007/BF01201728
Metodicheskie ukazaniya po izme-reniyu koncentracij vrednyh veshchestv v vozduhe rabochej zony. No 27. CHast' 2 M.: Rarog; 1992: 415-419. (In Russ.)
Pohanish R.P. Crotonaldehyde. In: Sittig’s hand-book of toxic and hazardous chemicals and carcinogens. 6th ed. Oxford, UK: Elsevier; 2012: 2044-2297. https://doi.org/10.1016/C2009-0-64361-0
Bagchi P., Geldner N., de Castro B.R., De Jesús V.R., Park S.K., Blount B.C. Crotonaldehyde exposure in US tobacco smokers and nonsmokers NHANES 2005-2006 and 2011-2012. Environ Res. 2018; 163: 1-9. https://doi.org/10.1016/j.envres.2018.01.033
Blumenstein J., Schulz R.P., Kohlpaintner C. Crotonaldehyde and cro-tonic acid. In: Ullmann’s encyclopedia of industrial chemistry. 7th ed. New York City (NY), USA: John Wiley; 2000. p. 1-9. https://doi.org/10.1002/14356007.a08_083
Shelekhova N.V. Ekspress-metod opredeleniya letuchih organicheskih primesej v spirtnyh distillirovannyh napit-kah na osnove sochetaniya GH/PID i GH/MSD. Sorbtsionnye i khromatografich-eskie protsessy. 2022; 22(1): 58-68. https://doi.org/10.17308/sorpchrom.2022.22/9021 (In Russ.)
Shelekhova N.V., Polyakov V.A. Sovershenstvovanie sistemy kontrolya tekhnologicheskih processov proizvodstva spirtnyh napitkov. Pivo i napitki. 2017; 1: 34-36. (In Russ.)
Shelekhova N.V., SHelekhova T.M., Skvorcova L.I., Poltavskaya N.V. Sovremennoe sostoyanie i perspektivy razvitiya kontrolya kachestva alkogol'noj produkcii. Pishchevaya promyshlennost'. 2019; 4: 117-119. (In Russ.)
Shelekhova N.V., Rimareva L.V. Upravlenie tekhnologicheskimi processami proizvodstva alkogol'noj produkcii s primeneniem informacionnyh tekhnologij. Khranenie i pererabotka sel'hozsyr'ya. 2017; 3: 28-31. (In Russ.)
Shelekhova N.V., Shelekhova T.M., Veselovskaya O.V., Skvorcova L.I. Opre-delenie soderzhaniya denaturiruyushchej dobavki (krotonovogo al'degida) v etilo-vom spirte i spirtosoderzhashchej produkcii metodom gazovoj hromatografii. Nauka i obrazovanie v zhizni sovremennogo ob-shchestva: sb. nauchnyh trudov po materi-alam Mezhdunar. nauchno-prakticheskoj konferencii: v 14 tomah, Tambov, 30 aprelya 2015 g. Tambov; 2015: 161-162. (In Russ.)
Rudakov O.B., Nikitina S.YU. Trendy v analiticheskom kontrole kachest-va pit'evogo etanola. Analitika i kontrol'. 2017; 21(3): 180-196. (In Russ.)
Markovskij M.G., Guguchkina T.I., Ageeva N.M. Krotonovyj al'degid: prichiny obrazovaniya i metodika opredeleniya. Bi-ologizaciya i ekologizaciya tekhnologii proizvodstv – prioritetnye napravleniya razvitiya vinodeliya: Nauchnye trudy GNU SKZNIISiV. Materialy nauchno-prakticheskogo foruma «Rol' ekologizacii i biologizacii v povyshenii effektivnosti pro-izvodstva plodovyh kul'tur, vinograda i produktov ih pererabotki», Krasnodar. 2013; 4: 185-187. (In Russ.)
Samohin A.S., Revel'skij A.I., CHepelyanskij D.A., Revel'skij I.A. Vozmozhnost' dostovernoj identifikacii neizvestnyh soedinenij pri ispol'zovanii programmy MS Search i kommercheskoj bazy dannyh mass-spektrov elektronnoj ionizacii. Mass-spektrometriya. 2011; 8(1): 65-67. (In Russ.)
Samohin A.S., Revel'skij I.A. Nadezhnoe sopostavlenie mass-spektrov, zaregistrirovannyh v identichnyh uslovi-yah, s pomoshch'yu metoda glavnyh com-ponent. Analitika i kontrol'. 2012; 16(3): 269-274. (In Russ.)
Kushnereva E.V. Metody opredele-niya krotonovogo al'degida v pishchevyh produktah. Politematicheskij setevoj el-ektronnyj nauchnyj zhurnal Kubanskogo gosudarstvennogo agrarnogo universiteta. 2013; 94: 312-324. (In Russ.)
Korotkova T.G. Raschet ravnovesi-ya krotonovogo al'degida v skheme bragorektifikacii. Izvestiya vysshih uchebn-yh zavedenij. Pishchevaya tekhnologiya. 2016; 4 (352): 100-102. (In Russ.)
Kushnereva E.V., Ageeva N.M., Guguchkina T.I. K voprosu biosinteza krotonovogo al'degida vinnymi drozhzhami i molochnokislymi bakteriyami v processe vinifikacii. Politematicheskij setevoj el-ektronnyj nauchnyj zhurnal Kubanskogo gosudarstvennogo agrarnogo universiteta. 2014; 95; 347-372. (In Russ.)
Markovskij M.G., Guguchkina T.I., Ageeva N.M. Razrabotka universal'noj metodiki opredeleniya krotonovogo al'degida v vinoprodukcii. Nauchnye trudy Gosudarstvennogo nauchnogo uchrezhdeniya Severo-Kavkazskogo zon-al'nogo nauchno-issledovatel'skogo insti-tuta sadovodstva i vinogradarstva Ros-sijskoj akademii sel'skohozyajstvennyh nauk. 2013; 4: 185-187. (In Russ.)
Nigmatullin A.T. Identifikaciya metodom hromato-mass-spektrometrii mikroprimesej v sinteticheskom etilovom spirte i poluchennom iz prirodnogo syr'ya: dis... kand. him. nauk. Ufa. 2006. 213 p.
Chumbalova ZH.A., Vetshtejn V.O. Analiticheskie vozmozhnosti spektro-fotometrii pri opredelenii krotonovogo al'degida. V sb. «Integraciya nauki i obra-zovaniya». Sb. statej po materialam mezhdunar. nauchno-prakticheskoj konfer-encii. 2017: 86-88.
GOST 31811-2012 «Spirt etilovyj i spirtosoderzhashchaya produkciya. Gazohromatograficheskij metod opredele-niya soderzhaniya krotonovogo al'degida (denaturiruyushchej dobavki)».
