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TERMINOLOrY: COCOA . Cocoa is a very broad term used to describe the plant theobroma cocao L, flavorants derived from that plant, and the characteristic flavor itself.,' The flavorants can be one of several materials, cocoa beans,.,cocoa bean shells or cocoa powder. The terms raw cocoa or c-aYao are ~usually applied to the unroasted bean.1 None of these terms has a chemical meaning, as "cocoa," in whatever form,i!5a com- bination of hundreds or thousands of chemical compounds. Cocoa should not be confused with chocolate which is a flavor synthesized by mixing cocoa with-other flavorants, principally vanillin and sugar.2 In the United States three types of cocoa powder are 1 recognized and have-definitions and standards of identity. These are (1) "breakfast cocoa" or high fat cocoa containing not less-than 22% cocoa fat, (2) "cocoa" or mediU'm fat cocoa containing between 10 and 22% cocoa fat, and (3) "low-fat cocoa" containing less than 10% cocoa fat. SOURCE: Material from any of these steps can be used to give particular types of cocoa flavor. The chemistry of cocoa is extremely com- plex and beyond the scope of this report. A recent review of this area is attached.3 0 The various forms of cocoa are derived from the theobroma cocoa plant which is indigenous to South and Central America. The bean is fermented, roasted and milled during processing. Synthetic cocoas have been available for a number of years. Exact compositions of the synthetics vary with the intended use and are usually proprietary. . . .~,. V5 , since earliest times4 both as a sweetner and to-add its own charac- teristic teristic flavor. In recent years it has commonly been added to USAGE: . Cocoa has gained wide appl;cation in the tobacco_industrv the burley tobacco of cic~arette blends to enhance the cocoa-like O aroma inherent in burley and, at the same time, suppress undesir- able odors, thereby improving the smoking quality. ~5 ~ N BIOLOGICAL DATA: C~ t11 Toxicity data on cocoa_is apparently limited to a 1941 study on guinea pigs.5 An extract of cocoa shell was found to lower the toxi- city of caffeine when injected intraperitoneally. This effect was !

., fairly substantial as the maximum tolerated, dose of caffeine was raised from 100 mg per kg to 150 mg per kg and the LD50 changed from 221 mg per kg to 250 mg per kg. , Studies of the biological effects of cocoa have centered on calcium assimilation due to cocoa's high oxalic acid content and the effects of theobromine and,caffeine. Several studies have indicated that although cocoa'does reduce calcium assimi- lation in laboratory animals 7,8,9, this effect is not great enough to merit concern in humans. •-. Theobromine and caffeine are found in cocoa in the range of approximately-20 mg/kg for the former and 200 mg/kg in the latter. 10,11 Both have effects on the central nervous.•system and are moderately toxic.12 The oral LD50 of caffeine-in female albino rats was found to be .192 g/kg body weight.-13 Deaths occurred- at 30.0 + 9.6 hrs. and were immediately due to respiratory fail- ure following tetanic convulsions or to cardivascular-collapse. The chronic toxicity of caffeine has also been studied14 in female albino rats when the dose was applied daily by intra- gastric cannula. Over 100 days the maximum daily dose producing no deaths was 110 ± 2.5 mg/kg. Fifty percent mortality was achieved using 150 ± 3.1 mg/kg. It is of interest that a high correlation has been found between the lethal effects of caffeine and the grouping of subject mice.15 The adverse effects are much lower when the subject$ are isolated rather than caged in groups. Caffeine has been found to be teratogenic in rats16 and mutagenic by the Ames test.17 The LDLo in humans is 26 mg/kg (oral) for theobromine and 7 mg/kg (iv) for caffeine.12 Possible carcino- genic effects are still being evaluated. -Caffeine and theobro- mine have been found in cigarette smoke.18 Attempts to study the large number of other compon~nts of cocoa are necessarily complex. In the attached article.3 is a list of 352 volatile compounds in cocoa compiled in 1975.19 This list could-doubtles_s be expanded today and, of course, would not include non-volatiles such as sugars and amino acids. Fifty-nine percent of the compQunds cited are generated by tobacco itself during burning.i A recent study20 using the Ames test to determine mutagenicity evaluated 39 of the compounds cited-and none was mutagenic. These are listed in Table 1. }fiqy w. ~ One report has been published by the National Cancer -Institute in which the effect of addition of cocoa to cigarettes was studied. Smoke condensate from cigarettes treated with 1% by weight cocoa F, was used in mouse skin painting experiments. A somewhat higher V :, degree of tumorigenic activity was found for this condensate than `,4 for the control. - ci ~ PYROLYTIC DATA: During the course of the NCI study21 some analysis of delivery of various chemicals was made. Cocoa addition gave increased phenol yields by approximately 25%. However, other compounds of interest such as acetal, acrolein, isoprene, hydrogen cyanide, formaldehyde, nitrogen oxides, and carbon monoxides were unaffected. No other studies of the effect of cocoa on the chemical composition of main-

