Cocoa is a daily basic food for many people all over the world. Also, people engaged in healthy lifestyle often prefer carob. The aim of the present study was to evaluate occurrence of Aspergillus, Penicillium, Fusarium and Alternaria secondary metabolites in cocoa and carob available in the Russian Federation and assess mycotoxin's intake with these products. Material and methods. Concentration of 27 mycotoxins in 63 samples of cocoa and carob products was determined by ultra high-performance liquid chromatography coupled to tandem mass-spectrometric detection (UPLC-MS/MS). The list of mycotoxins included regulated ones (aflatoxins, ochratoxin A, deoxynivalenol, fumonisins, T-2 toxin, zearalenone), their derivatives and structural analogs (A and B trichothecenes), and emergent mycotoxins (alternariol, its monomethyl ether, altenuene, tentoxin, citrinin, sterigmatocistin, cyclopiazonic and mycophenolic acids, enniatins, beauvericin). Results. 29 of 41 cocoa samples were positive for beauvericin, contamination level was from 1.6 to 2184.8 μg/kg. Tentoxin, sterigmatocystin and alternatiol monomethyl ether were detected in 3 samples; their concentration varied in the ranges 0.7-1.2, 1.5-3.3 and 4.0-7.8 μg/kg correspondingly. Carob samples were positive for alternariol (14 of 22 samples, 1.5-43.1 μg/kg); tentoxin (13 samples, 0.5-8.7 μg/kg), mycophenolic acid (6 samples, 6.9-8.2 μg/kg) and for alternatiol monomethyl ether (3 samples, 1.0-1.2 μg/kg). Several samples of cocoa were contaminated with regulated mycotoxins: zearalenone (18 of 41 samples, 2.1-24.6 μg/kg), ochratoxin A (14 samples, 0.75-12.0 μg/kg) and aflatoxin B1 (2 samples, 0.59 and 0.86 μg/ kg). Several carob samples were contaminated with fumonisin B2 (7 of 22 samples, 4.2-5.2 μg/kg), ochratoxin A (5 samples, 0.5-1.4 μg/kg) and aflatoxin B1 (3 samples, 0.15-0.18 μg/kg). The ochratoxin A content in two instant cocoa beverages exceeded its maximum level (5 μg/kg) set for some plant products. Conclusion. To the best of our knowledge, the present study is the first survey devoted to emergent mycotoxin contamination of carob and cocoa alternative products marketed in the Russian Federation. The high occurrence of such mycotoxins as aflatoxins, beauvericin and ochratoxin A in these products indicates a potential health risk and the need for a hygienic assessment of cocoa and carob products' contamination not only with regulated in cocoa products aflatoxin B1, but with other mycotoxin including emergent ones. The risk of dietary intake of aflatoxins, beauvericin and ochratoxin A with cocoa products (especially with instant cocoa beverages) has been revealed for children over 7 years old in organized groups.
Keywords: UHPLC-MS/MS; aflatoxins; carob; cocoa; contamination; emergent mycotoxins; mycotoxins; ochratoxin A.
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