} Table Non-Mutagenic Cocoa and S.moke Volatiles Alcohols Methanol Ethanol 2-Propanol alpha-Terpineol Geraniol Farnesol Fufurylalcohol Benzylalcohol 2-Phenylethanol 5-Hydroxymethylfurfural Aldehydes 3-Methylbutanal 2-Methylbutanal 2-Methylpropenal 2-Butenal Benzaldehyde Vanillin 5-Methylfufural Miscellaneous 3,5-Dirnethoxy 1:4-hydroxybenzoic Benzyl acetate Benzyl cyanide Pyrazine acid Ketones 2-Propanone 2-Butanone ..2, 3-Butanedione 2,3-Pentanedione 3-Penten-2-one 6-Me"thyl-5-hepten-2-one Acetophenone Phenols 2,3-Dimethylphenol Phenol o-Cresol p-Cresol m-Cresol 4-Ethylphenol 2-Methoxyphenol 2-Methylpyrr,azine 2,6-Dimethylpyrazine 1-Amino-2-methylpropane 2-Aminopentane ~- • .`

stream smoke have been undertaken. Phenols were also found when cocoa was pyrolyzed alone. In a report by Schlotzhauer22 a variety,of phenolic products plus palmetic and stearic acid were identified in pyrolyses carried- out between 350° and 750°C. The total phenolic yield was minor (0.049-0.101%) and relatively stable.over the temperature range. REGULATORY STATU9: f . ~ Cocoa is regulated as a food rather than a food additive. Therefore, a designation such as "generally regarded as safe" is not applicable. A variety of regulations.exist as to the acceptable con- stituents in the various commercial cocoa products (CFR 163.110).23

i. Kirk-Othmer Encylopedia of Chemical Technology, 2nd Edition, J. Wiley & Sons, New York, 1964. '.' 2. T. E. Furia, N. Bellanca, ed.,-Fenaroli's Handbook of Flavor Ingredients, CRC Press, Cleyeland, 1975. ` 3. G. F. Harllee, J. C. Leffingwell, Int. Tob. Int., 181, Iss5, (1979) 40; 181; Iss6 (1979) 18. jN- ; 4. G. C. Harlee, J. C. Leffingwell, "Composition-of Casing Materials: Cocoa, its Constituents and their Organoleptic Properties," 32nd Tobacco-Chemists Conference,, Montreal (1978). 5. Travais, R. C., Information on American Blended Cigarettes, 1959. 6. L. Millat, "Toxicity of Cacao Shells and the Influence of these on the Toxicity of Caffeine," Compt. Rend., 213 (1941) 591-3. 7. M. L. Brucher, J. M. Smith, T. S. Hamilton, H..H. Mitchell, "The Effect of Cocoa on Calcium Utilization...", J. Nutrion., 39 (1949) 445-61. , 8. H. H. Mitchell, T. S. Hamilton, "The Effect of Different Grades of Cocoa upon the Retention of Dietary Calcium by Growing Rats," J. Nutrion, 31 (1946) 377-86. 9. H. H. Mitchell, J. M. Smith, "The Effect of Cocoa on Utilization of Dietary Calcium," J. Am. Med. Assoc., 129 (1945) 871-3. 10. A. Fincke, "The Occurrence of Caffeine and Theobromine in Cocoa Fats," Fette, Seifen, Anstrichmittel, 65 (1963) 647-50. 11. A. Beinzail, "Xanthic Bases in Belgium Congo Cocoa Beans," Bull. Agr. Belg. Congo, 50 (1959) 689-96. 12. Registry of Toxic Effects of Chemical Substances, DHHS/NIOSH-80- 111, 1980. Pharmacol., 1 (1959) 750-7. t 14. E. M. Boyd, Mortimer Dolman, L. M. Knight,-E. P. Sheppard, "The Chronic Oral Toxicity of Caffeine," Can. J. Physiol. Pharmacol., 43 (1965) 995-1007. 13. E. M. Boyd, "The Acute Oral Toxicity of Caffeine," Toxicol. Appl. 15. E. N. Greenblatt, A. C. Osterberg, "Correlations of Activity and Lethal Effects of Excitatory Drugs in Grouped and Isolated Mice," J. Pharmacol. Exptl. Therap., 131 (1961) 115-91. 16. E. Schwam, M. Bertrand, "Regular and Specific Teratogenic Effect of Caffeine on Rodents," Compt. Rend. Soc. Biol., 159 (1965) 2199-202. 17. R. B. Kurzel. "The Effects of Environmental Pollutants on Human Reproduction," Env. Sci. Tech., 15 (1981) 626. Q ~ ~ : tD .. ::wwA, : .

18. J. N. Schumacher, et al, J. Agric and Food Chem., 25 (1977). 310-320. 19. T. E. Furia, N. Bellanca, ed.,'.fFenarolli's Handbook of Flavor Ingredients, 2nd Edition, CRC Press, Cleveland, 1975. ~ , 18 (1980), 219-232. 20. I. Florian, L. Rutberg, Toxicolo 21. Nat. Cancer. Inst., "Toward Less Hazardous Cigarettes," Report No. 3, NEW/NCI, 1976. . • . .- . . . •.4 .. . . / 22. W. S. Schlotzhauer, "Fatty Acid and Phenols from Pyrolysis of Cocoa Powder," Tob. Sci., XXII (1978) 1.. . .;~..; y. . ,. .. ,.. f.. 23. Code of Federal Reguiations, 21, Food and Drugs, 1977, p. 319. i . .~, -~~.